FLOTATION PLANT

OPTIMISATION
SECOND EDITION

Spectrum 25
Edited by Christopher J Greet
Flotation Plant
Optimisation
SECOND EDITION
Edited by Christopher J Greet

The Australasian Institute of Mining and Metallurgy

Spectrum Series 25

Published by:
The Australasian Institute of Mining and Metallurgy
Ground Floor, 204 Lygon Street, Carlton Victoria 3053, Australia
 © The Australasian Institute of Mining and Metallurgy 2019

No part of this publication may be reproduced, stored in a retrieval system or transmitted

in any form by any means without permission in writing from the publisher.

The Institute is not responsible as a body for the facts and opinions advanced in any of its
publications.

ISBN 978 1 925100 85 3

Cover images courtesy Christopher J Greet.

Front cover: One of four ball mills at the Candelaria copper/gold mine in Chile.
Back cover: One of two rough flotation lines at the Candelaria copper/gold mine in Chile.
 ‘Fall from ignorance, and you will rise to reason.’
Matshona Dhliwayo

‘Name the greatest of all inventors: Accident.’

Mark Twain

‘The great tragedy of science – the slaying of a beautiful hypothesis by an ugly fact.’
Anonymous

‘… to those who taught me that ‘hope is not a method’, and to those

whom I trust will learn to know and think about their process …’
FOREWORD
The first edition of this book brought together a group of flotation specialists, whose shared knowledge was intended to
bridge the gap between undergraduate course material and actual plant practice. In this aim, they succeeded admirably.
The second edition continues with this worthy goal in mind. It will also be invaluable for anyone looking to get the best
out of a flotation system.
A significant trend in recent years has been an increased focus on the effects of particle size and liberation on flotation
plant performance. It is worthwhile to recall Peter Munro’s advice in the foreword to the first edition (reproduced below).
He wrote that flotation is not a metaphysical process, which I interpret to mean that at the end of the day, everything
that happens in a flotation circuit can be explained in terms of the basic principles of physics and chemistry. He also
noted that flotation outcomes are completely describable in terms of the size and the liberation class of each particle. As
technology has improved, these factors have become easier to measure using techniques based on QEMSCAN and MLA, and
practitioners have been able to relate the outcomes from their flotation circuits more closely to the liberation properties of
their ores, at various stages of grinding.
It is appropriate therefore, that the reader will find instructive articles on process mineralogy and geometallurgy, as well
as methods for analysing all aspects of flotation plant performance. There are interesting descriptions of measurement
techniques for bubble size, gas holdup, bubble surface area flux and other parameters that may have a bearing on
performance. The all-important process of mass balancing for analysing the data from flotation tests, is well catered for.
Mass balancing is highly recommended for making sense of data that can sometimes appear nonsensical. At the same time,
excellent advice is given on the planning of plant trials, and the statistical analysis of data to illuminate trends or changes
in plant performance. Reagent chemistry and electrochemistry are treated in several chapters. Wise counsel on using
economics and communication to make the best use of the outcomes of metallurgical investigations for management
purposes, is included.
In the second edition, all chapters have been revisited and revised or edited where required. These tasks have mostly
been undertaken by the original authors. A new chapter has been added, Chapter 5, on the flotation of troublesome sulfide
and non-sulfide minerals. A new author has contributed to Chapter 6 on the characterisation of industrial cells. Two new
appendices – one in Chapter 8 and one in Chapter 9 – have also been added.
Chris Greet has acted as the volume editor, as he did for the first edition. He deserves our gratitude for his major
contribution to the Spectrum Series, and grateful thanks are also due to Magotteaux for their generous support.
Graeme J Jameson
Laureate Professor, University of Newcastle

FOREWORD (FIRST EDITION, 2010)

This book maintains a long tradition by the Australasian Institute of Mining and Metallurgy of publishing learned works in
flotation. Previous landmark publications by the Institute on this important subject are Principles of Flotation by I W Wark in
1938, Principles of Flotation by K L Sutherland and I W Wark in 1955 and Principles of Mineral Flotation The Wark Symposium,
edited by M H Jones and J T Woodcock in 1984.
 It is fitting that there has been a strong continuing interest in the science and engineering of the flotation process in
Australia as the industrial practice of sulfide mineral flotation was first developed at Broken Hill in New South Wales at the
beginning of the 20th century. This exciting story is lucidly told in Professor Alban Lynch’s book History of Flotation, released
by AusIMM in 2010. The importance of flotation to the mineral industry can be measured by Professor Geoffrey Blainey’s
evaluation that ‘(i)n the last thousand years of metallurgy it stands with the cyanide process, and the Bessemer process as
one of the three greatest advances’.1
I have been a practitioner in the flotation field since 1970 and have been fortunate to see it from different aspects.
From starting in production, then working with some of the early efforts to measure and control the process, going into
applied research to support concentrator operations, dabbling in new devices such as the development of the Jameson
cell followed by exposure to fundamental research on surface chemistry, flotation cell hydrodynamics and mathematical
modelling. I am currently a consultant looking at a wide range of commodities treated by the process in different countries.
Flotation is a fascinating subject covering a wide range of scientific and engineering disciplines that has never ceased to
interest me and provide intellectual stimulus.
There has been a continuing theme during my time in the field in the application of new technologies to improve our
understanding of the process. In Australia this technical understanding has come from research and academic institutions
such as the Commonwealth Scientific and Industrial Research Organisation (CSIRO), University of Melbourne, the Julius
Kruttschnitt Mineral Research Centre (JKMRC) at the University of Queensland, the Ian Wark Research Institute at the
University of South Australia and the Chemical Engineering Department of the University of Newcastle. Mining companies
both supported research and technology transfer through the Australian Minerals Industry Research Association (AMIRA)
and did significant work in their own right.
From a personal view, in the late 1960s to early 1970s, on-stream analysis produced real-time data for the control of
production plants; in the 1970s computers enabled modelling, simulation and control of the process, while in the 1980s
new techniques of surface analysis showed what was really happening on the surfaces of mineral particles, though to some
observers this may have proved Wolfgang Pauli’s observation that while solids are the creations of God, surfaces are the work
of the Devil! Advances in automated mineralogy, first the QEMSCAN, followed by the MLA, coincidentally both Australian
developments, allowed collection of detailed quantitative mineralogical data to supplement the traditional method of point
counting using an optical microscope. In the 1980s there was a revival of interest in the ‘chemical engineering’ approach
to transport processes in the pulp and froth phases brought on by the introduction of column flotation exemplified by the
work of Professor Jim Finch and Glen Dobby at McGill University in Canada. This culminated in the important concept of
bubble surface area flux of Gorain at the JKMRC. Throughout this time the size of conventional flotation machines increased
by a factor of over 200, especially rapidly in the last 15 years with more novel types used in particular applications.
However, the fundamentals of the flotation process have not changed and I exhort people in the field to remember two
fundamental points. These are:
•• Flotation is not a metaphysical process; though some of the earlier publications particularly focusing on chemistry may
have made it appear so.
•• Flotation outcomes are completely describable by using the axiom of size-by-size mineral particle behaviour by liberation
class.

1. Blainey, G, 1963. The Rush that Never Ended: A History of Australian Mining (Melbourne University Press: Melbourne).
 My career-long journey of discovery of the technical literature of the art of flotation started as a new graduate in Applied
Chemistry without any specific training in mineral processing, attempting to read the seminal works in the subject then
available in the excellent technical library of Mount Isa Mines Limited. As a notorious bibliophile, I have encompassed most
of the important publications though biased towards the ‘practical’ side.
What is missing in the English language literature of flotation is a single up-to-date volume covering all aspects of the
‘practical art’ as required by a mineral processing engineer either operating or supporting a flotation concentrator. Books
written to date have usually focused on the ‘science’ or chemistry of the process to the detriment of ‘practical’ aspects with
much useful information on the latter being either in monographs or scattered through many technical papers written
for journals and symposia. Even in the age of the internet, going through this large volume of material is a daunting
prospect. In my opinion the only comparable volume to this book is the venerable Froth Flotation 50th Anniversary Volume
published in the USA nearly 50 years ago.2 Even so it was not as oriented to practical plant problem solving as Flotation
Plant Optimisation.
This book is essentially a ‘how to’ manual and will be particularly useful as a conversion course for mineral processors such
as those whose undergraduate training has been primarily in chemical engineering. Its approach is based on the relevant
design and execution of a plant survey followed by the steps required to analyse the results to a suitable level of detail.
Chris Greet has assembled a great cast of contributors for this book, all authorities in their fields representing the leading
edge of accumulated current knowledge on relevant topics such as applied mineralogy, geometallurgy, flotation chemistry,
process analysis, mass balancing, experimental design and characterisation of industrial flotation machines. I know most
of the individual authors and can attest to their mastery of their particular areas of expertise. It has been a privilege to
have worked with them over the years and participated in the occasional ‘technical highs’ on the science and application of
flotation that have made working in the field so rewarding.
I commend the book to readers and can assure them that understanding the contents and applying the knowledge
gained to real mineral processing situations will result in improved metallurgical outcomes.
Peter Munro
Senior Principal Consulting Engineer, Mineralurgy Pty Ltd

2. Fuerstenau, D W (ed), 1962. Froth Flotation 50th Anniversary Volume (American Institute of Mining, Metallurgical and Petroleum Engineers, Inc:
New York).
ACKNOWLEDGEMENTS
Well, the cattle prod alluded to in the acknowledements to the first edition of this book appears to have worked! Kristy
Burt first broached the subject of a second edition of Flotation Plant Optimisation way back in late 2012, and I thought this
would be a walk in the park! Well. How wrong was I? Once again the weak link in the publishing chain was me. However,
after six years of following up, pushing, prodding and nagging we have finally pulled the second edition together due in
large part to Kristy’s determination and tenacity. I owe a great debt to Kristy and the AusIMM publishing team.
Again, the contributing authors (some old and some new) have my sincere thanks for offering your words of wisdom
and contributing to this work. Thank you for your patience, advice, contributions and your willingness to pass on your
knowledge. I know that your contributions do assist the reader in their endeavors to improve their operation.
It is incumbent on me to acknowledge not only Alan Buckley’s contribution to this work, but also his life’s work exploring
the surface chemistry of sulfide minerals and how this effects flotation. Alan’s passing in September 2017 represents a
significant loss to our industry. However, I would encourage young mineral scientists and engineers to use Alan’s legacy in
their work.
Magotteaux must be thanked for once again loosening the purse strings and sponsoring this work. In particular, Patrick
Viseur (my long suffering manager) must be acknowledged for approving the funding and seeing the value this volume has
and will continue to bring to the mining industry.
To the readers/users of this work I implore you to apply rigour to your work, gather the right data and analyse it correctly.
Proper data collection and analysis will bring rewards.
Finally, to my kids Erica, Jessica and Matthew: yes I may be dull, colorless and boring but I still love you and appreciate
your support.
Dr Christopher J Greet

ACKNOWLEDGEMENTS (FIRST EDITION, 2010)

I was reminded recently by my colleague, Jessica Kinal, of the day that the concept for this book was born. We were visiting
a mine in Indonesia when, to use Jessica’s word, I had just ‘bombarded’ this poor metallurgist with a detailed description of
the benefits of recovery-by-size, liberation analysis, pulp chemistry, circuit configuration and general flotation metallurgy.
It was at this point that Adrian Zarantonello suggested that I should write a book sharing my knowledge.
With the seed planted, and knowing that there are people better qualified than I to write the various chapters I set
about asking for help. I am humbled and grateful to those that contributed. My heartfelt thanks goes to: Bill Johnson,
Rob Morrison, Alan Butcher, Greg Harbort and Sarah Schwarz, Stephen Grano, Ron Woods, Alan Buckley, Kym Runge,
Tim Napier-Munn, Joe Pease and Dean David. Without their knowledge and wisdom the value of this book would be
much diminished.
I am appreciative of Magotteaux’s financial support for this project. The vision Philippe Steinier had in the early days of the
value of this project and how he convinced our masters in Belgium that it was the right thing to do must be acknowledged.
I must also thank my Manager Vincent Werebrouck for his continued support and friendship, particularly during the harsh
times we have experienced recently.
The many metallurgists I have had the privilege to meet and discuss various aspects of flotation with over the years are
too numerous to mention. However, their challenging questions, their thirst for knowledge and their desire to improve
their plant are the motivation behind this publication. I trust that you will gain value from this work.
The Australasian Institute of Mining and Metallurgy warrant special thanks for sticking with this project. Special thanks
must go to Angie Spry, Jenni Stiffe and Kristy Burt. It’s been a long road, and I am grateful for their support, professionalism
and their nagging. Next time maybe a cattle prod would come in handy! Thank you for your patience.
Finally, I would like to thank my family for their love and support, particularly my kids.
Dr Christopher J Greet
CONTRIBUTORS
CHRISTOPHER J GREET | EDITOR, CHAPTER 1, CHAPTER 9 APPENDIX
FAusIMM(CP), Manager Metallurgy – Minerals Processing Research, Magotteaux Australia Pty Ltd
Chris commenced his working life as a trainee metallurgist at Bradken’s Adelaide steel foundry
in 1978. He subsequently worked in a number of foundries before becoming a shift foreman at
Seltrust’s Teutonic Bore Mine in 1982. In 1985, he decided to formalise his knowledge by studying
for a Bachelor of Engineering in Metallurgical Engineering at the South Australian Institute of
Technology. Upon graduating he worked as a plant metallurgist at Ok Tedi Mining Limited and
Bradken Adelaide before undertaking a PhD at the Ian Wark Research Institute in 1992. Since leaving
the Wark, Chris has held applied research positions at Mount Isa Mines Limited, Pasminco, AMDEL,
and now with Magotteaux Australia, where he leads the technical group identifying the impact of
grinding chemistry on downstream processing.

ALAN BUCKLEY | CHAPTER 9

After obtaining a PhD in solid state physics in 1971, Alan carried out research using X-ray photo-
electron spectroscopy (XPS) while a Senior Teaching Fellow in Chemistry at Monash University.
On joining CSIRO in 1975, applied surface science utilising XPS was continued in Sydney, and a
long-standing collaboration with electrochemist Ron Woods, then at CSIRO in Melbourne, was
commenced on sulfide mineral processing research. By 1998, when Alan moved from CSIRO to
the University of New South Wales, sulfide mineral surface characterisation by means of XPS had
been augmented by static secondary ion mass spectrometry, surface enhanced Raman scattering
spectroscopy, synchrotron XPS and near-edge X-ray absorption spectroscopy. With a small group
of colleagues, he was instrumental in the establishment of a soft X-ray spectroscopy facility at
the Australian Synchrotron. Sadly, Alan passed away in 2017 and this book is being published in
his honour.

ALAN R BUTCHER | CHAPTER 4

Professor of Geomaterials and Applied Mineralogy, Geological Survey of Finland
Alan R Butcher has nearly 40 years of international experience as a field geologist, igneous
petrologist, isotope geochemist and applied mineralogist. His professional career has spanned
the entire spectrum from undergraduate and postgraduate teaching, to pure and applied research
and consulting, and commercialisation of mineral-based technologies. He is best known for his
enthusiastic evangelism and visionary development of new and emerging capabilities in the field
of automated mineralogy. Alan is currently a Research Professor at the Geological Survey of Finland,
where he is researching aspects of geomaterials and applied mineralogy, from a multi-scale, multi-
dimensional and multi-modal approach.
DEAN DAVID | CHAPTER 13
FAusIMM(CP), Technical Director Process, Wood
Dean gained a Bachelor of Applied Science (Metallurgy) from the SAIT (now the University of
South Australia) in 1982. For 14 years he worked for CRA (now Rio Tinto), including six years at
Argyle Diamonds in both project and operational roles. Dean joined JKTech as a consultant in
1996, then managed JKTech Consulting from 1999 to 2003. He joined GRD Minproc (now part
of Amec Foster Wheeler) as their Process Manager in 2003 and switched to Process Consultant
in 2005, then on to Technical Director Process in 2011. Dean has conducted many test work,
pilot plant and process implementation projects and managed day-to-day plant operations.
Dean’s experience covers hundreds of projects across the globe and across the mineral spectrum.
Expertise areas include geometallurgy, beneficiation, comminution, classification, physical
separations (flotation, gravity, magnetic), sample selection culminating in test program design
and interpretation leading to plant design and optimisation. Dean also conducts full day
geometallurgy courses suitable for all disciplines.

STEPHEN GRANO | CHAPTER 7

MAusIMM, Professor, Institute for Mineral and Energy Resources, University of Adelaide
Stephen Grano received his BEng (Metallurgical) in 1981 from the University of Queensland and
his PhD in 1997 from the University of South Australia. Early in his career, Stephen Grano gained
hands-on experience at Mount Isa Mines Ltd, working in the copper and lead/zinc concentrators
and heavy medium plant. A particular focus is the successful transfer of scientific research outcomes
into engineering practice through structured research and development programs within industry–
university partnerships. Stephen’s main roles, as the Executive Director of the Institute for Mineral
and Energy Resources, are to build inter-disciplinary project teams, make strategic investments into
capability, and to engage with industry and government stakeholders.

GREG HARBORT | CHAPTER 6

FAusIMM(CP), General Manager, Geometecon
Greg is a metallurgist with more than 30 years of experience in base metals, gold, industrial minerals,
flotation process design, research and development. Greg is a recognised specialist in flotation,
including metallurgical interpretation of mineralogical data and test results, flotation circuit
design and simulation. His process expertise extends to plant commissioning, pilot plant operation,
process optimisation, plant test programs, geometallurgical models and ultrafine grinding.
Previous employment has included Peko Mines as a production metallurgist, Xstrata Technology
as a development metallurgist with both the Jameson Cell and Isa Mill, JKTech as Technology
Manager and as Technical Director – Process for Wood plc. In his current role as General Manager for
Geometecon he is responsible for review and dissemination of information to the mining industry,
focusing on plant design and geometallurgy.
BILL JOHNSON | CHAPTER 2, CHAPTER 5, CHAPTER 8 APPENDIX
FAusIMM, Principal Consultant, Mineralis Consultants
Bill Johnson obtained a PhD in mineral processing from the University of Queensland in 1972.
After working for ASARCO in Arizona until 1976, he lectured at the University of Melbourne. He
joined the CSIRO Division of Mineral Engineering (1978–1982) where research on the Lead-Zinc
Concentrator at Mount Isa Mines Limited was his main project. In 1982, he moved to Mount Isa
where he continued research on the Lead-Zinc Concentrator and other plants and ores. He was the
Minerals Processing Research Manager (1989–1997). Development of a circuit for McArthur River
ore recommenced in 1989 under his direction, one key outcome being the IsaMill technology. He
was Professor of Minerals Engineering at the University of Queensland (1998–2005) and is presently
Principal Consultant at Mineralis Consultants (known as Mineralurgy until 2016) and an Adjunct
Professor at the Julius Kruttschnitt Mineral Research Centre.

ROB MORRISON | CHAPTER 3

MAusIMM, Consultant
Dr Rob Morrison is a metallurgical engineer with more than 40 years of experience in mineral
processing. His experience includes operations and process development during four years at
Bougainville Copper and plant design, construction and commissioning during six years with
Fluor Daniel Australia. For nine years Rob was Manager of JKTech. For the initial two years of its
operation, Rob was the leader of Program 2 of the Centre for Sustainable Resource Processing
and leader of AMIRA Project P754. For five years, he provided technical leadership to the Centre
for Advanced Mineral Separation – a Rio Tinto Centre of Excellence. After about ten years as Chief
Technologist at JKMRC, Rob retired from UQ at the end of 2017. He is currently an Honorary Professor
at JKMRC/SMI and a consultant to CRC ORE. Rob’s technical interests include energy efficient mineral
processing, advanced sorting techniques, characterisation of liberation and breakage, simulation
and measurement techniques. Rob has published more than 150 technical papers, contributed to
several textbooks and holds several patents.

PETER MUNRO | CHAPTER 5, CHAPTER 8 APPENDIX

FAusIMM, Principal Consultant, Mineralis Consultants Pty Ltd
Peter Munro graduated in Applied Chemistry from the University of Adelaide and worked in
production and technical roles in both the Lead-Zinc Concentrator and Copper Concentrator of
Mount Isa Mines Limited from 1970 to 1985. He was the Minerals Processing Research Manager
from 1985 to 1987 and the Lead-Zinc Concentrator Manager from 1987 to 1993. From 1993 to 2000
Peter worked in the Brisbane office of M.I.M. Holdings Limited as an internal consultant. From 2000
he was with Mineralurgy Pty Ltd, a specialist processing consultancy to the minerals industry where
he was Senior Principal Consulting Engineer. Since mid-2016 he has been a part of the Mineralis
Consultants group where he is a Principal Consultant.
TIM NAPIER-MUNN | CHAPTER 11
FAusIMM(CP), Julius Kruttschnitt Mineral Research Centre, The University of Queensland
Professor Tim Napier-Munn is a metallurgist who has spent nearly 50 years in the practice and
management of applied R&D in mineral processing and related disciplines. He has a Bachelor’s
and PhD degree from Imperial College, London, and a Master’s degree from the University of the
Witwatersrand in Johannesburg. Tim had an 11-year career with De Beers in South Africa and taught
mineral processing and statistics at Imperial College for three years. He joined the Julius Kruttschnitt
Mineral Research Centre (JKMRC) at The University of Queensland in 1985 where he was appointed
Director in 1997 and the inaugural Managing Director of JKTech Pty Ltd in 2001. Tim retired from the
latter two roles in 2004, and now divides his time between working with the JKMRC, and consulting
through JKTech. His book Statistical Methods for Mineral Engineers was published by the JKMRC in
2014. He is an Emeritus Professor at the University of Queensland and a Fellow of AusIMM.

THU NGUYEN | CHAPTER 6

MAusIMM, Process Specialist, JKTech Pty Ltd
Thu has over 20 years of experience in the mineral processing industry. In 1997, she graduated from
The University of Queensland with a Bachelor of Chemical Engineering (Honours) and spent her
early career at the CRC for Black Coal Utilisation working on the evolution of fuel nitrogen during
the initial stage of coal combustion. Thu then joined the AJ Parker CRC for Hydrometallurgy where
she was awarded a PhD in Materials Engineering. Currently a Process Specialist at JKTech Pty Ltd,
she is JKTech’s leading specialist in JKSimFloat undertaking optimisation projects, flotation plant
surveying and modelling, benchmarking, and process mineralogy and liberation analysis. Thu
delivers training in JKTech's specialist simulation software (JKSimFloat), flotation equipment and
MetSkill program.

JOE PEASE | CHAPTER 12

FAusIMM, Senior Principal Consulting Engineer, Mineralurgy Pty Ltd
Joe has degrees in Metallurgical Engineering and Economics and 35 years of experience in the
minerals industry. This includes roles in research, production metallurgy, financial analysis,
operations management, and development then global commercialisation of minerals technology.
He is a Director of CRC ORE, MIPAC Engineering and CEEC, and was formerly on the Boards of AMIRA,
JKMRC and the Ian Wark Institute. From his background with three different sectors (operations,
researchers and suppliers), Joe seeks to understand the business models, differences and find the
common ground between the sectors, for the benefit of all. As well as his Board and volunteer roles,
Joe works as a specialist consultant to the minerals industry.
KYM RUNGE | CHAPTER 10
Program Leader – Separation, Julius Kruttschnitt Mineral Research Centre
Dr Kym Runge is a mineral processing engineer specialising in flotation circuit analysis using
modelling and measurement techniques. Her expertise in flotation was initially developed at the
Julius Kruttschnitt Research Centre (JKMRC) where she studied for a PhD in flotation modelling
and was instrumental in the development of JKSimFloat, which is used extensively in the industry
for flotation circuit modelling and analysis. She also worked for 11 years as a flotation consultant
and researcher within Metso’s Process Technology and Innovation team and also has three years
industrial experience from when she worked at Pasminco’s Broken Hill flotation concentrator. At
the time of publication, she was the Group Leader of Separation at the JKMRC where she was
managing a team of researchers and supervising PhD students aiming to achieve step change
for industry.

SARAH SCHWARZ | CHAPTER 6

Principal Adviser – Productivity, Rio Tinto Kennecott Copper
Sarah has more than 20 years of experience in mineral processing (mainly flotation), including
operations, research and development as well as consulting. Sarah has a Bachelor of Engineering in
Metallurgical Engineering, as well as a PhD in Mineral Processing and an MBA, all awarded from the
University of South Australia. During her 11 years with JKTech she was involved in the development
and release of various versions of JKSimFloat and developing steady-state flotation models for plants
worldwide. Her various roles included Manager Training Courses, Manager Flotation Consulting,
Technology Transfer Manager, Comminution Group Manager and Group Metallurgist, as well as starting
up and managing the JKTech South America office in Santiago, Chile. She is currently the Principal
Adviser in Productivity for Rio Tinto Kennecott Copper with responsibility for identifying and facilitating
productivity improvements across the value stream, from the mine through to the refinery.

RONALD WOODS OAM | CHAPTER 8

FAusIMM, Adjunct Professor, School of Environment and Science, Griffith University
Ronald Woods obtained a University of London PhD from analytical chemistry research carried
out with Professor I M Kolthoff at the University of Minnesota. He joined CSIRO Division of Mineral
Chemistry in 1966 and carried out research on a range of subjects associated with mineral
processing and electrochemical power sources. He worked at that organisation until 1995, at
which time he was Research Manager of Metal Production. He received the Stokes Medal of the
RACI Electrochemistry Division in 1989 and was awarded a DSc (Eng) in 1994 by London University
for his work on electrochemical aspects of mineral processing. In more recent years, he has held a
number of research fellowships at universities in Australia and North America carrying out research
on mineral flotation from an electrochemical viewpoint. He was awarded the Antoine M. Gaudin
Award by the Society of Metallurgical Engineers (SME) in 2016.
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HOW TO USE THIS BOOK
It is intended that Chapter 1 (The Eureka Mine – an example of how to identify and solve problems in a flotation plant, by
Christopher J Greet) be used in parallel with subsequent chapters to gain a greater understanding of what is involved as one
goes through the process of optimising the plant.
The basic road map to follow on your quest to improve the metallurgical performance of your plant is given in the
diagram on the following page. The first step in this process is the acquisition of quality data from the plant (or mine, in the
case of a geometallurgical study (Chapter 13: Operational geometallurgy by Dean David)). Chapter 2 (Existing methods
for process analysis by Bill Johnson), provides details of how to collect, mass balance, size and interpret metallurgical data
collected from the plant. Mass balancing flotation data by Rob Morrison (Chapter 3) describes in detail the considerations
that must be taken into account when mass balancing survey data collected from a flotation plant. Having defined the
recovery-by-size characteristics of the concentrator, the next step is to establish their mineralogical character; that is, their
locking or liberation characteristics. Alan Butcher, in Chapter 4 (A practical guide to some aspects of mineralogy that
affect flotation), provides a summary of the mineralogical techniques available, their application and suitability to various
situations. The combination of recovery-by-size and liberation-by-size and mineral class will define whether the losses
occurring in the tailing stream are liberated or composite for each size fraction. The same can be determined for gangue
minerals reporting to the concentrate.
From the modal analysis it should become apparent if the ore contains any minerals that will present problems during
processing (Chapter 5: Some troublesome sulfide and non-sulfide minerals by Bill Johnson and Peter Munro). With
the weaknesses within the concentrator identified it is possible to start looking for the root cause. For example, are
the inefficiencies of the process related the equipment being used (Chapter 6: Characterisation measurements in
industrial flotation cells by Greg Harbort, Sarah Schwarz and Thu Nguyen)? If liberation is an issue then it may be a case
of adding additional size reduction capacity at an appropriate position within the circuit. However, if fine liberated values
are leaving the circuit via the tailing there may be a problem with the chemistry. Stephen Grano’s chapter (Chapter 7:
Chemical measurements during plant surveys and their interpretation) provides an explanation of the typical pulp
chemical measurements that can be made in the plant to identify where the chemistry of the system is not optimal for
separation. Ron Woods (Chapter 8: Electrochemical aspects of sulfide mineral flotation, with an appendix by Bill Johnson
and Peter Munro discussing sulfide mineral oxidation and the consequences for flotation) discusses the significance of
electrochemistry of the system and its impact on flotation. In some instances it is necessary to use more sophisticated
surface analysis techniques to identify the species on the surfaces of minerals particles. Chapter 9: Surface chemical
characterisation for flotation plant optimisation, by Alan Buckley presents the various techniques available (ie XPS, ToF-
SIMS), discusses their merits and describes how the data can be interpreted. The appendix to this chapter (written by
Christopher J Greet) provides some practical case studies where surface analysis has been used to assist in the diagnosis
of a problem.
The above describes the steps, with increasing degrees of sophistication, one may take to identify the where, what and
how in the focusing questions. The tremendous strength of these principles lies in the fact that they can be applied to
almost any processing operation, not only the flotation of base metal sulfides, and at any scale (ie laboratory, pilot plant
and industrial scale).
 Having identified where the weaknesses in your operation are, it is possible to devise laboratory experiments to test
potential solutions. These programs may range from a diagnostic test conducted on plant pulps to determine if changes
made in the plant have resulted in a positive shift in metallurgy to simple laboratory flotation tests to screen reagents. The
development of these ideas is discussed by Kym Runge in Chapter 10 (Laboratory flotation testing – an essential tool for
ore characterisation).
Invariably, encouraging laboratory solutions are applied to the operating plant with varying degrees of success.
In Chapter 11 (Designing and analysing plant trials), Tim Napier-Munn discusses the steps required to conduct a successful
plant trial and how the data generated may be analysed to give a statistically meaningful outcome.
Finally, Joe Pease (Chapter 12: Project evaluation and communication) supplies a philosophical note on how best to
communicate solutions developed by the technocrat to both operations personnel and management teams such that the
economic benefits can be realised.

Geometallurgy
(Chapter 13: Dean David)

Mass balancing
(Chapter 3: Rob Morrison)

Data acquisition
(Chapter 2: Bill Johnson) Mineralogy
(Chapter 4: Alan Butcher)

Troublesome minerals
Questions
(NEW Chapter 5: Bill Johnson and Peter Munro)
(What and where?)

Cell characterisation
(Chapter 6: Greg Harbort, Sarah Schwarz and Thu Nguyen)

Problem definition
Machine
Liberation
Chemistry Pulp chemistry
(Chapter 7: Stephen Grano)

Laboratory testing
(Chapter 10: Kym Runge)
Electrochemistry
(Chapter 8: Ron Woods)
NEW Appendix by
Trials and statistical analysis Bill Johnson and Peter Munro
(Chapter 11: Tim Napier-Munn)

Surface analysis
(Chapter 9: Alan Buckley)
Communication NEW Appendix by
(Chapter 12: Joe Pease) Chris Greet

Schematic showing the broad road map of how to identify and

quantify problems within base metal sulfide flotation plants.
CONTENTS
CHAPTER 1 1
The Eureka Mine – an example of how to identify and solve problems in a flotation plant
Christopher Greet
Appendix 1 – The down-the-bank survey 43
Appendix 2 – Estimated mineral assays from elemental data 49

CHAPTER 2 55
Existing methods for process analysis
Bill Johnson
Appendix – Two aspects of sampling 99

CHAPTER 3 105
Mass balancing flotation data
Rob Morrison

CHAPTER 4 137
A practical guide to some aspects of mineralogy that affect flotation
Alan R Butcher

CHAPTER 5 157
Some troublesome sulfide and non-sulfide minerals
Bill Johnson and Peter Munro

CHAPTER 6 171
Characterisation measurements in industrial flotation cells
Greg Harbort, Sarah Schwarz and Thu Nguyen

CHAPTER 7 199
Chemical measurements during plant surveys and their interpretation
Stephen Grano

CHAPTER 8 227
Electrochemical aspects of sulfide mineral flotation
Ronald Woods OAM
Appendix – General description of the oxidation of sulfides and the consequences for the flotation process 256
Bill Johnson and Peter Munro
CHAPTER 9 263
Surface chemical characterisation for flotation plant optimisation
Alan Buckley
Appendix – Practical examples of using surface chemistry to identify problems in flotation plants 294
Christopher Greet

CHAPTER 10 321
Laboratory flotation testing – an essential tool for ore characterisation
Kym Runge
Appendix – Worked examples 343

CHAPTER 11 361
Designing and analysing plant trials
Tim Napier-Munn

CHAPTER 12 391
Project evaluation and communication
Joe Pease

CHAPTER 13 407
Operational geometallurgy
Dean David
Return to contents

CHAPTER 1
The Eureka Mine – an example of how to
identify and solve problems in a flotation plant
Christopher J Greet

ABSTRACT
This chapter will provide a methodology for identifying and solving problems in a flotation
plant. To do this, a ‘mythical’ concentrator (The Eureka Mine) will be described and used to
demonstrate how to go about the process of identifying where the losses of valuable mineral
occur and what gangue species are diluting the concentrate. It is intended that this chapter
be used in parallel with subsequent chapters to guide the reader through the steps involved
in optimising the plant.

INTRODUCTION
Many of us have, at one time or another, flicked through the newspaper or searched online
for a job, and stumbled upon an ad not unlike the one that appears below. Whether we
are jaded with our current role, looking for a step up to the next level, or wanting a new
challenge, we prepare our resume and send it off in the hope that we may be the successful
candidate.
With the interview process out of the way, the waiting and self-doubt start. After what
seems an eternity you receive a phone call or letter telling you that you have got the job.
Congratulations! Now what? You’re new, you have ambition, you have drive and you want
to make your mark! But, there’s a right way and a wrong way to do this. The first thing to
remember is that this place has a history, and the people you are going to work with have been
here much longer than you have, so communication and respect are key to your success. You
need to discover the history of the concentrator and discuss its operation with other members
of staff (operators, metallurgical technicians, shift foremen, plant metallurgists, the chemist,
mechanical and electrical maintenance, the mine (ie geologists and mining engineers) and
the supply department). They will all give you their perspective and you need to respect
their point of view. You will also work out who among these people hold the knowledge, the
history; the real story of your concentrator.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 1

 CHRISTOPHER J GREET

SENIOR PROJECT METALLURGIST

The key objectives of this position are to:
•• identify opportunities for improvement within the process
•• develop, test, evaluate and implement process improvements
•• identify and evaluate new technologies that will improve our process
•• be actively involved in our future ores testing program.
Operating in a climate of continuous improvement, you will be required to actively participate in the promotion of safe work
practices, have good interpersonal skills and a professional work ethic.

Skills and experience

The successful applicant candidate will have the following attributes:
•• Bachelor of Engineering – Metallurgy or equivalent
•• five years or more process experience
•• a working knowledge of grinding and flotation processes
•• good communication skills
•• proven problem-solving skills
•• good time management skills
•• sound leadership qualities and management skills.

Employment conditions
Eureka Mining Limited is a wholly owned subsidiary of Stockade Resources Limited, an Australian-based mining and exploration
company with interests in Australia, New Guinea, Zambia and Peru.
Reporting to the Metallurgy Manager, the successful candidate will work closely with production to maintain and improve plant
performance. This is a residential position, with an attractive renumeration package commensurate with your qualifications and
experience.

To apply
Please submit your application including a cover letter and current copy of your resume via email to ...

While you are establishing relationships you need to determine what data exists (and what
is missing) to help you develop a technical perspective of how your concentrator performs.
The focusing questions in any process improvement strategy are:
•• Where and how do the losses of valuable mineral occur?
•• What gangue minerals are diluting the concentrate and how did they get there?
The intention of this book is to provide you with a sequence of logical steps to collect the
necessary data to define the problem(s) in your operation. Once the problems are defined you
can prioritise them and develop experimental strategies that may lead to solutions that can be
implemented in the plant.
To illustrate this journey we will consider the performance of the Eureka Mine. The Eureka
Mine treats a complex polymetallic sulfide ore supplied from an underground mine and
produces three saleable concentrates. This chapter provides a description of the Eureka
Concentrator and its metallurgical performance since commissioning. It demonstrates
the methodology to collect plant data, analyse and interpret it to determine where the
metallurgical problems – and potential solutions – lie.

2 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

THE EUREKA MINE

Location and history
Extensive geological surveying of the region north of Laylor River by Stockade Resources
Limited resulted in the discovery of the Eureka deposit in 1990. Throughout 1991 and 1992,
drilling continued to delineate the deposit. Preproduction geological studies indicated
Probable Reserves of approximately 25 Mt of greater than 15 per cent zinc plus lead, with
economically significant copper, silver and gold grades.
A one million tonnes per annum processing plant was commissioned by Stockade in 1995 to
treat ore with an average head grade of 0.4 per cent copper; 3 per cent lead; 12 per cent zinc;
130 g/t silver and 2.0 g/t gold.

Geology
The Eureka volcanogenic massive sulfide deposit occurs within the Laylor-Eureka Volcanic
sequence of the Mount Rush Volcanics. The deposit was formed when hot mineralised
solutions spewed on to the ocean floor and were rapidly quenched by the surrounding
seawater. Hence, the sulfide minerals precipitated from solution formed very fine crystals and
intricate mineral textures. Subsequent geological changes to the orebody were few; therefore,
many of the original fine-grain textures remained intact.

Deposit mineralogy
To fully appreciate the complexity of flotation at Eureka requires a rudimentary understanding
of the mineralogy of the orebody. Eureka is unusually sulfide-rich and contains a relatively
simple mineral suite: 58 per cent pyrite, 20 per cent sphalerite, four per cent galena,
two per cent arsenopyrite and one per cent chalcopyrite, with minor amounts of tetrahedrite.
The remaining 15 per cent of the ore consists of: quartz, barite, calcite, chlorite, sericite and
siderite.
Macroscopically, the mineral textures are diverse; however, the orebody can be divided
into two distinct metal zones. The demarcation between the two zones is set, arbitrarily, at
100 g/t of silver and represents a continuous horizon across the deposit. Above this level is
the hanging wall enrichment zone characterised by higher lead, zinc, silver, gold and arsenic
grades. Macroscopically, the sulfides within the enrichment zone tend to be banded and very
fine grained. The footwall-depleted zone occurs below the 100 g/t silver horizon. Pyrite and
chalcopyrite are the dominant minerals in this part of the orebody, with reduced lead, zinc,
silver, gold and arsenic grades. The footwall-depleted zone is highly recrystallised, therefore
the grain structure is comparatively coarse compared with those observed in the hanging
wall enrichment zone.
The Eureka orebody is relatively free of non-sulfide gangue mineralisation. Pyrite is the
dominant gangue mineral and is associated with all other minerals within the deposit.
Therefore, the properties of pyrite will influence greatly the behaviour of all other minerals
during processing.
The pyrite textures vary markedly across the deposit from coarse recrystallised grains in the
footwall-depleted zone to compact microcrystalline masses, spongy and colliform clots, such
as melnokovite (an amorphous pyrite of colloidal origin). Ultra-fine intergrowths of pyrite
with other sulfides are common, particularly with galena and arsenopyrite (Figure 1). The
association of auriferous arsenopyrite with pyrite is also of significance.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 3

 CHRISTOPHER J GREET

A B

C D

FIG 1 – Photomicrographs of various galena ore textures: (A) galena replacement in pyrite matrix, like
melnokovite (magnification ×10); (B) galena blebs in pyrite matrix (magnification ×20); (C) galena in
crystal voids around pyrite (magnification ×5); and (D) galena replacement in melnokovite colloform
(magnification ×40). (Note: the blue/grey areas are galena and the golden areas are pyrite.)

Process description
Laboratory testing of the Eureka ore clearly demonstrated that it was possible to produce
saleable copper, lead and zinc concentrates. The flow sheet developed in the laboratory was
tested at pilot scale to prove the selected process route was robust and to produce sufficient
quantities of concentrate for smelter testing. The final Eureka process flow sheet is presented
in Figure 2.
Mine geologists classify the ore into broad types based on texture: enrichment zone ore
(banded), or footwall depleted zone ore (coarse grained) and estimated pyrite content. Each
ore type is crushed in batches to nominally 100 per cent passing 100 mm, in the underground
jaw crusher before being trucked to the surface in 50 t dump trucks. Upon delivery to the

Copper Circuit Lead Circuit Zinc Circuit

Cu Ro Pb Ro Pb Scav Zn Ro Zn Scav
Feed Zn Scavenger Tailing

Grinding st
Zn 1 Cl
P80 = 75 microns

Copper Cleaner Concentrate

Cu Cl
Pb 1st Cl Zn 2nd Cl

Zinc 2nd Cleaner Concentrate

nd Zinc Regrinding
Pb 2 Cl Lead Regrinding
P80 = 38 microns
P80 = 38 microns

Pb 3rd Cl

Lead 3rd Cleaner Concentrate

FIG 2 – The Eureka Concentrator flow sheet.

4 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

run-of-mine (ROM) pad each ore type is stockpiled separately. The ore is fed onto a conveyor
belt that leads to an open stockpile in specific ratios of each ore type. Apron feeders under the
open stockpile feed the blended ore onto the primary mill feed conveyor at nominally 120 t/h.
The primary mill is a low aspect ratio semi-autogenous grinding (SAG) mill in open circuit.
The SAG mill product discharges into a common sump shared with the ball mill. The pulp
is pumped from the mill discharge sump to cyclones in closed circuit with a secondary ball
mill. The cyclone underflow feeds the secondary ball mill, and cyclone overflow reports to
flotation feed. The mill and cyclone configuration is designed to produce flotation feed P80
of 75 µm.
Secondary cyclone overflow feeds a sequential copper/lead/zinc flotation circuit. Each
flotation section consists of a rougher/scavenger, with the rougher concentrate reporting
to the cleaner circuit. Copper cleaning is achieved without regrinding and with only one
stage of cleaning. Lead rougher concentrate feeds the first of three stages of cleaning. Lead
scavenger concentrate and lead first cleaner tailings are reground and recycled to the head of
the lead rougher. Lead scavenger tailings report to zinc circuit feed. Zinc rougher concentrate
reports to two stages of cleaning. Zinc scavenger concentrate and zinc first cleaner tailings are
reground and recycled to zinc rougher feed. The concentrates produced from the copper, lead
and zinc flotation circuits are pumped to thickeners. Thickened concentrates are filtered for
stockpiling before loading into rail cars for shipment to the smelter.
Flotation tailings are dewatered and used as paste backfill in the underground workings.

Metallurgical performance
The Eureka Concentrator was commissioned in December 1995 and reached name plate
throughput by July 1996. A further 18 months were required to achieve the design concentrate
grades and recoveries. Typical metallurgical performance since 1998 is summarised in Table 1.

DATA ACQUISITION
Measurement is the first step to understanding how your plant is performing. In a modern
concentrator, the process can be monitored using a multitude of sensors; however, the data
collected from inventory samples on a shift, daily, weekly and monthly basis, coupled with
well-executed metallurgical surveys, is invaluable to define where valuable mineral losses
occur and what gangue minerals are diluting the concentrate.
As the new metallurgist, the first step is to acquaint yourself with the existing plant data.
That is, review the shift mass balance data, interrogate the monthly composite data and
examine the results of any previous plant surveys. This should provide some indication

TABLE 1
Typical metallurgical performance of the Eureka Concentrator since 1998.
Stream Wt % Grade (%) Recovery (%)
Ag (ppm) Cu Pb Zn Ag Cu Pb Zn
Flotation feed 100.0 130 0.4 3.1 12.4 100.0 100.0 100.0 100.0
Cu concentrate 0.9 3190 25.4 5.2 6.2 21.9 53.2 1.5 0.4
Pb concentrate 3.6 1356 1.2 61.5 10.8 37.6 10.1 70.4 3.1
Zn concentrate 20.0 102 0.3 2.0 53.4 15.9 16.4 13.0 86.9
Final tailing 75.3 42 0.1 0.6 1.6 24.6 20.3 15.1 9.6

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 5

 CHRISTOPHER J GREET

of where the metallurgical weaknesses lie. Unfortunately, often the only readily available
up-to-date information are shift mass balances. Therefore, it is good practice to organise a
plant survey as soon as possible to quantify the metallurgical performance of each section
of the plant.
The shift data for the copper, lead and zinc circuits of the Eureka Concentrator for the first
half of 1998 appear in Figure 3.
These data suggest that, with the exception of lead and zinc concentrate grades, the plant
performance is somewhat unstable. The copper concentrate grade and recovery fluctuate
widely, and lead recoveries are highly variable with greater than ten per cent zinc grade in
the lead concentrate, and zinc recoveries are usually in the low to middle 80s.
Your ‘gut feeling’ probably tells you that copper, lead and zinc recoveries are lower than
expected, so it should be possible to improve performance. But you don’t know what the
limiting factors are. You need a comprehensive plant survey to identify the targets.
Now you need to decide what level of detail the survey needs. This will obviously depend
on what work has been completed previously. In this example it will be assumed that the
available data is scattered and incomplete. Therefore, the survey objective will be to collect
as much data as possible to provide sufficient information to describe the pulp chemistry
and metallurgical performance. Ideally, both sets of data can be collected together so they
complement each other. To add further value to your survey, collecting gas hold-up, superficial
gas velocity and bubble size data will provide information about the hydrodynamics of the
flotation cells.

The metallurgical survey (Chapter 2)

Why don’t metallurgists do surveys?
I have visited many plants around the world and observed a wide spectrum of knowledge
and experience. But there are few plants that conduct frequent, well-focused surveys and
have a clear understanding of their metallurgical performance problems and opportunities.
There are many reasons for this, but generally distil to not knowing how to conduct a survey
and the fear of mass balancing.

What do I have to do?

The objectives of the survey(s) are to provide information about rougher/scavenger flotation
performance in each of the flotation circuits and to examine how the concentrates upgrade
during cleaning. Firstly, conduct ‘block’ surveys of each of the flotation sections (roughers,
scavengers and cleaners) for each product. Ideally, you can include a more detailed down-
the-bank survey of the rougher/scavenger sections. An example of a down-the-bank survey is
provided in Appendix 1. To gain greater appreciation of how the circuit operates you should
conduct repeat surveys over a number of days, and for different ore types. It is useful to have
one detailed survey and several less detailed block surveys to give a more balanced view of
metallurgical performance.
Organisation and communication are key to successful concentrator surveys. The first step
is to decide on the sampling points and the type of sample to be taken. A list of samples for
the Eureka Concentrator is given in Table 2. All tailings samples should be taken in duplicate
to ensure sampling consistency and as internal checks (the recovery calculation depends on
the tailings assay).

6 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

90.0 30.0
A
75.0 27.0

Cu recovery, %

Cu grade, %
60.0 24.0

45.0 21.0

30.0 18.0

15.0 15.0

0.0 12.0
98

98

98

98

98

98

98

98

98

98

98

98

98
/

/
01

01

01

02

02

03

03

04

04

05

05

06

06
1/

9/
/

7/

4/

/
15

29

12

26

12

26

23

21

18
Time, days
Cu recovery Cu grade

90.0 90.0
B
75.0 75.0

Pb and Zn grade, %
Pb recovery, %

60.0 60.0

45.0 45.0

30.0 30.0

15.0 15.0

0.0 0.0
8

8
/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9
1
01

05
04

06

6
/0

/0

/0

/0

/0

/0

/0

/0

/0
1/

9/

7/

4/
15

29

12

26

12

26

23

21

18

Time, days
Pb recovery Pb grade Zn grade in Pb con

100.0 60.0
C
90.0 50.0
Zn and Fe grade, %
Zn recovery, %

80.0 40.0

70.0 30.0

60.0 20.0

50.0 10.0

40.0 0.0
8

8
/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9

/9
1
01

05
04

06

6
/0

/0

/0

/0

/0

/0

/0

/0

/0
1/

9/

7/

4/
15

29

12

26

12

26

23

21

18

Time, days
Zn recovery Zn grade Fe grade in Zn con

FIG 3 – Time series data for: (A) copper; (B) lead and (C) zinc circuits.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 7

 CHRISTOPHER J GREET

TABLE 2
The sampling points and sample type for the metallurgical survey of the Eureka flotation circuit.
Sample Process stream Sample type Sample Process stream Sample type
number number
1 Flotation feed (ball mill Half moon cutter 18 Lead second cleaner tailing A Dip sample
cyclone overflow)
2 Copper rougher concentrate Lip sample 19 Lead second cleaner tailing B Dip sample
3 Copper rougher tailing A Dip sample 20 Lead third cleaner concentrate Lip sample or OSA
4 Copper rougher tailing B Dip sample 21 Lead third cleaner tailing A Dip sample
5 Copper cleaner concentrate Lip sample or OSA 22 Lead third cleaner tailing B Dip sample
6 Copper cleaner tailing A Dip sample 23 Zinc rougher concentrate Lip sample
7 Copper cleaner tailing B Dip sample 24 Zinc rougher tailing A Dip sample
8 Lead rougher concentrate Lip sample 25 Zinc rougher tailing B Dip sample
9 Lead rougher tailing A Dip sample 26 Zinc scavenger concentrate Lip sample
10 Lead rougher tailing B Dip sample 27 Zinc scavenger tailing A Dip sample or OSA
11 Lead scavenger concentrate Lip sample 28 Zinc scavenger tailing B Dip sample or OSA
12 Lead scavenger tailing A Dip sample 29 Zinc first cleaner concentrate Lip sample
13 Lead scavenger tailing B Dip sample 30 Zinc first cleaner tailing A Dip sample
14 Lead first cleaner concentrate Lip sample 31 Zinc first cleaner tailing B Dip sample
15 Lead first cleaner tailing A Dip sample 32 Zinc second cleaner concentrate Lip sample or OSA
16 Lead first cleaner tailing B Dip sample 33 Zinc second cleaner tailing A Dip sample
17 Lead second cleaner concentrate Lip sample 34 Zinc second cleaner tailing B Dip sample

Other samples that may be redundant in the mass balance still provide valuable data to
confirm the mass balance ‘makes sense’ – for example, copper rougher feed, lead rougher
feed and zinc rougher feed.
With the sample list decided, the next step is to brief the survey team, prepare the equipment
and ensure that the plant is running in a representative and steady state condition for the
survey. Set the ground rules for the survey (ie number of rounds over what time interval) and
delegate tasks to each survey member so that:
•• sufficient sample buckets with lids are cleaned, weighed and labelled
•• the sampling equipment is checked, clean and ready for use
•• everyone knows what is expected of them.
You need to inform operations that you intend to conduct a plant survey(s) and what the
objectives of the work are. Check that the plant will be available and at steady-state at the
planned survey time. You must inform the chemical laboratory of the expected sample load
and assay requirements.
The day before the survey you should conduct a full plant ‘dress rehearsal’ to ensure everyone
knows their role and sample points. All sample points should be checked and cleaned,
including flotation cell lips. Sample buckets should be pre-labelled. Most importantly, check
that the work area, access to sample points and sampling methods are safe.
On the day of the survey, attend the production meeting to establish the plant condition and
whether it is expected to operate at steady state. Inform operations that the survey will proceed.

8 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

Set out the buckets and samplers in the correct positions, check and clean the sample points and
flotation cell lips again, have a safety and procedures pre-start with the survey team.
When you are ready for ‘kick off’, do a final check that the plant is at steady state – feed
tonnage, head grades and performance. If so, you are ready to start the survey.
A survey of this type should be conducted over three residence times, with multiple rounds
of samples collected to form a composite. In this example, the survey was conducted over
three hours, during which four ‘cuts’ from each sampling point were collected randomly.
Once completed, gather the samples and take them to the laboratory.

What data do I need?

In the laboratory the samples are weighed (for wet weight), filtered, dried, weighed (for dry
weight), prepared and submitted for assay. A summary of this data is shown in Table 3. Wet
and dry weights determine per cent solids of each sample and are necessary for the mass and
water balance.
Regarding assays, as well as the valuable elements (in Eureka’s case – copper, lead, zinc,
silver and gold), it is wise to assay for other elements. For example, iron and sulfur aid
mineral conversions to yield information about the sulfide gangue deportment. Information
on deleterious trace elements like arsenic, antimony, bismuth, mercury and/or cadmium is
important to understand their deportment and minimise their recovery as they will effect
concentrate grade and payment terms.
Other useful data when analysing the survey mass balance are:
•• plant throughput at the time of the survey
•• reagent additions and other plant operating parameters (ie air flow rates and pulp levels)
•• on-stream analysis (OSA) readings
•• information about the ore being treated.
For a one-off survey some of this information may not be of great value. However, when the
analysis is extended to include other surveys on other ore blends, circuit configurations and
reagent suites, these data provide a vital link for comparison.

How do I analyse the data collected (Chapter 3)?

Once the assays have returned from the chemical laboratory the fun starts! You will be
confronted with a list of numbers similar to those shown in Table 4. This may appear daunting,
but once you have organised the data into a logical format you will be in a position to mass
balance this survey.
To start the mass balancing process, first check that you have received all the assays and that
they make sense. For example, do the tailing assays match? Do the concentrate assays follow
a logical trend (for example, the rougher concentrate grade is higher than the scavenger
concentrate, the concentrate grades increase from the first to the third cleaner)? Do the assays
match the mineralogy? If the numbers make sense, you can start mass balancing. This can
include a water balance, using the per cent solids values for each process stream as though it
were an assay.
There are numerous mass balancing packages available, but the basic steps are the same.
Unfortunately, it is not a case of plugging the numbers in and pressing ‘GO’.
The basic steps to mass balancing a survey are given below. A more detailed explanation is
given in Chapter 3.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 9

 CHRISTOPHER J GREET

TABLE 3
Raw data from the metallurgical survey of the Eureka Concentrator.
Sample Process stream Sample weight (g) % Solids
number
Gross wet Bucket Cutter Net wet Dry
1 Flotation feed 2083.5 202.6 1880.9 909.8 48.4
2 Copper rougher concentrate 1961.2 229.2 347.8 1384.2 708.2 51.2
3 Copper rougher tailing A 2509.5 466.3 2043.2 949.7 46.5
4 Copper rougher tailing B 2480.9 466.0 2014.9 936.1 46.5
5 Copper cleaner concentrate 1386.7 225.0 324.8 836.9 536.3 64.1
6 Copper cleaner tailing A 1622.0 202.6 1419.4 144.8 10.2
7 Copper cleaner tailing B 1668.4 202.6 1465.8 141.8 9.7
8 Lead rougher concentrate 4842.2 225.3 341.0 4275.9 2695.1 63.0
9 Lead rougher tailing A 2395.6 464.3 1931.3 812.3 42.1
10 Lead rougher tailing B 2374.1 477.7 1896.4 772.0 40.7
11 Lead scavenger concentrate 1317.1 206.9 340.9 769.3 482.4 62.7
12 Lead scavenger tailing A 2416.1 465.0 1951.1 823.7 42.2
13 Lead scavenger tailing B 2357.1 446.3 1910.8 782.0 40.9
14 Lead first cleaner concentrate 10638.1 190.4 341.1 10106.6 6660.8 65.9
15 Lead first cleaner tailing A 2646.2 234.5 2411.7 1347.1 55.9
16 Lead first cleaner tailing B 2640.5 224.8 2415.7 1343.7 55.6
17 Lead second cleaner concentrate 5832.8 214.4 325.3 5293.1 3547.9 67.0
18 Lead second cleaner tailing A 2814.2 233.6 2580.6 1608.0 62.3
19 Lead second cleaner tailing B 2828.9 228.2 2600.7 1424.7 54.8
20 Lead third cleaner concentrate 2721.8 200.6 341.0 2180.2 1395.7 64.0
21 Lead third cleaner tailing A 2905.2 238.1 2667.1 1635.1 61.3
22 Lead third cleaner tailing B 2881.6 225.8 2655.8 1650.7 62.2
23 Zinc rougher concentrate 2779.3 226.4 341.2 2211.7 1287.8 58.2
24 Zinc rougher tailing A 2090.7 224.9 1865.8 681.5 36.5
25 Zinc rougher tailing B 1992.0 234.7 1757.3 638.8 36.4
26 Zinc scavenger concentrate 1565.6 200.4 324.9 1040.3 500.5 48.1
27 Zinc scavenger tailing A 1983.0 234.9 1748.1 629.1 36.0
28 Zinc scavenger tailing B 1753.0 225.5 1527.5 536.5 35.1
29 Zinc first cleaner concentrate 3945.3 202.4 341.2 3401.7 1947.7 57.3
30 Zinc first cleaner tailing A 2316.8 225.6 2091.2 1004.9 48.1
31 Zinc first cleaner tailing B 2321.4 225.4 2096.0 1005.5 48.0
32 Zinc second cleaner concentrate 4209.1 211.9 341.2 3656.0 2020.2 55.3
33 Zinc second cleaner tailing A 2466.7 225.5 2241.2 1250.5 55.8
34 Zinc second cleaner tailing B 2474.3 234.0 2240.3 1248.2 55.7

10 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

TABLE 4
Raw assay data from the metallurgical survey of the Eureka Concentrator.
Sample Process stream % Solids Raw assays
number Ag (ppm) Cu (%) Pb (%) Zn (%) Fe (%)
1 Flotation feed 48.4 135 0.43 4.02 15.80 14.30
2 Copper rougher concentrate 51.2 588 16.50 15.20 12.30 14.20
3 Copper rougher tailing A 46.5 92 0.19 4.04 15.40 13.40
4 Copper rougher tailing B 46.5 98 0.21 4.04 15.60 13.60
5 Copper cleaner concentrate 64.1 229 22.40 4.07 7.80 16.10
6 Copper cleaner tailing A 10.2 524 15.45 16.30 11.30 13.80
7 Copper cleaner tailing B 9.7 424 5.50 26.40 18.50 9.00
8 Lead rougher concentrate 63.0 184 0.32 21.42 29.97 8.97
9 Lead rougher tailing A 42.1 43 0.16 1.22 17.90 13.60
10 Lead rougher tailing B 40.7 34 0.16 1.25 16.60 13.50
11 Lead scavenger concentrate 62.7 179 0.36 8.16 39.84 11.57
12 Lead scavenger tailing A 42.2 38 0.14 0.67 15.20 13.90
13 Lead scavenger tailing B 40.9 18 0.15 0.50 14.60 13.70
14 Lead first cleaner concentrate 65.9 600 0.30 44.68 14.10 4.10
15 Lead first cleaner tailing A 55.9 184 0.28 18.50 30.65 8.80
16 Lead first cleaner tailing B 55.6 176 0.28 20.50 30.75 9.00
17 Lead second cleaner concentrate 67.0 960 0.51 50.90 10.10 2.50
18 Lead second cleaner tailing A 62.3 814 0.23 47.30 13.40 3.85
19 Lead second cleaner tailing B 54.8 800 0.27 47.40 13.60 3.95
20 Lead third cleaner concentrate 64.0 1060 1.08 60.00 9.40 1.70
21 Lead third cleaner tailing A 61.3 890 0.32 47.00 11.26 2.40
22 Lead third cleaner tailing B 62.2 900 0.40 49.00 11.34 2.80
23 Zinc rougher concentrate 58.2 53 0.33 1.63 45.10 8.40
24 Zinc rougher tailing A 36.5 16 0.13 0.45 1.72 15.35
25 Zinc rougher tailing B 36.4 15 0.13 0.55 1.74 15.65
26 Zinc scavenger concentrate 48.1 72 0.47 2.23 15.20 14.30
27 Zinc scavenger tailing A 36.0 12 0.09 0.32 0.85 15.32
28 Zinc scavenger tailing B 35.1 13 0.11 0.36 0.87 15.48
29 Zinc first cleaner concentrate 57.3 43 0.33 1.30 55.70 6.00
30 Zinc first cleaner tailing A 48.1 63 0.38 2.02 19.40 12.10
31 Zinc first cleaner tailing B 48.0 60 0.42 1.94 19.60 12.30
32 Zinc second cleaner concentrate 55.3 39 0.29 1.17 58.40 5.30
33 Zinc second cleaner tailing A 55.8 62 0.48 1.60 42.70 8.50
34 Zinc second cleaner tailing B 55.7 64 0.44 1.64 44.70 8.50

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 11

 CHRISTOPHER J GREET

Step 1
Determine the plant throughput when the survey was completed. If the feed tonnage is not
available, assign the fresh flotation feed a value of 100 per cent.

Step 2
Balance the ‘outer’ circuit. That is, complete a mass balance of the feed, final concentrate
and tailing for the copper, lead and zinc circuits (Figure 4). This will provide estimates of
the tonnes of copper, lead and zinc concentrates. These values can be used in subsequent
balances to estimate tonnages of the internal process streams within rougher, scavenger and
cleaner circuits.
Assign each process stream a number and identify each of the nodes. The process streams
are:
1. flotation feed
2. copper cleaner concentrate
3. copper rougher tailing
4. lead third cleaner concentrate
5. lead scavenger tailing
6. zinc second cleaner concentrate
7. zinc scavenger tailing.
The nodes are:
1. flotation feed = Cu cleaner concentrate + Cu rougher tailing (or, 1 = 2 + 3)
2. Cu rougher tailing = Pb third cleaner concentrate + Pb scavenger tailing (or, 3 = 4 + 5)
3. Pb scavenger tailing = Zn second cleaner concentrate + Zn scavenger tailing (or, 5 = 6 + 7).
In this case, at the time of surveying the plant, throughput was 120 t/h.
The tailing assays are reasonably similar and in the expected range, indicating good
sampling practice. Therefore, taking an average of the two tailing sample assays is acceptable.
If one assay was considerably higher than the other (for example, the copper cleaner tailing A, in
Table 4), it suggests that this dip sample has been contaminated with froth during collection,
and this assay may have to be rejected from the data set. However, caution is needed when
rejecting assays – this sample has a similar assay to the copper rougher concentrate, so it is
possible that samples were wrongly labelled.
Having sorted the data and identified the process streams, nodes and feed tonnage, the
numbers can be plugged into your mass balancing program. In this case MATBAL, using

3. Cu scav tailing 5. Pb scav tailing

1. Flotation feed Cu Circuit Pb Circuit Zn Circuit 7. Zn Scav Tail

(1) (2) (3) (Final Tail)

2. Cu Clnr Con 4. Pb 3rd Clnr Con 6. Zn 2nd Clnr Con

(Final Cu Con) (Final Lead Con) (Final Zn Con)

FIG 4 – The ‘outer’ circuit.

12 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

a Monte Carlo simulation, was employed. The resultant mass balance is shown in Table 5.
This includes a sigma value. If sigma is less than five per cent then the data are considered
to be good.

Step 3
The next step is to balance the internal or ‘inner’ circuits within the copper, lead and zinc
circuits. These internal balances are broken into ‘bite size’ pieces to simplify the balancing
process and generate tonnage estimates for subsequent ‘inner’ circuit balances.
The copper circuit (Figure 5) is comparatively easy to balance using the tonnage estimates
for the flotation feed and copper cleaner concentrate generated in the ‘outer’ circuit mass
balance. The process streams are:
1. flotation feed (120 t/h)
2. copper rougher concentrate
3. copper rougher tailings
4. copper cleaner concentrate (1.21 t/h)
5. copper cleaner tailings.

TABLE 5
Adjusted assays for the ‘outer’ circuit mass balance.
No Stream t/h ∑ Adjusted assays (%)
Ag (ppm) Cu Pb Zn Fe
1 Flotation feed 120.00 0.09 135 0.43 3.99 15.04 13.17
2 Cu cleaner concentrate 1.21 3.31 229 22.40 4.07 7.80 16.11
3 Cu rougher tailing 118.79 0.10 95 0.21 3.99 15.12 13.14
4 Pb 3rd cleaner concentrate 6.76 2.19 1060 1.07 61.01 9.42 1.70
5 Pb scavenger tailing 112.03 0.16 28 0.15 0.55 15.46 13.83
6 Zn 2nd cleaner concentrate 27.70 2.14 39 0.29 1.18 59.92 5.35
7 Zn scavenger tailing 84.33 0.73 12 0.11 0.34 0.86 16.62

1. Flotation feed Cu rougher (1) 3. Cu rougher tailing

2. Cu rougher concentrate
5. Cu cleaner tailing

Cu cleaner (2)

4. Cu cleaner concentrate
(Final Cu Con)

FIG 5 – The copper circuit ‘inner’ mass balance.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 13

 CHRISTOPHER J GREET

The nodes are:

1. flotation feed + Cu cleaner tailings = Cu rougher concentrate + Cu rougher tailings (or, 1
+ 5 = 2 + 3)
2. Cu rougher concentrate = Cu cleaner concentrate + Cu cleaner tailings (or, 2 = 4 + 5).
The resultant mass balance assays are shown in Table 6.
A similar approach is adopted for the lead circuit (Figure 6) where the circuit is balanced in
four parts:
1. lead second and third cleaners
2. lead first cleaner
3. lead scavenger
4. lead rougher/cleaner circuit.
TABLE 6
Adjusted assays for the copper circuit ‘inner’ mass balance.
No Stream t/h ∑ Adjusted assays
Ag (ppm) Cu Pb Zn Fe
1 Flotation feed 120.00 0.10 135 0.44 3.99 15.04 13.17
2 Cu cleaner con 2.39 1.23 588 14.78 15.20 12.75 13.10
3 Cu rougher tailing 118.79 0.10 95 0.21 3.99 15.12 13.14
4 Cu cleaner con 1.21 0.09 229 23.63 4.14 7.71 16.83
5 Cu cleaner tailing 1.18 2.52 424 5.59 26.69 18.00 9.22

Pb rougher feed Balance 3

1. Cu rougher tailing Pb rougher 3. Pb rougher tailing Pb scavenger 5. Pb scavenger tailing

(1) (2)

2. Pb rougher concentrate
4. Pb scavenger concentrate
Balance 2
Pb 1st cleaner feed Pb 1st cleaner 7. Pb 1st cleaner
(3) tailing
6. Pb 1st cleaner concentrate

Pb 2nd cleaner feed Pb 2nd cleaner 9. Pb 2nd cleaner tailing

(4)

8. Pb 2nd cleaner concentrate

Balance 1
Pb 3rd cleaner feed Pb 3rd cleaner 11. Pb 3rd cleaner tailing
(5)

10. Pb 3rd cleaner concentrate

(Pb final con)

FIG 6 – The ‘inner’ mass balances for the lead circuit.

14 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

While this arrangement may appear to be counter intuitive, the reasons for moving
backwards through the lead circuit are driven by the need to estimate tonnage figures for the
recycle streams.
In Balance 1 (the lead second and third cleaners), by using the third cleaner concentrate
estimated tonnage generated in the ‘outer’ mass balance in Step 2 it is possible to estimate
the tonnage for the lead first cleaner concentrate and the lead second cleaner tailing. Using
these two values, it is then possible to mass balance the lead first cleaner. This gives tonnage
estimates for lead rougher concentrate and lead first cleaner tailings.
Balance 3 uses the tonnage estimate for the lead scavenger tailings from the ‘outer’ balance
of Step 2. The mass balance of the lead scavengers estimates the tonnage of lead scavenger
concentrate.
Once these three ‘inner’ mass balances are complete it is possible to fix certain tonnages
(ie copper rougher tailings, lead scavenger tailings, lead first, second and third cleaner
concentrates) and complete a mass balance of the lead circuit. The process streams used for
this balance are:
1. copper rougher tailings
2. lead rougher concentrate
3. lead rougher tailings
4. lead scavenger concentrate
5. lead scavenger tailings
6. lead first cleaner concentrate
7. lead first cleaner tailings
8. lead second cleaner concentrate
9. lead second cleaner tailings
10. lead third cleaner concentrate
11. lead third cleaner tailings.
The nodes are:
1. Cu rougher tailings + Pb scavenger concentrate + Pb first cleaner tailings = Pb rougher
concentrate + Pb rougher tailings (or, 1 + 4 + 7 = 3 + 3)
2. Pb rougher tailings = Pb scavenger concentrate + Pb scavenger tailings (or, 3 = 4 + 5)
3. Pb rougher concentrate + Pb second cleaner tailings = Pb first cleaner concentrate + Pb first
cleaner tailings (or, 2 + 9 = 6+ 7)
4. Pb first cleaner concentrate + Pb third cleaner tailings = Pb second cleaner concentrate + Pb
second cleaner tailings (or, 6 + 11 = 8 + 9)
5. Pb second cleaner concentrate = Pb third cleaner concentrate + Pb third cleaner tailing (or,
8 = 10 + 11).
The mass balanced assays for the lead circuit are shown in Table 7.
The same approach is used for mass balancing the inner circuits for zinc flotation (Figure 7).
The first balance (Balance 1) is for the zinc first and second cleaner, while Balance 2 is for the
zinc scavenger circuit. When these two internal mass balances are complete, it is possible to
mass balance the zinc circuit while fixing certain flows. The process streams used are:
1. lead scavenger tailings
2. zinc rougher concentrate
3. zinc rougher tailings

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 15

 CHRISTOPHER J GREET

4. zinc scavenger concentrate

5. zinc scavenger tailings
6. zinc first cleaner concentrate
7. zinc first cleaner tailings
8. zinc second cleaner concentrate
9. zinc second cleaner tailings.

TABLE 7
Adjusted assays for the ‘inner’ lead circuit mass balance.
No Stream t/h ∑ Adjusted assays (%)
Ag Cu Pb Zn Fe
1 Cu rougher tailing 118.79 0.05 87 0.20 4.00 14.86 13.17
2 Pb rougher con 134.72 1.66 208 0.32 21.53 29.91 8.81
3 Pb rougher tailing 122.16 0.09 40 0.16 1.23 17.25 13.68
4 Pb scavenger con 10.14 1.34 179 0.36 8.20 39.79 11.55
5 Pb scavenger tailing 112.02 0.09 27 0.15 0.59 15.20 13.86
6 Pb 1st cleaner con 110.85 0.10 631 0.30 44.67 13.63 3.91
7 Pb 1st cleaner tailing 127.95 1.17 162 0.28 19.48 30.99 9.18
8 Pb 2nd cleaner con 31.98 0.09 940 0.51 50.72 10.54 2.45
9 Pb 2nd cleaner tailing 104.08 0.11 602 0.25 43.65 13.91 4.06
10 Pb 3rd cleaner con 6.75 0.09 1077 1.08 60.39 9.35 1.71

Zn rougher feed Balance 2

1. Pb rougher tailing Zn rougher 3. Zn rougher tailing Zn scavenger 5. Zn scavenger tailing

(1) (2)

2. Zn rougher concentrate
4. Zn scavenger concentrate

Zn 1st cleaner feed Zn 1st cleaner 7. Zn 1st cleaner

(3) tailing
6. Zn 1st cleaner concentrate

Zn 2nd cleaner feed Zn 2nd cleaner 9. Zn 2nd cleaner tailing

(4)

Balance 1

8. Zn 2nd cleaner concentrate

(Zn final con)

FIG 7 – The ‘inner’ mass balances for the zinc circuit.

16 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

The nodes are:

1. Pb scavenger tailings + Zn scavenger concentrate + Zn first cleaner tailings = Zn rougher
concentrate + Zn rougher tailings (or, 1 + 4 + 7 = 3 + 3)
2. Zn rougher tailings = Zn scavenger concentrate + Zn scavenger tailings (or, 3 = 4 + 5)
3. Zn rougher concentrate + Zn second cleaner tailings = Zn first cleaner concentrate + Zn
first cleaner tailings (or, 2 + 9 = 6 + 7)
4. Zn first cleaner concentrate = Zn second cleaner concentrate + Zn second cleaner tailings
(or, 6 = 8 + 9).
The adjusted assays for the zinc circuit are shown in Table 8.

Step 4
With the inner mass balances complete, it is now possible to balance the whole circuit
(Table 9). When reviewing your mass balance, you should check that the internal workings of
the circuit are balanced. For example, in the copper circuit the feed to the copper rougher is
fresh flotation feed plus copper cleaner tailings. The sum of these recovery values should be
the same as the copper rougher concentrate plus the tailing. That is, for copper:

Rflotation feed + RCu cleaner tailings = RCu rougher con + RCu rougher tailings

100.00 + 12.54 = 66.15 + 46.39

112.54 = 112.54
The balance holds, which gives us confidence in the calculations.

What does it mean? (Chapter 2)

With the mass balance completed, it is time to analyse the data and determine what it means.
The intent is to establish the weaknesses in the circuit and determine what additional tests
are needed to give more definition to the data. It is now possible to convert the elemental
assays to estimates of mineral contents to understand the behaviour of important minerals.
This uses assumptions about the elemental composition of the minerals of interest in your

TABLE 8
Adjusted assays for the ‘inner’ zinc circuit mass balance.
No Stream t/h ∑ Adjusted assays (%)
Ag Cu Pb Zn Fe
1 Pb scavenger tailing 112.02 0.07 28 0.15 0.57 15.15 13.20
2 Zn rougher con 43.74 0.07 53 0.33 1.52 44.32 7.98
3 Zn rougher tailing 89.83 0.18 16 0.13 0.47 1.74 15.69
4 Zn scavenger con 5.51 2.56 72 0.47 2.26 15.17 14.29
5 Zn scavenger tailing 84.32 0.09 12 0.11 0.36 0.86 15.78
6 Zn 1st cleaner con 37.44 0.09 43 0.33 1.32 54.80 6.15
7 Zn 1st cleaner tailing 16.04 0.10 63 0.40 2.04 19.55 12.53
8 Zn 2nd cleaner con 27.70 0.09 39 0.29 1.22 58.66 5.34
9 Zn 2nd cleaner tailing 9.74 0.47 64 0.46 1.61 43.84 8.42

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 17

 CHRISTOPHER J GREET

system, as illustrated in Appendix 2. Conversion to minerals allows you to examine the

flotation behaviour of iron sulfide and non-sulfide gangue species. Combining the calculated
non-sulfide gangue mass balanced data with the water recovery data gives an insight into
recovery mechanisms (entrainment versus genuine flotation). Chapter 2 provides a detailed
description of how to analyse and interpret your plant survey data.
The copper grade/recovery curve for the copper circuit is shown in Figure 8. Combined with
Table 9 this indicates a small circulating load (about 12 per cent) of copper returning to the
rougher feed via the copper cleaner tailings. This is not a major concern; however, the poor
selectivity for chalcopyrite against galena and sphalerite during copper roughing (ie the high
lead and zinc grades) is an issue and requires further investigation.
Figure 9 shows the lead grade/recovery curve. There is a large circulating load of galena in
the lead circuit centred around the lead first cleaner bank. Table 9 also shows there is a large
circulating load of sphalerite in the lead circuit. This suggests there may be liberation issues
in this circuit and warrants further investigation.
The zinc grade/recovery curve (Figure 10) also reveals circulating loads of zinc around the
zinc first cleaner. While these loads are not as severe as the lead circuit, they will undoubtedly
impact zinc metallurgy. Table 9 suggests there may be an issue with iron, particularly around
the rougher/scavenger/first cleaner circuit. This needs further investigation.
It is apparent that there are opportunities for improvement in all three circuits. Since
improvements in the copper circuit will impact the lead and zinc circuits, you should always
start at the front of the circuit and work downstream. The test programs need to be prioritised to
focus resources on the projects with the greatest potential metallurgical (and financial) benefit
to the plant. This survey data indicates the lead circuit is very unstable with high circulating
loads. This could be detrimental to both the lead and zinc circuit performance. Further work
should be completed to determine the recovery-by-size and liberation characteristics through
the lead circuit to see where improvements may be made.

25.0

Cu cleaner concentrate

20.0
Cu grade, %

15.0
Cu rougher concentrate

10.0
Cu rougher feed

5.0

Flotation feed
0.0
0.0 20.0 40.0 60.0 80.0 100.0 120.0
Cu recovery, %
FIG 8 – The copper grade/recovery curve for the copper circuit within the Eureka Concentrator.

18 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

TABLE 9
Mass balance of copper, lead and zinc circuits of the Eureka Concentrator.
No Stream t/h ∑ Cu (%) Pb (%) Zn (%) Fe (%)
Grade Recovery Grade Recovery Grade Recovery Grade Recovery
1 Flotation feed 120.00 0.05 0.43 100.00 4.00 100.00 14.92 100 13.06 100.00
2 Cu rougher con 2.39 0.41 14.29 66.15 15.10 7.50 12.76 1.70 13.10 1.99
3 Cu rougher tailing 118.79 0.05 0.20 46.39 4.00 98.97 14.99 99.48 13.02 98.69
4 Cu cleaner con 1.21 0.11 22.74 53.61 4.07 1.03 7.71 0.52 16.84 1.31
5 Cu cleaner tailing 1.18 0.84 5.52 12.54 26.54 6.47 17.99 1.18 9.22 0.69
6 Pb rougher con 134.72 3.12 0.32 85.07 21.44 611.75 29.86 228.56 8.84 77.31
7 Pb rougher tailing 122.16 0.23 0.17 39.52 1.24 31.39 17.40 119.05 13.52 105.65
8 Pb scav con 10.14 3.00 0.36 7.25 8.17 17.72 39.71 23.11 11.58 7.70
9 Pb scav tailing 112.02 0.10 0.14 32.27 0.58 13.67 15.33 95.94 13.70 97.95
10 Pb 1st cleaner con 110.85 0.10 0.30 64.56 44.68 1030.87 13.63 84.37 3.91 27.69
11 Pb 1st cleaner 127.95 2.27 0.28 70.95 19.41 526.44 30.92 225.02 9.21 76.58
tailing
12 Pb 2nd cleaner con 31.98 0.10 0.51 31.72 50.75 337.91 10.54 18.84 2.45 5.00
13 Pb 2nd cleaner 104.08 0.11 0.25 50.44 43.64 945.57 13.91 80.84 4.06 26.95
tailing
14 Pb 3rd cleaner con 6.75 0.09 1.08 14.12 60.64 85.30 9.36 3.53 1.71 0.74
15 Pb 3rd cleaner 25.23 0.13 0.36 17.60 48.10 252.61 10.86 15.30 2.65 4.26
tailing
16 Zn rougher con 43.74 0.39 0.33 27.91 1.48 13.51 44.77 109.42 8.00 22.33
17 Zn rougher tailing 89.93 0.24 0.13 21.96 0.50 9.38 1.74 8.75 16.30 93.53
18 Zn scav con 5.51 3.59 0.47 5.12 2.23 2.58 15.14 4.71 14.26 5.07
19 Zn scav tailing 84.32 0.07 0.10 16.85 0.39 6.79 0.86 4.04 16.44 88.46
20 Zn 1st cleaner con 37.44 0.09 0.33 24.19 1.30 10.16 55.33 115.74 6.17 14.74
21 Zn 1st cleaner 16.04 1.07 0.40 12.49 1.99 6.64 19.52 17.52 12.51 12.83
tailing
22 Zn 2nd cleaner con 27.70 0.09 0.29 15.42 1.19 6.88 59.41 91.91 5.38 9.50
23 Zn 2nd cleaner 9.74 0.38 0.46 8.76 1.62 3.28 43.76 23.83 8.41 5.23
tailing

Sample identification and storage

At the risk of stating the obvious, it is important to have a workable sample identification
and storage system. A lack of attention to detail will lead to mistakes in the assay laboratory
with poor labelling, and can jeopardise the ability to locate samples for check assaying or
for further testing (for example, sizing or mineralogical examination). Therefore, you need
to set up a system of identification that is both simple and effective. For example, label all
surveys with an ‘S’ and number them consecutively, with each sample in that survey also
given a number. If the survey described in this chapter is the tenth survey completed in
the Eureka Concentrator, the identification code would be S10/1 to S10/34, where sample

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 19

 CHRISTOPHER J GREET

70.0

Pb 3rd cleaner concentrate

60.0
Pb 2nd cleaner concentrate
50.0 Pb 2nd cleaner feed
Pb grade, %

st
Pb 1 cleaner concentrate
40.0

Pb 1st cleaner feed

30.0

Pb rougher concentrate
20.0

Cu rougher tailing
10.0 Pb rougher feed

Flotation feed
0.0
0.0 200.0 400.0 600.0 800.0 1000.0 1200.0 1400.0 1600.0 1800.0
Pb recovery, %
FIG 9 – The lead grade/recovery curve for the lead circuit within the Eureka Concentrator.

70.0

Zn 2nd cleaner concentrate

60.0
st
Zn 1 cleaner concentrate

50.0
Zn rougher concentrate
Zn grade, %

Zn 1st cleaner feed

40.0

30.0

20.0
Zn rougher feed
Pb rougher tailing
10.0

Cu rougher tailing Flotation feed

0.0
40.0 60.0 80.0 100.0 120.0 140.0 160.0
Zn recovery, %
FIG 10 – The zinc grade/recovery curve for the zinc circuit within the Eureka Concentrator.

numbers 1 to 34 correspond to the sample numbers in Table 2. The next survey would be
S11, and so on. Flotation tests could be identified according to the operator’s initials, for
example, CG351/1 to CG351/5, which would be read as flotation test 351 completed by CG
with five test products.
Once a numbering system is in place it is easy to develop a storage system. Your storage
system must set rules regarding the length of time to keep samples, and allow the laboratory
technicians time to periodically maintain the storage facility. For example, it is wise to keep
flotation test products for three months and plant surveys for up to 12 months. It is also
wise to have a clean-up every three months to dispose of samples that have passed their
storage date.

20 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

The pulp chemistry survey (Chapter 7)

Concurrent to the metallurgical survey, pulp chemical data was collected from the plant to
determine the pulp chemical conditions.

What do I have to do?

The pulp chemical survey involves collecting Eh, pH, dissolved oxygen and temperature data
from the following process streams:
•• SAG mill discharge
•• cyclone underflow
•• ball mill discharge
•• cyclone overflow
•• copper circuit feed
•• lead circuit feed
•• zinc circuit feed
•• final tailings.
To complete a pulp chemical survey, a sample of slurry is ‘cut’ from the process stream
of interest and poured into a small beaker. The sample is stirred gently with the probes for
two minutes or until equilibrium readings are obtained. The Eh, pH, dissolved oxygen and
temperature data are recorded on a data logger and can be downloaded to a laptop computer
to be manipulated.
All of the probes should be regularly checked to ensure they are clean and in good working
order. It is imperative that they are calibrated before each use. The pH probe should be
calibrated using pH buffer solutions seven and ten if this is the range expected in the plant.
Alternative buffer solutions should be used if the pulp pH is outside this range. The Eh
probe should be calibrated, for example, using Zobell solution (1:1 solution of Part A and B
= 231 mV at 24°C). The dissolved oxygen probe is calibrated in a 0.2 g/L solution of sodium
sulfite for the zero calibration, and air. The temperature probe can be calibrated with the aid
of a thermometer, using iced and heated water to give a two-point calibration.
To complete the data set, ethylene diamine tetra acetic acid di-sodium salt (EDTA) extractions
should be completed on the same process streams as the pulp chemistry. For the Eureka
survey each stream was ‘cut’ and the sample poured into a small, wide mouth screw-top
sample bottle. The samples were taken to the laboratory and the wet weight recorded. The
EDTA extraction procedure was:
1. stir the pulp sample with a 25 ml syringe to homogenise slurry
2. syringe a 25 ml aliquot of slurry from the sample bottle and weigh
3. inject the contents of the syringe into a 400 ml beaker containing 250 ml of three per cent
(by weight) EDTA solution, pH modified to 7.5 with sodium hydroxide
4. thoroughly mix the slurry and EDTA solution using a magnetic stirrer for five minutes
5. filter the slurry using a 0.2 µm millipore filter
6. submit the filtered EDTA solution for assay.
The remainder of the pulp sample was pressure filtered and dried. The dry solids were
weighed and submitted for assay.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 21

 CHRISTOPHER J GREET

What data do I need?

The pulp chemical data (pH, Eh, dissolved oxygen and temperature) are stored on a data
logger. These need to be downloaded into Excel, massaged and put into a logical format for
analysis and interpretation.
The samples for EDTA extraction (solids and liquids) are prepared and submitted for assay.
Usually these samples are assayed for the base metals of interest; in this case, solids and
liquids were assayed for copper, lead, zinc and iron.
As with the metallurgical surveys, other data that can be useful when analysing the EDTA
survey are:
•• the throughput at the time of the survey
•• reagent additions and other plant operating parameters (ie air flow rates and pulp levels)
•• OSA readings
•• information about the ore being treated.
In the context of a one-off survey some of this information may not be of great value;
however, when the analysis is extended to include other surveys on other ore blends, circuit
configurations and reagent suites, these data provide an important comparison.
It can be beneficial to collect process water samples routinely (ie on a monthly basis and
during some pulp chemistry surveys) to determine the free ions in solution (ie base metal ions
(copper, lead, zinc, iron), calcium, magnesium, sulfate and chloride).

How do I analyse the data?

With the exception of Eh, the other pulp chemical measurements can be read directly from
the measured data. The Eh should be adjusted so that it is referenced against the standard
hydrogen electrode (SHE). Chapter 7 provides an explanation of how to manipulate and
analyse the data you have collected.
One method of analysing the EDTA data is given by Rumball and Richmond (1996), who
developed a simple relationship for calculating the percentage of oxidised mineral present in
a pulp from EDTA extraction data (Equation 1):
Mass of M in EDTA solution # 100
% EDTA extractable M = (1)
Mass of M in solids
where:
M is the metal ion under investigation
The data is generally presented graphically with the pulp chemical parameter on the y-axis
and the circuit position on the x-axis. The process streams are set to mimic the normal flow of
the slurry through the circuit. In this case:
1. SAG mill discharge
2. cyclone underflow
3. ball mill discharge
4. cyclone overflow
5. copper rougher feed
6. lead rougher feed
7. zinc rougher feed
8. final tailing.

22 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

When investigating the pulp chemistry in your circuit you might be tempted to sample
every stream in the concentrator. While this may be a good idea initially to understand the
variation between streams, it is soon apparent that some of this data is redundant. For example,
concentrate streams usually have high dissolved oxygen contents and very oxidising pulp
potentials because froth contains significant air. Therefore, a pulp chemistry survey of the
primary grinding/rougher flotation circuit might be skewed by measuring the pulp chemistry
of the rougher concentrate. However, if you are examining the pulp chemistry of a regrind/
cleaner circuit, you should collect a sample of the fresh concentrate feed to regrinding. If you
are comparing the surface analysis of streams (eg rougher concentrate and rougher tailing)
then you should collect the pulp chemistry of both streams.

What does it mean?

The pH, Eh, dissolved oxygen and temperature data should be plotted in a way that represents
the pulp flow profile through the circuit to aid interpretation. The profiles through the Eureka
circuit are displayed in Figures 11 to 14.
The pH profile (Figure 11) indicates that grinding occurs at natural pH (in the range 8.0
to 8.5). The slight reduction in pH in the ball mill discharge may be due to pyrite oxidation.
Sodium metabisulfite (SMBS) was added to the copper rougher feed to depress galena during
copper flotation. The addition of SMBS reduced pH to approximately 6.0. The pH was then
increased to 8.0 for galena flotation and 11.5 for sphalerite flotation by adding lime.
Figure 12 is the Eh profile through the circuit. Eh shifted to slightly less oxidising as the pulp
flowed from the SAG mill through the ball mill, then became more oxidising during flotation
due to the air addition.
The dissolved oxygen profile (Figure 6) through the circuit indicates that the oxygen content
of the pulp was negligible during both grinding and flotation. By the end of the circuit, after
zinc flotation dissolved, oxygen content had increased to 4.5 ppm in the final tailing. This
suggests that the ore is very reactive and consumes oxygen throughout the process.

12.0

10.0

8.0
pH

6.0

4.0

2.0

0.0
w

g
e

d
rg

rg

ee

ee

ee

lin
flo

flo
ha
ha

ai
rf

rf

rf
r

er
de

rt
he
sc

sc

he

he
ov
un

he
di

di

ug

ug

ug
e

ug
on
e

ill
i ll

ro

ro

ro
on
m

ro
l
yc

Pb

Zn
l

ll
G

yc

Zn
Ba

C
SA

Circuit position

FIG 11 – The pH profile through the grinding and flotation circuits of the Eureka Concentrator.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 23

 CHRISTOPHER J GREET

200.0

160.0
Eh, mV (SHE)

120.0

80.0

40.0

0.0
ow

ow

g
e

d
ed

ed
g

ilin
rg

ee
ar

fe

fe
r fl

rfl
ha

rf

ta
ch
de

r
he

he
sc

he
ov

r
s
un

he
di
di

ug

ug

ug
ne

ug
ne
ill

ill

ro

ro

ro
lo
m
m

ro
lo

yc

Pb

Zn
ll
G

yc

Zn
Ba

C
SA

Circuit position

FIG 12 – The Eh profile through the grinding and flotation circuits of the Eureka Concentrator.

6.0

5.0

4.0
DO, ppm

3.0

2.0

1.0

0.0
ow

ow

g
ge

ed

ed

d
g

ilin
ee
ar

fe

fe
ar

r fl

rfl

rf

ta
ch
ch

de

r
he

he

he
ov

r
s
s

un

he
di
di

ug

ug

ug
e

ug
on
ne
ill

ill

ro

ro

ro
lm
m

ro
l
lo

yc

Pb

Zn
G

yc

C
l

Zn
Ba

C
SA

Circuit position

FIG 13 – Dissolved oxygen profile through the grinding and flotation circuits of the Eureka Concentrator.

The pulp temperature ranged from 33°C to 35°C in most of the circuit (Figure 14). The
spike in pulp temperature in the ball mill discharge is due to part of grinding energy being
dissipated as heat.
The Eh-pH data for the grinding and flotation circuits are plotted in Figure 15 to determine
where the reactions are occurring. From the Nernst Equation 2 there is a dependence of redox
potential on pH:
a
E = E 0 + 0.059 log10 f Reactants p (2)
n a Products

Applying the Nernst equation to water results in a Pourbaix diagram that describes three
domains separated by lines of equilibria. The uppermost is the water-oxygen line (Equation 3),
above which water decomposes and oxygen is evolved and below which water is stable:

24 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

45.0
40.0
35.0

Temperature, oC
30.0
25.0
20.0
15.0
10.0
5.0
0.0
w

g
e

d
rg

rg

ee

ee

ee

lin
flo

flo
ha
ha

ai
rf

rf

rf
r

er
de

rt
he
sc

sc

he

he
ov
un

he
di

di

ug

ug

ug
e

ug
on
e

ill
i ll

ro

ro

ro
on
m

ro
l
yc

Pb

Zn
l

ll
G

yc

Zn
Ba

C
SA

Circuit position

FIG 14 – Temperature profile through the grinding and flotation circuits of the Eureka Concentrator.

250

200 6
8

150
Eh, mV (SHE)

4
5
100 1
1. SAG mill discharge
2
2. Cyclone underflow
50 3. Ball mill discharge
4. Cyclone overflow 7
5. Cu rougher feed 3
0 6. Pb rougher feed
7. Zn rougher feed
8. Final tailing
-50
4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0
pH

FIG 15 – The Eh-pH curve for the grinding and flotation circuits of the Eureka Concentrator.

E0 = +1.23 + 0.015 log 10 p0 − 0.059 pH (3)

2 2

This can be simplified further (Johnson, 1988; Natarajan and Iwasaki, 1973) for an oxygenated
aqueous solution with no well-defined redox couples to:

E0 = +0.9 - 0.059 pH (4)

2

Broadly, if the changes in Eh and pH result in a line parallel to the water-oxygen line
this means that water equilibria is being maintained. That is, any change in Eh is directly
proportional to a change in pH with a relationship similar to Equation 4. If the changes in
Eh and pH result in a line that is perpendicular to the water-oxygen line, this suggests that
oxidative reactions are occurring.
Figure 15 shows that the Eh-pH lines between points 1 and 4 are perpendicular to the water-
oxygen line. This indicates that oxidative reactions are occurring in the grinding circuit. It is

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 25

 CHRISTOPHER J GREET

likely that these oxidative reactions are corrosion of the grinding media and oxidation of
the sulfide minerals. As the pH is decreased across the ball mill, pyrite oxidation (an acidic
reaction) may be one of the dominant reactions. The changes in the Eh-pH curve between
points 4 and 5, 5 and 6, and 6 and 7 can be attributed to the addition of reagents that alter pH:
SMBS to copper flotation, lime to the lead and zinc circuits.
The EDTA extractable copper, lead, zinc and iron data are shown in Figure 16. The EDTA
extractable copper profile (Figure 9) suggests that the percentage of oxidised chalcopyrite
remained negligible throughout the grinding circuit. The EDTA extractable copper increased
during copper flotation to approximately 2.5 per cent and increases to 17 per cent in the
zinc rougher feed (which can be attributed to the addition of copper sulfate for sphalerite
activation).
Notably, the percentage of EDTA extractable lead is at least an order of magnitude greater
than the values for zinc and iron. This is because galena is a reactive mineral when in contact
with other sulfide minerals, particularly pyrite. The EDTA extractable lead profile shows
the percentage of oxidised galena remained approximately constant through the grinding
circuit, with values of around 1.0 per cent. It increased in the cyclone overflow and remained
reasonably constant through the copper circuit. After lead flotation, the lead scavenger
tailing had 17 per cent EDTA extractable lead, increasing to almost 40 per cent after zinc
flotation. This suggests that the lead species remaining in lead scavenger tailing are more
heavily oxidised.
The EDTA extractable zinc profile exhibits a similar trend to that observed for lead.
Through the grinding circuit the percentage EDTA extractable zinc was approximately
constant at around 0.1 per cent. This indicates that sphalerite oxidation was largely
unchanged through grinding. It then increased during the copper and lead flotation circuits
from 0.13 to 0.37 per cent and then significantly increased after zinc flotation to 1.0 per cent.
This indicates that the zinc species that remained in zinc scavenger tailings were more
heavily oxidised.

42.0 1.2
EDTA extractable Zn and Fe, %
EDTA extractable Cu and Pb, %

35.0 1.0

28.0 0.8

21.0 0.6

14.0 0.4

7.0 0.2

0.0 0.0
w
w

g
e

ed
ge

ee

ee

ilin
rg

flo
o

fe
ar
rfl
ha

rf

rf
er

ta
h
de

r
he
sc

he

he
sc

ov

l
na
un
di

di

ug

ug
ug
ne

Fi
ne
il l

ill

ro

ro

ro
lo
m

m
lo

yc

Zn
Pb
G

ll
yc

C
Ba

C
SA

Circuit position
Cu Pb Zn Fe

FIG 16 – The EDTA extractable copper, lead, zinc and iron profiles
through the grinding and flotation circuits of the Eureka Concentrator.

26 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

The EDTA extractable iron profile gives the best indication of the impact of grinding
media corrosion on the system. In primary grinding it ranged from 0.05 to 0.16 per cent, and
then increased to 0.30 per cent in cyclone overflow. That is, the pulp entering the flotation
circuit contains elevated levels of EDTA extractable iron, presumably after contact with the
forged grinding media. Interestingly, the levels decreased through the flotation circuit. This
is probably due to the continuing oxidation of the iron species to higher-level iron oxides,
which are not soluble in EDTA.

Summary of data acquisition

The metallurgical survey suggests a number of opportunities to improve the metallurgical
performance of the Eureka Concentrator. These may be liberation related, and further data is
required to identify liberation characteristics. The data strongly suggests that the first priority
is to improve lead flotation.
The pulp chemistry suggests the ore is reasonably reactive, particularly during grinding.
This needs consideration, but not until the liberation issues have been resolved.

PROBLEM DEFINITION
From the metallurgical survey the circulating load in the lead rougher/lead first cleaner
circuit was extremely high (Table 10) for both lead and zinc. In fact, copper scavenger tailings
contributed only 15.4 and 28.6 per cent of lead and zinc units in lead rougher feed. The recycle
from the lead first cleaner tailing contributed by far the most lead and zinc to the lead rougher
feed (81.9 and 64.7 per cent, respectively).

Recovery by size (Chapter 2)

The mass balanced data provides information about the grades and recoveries in the circuit.
The data also provides information about the circulating loads. To gain a greater appreciation
of the problems and their magnitude, samples from selected process streams should be sized
and each size fraction assayed. Mass balancing the size fractions allows the performance of
each size fraction to be assessed.
Table 9 and Figure 9 indicate that the lead rougher/first cleaner section has a large circulating
load of galena and sphalerite. This may be due to composite particles and is likely to cause
circuit instability; however you need more information to be sure. You need data on the size
and mineralogy of circuit losses, so the first step in this is to examine recovery-by-size from
lead rougher feed.

TABLE 10
Mass balanced data for the lead rougher feed, with respect to flotation feed. Note: both the lead scavenger
concentrate and the lead first cleaner tailing are recycled back to the head of the lead rougher.
Stream t/h Grade (%) Recovery (%)
Cu Pb Zn Fe Cu Pb Zn Fe
Cu scav tailing 118.8 0.2 4.0 15.0 13.0 46.4 99.0 99.5 98.7
Pb 1st cleaner tailing 128.0 0.3 19.4 30.9 9.2 71.0 526.4 225 76.6
Pb scav concentrate 10.1 0.4 8.2 39.7 11.6 7.2 17.7 23.1 7.7
Pb rougher feed 256.9 0.3 11.8 23.9 11.1 124.6 643.1 347.6 183

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 27

 CHRISTOPHER J GREET

What do I have to do?

When you conducted the survey you may have intended to size the samples for a recovery-
by-size analysis. However, before launching the task of sizing every sample from the survey
you should first mass balance the survey. You can only justify the expense and time for sized
analysis if you know the survey is ‘good’, ie that it balances. If you establish that the mass
balance is good, you then decide if recovery-by-size analysis is warranted and on which
samples. You may not need to size every sample in the survey, depending on what the survey
reveals about plant performance. For example, sizing concentrate and tailings from a section
show which size fractions of the valuable species are not being recovered efficiently and
which size fractions of the gangue species are being recovered. Sometimes a down-the-bank
survey adds value by identifying where size fractions are recovered. This can determine the
kinetics of various species on a size basis.
With these decisions made, you need to retrieve the samples from storage, ensure that you
have sufficient sample for sizing (around 200 g), and determine what sizes you require. If you
need size fractions below 38 µm you will need to use a cyclosizer, which gives six more size
fractions. If a cyclosizer is used in concert with a pre-cyclone and a centrifuge this can be
extended to seven.

What data do I need?

With the sizing completed you need the mass collected in each size fraction. For a simple
sieve analysis you need to determine if there is enough mass in each size fraction for assay
(usually around 5 g). If you do not have enough sample in a size fraction you either need
another sizing on the sample or you can combine some size fractions for assay. If you do
combine size fractions you must apply this to all of the samples in this data set. So, if you had to
combine the +300, +212 and +150 µm fractions in the feed sample, you need to do the same for
all other samples in this survey.
If you size the subsieve fractions using a pre-cyclone/cyclosizer/centrifuge combination,
you need to know the water temperature, elutriation time, water flow rate and the specific
gravity of the minerals being separated. With this information, the cyclosizer manual
(Warman International Limited, 1991) can be used to calculate the ‘cut’ size for each cyclone.
For quartz, the cyclone ‘cut’ sizes for the cyclosizer at a flow rate of 11.6 L/min, a water
temperature of 20°C and an infinite elutriation time are:
•• C1 = 44 µm
•• C2 = 33 µm
•• C3 = 23 µm
•• C4 = 15 µm
•• C5 = 11 µm.
The pre-cyclone generally ‘cuts’ at about 7 µm. To convert the quartz ‘cut’ sizes to minerals
such as chalcopyrite, galena, sphalerite and pyrite, multiply by the overall correction factor:
f = fT × fSG × fFM × fET (5)
where:
fT is the temperature correction factor
fSG is the mineral specific gravity correction factor
fFM is the flow meter reading correction factor
fET is the elutriation time correction factor

28 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

You should correct for each mineral in the system as each mineral has a different specific
gravity (SG). The cyclone ‘cut’ sizes for each of the cyclosizer cones are in Table 11. When
dealing with elements that are present in parts per million (eg platinum-group minerals,
gold and silver) an understanding of their mineral associations is required. For example, if
the silver is associated predominantly with galena the cyclosizer cyclone cut sizes should be
calculated using a fSG based on the SG of galena. The same applies to gold that is associated
with pyrite; the fSG should be based on the SG of pyrite.
Note that the pre-cyclone, cyclosizer and/or the centrifuge size on hydraulic characteristics
rather than particle dimensions as obtained by screen sizing above 38 µm. Screen sizing is not
affected by particle SG; hydraulic sizing is. When the two sizing methods are used together
the transition point from one technique to the other can lead to some unusual shaped curves
due purely to the change in the sizing method. To overcome this, it is usual to combine the
-53 µm to +C2 size fractions to smooth the curves and remove the transition effect.
If you are considering a mineralogical analysis, you now need to ‘split’ out a small
representative portion from the samples of interest before pulverising the samples for assay.
Once you have reviewed the weights in each size fraction for each sample, decided which size
fractions to combine and ensured that there is enough sample for assay in each size fraction,
the samples can be prepared and submitted for assay.

How do I analyse the data collected?

When the assays return you must check that the assays are in good order. Calculate the
combined head assay from the size fraction assays and compare it with the actual head
assay. If they agree closely, you can assume that both the sizing and the assays were
completed properly.
To construct a graph like Figure 17, you need size and assay data for copper rougher
tailings, lead first cleaner tailings, lead scavenger concentrate and lead rougher feed. To
simplify the analysis only the lead assay data will be considered in this example. The starting
point to determine recovery-by-size in this part of the circuit is the mass balanced data from

TABLE 11
Cyclosizer cyclone ‘cut’ sizes for quartz, chalcopyrite, galena, sphalerite and pyrite.
Mineral
Correction factor Quartz Chalcopyrite Galena Sphalerite Pyrite
fT 0.9815 0.9815 0.9815 0.9815
fSG 0.7181 0.5038 0.7416 0.6423
fFM 0.9519 0.9519 0.9519 0.9519
fET 1.0063 1.0063 1.0063 1.0063
f 0.6751 0.4737 0.6972 0.6038
Cyclone ‘cut’ size
C1 44 30 21 31 27
C2 33 22 16 23 20
C3 23 16 11 16 14
C4 15 10 7 11 9
C5 11 7 5 8 7

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 29

 CHRISTOPHER J GREET

100.0

90.0

80.0
Pb distribution, %

70.0

60.0

50.0
40.0
30.0
20.0 Pb rougher feed

10.0 Pb 1st cleaner tail

0.0 Pb scav con
Total
-5.6 +5.6 Cu scav tail
+7.6 +11.6 +16.7
Particle size, microns +22.2

FIG 17 – Lead distribution by size in the process streams contributing to the lead rougher feed.

the plant survey in Table 9 and for this section in Table 10. Using the mass balanced tonnages
for each process stream in Table 10, the size distribution for each sample point was applied
to calculate the solids flow in each size fraction (Table 12). The weight per cent and the assay
for each size fraction are used to calculate the head grade:
n (mi # ai)
Head grade = / /m (6)
i=1 i
where:
m is the weight per cent in size fraction i
a is the assay for that size fraction
This calculated head grade is then compared with the assay of the head sample to determine
how well the sizing and assay procedures have been completed. Unfortunately, in this
instance the mass and assay of the -5.6 µm fraction was calculated by difference. That is:
n-1
m-5.6nm = mH - /m i
(7)
i=1

and
n-1
e mH # a H - e / mi # ai oo
i-1
a-5.6nm = (8)
m-5.6nm

where:
mH and aH are the weight per cent and assay for the head
By calculating weight per cent and assay for the finest size fraction, all errors associated with
sizing, assaying and sampling accumulate to this size fraction. In an ideal world a sample of
this material would be collected.

30 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

TABLE 12
The lead recovery-by-size data for the lead rougher feed calculated from the copper
rougher tailing, lead first cleaner tailing and the lead scavenger concentrate.
Stream/size Wt Wt Pb parameter (%)
% (t/h) Grade Distribution Recovery to Pb Ro feed
Cu scavenger tailing
+22.2 µm 48.79 57.96 4.06 49.49 7.73
+16.7 µm 6.66 7.91 3.00 5.00 0.78
+11.6 µm 10.18 12.09 1.88 4.78 0.75
+7.6 µm 5.32 6.32 2.54 3.38 0.53
+5.6 µm 3.77 4.48 2.24 2.11 0.33
-5.6 µm 25.28 30.03 5.58 35.24 5.51
Head 100.00 118.79 4.00 100.00 15.62
Pb first cleaner tailing
+22.2 µm 82.44 105.48 22.12 93.96 76.72
+16.7 µm 6.13 7.84 8.84 2.79 2.28
+11.6 µm 3.19 4.08 8.64 1.42 1.16
+7.6 µm 1.17 1.50 5.10 0.31 0.25
+5.6 µm 0.81 1.04 4.10 0.17 0.14
-5.6 µm 6.26 8.01 4.18 1.35 1.10
Head 100.00 127.95 19.41 100.00 81.65
Pb scavenger con
+22.2 µm 70.32 7.13 9.66 83.14 2.26
+16.7 µm 10.48 1.06 8.20 10.52 0.29
+11.6 µm 6.69 0.68 2.62 2.15 0.06
+7.6 µm 2.15 0.22 3.20 0.84 0.02
+5.6 µm 1.37 0.14 3.68 0.62 0.02
-5.6 µm 8.99 0.91 2.49 2.74 0.07
Head 100.00 10.14 8.17 100.00 2.72
Pb rougher feed
+22.2 µm 66.40 170.57 15.46 86.72 86.72
+16.7 µm 6.55 16.82 6.05 2.25 2.25
+11.6 µm 6.56 16.85 3.55 1.97 1.97
+7.6 µm 3.13 8.03 3.03 0.80 0.80
+5.6 µm 2.20 5.65 2.62 0.49 0.49
-5.6 µm 15.16 38.95 5.22 6.68 6.68
Head 100.00 256.88 11.84 100.00 100.00

From the tonnes and assay of each size fraction you can calculate the distribution-by-size
and recovery-by-size for each stream. The distribution within a process stream is given by:
(mi # ai)
Distributiona = f p 100 (9)
(mH # aH) #

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 31

 CHRISTOPHER J GREET

The distribution of lead by stream is shown in Table 12. In this case the recovery-by-size
is calculated for lead rougher feed because the copper scavenger tailings, lead first cleaner
tailings and lead scavenger concentrate combine to form the lead rougher feed. So, the
recovery for each size fraction, i, is given by:
J n N
/
K (m P # aP) O
Recoveryi,a = K P = 1 O # 100 (10)
K (m # a ) O
L H H P
where:
P are the process streams of interest
A similar approach is adopted for the more traditional recovery-by-size curves in Figure 18
and Figure 20.

What does it mean?

Figure 17 shows the galena distribution by size for the three process streams contributing to
the lead rougher feed. The majority of galena in lead rougher feed is coarse (+20 µm) lead
recycled from lead first cleaner tailings (80 per cent of the total lead in the lead rougher feed).
Thus, the flotation characteristics of the lead rougher/scavenger unit are dominated by the
behaviour of this material.
Recovery-by-size data for lead final concentrate is shown in Figure 18. This shows that lead
final concentrate is predominantly fine (-20 µm) galena, with over 90 per cent lead recovery
for the size fractions between 5 µm and 20 µm. Recovery decreases for finer or coarser than
this. Recovery of gangue minerals (sphalerite, iron sulfides and non-sulfide gangue) are low
across all size fractions.
Galena distribution by size in the lead scavenger tailing with respect to flotation feed, is
shown in Figure 19. Galena losses are bimodal, with significant losses (5.6 per cent) in the
fine (-5 µm) fraction and19.9 per cent in the coarse (+20 µm) fraction. The losses in the coarse
fractions are the biggest target. The losses are likely to be in galena-bearing/sphalerite-rich
composites.

90.0

80.0

70.0

60.0
Recovery, %

50.0

40.0

30.0

20.0

10.0

0.0
1.0 10.0 100.0 1000.0
Geometric mean particle size, microns
Lead Zinc Copper Iron Silica

FIG 18 – Recovery-by-size data for the lead final concentrate, with respect to flotation feed for the Eureka Concentrator.

32 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

6.0

Distribution (with respect

5.0

to flotation feed), %
4.0

3.0

2.0

1.0

0.0 2.3

6.0

7.9

11.7

17.6

28.0

41.0

48.8

63.0

89.2

126.1

178.3
Geometric mean particle size, microns

FIG 19 – The galena distribution by size, with respect to flotation feed, in the lead scavenger tailing for the Eureka Concentrator.

100.0

90.0

80.0

70.0
Recovery, %

60.0

50.0

40.0

30.0

20.0

10.0

0.0
1.0 10.0 100.0 1000.0
Geometric mean particle size, microns
Lead Zinc Copper Iron Silica

FIG 20 – Recovery-by-size data for the zinc final concentrate, with respect to flotation feed for the Eureka Concentrator.

Figure 20 shows recovery-by-size for the zinc final concentrate. It shows a peculiar behaviour
of coarse (+20 µm) galena with recovery as high as 60 per cent. This is presumed to also be
related to galena-bearing/sphalerite-rich composite particles).

Mineralogy (Chapter 4)
Once the recovery-by-size data has been analysed and theories developed, select streams
should be examined mineralogically. This is a relatively expensive process and should only
be conducted after considering the work already discussed. In this case the recovery-by-size
analysis shows a significant recycle of lead first cleaner tailings to lead rougher feed, and
that most of this is in the +20 µm size fraction. It is hypothesised that this is due to galena/
sphalerite composites. Mineralogical examination will test this hypothesis.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 33

 CHRISTOPHER J GREET

What do I have to do?

The company performing a mineralogical analysis needs representative, unpulverised
samples of each stream. For a liberation analysis you will need to provide sized fractions
from the unpulverised samples. These should be available from the recovery-by-size analysis
if it has been conducted.
Several methods are available to collect mineralogical data; from optical microscopy
through to automated methods such as QEMSCAN and Mineral Liberation Analyser (MLA).
Chapter 4 describes the methods available.

What data do I need?

The mineralogist will need a scope of work and assays of the samples to be examined. This
will inform the mineralogist of the questions you want answered. For example, at Eureka you
are interested in the locking and liberation characteristics of galena and sphalerite around
the lead rougher/first cleaner circuit. Supplying the sample assays allows the mineralogist to
reconcile calculated head grade based on minerals with head assays.

How do I analyse the data collected?

The mineralogical report will depend on the mineralogical technique used. The report should
include, for each sample, the percentage of liberated mineral, the percentage and composition
of binary particles and the percentage and composition of more complex composite particles.
Table 13 is a simplified list of the liberation data for galena in lead rougher feed for the Eureka
Concentrator. This shows that of the lead in the +28 µm fraction, 66 per cent occurs as liberated
galena particles and 28 per cent occurs as binary composites with sphalerite. Minor amounts
of galena are associated with pyrite in ternary particles.

What does it mean?

Mineralogical examination of streams feeding lead rougher show that about one third of the
galena occurs as coarse (+20 µm) galena/sphalerite composite particles (Figure 21), and the
majority of this material emanates from the lead first cleaner tailing. Two thirds of the galena
in lead rougher feed is liberated, which infers that the maximum lead recovery to a high-
grade final lead concentrate would be approximately 70 per cent. Therefore, galena liberation
is considered to be the limiting factor for improved metallurgical performance.

TABLE 13
Galena liberation by size and mineral class for the lead rougher feed of the Eureka Concentrator.
Size (µm) Liberation class (%) Total (%)
Liberated Binary with … Ternary
Sphalerite Pyrite Gangue
+89 26 54 5 4 11 100
+28 66 28 3 0 2 100
+10 69 25 5 1 1 100
+6 93 6 0 0 0 100
-6 94 5 0 0 0 100
Head 66 28 3 0 2 100

34 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

100

90

80

70

60
Distribution

50

40
Liberated
30
Ga-Sp
20
Ga-Py
10 Liberation class
Ga-Gn
0
Head Ternary
2.3
6.0
10.1
28.2
Size, microns 89.2

FIG 21 – Size by liberation class data for the lead rougher feed. Ga – galena, Sp – sphalerite, Py – pyrite, Gn – gangue.

Problem definition summary

The metallurgical survey suggested the lead circuit was potentially unstable with large
circulating loads of galena and sphalerite between the lead rougher and first cleaner.
Recovery-by-size and liberation analysis has indicated limited recovery of +20 µm galena
in the lead circuit. Liberation analysis shows that the galena in this fraction is locked with
sphalerite. Thus, the problem is: poor liberation of galena in the +20 µm size fraction.

SOLUTION DEVELOPMENT AND TESTING

It is apparent that finer grinding is needed to improve liberation. The next step is to conduct
a series of laboratory tests to examine the impact of regrinding lead first cleaner tailings (the
main feed source to the lead rougher).

Laboratory investigation (Chapter 10)

What do I have to do?
As the lead first cleaner tailing contributed the highest material flow to lead rougher feed and
contains a significant amount of plus 20 µm galena/sphalerite composite particles, this is the
first target for a series of laboratory flotation tests at different regrind sizes to improve lead
rougher flotation. Your job is to design this program.
To conduct the tests, pulp was collected from the lead first cleaner tailing and a bulk sample
of process water was collected. The pulp was filtered and ‘cut’ into 1000 g lots. The test
program called for one test to be completed without regrinding, and then tests conducted
with 5, 10, 15 and 20 minute regrinding. Flotation tests were conducted in a 2.5 L flotation
cell. Timed concentrates were collected after 0.5, 1.5, 2.0, 2.0, 2.0, 2.0 and 2.0 minutes for a total

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 35

 CHRISTOPHER J GREET

60.0

55.0

50.0
Pb grade, %

45.0

40.0

35.0

30.0

25.0
10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0
Pb recovery, %
No regrinding 5 minutes regrinding 10 minutes regrinding
15 minutes regrinding 20 minutes regrinding

FIG 22 – Lead grade/recovery curves for lead rougher flotation tests conducted
on lead first cleaner tailing, demonstrating the effect of regrinding.

flotation time of 12 minutes. The seven concentrate and tailing samples from each test were
prepared and submitted for assay.

What data do I need?

You need the weights and assays for each of the concentrates and tailing samples to complete a
mass balance for each test. Test conditions such as pH, reagent additions and any observations
should be recorded.

How do I analyse the data collected?

Spreadsheet analysis of the weights and assays calculates cumulative grades and recoveries
for each test. These numbers can be used to construct lead grade/recovery curves (Figure 22).
The mass balanced data can also be used to determine the kinetics (ie flotation rate constant
and maximum recovery) using Equation 11, and the selectivity for galena against the
gangue minerals.

R = Rmax × (1 - e-kt) (11)

To assist interpretation the kinetic data and the selectivity data can be tabulated. For example,
Table 14 shows lead concentrate grade and zinc and iron sulfide recoveries at 80 per cent lead
recovery. Selectivity curves can also be drawn.

What does it mean?

Laboratory lead rougher flotation tests suggested that regrinding significantly improved
the position of the lead grade/recovery curve. Figure 22 shows that the grade recovery
curve continues to improve with increasingly fine regrinding. At 80 per cent lead recovery,
lead grade increased from 30.8 per cent (no regrinding) to 42.2 per cent after 20 minutes
regrinding. The improvement was due to better selectivity for galena against sphalerite and
iron sulfides (Table 14).

36 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

TABLE 14
Lead grade and diluent recoveries, at 80 per cent lead recovery, for lead rougher flotation
tests conducted on lead first cleaner tailing demonstrating the impact of regrinding.
Test description Pb grade (%) Diluent recovery (%)
Zn IS
No regrinding 30.8 71.2 51.6
5 minutes regrinding 34.3 61.9 37.2
10 minutes regrinding 37.6 50.8 30.4
15 minutes regrinding 42.0 42.6 24.3
20 minutes regrinding 42.2 42.2 25.8

The improved selectivity for galena against sphalerite improves lead metallurgy; it is
expected that zinc metallurgy would also improve.

Plant trial (Chapter 11)

It was found that more regrind power was needed to improve lead metallurgical performance.
Recalling the first comment in this chapter about utilising the available resources and people,
the problem was discussed with the operations team and a solution was quickly found.
Capital was not readily available but an experienced flotation operator suggested swapping
the lead and zinc regrinding mills since the zinc regrinding mill was larger and better suited
to the higher tonnages in the lead circuit.
This was accomplished by a simple change in the pipe work. The existing pipe work was
left intact to allow a plant trial to be conducted. A randomised block on/off trial was designed,
following the guidelines prescribed in Chapter 11. This would use shift mass balanced data to
statistically analyse metallurgical performance with and without increased lead regrinding.
When the new lead regrind mill was turned on, the impact on lead and zinc metallurgy was
immediate and dramatic. Because of the magnitude of the improvements, the on/off trial was
no longer required. Changes of this magnitude are not always apparent and strong statistical
analysis is often required to determine if a statistically significant change was caused by your
trial. Sometimes trials must run for several months before reaching certainty.
Lead recovery to final concentrate from June 1998 to February 2000 is shown in Figure 23.
Lead recovery has increased from an average of five per cent to 81.5 per cent due to the
application of an effective regrinding stage.
Despite not undertaking the randomised block trial as first thought, it was possible to
complete a statistical analysis using plant data from before and after the change. Using
the Student t-test to analyse the data showed that the additional lead regrinding had the
following results:
•• lead recovery improved by 16.5 ± 2.5 per cent with greater than 99 per cent confidence
•• lead concentrate grade improved by 4.0 ± 0.8 per cent with greater than 99 per cent
confidence
•• zinc grade in the lead concentrate reduced by 1.8 ± 0.6 per cent with greater than 99 per cent
confidence.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 37

 CHRISTOPHER J GREET

90.0

85.0 New Pb Feed distributor

80.0
MF4 used as
Average % Rec.

lead regrind mill

75.0

70.0 Complete Pb froth level control

+ new 6" Pb regrind cyclones
+ dedicated float operators
65.0

60.0 Initial Pb froth level control

Level on Pb conditioning
tank dropped
55.0

50.0
13-May-98

26-May-99
5-May-99
18-Nov-98

10-Nov-99
18-Feb-98

11-Mar-98

10-Feb-99

24-Mar-99
16-Sep-98

29-Sep-99
28-Jan-98

2-Feb-00
20-Jan-99

3-Mar-99

8-Sep-99

12-Jan-00
7-Jan-98

15-Jul-98

26-Aug-98

30-Dec-98

28-Jul-99

18-Aug-99

22-Dec-99
22-Apr-98

24-Jun-98

5-Aug-98

9-Dec-98

14-Apr-99

16-Jun-99

1-Dec-99
1-Apr-98

3-Jun-98

7-Jul-99
28-Oct-98

20-Oct-99
7-Oct-98

W/E
Average Average CL UCL LCL

FIG 23 – Lead recovery versus time data from June 1998 to February 2000. Some milestones are highlighted.

These changes to the lead circuit decreased the amount of sphalerite reporting to lead
concentrate and made this sphalerite available for recovery in the zinc circuit. This improved
zinc metallurgy, with:
•• zinc recovery increased by 1.5 ± 0.4 per cent with >99 per cent confidence
•• the zinc concentrate grade increased by 2.1 ± 0.5 per cent with >99 per cent confidence.
Other statistical methods (for example, comparison of regression lines and multiple linear
regression modelling) produced similar values.

THE CYCLE BEGINS AGAIN

Despite introducing extra regrinding in the lead circuit, resulting in a massive improvement
in metallurgical performance, there is still room for improvement. As the Senior Project
Metallurgist it is now your job to identify the next set of targets and solutions. You’ve only
solved part of the problem: a Senior Project Metallurgist’s work is never done!
Next areas to target to improve metallurgy are:
•• optimisation of lead and zinc regrinding circuits to further improve grind size and
liberation, and subsequently concentrate grades and recoveries
•• optimisation of flotation chemistry to improve selectivity of valuable minerals against
gangue minerals, and consequently increase concentrate grades
•• continue minimising variations in the process.

More surveys
It is necessary to continue monitoring the process through:
•• analysis of shift mass balances
•• analysis of monthly composite samples (by size and liberation class)
•• routine metallurgical and pulp chemical surveys
•• flotation cell characterisation (Chapter 6)
•• the introduction of a future ores testing program (Geometallurgy, Chapter 13).
After all, to measure is to know!

38 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

Chemistry
With the improvements in the lead circuit through better regrinding, it is time to study the
chemistry of the system.

Pulp chemistry
The pulp chemistry indicated that the lead rougher operated in oxidising conditions with
Eh values between 150 and 200 mV (SHE). Figure 15 shows the Eh-pH curve for the circuit.
The curve is essentially parallel to the water-oxygen line, which suggests that changes in Eh
or pH were due to maintenance of water equilibria. This indicates the system is operating in
oxidising conditions.

Solution chemistry
The EDTA extractable lead increased from approximately five per cent in copper rougher
tailings to 17 per cent in lead scavenger tailing. EDTA extractable zinc and iron values were
an order of magnitude lower than those for lead. This suggests the galena in lead circuit
feed is moderately oxidised, while galena remaining in the lead scavenger tailing is heavily
oxidised. A significant quantity of galena oxidation products are present in the pulp which,
under certain conditions, could cause inadvertent activation of sphalerite by lead.

Surface chemistry
To test the theory you developed from pulp chemistry observations, it is wise to complete
surface analysis on selected samples. Chapter 9 provides details of types of surface analysis
and how they may be used to provide more information. A practical example is provided in
he appendix for Chapter 9.

What do I have to do?

To undertake the surface analysis to validate your hypothesis, you need a scope of work for
the provider. You must provide the surface scientist with a focused question to define your
objectives from surface analysis. In this case you are interested in understanding the surface
chemistry of liberated sphalerite that reports to the lead rougher concentrate, and how this
compares with free sphalerite in the lead rougher tailing. This means the surface scientist will
examine liberated sphalerite in lead rougher concentrate and tailing process streams to identify
differences that may explain why some liberated sphalerite is recovered to rougher concentrate.
The surface scientist will suggest the surface analysis technique they consider is best for your
application. Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) is frequently used
because of its high surface sensitivity and its ability to analyse individual particles.

What data do I need?

When collecting the samples for surface analysis, it is important to use the right sample
preparation protocols. The surface scientist will provide you with these. Generally, once
the samples have been collected they need to be purged with nitrogen to remove oxygen to
prevent further oxidation. The sample is then sealed in a sample vial and snap frozen in liquid
nitrogen. Sample pairs are sent to the surface analysis facility frozen in a cryogenic container.
Ideally, when you collect samples for surface analysis, you should complete a block
survey of that part of the circuit. In this case, a block survey of the lead rougher circuit is
appropriate. The survey creates a reference point of metallurgical performance that can be
used for comparison. It is also wise to complete a pulp chemical and EDTA extractable metal

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 39

 CHRISTOPHER J GREET

ion analysis on the process streams where the surface analysis samples were collected. This
information should be supplied to the surface scientist to help them understand the system
chemistry and explain their observations.

How do I analyse the data collected?

The surface scientist will provide you with an analysis of the findings. You are not expected
to know everything; however, you should read the surface analysis report and ask questions
when you don’t understand. You want to understand how the surface scientist reached their
conclusions, and you should understand these techniques and the value they can add to an
investigation. It is important to link the surface chemical observations to the pulp chemistry
and metallurgical performance of the plant. After all, the data generated will be used to test
your theories of what is happening (in this case identifying the activating species on liberated
sphalerite). You will use this to propose solutions for testing in the laboratory.

What does it mean?

Surface analysis was conducted on samples of lead rougher concentrate and tailings using
ToF-SIMS to determine the dominant species on the surfaces of liberated sphalerite particles.
The investigation indicated that liberated sphalerite particles in lead rougher concentrate had
statistically more collector, copper, silver and lead species on their surfaces than those in the
tailing (Figures 24 and 25).
The conclusions reached from the chemical analysis were:
•• The flotation pulp in the lead rougher was in oxidising conditions.
•• The level of EDTA extractable lead in the lead circuit was high, indicating the presence of
a large quantity of galena oxidation species capable of activating sphalerite.

(+) SIMS sphalerite

A
Normalised Intensity

0.3
0.25 Pb cleaner con
0.2 Pb cleaner tail
0.15
0.1
0.05
0
Si

Pb
g
Ag

Zn

H
Fe
a

H
M

O
O

Pb
Fe

(+) Fragment

(-) SIMS sphalerite

B
Normalised Intensity

0.5
Pb cleaner con
0.4
Pb cleaner tail
0.3
0.2
0.1
0
C CH O OH S SO3 SO4 IEX
(-) Fragment

FIG 24 – Positive and negative mass spectra for sphalerite particles in the lead cleaner
concentrate and tailing process streams – confidence intervals calculated for 95 per cent.

40 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

FIG 25 – ToF-SIMS images of sphalerite particles within the lead rougher

concentrate: (A) the zinc ion image; and (B) the lead ion image.

•• The surface analysis confirmed the suspicion that the liberated sphalerite was activated by
lead ions. Copper and silver were also observed on the surfaces of sphalerite particles, but
in lower concentrations.
This suggests that some of the sphalerite is being recovered to lead concentrate because it is
activated by lead ions. You should propose that laboratory test work be completed examining
the effect of various reagents to depress activated sphalerite. Should these tests prove positive,
and the solution is economically sound, then it should be tested in the plant using statistically
rigorous trial methodology.

COMMUNICATION
The technical aspects of concentrator performance are very important in achieving optimum
metallurgy. However, the best technical expertise is of little consequence if people and
maintenance issues are not adequately addressed.
Process variations are probably the hardest to monitor and control and can result in operations
personnel treating symptoms rather than causes (ie ‘firefighting’). In most instances, process
variations such as ore hardness, mineralogical changes and head grade variation are very
difficult to measure online but can be partly managed with an effective ore characterisation
program (geometallurgy) and good communication between the mine and the mill.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 41

 CHRISTOPHER J GREET

Behavioural variations are often easily identified but difficult to correct because of the
human factor. One way to minimise behavioural variations in a concentrator is to document
and standardise each task so that each operator performs the same task the same way.
Unfortunately, this is easier said than done.
An important strategy to maximise metallurgical performance is to develop a proactive,
hands-on metallurgical team to establish and maintain metallurgical targets and procedures.
The metallurgist should be regarded as a member of the team with specialist knowledge to
call on when problems arise.

CONCLUSIONS
At the Eureka Concentrator, the use of classical metallurgical techniques (recovery- and
liberation-by-size analysis) has proved highly effective at determining the source of the
metallurgical problem. Initially, galena/sphalerite liberation was identified as a significant
impediment to better lead and zinc metallurgy. With the successful application of more
regrinding capacity, the focus shifted from liberation to chemistry. The use of pulp and
solution chemistry indicated that inadvertent activation of sphalerite by lead, copper and
silver ions was probably the reason for high recovery of liberated sphalerite into the final lead
concentrate. The judicious application of appropriate surface chemical techniques provided
confirmatory evidence. The Eureka metallurgists have now identified the reasons for the
losses of sphalerite from the circuit and can now develop solutions to this problem for testing
in the laboratory before plant trials.

REFERENCES
Johnson, N W, 1988. Application of electrochemical concepts to four sulphide flotation separations, in
Proceedings Electrochemistry in Mineral and Metal Processing II, pp 131–149.
Natarajan, K A and Iwasaki, I, 1973. Practical implications of Eh measurements in sulphide flotation
circuits, in AIME Transactions, 256:323–328.
Rumball, J A and Richmond, G D, 1996. Measurement of oxidation in a base metal flotation circuit by
selective leaching with EDTA, International Journal of Mineral Processing, 48:1–20.
Warman International Limited, 1991. Cyclosizer Instruction Manual – Particle Size Analysis in the Sub-Sieve
Range, Bulleting WCS/2 (Warman International Limited: Sydney).

42 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

Appendix 1 – The down-the-bank survey

INTRODUCTION
Often it is of value to complete metallurgical surveys where samples are collected down a
bank of flotation cells. This type of survey is referred to as a down-the-bank survey, and differs
from a block survey, as it provides more detailed information about the flotation behaviour of
the various species contained within the feed down-the-bank of flotation cells. In conducting
a block survey, you collect samples of the feed, concentrate and tailing from the section of the
circuit in which you are interested. This information provides you with data about the overall
performance of that block of cells. The down-the-bank survey provides detail of the internal
workings of that block of flotation cells.

HOW DO I DO A DOWN-THE-BANK SURVEY?

Chapter 2 provides a detailed description of the two common methods employed. An
example using one of those methods is given below. The first step in completing a down-the-
bank survey is to identify the samples that you wish to collect. Figure A1 is a schematic of the
bank of 12 flotation cells you want to survey. You have decided to divide the flotation cells
into groups such that you will collect five concentrate samples, in addition to the combined
concentrate sample that the bank produces. The sample list is given in Table A1.

1. T bank feed 8. T bank tailing

Cell 1 Cell 2 to 4 Cell 5 to 7 Cell 8 to 10 Cell 11 and 12

3. Con 1 4. Con 2 5. Con 3 6. Con 4 7. Con 5

2. T bank combined concentrate

FIG A1 – A bank of 12 flotation cells, and the cell grouping for a down-the-bank survey.

TABLE A1
The sample list for a down-the-bank survey conducted
on the bank of 12 flotation cells pictured in Figure A1.
Sample number Sample name Sample type
1 T bank feed Dip sample
2 T bank combined concentrate Lip or OSA sample
3 Con 1 – T bank cell 1 Timed lip sample
4 Con 2 – T bank cells 2 to 4 Timed lip sample
5 Con 3 – T bank cells 5 to 7 Timed lip sample
6 Con 4 – T bank cells 8 to 10 Timed lip sample
7 Con 5 – T bank cells 11 and 12 Timed lip sample
8 T bank tailing A Dip sample
9 T bank tailing B Dip sample

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 43

 CHRISTOPHER J GREET

With the sampling points identified, you need to communicate your intentions to various
people involved and prepare your equipment. The same actions discussed above in the
section ‘The Metallurgical Survey, What do I have to do?’ apply to conducting a down-the-bank
survey. Communication and organisation are the keys to success.
In terms of sampling equipment, you will need:
•• dip and lip samplers that are clean and in good working order
•• sufficient clean buckets, with lids, that have been tared
•• a stop watch for timing the lip sample collection
•• a notebook to record the times and any other observations that may be of use later.
Conducting a down-the-bank survey is usually a job for two people. One person collects
the sample, and the other measures and records the time taken to collect each of the timed lip
samples. Prior to conducting the survey, it is wise to inspect the flotation bank to be sampled,
clean the cell lips to ensure that the froth flows freely, make the work area safe and free
of tripping hazards and establish how the lip sampling is going to occur. Next, perform a
dry run to practise how the timed samples will be collected. One method of sampling that
works effectively is for the sampler to yell ‘GO’ and ‘STOP’ as he/she starts and finishes the
sample collection. On these commands the time keeper starts and stops the stop watch. It is
imperative that the two people collecting the timed lip samples agree on the methodology,
and work in concert. So, with all the preparations complete and the plant operating correctly,
it is time to conduct the survey.
As with other surveys, you would have decided beforehand how many ‘cuts’ from each
process stream will be taken over a specified sampling time. The two people detailed to
conduct the down-the-bank survey will then collect the nine samples over the prescribed
sampling period. Once the sampling is finished, the samples are gathered together and taken
to the laboratory.

What data do I need?

In the laboratory the samples are weighed (for wet weight), filtered, dried, weighed (for dry
weight), prepped and submitted for assay. A summary of this data is given in Table A2. The
wet and dry weights are used to determine the per cent solids of each sample, and calculate
a water balance. In terms of assays, the suite chosen should contain all the elements that have
a significant bearing on metallurgical performance. In this example, Eureka’s standard assay
suite is: silver, copper, lead, zinc, iron and silica.
You will also need the times recorded for the timed lip samples, the lip lengths of the
flotation cells and the lip sample cutter length. With these data it will be possible to calculate
the flow rate of concentrate from each of the groups of flotation cells. The data are supplied
in Table A3.
Other data that can be useful when analysing the plant survey mass balance are:
•• the throughput at the time of the survey
•• reagent additions and other plant operating parameters (ie airflow rates and pulp levels)
•• OSA readings
•• information about the ore being treated.
In the context of a one-off survey some of these pieces of information may not be of great
value; however, when the analysis is extended to include other surveys on other ore blends,
circuit configurations and reagent suites, these data provide a vital link in the comparison.

44 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

TABLE A2
Summary of the down-the-bank survey data collected.
No Sample name Weights (g) % solids
Gross Tare Wet Dry
Bucket Lip
1 T bank feed 1585.3 350.0 1235.3 471.9 38.2
2 T bank combined con 1891.1 350.0 245.0 1296.1 331.8 25.6
3 Con 1 – Cell 1 1789.7 350.0 245.0 1194.7 630.8 52.8
4 Con 2 – Cells 2 to 4 2217.0 350.0 245.0 1622.0 361.7 22.3
5 Con 3 – Cells 5 to 7 2049.4 350.0 245.0 1454.4 315.6 21.7
6 Con 4 – Cells 8 to 10 2142.3 350.0 245.0 1547.3 379.1 24.5
7 Con 5 – Cells 11 and 12 1795.6 350.0 245.0 1200.6 187.3 15.6
8 T bank tailing A 1428.8 350.0 1078.8 372.2 34.5
9 T bank tailing B 1610.0 350.0 1260.0 459.9 36.5

TABLE A3
Lip sample details.
No Sample name Sample time (s) Length (mm)
Cell lip Cutter lip
3 Con 1 – Cell 1 31.6 1250 × 2 105
4 Con 2 – Cells 2 to 4 28.9 1250 × 6 105
5 Con 3 – Cells 5 to 7 28.4 1250 × 6 105
6 Con 4 – Cells 8 to 10 30.8 1250 × 6 105
7 Con 5 – Cells 11 and 12 39.7 1250 × 4 105

How do I analyse the data collected?

The assays will be returned to you in a form similar to that shown in Table A4. Before
proceeding with mass balancing the survey it is necessary to check these numbers are in
good order. In this example, the tailing assays are in good agreement, and the silver, copper
and lead assays all trend in the right way (ie from higher assays in Con 1 to progressively
lower numbers by Con 5). Further, the combined concentrate assay falls within the extremes
of Con 1 and Con 5 assays.
Mass balancing this survey involves several steps. The first step is to calculate the mass flow
rate from the timed lip samples. The mass flow rate is given by:
Dry weight of sample, g 3600 Cell lip length, mm
tph = # 6 #
number of cell lips # (1A)
Sample time, s 10 Cutter lip length, mm

Thus, by substituting the dry weights for each of the timed concentrate samples from
Table A2, and the sample times, number of cell lips, cell lip length and cutter lip length
from Table A3 in Equation A1, you can calculate the tonnes per hour recovered into each
concentrate. For example, for Con 1 – cell 1, Equation A1 becomes:

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 45

 CHRISTOPHER J GREET

TABLE A4
Elemental assays for the down-the-bank survey.
No Sample name Assay (%)
Ag (ppm) Cu Pb Zn Fe SiO2
1 T bank feed 98 0.05 2.84 10.7 15.5 21.9
2 T bank combined con 444 0.24 14.20 11.1 23.0 9.2
3 Con 1 – Cell 1 644 0.47 21.40 10.7 21.2 7.6
4 Con 2 – Cells 2 to 4 490 0.28 15.70 11.3 22.9 8.5
5 Con 3 – Cells 5 to 7 406 0.21 12.60 11.3 23.8 9.1
6 Con 4 – Cells 8 to 10 346 0.18 10.60 11.6 24.2 10.0
7 Con 5 – Cells 11 and 12 306 0.18 9.15 11.7 24.3 10.9
8 T bank tailing A 70 0.02 2.04 10.5 14.8 22.6
9 T bank tailing B 72 0.02 2.13 10.6 14.9 22.6

630.8, g 3600 1250, mm

tphCon1 = # #2#
31.6, s 10 6 105, mm

tphCon1 = 1.71 tph

So, from the timed lip sample collected from Cell 1, the tonnes per hour recovered are 1.71.
The same calculation was completed for each of the other concentrates. The values obtained
are given in Table A5. The tonnage distribution over the five concentrate samples was
calculated and also appears in Table A5.
The next step is to mass balance the ‘outer’ circuit. The process streams are:
1. T bank feed
2. T bank combined concentrate
3. T bank tailing.
There is only one node in this mass balance:
T bank feed = T bank combined concentrate
+ T bank tailing (1 = 2 + 8).

TABLE A5
The tonnes per hour and distribution of tonnes for the five
concentrates collected in the down-the-bank survey.
No Sample name Tonnage data
Tonnes per hour Distribution
3 Con 1 – Cell 1 1.71 14.55
4 Con 2 – Cells 2 to 4 3.22 27.36
5 Con 3 – Cells 5 to 7 2.86 24.30
6 Con 4 – Cells 8 to 10 3.17 26.91
7 Con 5 – Cells 11 and 12 0.81 6.88
Total 11.76 100.00

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 CHAPTER 1 | THE EUREKA MINE

In completing this mass balance, it was assumed that the feed tonnage was 100 per cent.
The mass balanced data are provided in Table A6. The mass balance has calculated that the
tonnes of concentrate produced is 6.96 t/h, compared to 11.76 determined from the timed lip
tonnages. The difference is reconciled by applying the tonnage distribution from Table A5 to
the mass balanced tonnage given in Table A6. Thus, using the ‘outer’ circuit mass balanced
tonnage new values are calculated for each of the concentrates. These new values are
presented in Table A7 and are used in the second mass balance incorporating the down-the-
bank concentrates.
The down-the-bank mass balance has eight process streams:
1. T bank feed
2. T bank combined concentrate
3. Con 1 – Cell 1
4. Con 2 – Cells 2 to 4
5. Con 3 – Cells 5 to 7
6. Con 4 – Cells 8 to 10
7. Con 5 – Cells 11 and 12
8. T bank tailing.
There are two nodes:
1. T bank feed = Con 1 + Con 2 + Con 3 + Con 4 + Con 5 + T bank tailing (ie 1 = 3 + 4 + 5 + 6 +
7 + 8)
2. Con 1 + Con 2 + Con 3 + Con 4 + Con 5 = T bank combined concentrate (ie 3 + 4 + 5 + 6 + 7
= 2).

TABLE A6
The mass balanced data for the ‘outer’ balance.
No Sample time Wt Adjusted assay (%)
(%) Ag (ppm) Cu Pb Zn Fe SiO2
1 T bank feed 100.00 98 0.04 2.91 10.67 15.48 21.78
2 T bank combined con 6.96 444 0.24 14.20 11.10 23.00 9.23
3 T bank tailing 93.04 72 0.03 2.07 10.63 14.92 22.72

TABLE A7
The ‘new’ tonnes per hour for the five concentrates collected in the down-the-bank survey calculated from
the tonnage distribution and the ‘outer’ mass balanced tonnage recovered into the combined concentrate.
No Sample name New tonnes per hour
3 Con 1 – Cell 1 1.01
4 Con 2 – Cells 2 to 4 1.90
5 Con 3 – Cells 5 to 7 1.69
6 Con 4 – Cells 8 to 10 1.87
7 Con 5 – Cells 11 and 12 0.48
Total 6.96

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 47

 CHRISTOPHER J GREET

The mass balance is accomplished by fixing the tonnage values for the T bank feed, and the
five down-the-bank concentrates, then using a mass balancing software fitting the data. The
down-the-bank mass balance is given in Table A8.
The mass balanced down-the-bank data can now be used to construct a lead grade/recovery
curve for this bank of flotation cells, as shown in Figure A2. This data can also be used to
generate kinetic data, examining the flotation rate constant and maximum recovery of the
various species.

TABLE A8
The down-the-bank mass balance.
No Sample name Wt (%) Weight (%) Recovery (%)
Ag Cu Pb Zn Fe SiO2 Ag Cu Pb Zn Fe SiO2
1 T bank feed 100.00 98 0.04 2.9 10.6 15.5 21.8 100.0 100.0 100.0 100.0 100.0 100.0
2 T bank 7.00 440 0.26 14.0 11.3 23.3 9.1 31.5 42.0 33.6 7.4 10.5 2.9
combined con
3 Con 1 – Cell 1 1.02 644 0.47 21.4 10.7 21.2 7.6 6.7 11.2 7.5 1.0 1.4 0.4
4 Con 2 – Cells 2 to 4 1.91 490 0.28 15.7 11.3 22.9 8.5 9.6 12.5 10.3 2.0 2.8 0.7
5 Con 3 – Cells 5 to 7 1.70 406 0.21 12.6 11.3 23.8 9.1 7.0 8.3 7.4 1.8 2.6 0.7
6 Con 4 – 1.88 346 0.18 10.6 11.6 24.2 10.0 6.6 7.9 6.9 2.0 2.9 0.9
Cells 8 to 10
7 Con 5 – 0.49 306 0.18 9.2 11.7 24.3 10.9 1.6 2.1 1.5 0.6 0.8 0.2
Cells 11 and 12
8 T bank tailing 93.00 72 0.03 2.1 10.6 14.9 22.7 68.5 58.0 66.4 92.6 89.5 97.1

25.0

20.0
Pb grade, %

15.0

10.0

5.0

0.0
0.0 10.0 20.0 30.0 40.0 50.0 60.0
Pb recovery, %
OUTER balance data Down-the-bank balanced data

FIG A2 – The lead grade/recovery curve constructed from the mass balanced down-the-bank survey data.

48 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

Appendix 2 – Estimated mineral assays from

elemental data
INTRODUCTION
As iron occurs in a variety of minerals present in the Eureka orebodies, interpretation of iron
deportment from elemental assay data from flotation tests and plant surveys is a complex
issue. Therefore, by making a few simple assumptions regarding the composition of the
dominant sulfide minerals present in the orebody, it is possible to estimate mineral assays
from the elemental assay data.

ASSUMPTIONS
The first set of assumptions relate to the minerals themselves. That is, the dominant sulfide
minerals are: galena, sphalerite, chalcopyrite and pyrite. The lead occurs as galena, the zinc
as sphalerite, the copper as chalcopyrite, and the iron occurs in sphalerite, chalcopyrite and
pyrite.
The mineral conversions are based on the assumption that each mineral is ‘pure’; for
example, galena is PbS, pyrite is FeS2, etc.
Eureka sphalerites are known to contain, in solid solution, moderate iron levels. In this
exercise 3.0 per cent was chosen. This value is an estimate of the average value.
A calculated assay of the non-sulfide gangue (NSG) is made by assuming that everything
that is not galena, sphalerite, chalcopyrite, or pyrite is non-sulfide gangue.

MINERAL CONVERSIONS
Each conversion is based on the atomic mass of the elemental components of the mineral.

Galena
Galena contains lead (207.2 amu) and sulfur (32.06 amu); therefore, the atomic mass of galena
(PbS) is:
PbS = Pb + S
PbS = 207.2 + 32.06 amu

PbS = 239.26 amu

Thus, ‘pure’ galena contains 86.6 per cent lead and 13.4 per cent sulfur. The conversion
factor (fGa) to convert the lead assay to galena is given by:

fGa = PbS amu

Pb amu

fGa = 239.26
207.2

fGa = 1.155
So, an assay of ten per cent lead is equivalent to 11.6 per cent galena.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 49

 CHRISTOPHER J GREET

The sulfur in galena conversion factor (fSGa) is given by:

% sulfur in PbS
fSGa =
% lead in PbS

fSGa = 13.4
86.6

fSGa = 0.155
Sphalerite
‘Pure’ sphalerite (contains no iron) is made up of zinc (65.38 amu) and sulfur (32.06 amu),
therefore the atomic mass of ‘pure’ sphalerite (ZnS) is:

ZnS = Zn + S

ZnS = 65.38 + 32.06 amu

ZnS = 97.44 amu

Thus, ‘pure’ sphalerite contains 67.1 per cent zinc and 32.9 per cent sulfur. Unfortunately,
Eureka sphalerite contains an average of 3.0 per cent iron in solid solution. Further, it is
assumed that the iron replaced zinc in the sphalerite lattice. Thus, the composition of Eureka
sphalerite is 64.1 per cent zinc, 3.0 per cent iron and 32.9 per cent sulfur. Hence, the conversion
factor (fSp) to convert the zinc assay to sphalerite is given by:

fSp = 100.00
% Zn in sphalerite

fSp = 100.00
64.1

fSp = 1.560

So, an assay of ten per cent zinc is equivalent to 15.6 per cent sphalerite. To determine the
amount of iron present in sphalerite, it is simply a matter of multiplying the zinc assay by the
ratio of the per cent iron in the sphalerite and the per cent zinc in the sphalerite. So, the iron
in the sphalerite conversion factor (fFeSp) is given by:

% iron in sphalerite
fFeSp =
% zinc in sphalerite

fFeSp = 3.0
64.1

fFeSp = 0.047

Thus, for a sample containing ten per cent zinc, the per cent iron associated with the
sphalerite is 0.47 per cent (ie 10 × 0.047). To check this, convert the zinc assay to per cent
sphalerite (ie 10 × 1.560), and multiply by the amount of iron in solid solution in sphalerite
(ie 3.0 per cent), and the per cent iron associated with sphalerite is 0.47 per cent.

50 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

Similarly, the sulfur in the sphalerite conversion factor (fSSp) is given by:
% sulfur in sphalerite
fSSp =
% zinc in sphalerite

fSSp = 32.9
64.1

fSSp = 0.513

Thus, for a sample containing ten per cent zinc, the per cent sulfur associated with the
sphalerite is 5.13 per cent (ie 10 × 0.513). To check this, convert the zinc assay to per cent
sphalerite (ie 10 × 1.560), and multiply by the amount of sulfur in sphalerite (ie 32.9 per cent),
and the per cent sulfur associated with sphalerite is 5.13 per cent.

Chalcopyrite
Chalcopyrite is made up of copper (63.55 amu), iron (55.85 amu) and sulfur (32.06 amu);
therefore, the atomic mass of chalcopyrite (CuFeS2) is:

CuFeS2 = Cu + Fe + S

CuFeS2 = 63.55 + 55.85 + (2 × 32.06) amu

CuFeS2 = 183.52 amu

Thus, stoichiometric chalcopyrite contains 34.63 per cent copper, 30.43 per cent iron
and 34.94 per cent sulfur. Hence, the conversion factor (fCh) to convert the copper assay to
chalcopyrite is given by:
CuFeS2 amu
fCh =
Cu amu

fCh = 183.52
63.55

fCh = 2.888

So, an assay of ten per cent copper is equivalent to 28.9 per cent chalcopyrite. To determine
the amount of iron present in chalcopyrite, it is simply a matter of multiplying the copper
assay by the ratio of the per cent iron in the chalcopyrite and the per cent copper in the
chalcopyrite. So, the iron in chalcopyrite conversion factor (fFeCh) is given by:
% iron in chalcopyrite
fFeCh =
% copper in chalcopyrite

fFeCh = 30.43
34.63

fFeCh = 0.879

Thus, for a sample containing ten per cent copper, the per cent iron associated with the
chalcopyrite is 8.8 per cent (ie 10 × 0.879). To check this, convert the copper assay to chalcopyrite

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 51

 CHRISTOPHER J GREET

(ie 10 × 2.888), and multiply this by the amount of iron in solid solution in chalcopyrite
(ie 30.43 per cent), and the per cent iron associated with chalcopyrite is 8.8 per cent.
Similarly, the sulfur in chalcopyrite conversion factor (fSCh) is given by:
% sulfur in chalcopyrite
fSCh =
% copper in chalcopyrite

fSCh = 34.94
34.63

fSCh = 1.009

Thus, for a sample containing ten per cent copper the per cent sulfur associated with
the chalcopyrite is 10.1 per cent (ie 10 × 1.009). To check this, convert the copper assay to
chalcopyrite (ie 10 × 2.888), and multiply this by the amount of sulfur in solid solution
in chalcopyrite (ie 34.94 per cent), and the per cent sulfur associated with chalcopyrite is
10.1 per cent.

Pyrite
Assuming that pyrite is the dominant iron sulfide mineral present (ie no pyrrhotite), it is
relatively easy to calculate the per cent pyrite in a sample. Pyrite contains iron (55.85 amu)
and sulfur (32.06 amu); therefore, the atomic mass of pyrite (FeS2) is:

FeS2 = Fe + S

FeS2 = 55.85 + (2 × 32.06) amu

FeS2 = 119.97 amu

Thus, ‘pure’ pyrite contains 46.6 per cent iron and 53.4 per cent sulfur. Depending on the
assay data, the pyrite content of the ore can be calculated using either the iron or the sulfur
assay. Generally speaking, the estimation of the pyrite concentration is more accurate using
the sulfur assay because it is assumed that the vast majority of the sulfur in the ore is
associated with the sulfide minerals. Iron, on the other hand, can be present in the sulfides
as well as the non-sulfide gangue; for example, as iron oxides such as hematite or magnetite,
and feldspars to name but a few. Thus, the pyrite conversion factor (fFePy) based on the iron
assay is given by:
FeS2 amu
fFePy =
Fe amu

fFePy = 119.97
55.85

fFePy = 2.148
So, based on the conversion factor developed from the iron assay, an assay of ten per cent
iron is equivalent to 21.5 per cent pyrite.
Using sulfur, the pyrite conversion factor (fSPy) is given by:

52 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 1 | THE EUREKA MINE

FeS2 amu
fSPy =
S2 amu

fSPy = 119.97
64.12

fSPy = 1.871

So, based on the conversion factor developed from the sulfur assay, an assay of ten per cent
iron is equivalent to 18.7 per cent pyrite.
Unfortunately, iron is also associated with sphalerite and chalcopyrite in the ore, so these
contributions must be subtracted from the iron assay before determining the pyrite content.
Thus, the pyrite conversion factor (fFePy) based on the iron assay becomes:

fFePy = 2.148 × (% Fe − (% iron in sphalerite + % iron in chalcopyrite))

From the discussion above the conversion factor for iron in sphalerite from the zinc assay
was determined to be 0.047, and a similar calculation revealed that the conversion factor for
iron in chalcopyrite is 0.879. So, the per cent pyrite is given by:

fFePy = 2.148 × (% Fe − ( 0.047 × % Zn + 0.879 × %Cu))

Thus, if an ore sample contained ten per cent iron, ten per cent zinc, and 0.1 per cent copper,
the per cent pyrite is 20.28 per cent. However, if the pyrite conversion factor (fSPy) is based on
the sulfur assay then:

fSPy = 1.871 × (% S − (% sulfur in galena + % sulfur in sphalerite + % sulfur in chalcopyrite))

From the discussion above the conversion factor for sulfur in galena from the lead assay
is 0.155; sulfur in sphalerite from the zinc assay was determined to be 0.513, and a similar
calculation revealed that the conversion factor for sulfur in chalcopyrite is 1.009. So, the
per cent pyrite is given by:

fSPy = 1.871 × (% S − ( 0.155 × % Pb + 0.513 × % Zn + 1.009 × %Cu))

Thus, if an ore sample contained ten per cent sulfur, ten per cent lead, ten per cent zinc, and
0.1 per cent copper, the per cent pyrite is 6.0 per cent.

Non-sulfide gangue
If it is assumed that galena, sphalerite, chalcopyrite and pyrite are the only significant sulfide
minerals present in the orebody, it is possible to estimate the percentage of non-sulfide
gangue present. This is achieved by subtracting the per cent galena, sphalerite, chalcopyrite
and pyrrhotite from 100 per cent. That is:

% NSG = 100 – (%Ga + %Sp + %Ch + %IS)

Thus, if a sample assayed ten per cent lead, zinc and iron and 0.1 per cent copper, the
per cent non-sulfide gangue is 57.8 per cent.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 53

 CHRISTOPHER J GREET

FINAL COMMENT
These element to mineral conversions have been completed based on a lead/zinc ore;
however, a similar approach can be applied to other ore types provided the stoichiometry
of the minerals in the system is known, and the assumptions made in the calculations are
clearly explained.

54 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

Return to contents

CHAPTER 2
Existing methods for process analysis
Bill Johnson

ABSTRACT
This introductory chapter describes options for surveying flotation banks and calculation of
their solid and water balances, including mineral recoveries. The calculation and interpretation
of mineral recovery-size data and the more advanced mineral recovery-size-liberation data
are then covered. The related role of surface analysis for elucidating unexplained process
weaknesses in the mineral recovery-size-liberation data is described. This chapter is aimed
at recognition of the location and magnitude of process weaknesses in industrial plants and
identification of the mechanism involved in each, allowing technical solutions for some or
all weaknesses to be proposed and evaluated. Later chapters expand on topics covered here.

INTRODUCTION
The first step in analysis of the flotation process is to obtain a mass or solid balance, which
may be accompanied by a water balance, from surveying of the relevant portions of the
plant. The key benefit of obtaining the corresponding water balance is that water flow rates,
and hence pulp flow rates, can be calculated and hence residence times can be calculated, ie
kinetic data can be obtained.
Decisions must be made in the design of an experiment or survey on the level of sampling
detail that is appropriate for each portion of the plant. In general, the following options for
sampling detail exist and different levels of detail may be selected for various parts of the
plant:
•• block level, eg grouping of all cleaner banks or rougher banks
•• bank level, eg obtaining of information on feed, combined concentrate and tailing assays
•• down-the-bank data (where data on each concentrate or on groupings of concentrates are
obtained).
Of course, the whole plant may be treated as a block and this treatment is applied commonly
for obtaining shift or daily composite samples from automatic inventory samplers from which
shift or daily metallurgical performance is often calculated routinely. Such data can also be

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 55

 BILL JOHNSON

complementary to surveys on the banks or blocks in the circuit. In normal metallurgical

accounting, daily samples from inventory samplers are often used to prepare monthly
composite samples for the feed to and products from a concentrator.
Samples from inventory samplers on all the inputs to and products from a plant can be
processed at various levels of detail, to establish causes of misplaced valuable mineral and
causes of dilution of concentrates by unwanted minerals. In broad terms, these are at the
recovery-size level for each of the minerals, and at the next level, which can be summarised
as the recovery-size-liberation level. Analysis of such data allows definition of the weaknesses
(and strengths) of the plant.
While such data from inventory samples are valuable, the overall plant data do not provide
clues to the location of the weaknesses in the plant, eg rougher section, cleaner section or
retreatment section. Hence, surveys of the whole plant or of individual sections at appropriate
times are needed to identify the origin of the weakness and to check progress during later
corrective steps. Judgement is required in the frequency and design of such surveys.
Surveys of the sections in a pilot plant circuit can be conducted by similar methods as for
concentrators with some modification of the scale of sampling equipment. Such surveys can
serve two purposes. One is to record the behaviour of an ore source or ore type in a new
orebody for later comparison with the behaviour in a full-scale plant. The availability of
detailed data within the pilot plant circuit and at a sized level for minerals (at least) will greatly
improve the ability to perform troubleshooting in the later start-up of a new concentrator.
A second purpose can be to perform a cycle of recognition of process weaknesses with later
correction in a pilot plant scale development of a new flow sheet.
As far as possible, such process development ought to be conducted at the laboratory scale
where the development costs are much lower. Nevertheless, the methodology can be applied
to pilot plants along the lines discussed earlier for full-scale plants.
Samples produced from open circuit laboratory flow sheets or from closed circuit laboratory
cycle tests can also be subjected to analysis at the mineral recovery-size-liberation level. The
samples are easier to obtain in this laboratory situation but care is required to ensure enough
sample exists for the envisaged procedure. For closed circuit cycle tests, the circuit must be at
equilibrium for those cycles from which the samples are taken.
Paired surveys are sometimes employed to provide insights. These surveys should be
conducted with the same feed to plant or pilot plant scale processes. For plants in particular,
the two surveys would normally be conducted within one day. For one of the surveys, a major
change in conditions would be implemented and the effect of the change would be evaluated
by comparison with the ‘reference’ data under normal conditions. Such paired tests can be
valuable when surface analysis is included in the design for the experiment as convenient
‘reference’ surface analysis data are provided from the survey under normal conditions.
In past analysis of recovery-size data for minerals, there has been the convenient assumption
that the solids were fully dispersed in the pulp. In other words, it has been assumed that any
mineral reporting in a given size fraction in the recovery-size data existed in that fraction
in the real pulp. While this is likely to be a sound assumption for most pulps, it is expected
that there are pulps for which the lack of dispersion is sufficient to transfer minerals from
one size fraction to another during the sizing procedure due to shearing apart of aggregated
particles. In a plant pulp, a liberated valuable particle that adheres to other gangue minerals
by some mechanism will usually be less recoverable. Further, if the liberated valuable particle

56 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

is recovered, the grade of the concentrate will be detrimentally affected due to the adhering
gangue mineral.
For convenience, hand-held samplers will be considered in three categories: conventional
hand-held or manual samplers for sampling streams at weirs or leaving launders or pipes,
dip samplers for sampling the pulp in the pulp zone of a flotation cell, and lip sampling for
providing a sample of the concentrate from one or more flotation machines, which usually
also involves obtaining a value for the flow rate of solid by a timing procedure. Manual
samplers for sampling streams at weirs, leaving launders or pipes may be used in conjunction
with control samplers for online analysis systems and with well-formed sampling points in
automatic inventory samplers in special circumstances. For large tank cells, suitable portable
pumps or siphons may be used to obtain pulp or tailing samples.
There were major changes in the type and scale of cells employed in the last two decades
of the 20th century; this trend has continued in the first two decades of the 21st century.
The introduction of flotation cells with washed froth technology has changed the nature of
sampling problems. Further, the installation of very large tank cells has increased sampling
difficulties in many new plants due to lack of access to the large machines and decisions made
during the plant layout phase of design, which tend to increase sampling difficulties (see ‘Lip
Sampling’ in the Appendix).

SOLID BALANCE AND WATER BALANCE CALCULATION BY SURVEYING

Solid balance
A solid balance is calculated after carefully planned data collection in a plant. A water
balance can also be calculated from the same survey provided the relevant per cent solid
data are collected. The complete procedure is relatively long and involves many steps,
requiring careful planning, a plant at steady state during the survey, careful checking of
the results and the execution of the necessary metallurgical calculations. The steps are
summarised as follows:
1. establish objectives, ie type of survey, level of detail, etc
2. plan survey
•• determine number of people/skill levels
•• prepare all sampling equipment that match tasks
•• review plans with sampling staff
•• check condition of sampling points
•• practise at sampling points
3. ensure circuit is at steady state and fixed ore source to continue
•• steady inputs
•• steady circulating loads
•• steady assays from online systems
4. execute survey (one to three hours)
•• continue to monitor that the circuit is at steady state (see 3)
5. filter/dry products, perform sample preparation and extract samples for analysis
6. construct initial mass balance and review the quality of the survey
7. move to next steps, if warranted, for more detailed data, eg sizing of samples and assaying
of size fractions, obtaining liberation data on size fractions.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 57

 BILL JOHNSON

From the work involved in the listed points 1 to 7, the planning and execution of a plant
survey to obtain a solid balance is a major task. In contrast, a solid balance is easily obtained
from a laboratory batch testing procedure from the readily obtained weights of dry solid in
the various concentrates and tailings, along with their assay values.
There are a limited number of methods for surveying a plant bank to enable the calculation
of a solid balance and related metallurgical information.
To provide clarity on the key aspect of obtaining a solid balance, it is valuable to state what the
generation of a solid balance does not involve. It does not involve obtaining estimates of the flow
rates of solid in the relevant streams by independent and quite different means, and assembling these
values from disparate sources. An example of such poor practice in a rougher would be obtaining
the solid balance by use of the feed solid flow from the weightometer, from timed lip sampling for the
concentrate and from instrumentation (volumetric flow and pulp density) for the tailing. In contrast,
it does involve using principally or solely the assay values for the relevant streams and a known reliable
tonnage (eg from a weightometer) as the scaling factor.
A survey of a total plant (many banks) or part of a plant (one bank or a limited number
of banks) is obtained by matching the limited number of methods to the type of equipment
in each part of the plant and the availability of sampling points, and from consideration of
the purpose of the survey, ie the type of metallurgical data required from the survey. The
limited number of methods will be described in following sections. The methods represent
the building blocks from which surveys are designed and conducted.

Water balance
The water flow rate in a stream can be calculated from the value for the solid flow rate that has
been determined as part of the solid balance. The following relationship holds:
Flow rate of solid (100 - per cent solids by weight)
Flow rate of water = (1)
Per cent solids by weight
The per cent solid value (by weight) for flotation concentrates requires some discussion for
the concentrate stream. The value of interest for analysis of flotation data is the per cent solid
value for the concentrate as it traverses the cell lip. The value for the per cent solid in the
concentrate should not reflect the water that has been added to the cell launder, to the pump
box or to the gland seal system for the concentrate pump. Taking the concentrate sample at
the cell lip provides the required per cent solid value.
Similarly, in laboratory batch tests, the water in the concentrate (for process analysis purposes)
should not include water that is added to wash the cell lip or the scraper during the collection of
a given concentrate. This can be arranged by adding such additional water from a wash bottle
for each concentrate and weighing the wash bottle before and after each concentrate is gathered.

Description of some basic designs for data acquisition

Three traditional designs for acquisition of metallurgical data are depicted in Box 1. These
designs are presented as an introduction, noting that knowledge of these designs can assist
in determining the design of a survey for acquiring metallurgical data in more complicated
situations. These designs can be summarised as listed:
•• two product (samples of feed, one concentrate and single tailing)
•• three product (samples of feed, two concentrates and single tailing)
•• four product (samples of feed, three concentrates and single tailing).

58 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

Conceptually, the five-product and ‘higher’ cases could be used but these cases are almost
without exception impractical. In fact, the three- and four-product cases can only be utilised
under appropriate circumstances, which are now discussed.
To apply the two-product design in Box 1, the following form of the two-product equation
is used to calculate the fractional recovery of solid (ie the solid split):
a (f - t)
Solid recovery (fractional) = F = - (2)
(c t)
The concentration of at least one mineral (eg chalcopyrite or the copper assay) in the feed
needs to be significantly different from the value for the tailing, ie there must be a clear
difference between feed and tailing assays in the numerator, otherwise f - t will be a very low

Definitions
Let f, c and t be the assays for a particular element in the feed, concentrate and tailings
Let F = t/h of solid in feed
Let α, β and γ = t/h of solid in concentrate(s)

Solid and element balances for three cases

TWO PRODUCTS THREE PRODUCTS FOUR PRODUCTS
(one equation with one unknown α) (two equations with (three equations with
two unknowns α and β) three unknowns α, β and γ)

F F–α F F–α–β F F–α–β–γ

α α β α β γ

Element 1 (Major separation occurring)

fF = cα + t(F – α) fF = c1α + c2β + t(F – α – β) fF = c1α + c2β + c3γ + t
(F – α – β – γ)
Element 2 (Major separation occurring also for the second element)
Not needed to solve for α, if F is flF = c11α + c21β + t1 f1F = c11α + c21β + c31γ + t1
known or set to 100. (F – α – β) (F – α – β – γ)
Element 3 (Major separation occurring also for the third element)
Not needed to solve for α, if F is Not needed to solve for α and β, if F is f11F = c111α + c211β + c311γ + t11(F – α
known or set to 100. known or set to 100. – β – γ)
Solving for single unknown, α. Solve for α and β using two Solve for α, β and γ using three
fF = cα + tF - tα simultaneous equations. simultaneous equations.
` a = f-t
F c-t
or ` a = F f - t
c-t

BOX 1 – Three traditional designs for acquisition of metallurgical data, including the commonly used two-product formula.

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 BILL JOHNSON

value (and possibly negative), and very susceptible to considerable error from sampling and
assaying. Therefore, the calculated fractional solid recovery will be prone to unacceptable
errors. One contributor to the overall sampling error, the fundamental error, is very dependent
on the sample mass and this issue is described in the appendix.
This separation of the mineral in question would then normally result in a significant
difference for the denominator (c - t). The assay values (feed, concentrate and tailing) for the
key element (eg copper) can then be used as shown in Box 1 to calculate the solid recovery
(α/F) or the absolute value for α if F is known. In addition to a large separation occurring for
the element used in the calculation, it is desirable that the selected element can be assayed
accurately and that sampling errors are not unusually high. Low-grade samples containing
some free gold can introduce large sampling errors.
To apply the three-product case, the concentration of at least one mineral in the feed would
need to be significantly elevated in the first concentrate while the concentration of a second
mineral would need to be significantly elevated in the second concentrate. A typical example
is the separation of galena (PbS) and sphalerite (ZnS) into two separate concentrates and the
two equations in the three-product case in Box 1 are solved by use of lead and zinc assays to
obtain the solid balance.
The four-product case can be thought of as an extension of the three-product case; however,
three different minerals require concentrating into their respective concentrates. An example
is the concentration of chalcopyrite, galena and sphalerite into their respective concentrates
and the use of copper, lead and zinc assays to solve the three equations in the four-product
case, to obtain the solid balance.
The three- and four-product cases can usually only be applied to the feed and products of
a concentrator (ie inventory sampler products and shift or daily performance calculations) of
a concentrator with multiple single mineral concentrates, as the special conditions for their
successful application exist for the products from such concentrators and do not usually exist
along individual banks. Therefore, the three- and four-product cases and ‘higher’ cases can
usually be expected to play no role or only a supporting role in designing a survey for the
banks in a concentrator. In contrast, the two-product case has often an important role in data
acquisition from individual banks within a flotation plant.

Description of some designs for data acquisition from individual banks

A traditional approach to data acquisition for a bank of small flotation machines is depicted
in Box 2. Provision is made in Box 2 for intermixing or exchange of pulp between adjacent
pulp zones. This situation existed in the layout of many commercial flotation machines that
were bolted together to form banks and that were relatively small in volume, eg less than
10 to 20 m3 per impeller. Often, these banks contained ten to 20 flotation machines in series in
order to provide the required residence time for relatively large tonnages of solid and pulp,
given the relatively small flotation machines.
For some banks in a plant, the objective of the survey may be to obtain the overall
performance for the bank (and not down-the-bank data). However, because no sampling
point exists for the combined concentrate from the bank, a more detailed design for data
collection (obtaining down-the-bank data) may be required, making use of access to the
concentrate discharge lips for example (to compensate for the absence of a sampling point
for the combined bank concentrate).

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

Individual concentrates from cells

f X Feed sampling point

c1, c2 … cn ● Sampling points for concentrate from each cell
p1, p2 … pn ◦ Sampling points for pulp region in each cell
t □ Sampling point for bank tailing after last cell

◦
Note: for the last cell in the bank, the tailing sample can be taken from the tailing stream (□) or from the pulp in the last cell ( )
(if the mixing state is known for the last cell).
M = exchange of pulp due to intermixing between adjacent cells (zero if cells are isolated) in units of M t/h of solid
Assays for calculating of solid balance for each cell using two product equation (ie ignoring the solid flows (M) from intermixing):
Feed assay Concentrate assay Tailing assay
Cell 1 f c1 p1
Cell 2 p1 c2 p2
¦ ¦ ¦ ¦
Cell n pn-1 cn pn
For the first cell in the bank: let C = t/h of solid in concentrate, F = t/h of solid in feed, and T = t/h of solid in tailing.
Stating the two-product equation and inserting the symbols for cell 1:
Solid recovery * = C = f - t
F c-t
C = f - p1
F c1 - p1
f - p1
C = F#
c1 - p1
T=F-C
*expressed as a fraction
This calculation is reapplied for cell 2, cell 3, etc.

BOX 2 – Bank survey design involving repeated use of the two-product equation.

The approach depicted in Box 2 represents repeated application of the two-product equation
to the data for each machine to obtain the solid balance. It must be recognised that the method
is based on some simplifying assumptions:
•• the pulp zone of each machine is perfectly mixed (to allow ready and reliable sampling via
a dip sampler)
•• the effect of the intermixing flow rates (M) is disregarded in the mass balance for each
machine (see Box 2).
There are some other properties of this type of sampling:
•• A relatively large number of samples are required (compared to some other options) as a
pulp sample from each cell is required.

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 BILL JOHNSON

•• Experimental error in sampling, preparation and assaying of the series of pulp samples
can result in irregularities in the data, particularly towards the end of the bank where the
additional recovery in each cell is low. For example, the recorded assay for the valuable
element in the pulp region of cell n can exceed its assay in cell n-1. It should be noted that
data smoothing techniques available since approximately 1970 may handle this issue but,
for manual calculations, this property remains a difficulty.
Use of the approach in Box 2 declined during the period from 1970 to approximately 1990
because a more effective method emerged in terms of the quantity of samples required and
its theoretical basis. This more effective method will be discussed shortly in conjunction with
Box 4. However, since approximately 1990, a change in the type and volume of flotation
machines being installed (ie the use of large tank cells) has resulted in increased use of a
closely related variant of the method in Box 2. This variant is illustrated in Box 3.

Individual concentrates from cells

F X Feed sampling point

c1, c2 … cn ● Sampling points for concentrate from each cell
t1, t2 … tn ◦ Sampling points for tailing from each cell

Assays for calculating of solid balance for each cell using two product equation:
Feed assay Concentrate assay Tailing assay
Cell 1 f c1 t1
Cell 2 t1 c2 t2
¦ ¦ ¦ ¦
Cell n tn-1 cn tn

For the first cell in the bank: let C = t/h of solid in concentrate, F = t/h of solid in feed, and T = t/h of solid in tailing.
Stating the two-product equation and inserting the symbols for cell 1:

Solid recovery * = C = f - t
F c-t
C = f - t1
F c1 - t1
f - t1
C = F#
c1 - t1
T=F-C
* expressed as a fraction.

This calculation is reapplied for cell 2, cell 3, etc.

BOX 3 – Bank survey design involving repeated use of the two-product equation for a series of tank cells.

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

The design of the tank cells precludes the possibility of any intermixing of pulp zones and
removes any objections on this basis. However, for taking dip samples from the pulp zone of
each cell, the degree of mixing in the pulp zone must be considered; the degree of mixing in
the pulp zone is also relevant for the correct use of portable pumps or siphons for obtaining
a pulp sample. However, it is also possible for valid sampling points to exist in the pipework
between the cells, eliminating the use of dip samples, which is time consuming and presents
difficulties if the pulp zone is not perfectly mixed. Banks of unit tank cells contain typically six
to ten cells and the moderate number of cells makes the workload of the method of sampling
manageable. When there is adequate access to the cell lips, a viable method to sample tank
cells down the bank is the timed concentrate sampling method, which is now discussed.
A competing method for sampling a bank emerged from approximately 1970 (Box 4).
It required samples of the feed, tailing and the various concentrates for which some grouping
was possible. For each concentrate or concentrate grouping, the flow rate of solid discharging
from the various cell lips also had to be determined (Restarick, 1976).
From Box 4, no assumptions on pulp intermixing between machines or the level of mixing
within machines were required, the only possible exception being the collection of the tailing
sample from the pulp zone (for which an alternative point, sampling the combined tailing
stream after exiting the last cell, exists in some cases). The elimination of all or virtually
all the pulp sampling reduced the quantity of work. However, a more advanced method
of concentrate sampling, preferably requiring two people, was required to obtain values
for the solid flow rate for each machine or grouping of machines. Details of this aspect of
the sampling are provided in the appendix, where its application to large circular cells is
discussed in addition to its original application to small rectangular cells.
In Box 4, the two-product equation is demonstrated to be a special case of a general equation
for removal of many concentrates (designated as n). Box 4 presents the general equation and
the method for initial examination of the data from the survey. Concentrate assays and flow
rates by lip sampling must be obtained for each concentrate and a feed and tailing assay for
the bank must also be obtained.
It is important to discuss the reliability that can be attributed to the measured values for the
solid flow rate (C1, C2, C3, … Cn) in each concentrate (see Box 4) and hence the appropriate
means for processing the data from this type of sampling.

Reliability of measured concentrate flow rates

A method of bank surveying has been described (Box 4) requiring both the assay and
concentrate solid flow rate for each flotation machine or grouping of machines along the
bank. In using this method, it is important to appreciate the reliability of the method, in
particular the required reliability for the measured flow rates of solid in each concentrate.
As a minimum, the measured solid flow rate values for each of the concentrates along a
bank must be correct on a relative basis. It is therefore advisable that the same lip sampling
personnel (usually two people) conduct all the tonnage measurements along a given bank. It
is also advisable that the personnel receive prior training on the use of correct methods and
that the training includes a convenient small sampling exercise where the correctness of the
measured flow rates on an absolute basis could also be established for the personnel.
By way of guidance, traditional sources of absolute solid tonnages, eg a weightometer on
the grinding circuit feed, should always be used as the ‘scaling tonnage’ in processing of plant
surveys (Box 4) and surveys should be designed to ensure that such sources of absolute solid

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 BILL JOHNSON

Individual concentrates from cells

f X Feed sampling point
Sampling points for concentrate from each cell allowing estimate of solid flow rate (C1, C2 … Cn) where
c1, c2 … cn ●
the values are correct on a relative basis (as minimum standard) and provision of solid assay (c1, c2, … cn)
t □ Tailing sample point (after end of bank or possibly pulp region in last machine)
General case: let Ci = t/h of solid in the ith concentrate, F = t/h of solid in the feed to bank and T = t/h of solid in the bank tailing.
It can be shown that: n
/ C (C - t)
i i n
F= i=1
f-t
and T = F - /C i
i=1

The calculated value for F is compared with its known value from the weightometer. The observed lip tonnages for each concentrate
(C1, C2 … Cn) are then rescaled upwards or downwards to ensure the value for F based on the rescaled values for C1, C2, … Cn equals
the true value from the weightometer.
For the general case above applied to a bank with seven concentrates:

Individual concentrates from cells

For n = 7 in the above equation:
7
/ C (C - t)
i i 7
F= i=1
f-t
and T = F - /C i
i=1

Rewriting the two-product equation where F is calculated from the concentrate flow rate C and the feed (f) and the product assays
(c and t):
F = C (c - t) and T = F - C
f-t
It can be observed that the two-product equation for F is a special case of the above equations for F with 7 and n cells in the bank.

BOX 4 – Bank survey requiring assays for the feed, tailing and concentrates and the relative flow rates for each concentrate
(no knowledge of the degree of intermixing (M) is needed for legitimate use of this method – see also Box 2).

tonnages are available. In some cases, extra metallurgical samples may have to be taken to
link the plant section being surveyed in detail to the source of an absolute solid tonnage, eg
weightometer, thereby removing reliance on the correctness of concentrate tonnages on an
absolute basis.

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

Figure 1 summarises the metallurgical performance information that can be calculated

correctly for various levels of reliability of the measured solid flow rates in the concentrate.
In summary, the measured solid flow rates in the concentrate from lip sampling should only
be taken as correct on an absolute basis in unusual circumstances where a large amount of
training and checking has been completed by the lip sampling personnel. Further, an unusual
set of circumstances needs to exist where traditional scaling tonnages, eg weightometer
tonnages, do not exist. In other unusual circumstances, the combination of a magnetic flow

CASE 1
Grade

Recovery

CASE 2
Grade

Recovery

CASE 3
Grade

Recovery

FIG 1 – Illustration of the reliability of calculated metallurgical performance for a valuable mineral/element using the method
with measured lip tonnages (see also Box 4). Case 1: Lip tonnages correct on absolute basis, ie compatible with reference
tonnage and correct relative to each other. Residence times are measured correctly. Case 2: Lip tonnages correct relative to
each other but all ten per cent too high in comparison to reference tonnage (lip tonnages not rescaled as described in Box 4).
Calculated residence times are lower by ten per cent than correct value. Position of grade-recovery curves for cases 1 and 2 is
the same. Case 3: Lip tonnages correct relative to each other but all 15 per cent too low in comparison to reference tonnage
(lip tonnages not rescaled as described in Box 4). Calculated residence times are higher by 15 per cent than correct value.
Position of grade-recovery curves for cases 1, 2 and 3 is the same. Case 4: Lip tonnages not correct relative to each other.
Position of grade recovery curve becomes subject to additional errors and is no longer the same as for cases 1, 2 and 3.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 65

 BILL JOHNSON

meter and a density gauge (both of which are calibrated properly and checked regularly) may
be used to provide a scaling factor for the tonnes per hour of solid for a key stream in a survey
of some peripheral part of a circuit.

CALCULATION OF MINERAL RECOVERIES

The traditional technologies for obtaining the composition of ore samples have provided
elemental assays. While assays for elements are very useful for providing information for
downstream processes, such as smelting, elemental assays would not normally be the first
choice for a concentrator metallurgist in most circumstances in a perfect world.
It is now possible to obtain the assays for minerals directly; however, there are various
limitations to the currently available methods.
The most basic information on the behaviour of a mineral is its recovery, ie its distribution
between the concentrate and tailing streams for a separation. Hence, in this section, the
objective is to discuss the calculation of recovery values for minerals from survey data. The
necessary prerequisite is to obtain mineral assays by suitable means.

Obtaining mineral assays

After laboratory preparation of dry solid from each sampling point in the survey, the next
step is to submit representative portions of each sample for assaying. Metallurgists would
prefer to receive assays of both minerals and elements, each for different purposes.
Traditionally, the industrial assaying methods (atomic absorption spectroscopy (AA), X-ray
fluorescence (XRF), inductively coupled plasma emission spectroscopy (ICP) and fire assaying)
have provided the concentration of valuable metallic elements such as Cu, Ni and Au and
the concentration of other metallic elements such as Fe, often contained in both gangue and
valuable minerals. There has been an increase in the ability to provide assays for entities often
associated with gangue minerals, such as silica (SiO2) and calcium oxide (CaO). Elements such
as barium may be associated solely with the mineral barite (BaSO4) in some ores.
These methods do not provide mineral assays but provide the total concentration of
elements such as copper, iron and silica resulting from the various minerals in which they
exist. The iron assay represents this element in gangue sulfide minerals such as pyrite and
pyrrhotite, in non-sulfide gangue minerals such as dolomite and various silicate minerals
and may include iron in a valuable copper-bearing mineral such as chalcopyrite (CuFeS2) or
bornite (Cu5FeS4). Equally, a silica assay usually does not reflect the occurrence of one non-
sulfide gangue mineral.
In the supergene or oxidised portion of a copper orebody, a copper assay is likely to reflect
the existence of various co-dominant copper-bearing minerals such as chalcocite (Cu2S),
covellite (CuS), native copper (Cu), secondary chalcopyrite (CuFeS2), bornite (Cu5FeS4) and
others. Clearly, in these examples, mineral assays cannot be calculated from the elemental
assays alone.
In the fortunate case where all the copper exists as chalcopyrite, which is often the case in
the deeper primary zone in a copper orebody, the stoichiometry of the mineral can be used
to convert the copper assay to a chalcopyrite assay. In the primary zones of orebodies, it
is reasonably common for the valuable element to reside in just one mineral. However, for
species such as iron or silica, this situation is almost non-existent.
Mineral assays can be obtained by three methods:
1. the use of a quantitative analysis method for minerals such as quantitative X-ray diffraction

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

2. the use of point counting or related methods involving an optical microscope, image
analyser or automated electron microscope for mounted samples, often size fractions and
sometimes on the original sample containing all sizes
3. the use of approximate methods for conversion of elemental assays to mineral assays
where the approximations are specific to a given ore or site.
Methods 1 and 2 provide mineral assays but some understanding of their limitations is
required. Quantitative X-ray diffraction is suitable for assaying total samples or individual size
fractions from samples; the method is suited for minerals with high assays and is particularly
suited for non-sulfide gangue minerals. Point counting or related methods as practised via
an optical microscope are usually applied to size fractions and the finest size fraction from a
given sample cannot be measured by this method. In this situation, assumptions for the finest
size fraction have been needed to sum the data across the size fractions to obtain the mineral
head grade. Methods for obtaining mineral assays with an automated electron microscope
are also usually applied to size fractions; the ability to measure the finest size fraction has to
be determined on a case by case basis.
In general, these mineral assay methods are less accurate than traditional assaying methods
for elements and they have increased technical difficulty and/or become much more costly
if minerals are being assayed in the low concentration region of less than one per cent by
weight. In practice, methods 1 and 2 are often used in conjunction with elemental assays.
A very powerful application of method 2, particularly with an automated electron
microscope, is for an ore with multiple minerals reporting to one concentrate, eg an ore
with several copper sulfide minerals. Mineral assays can be obtained for each copper sulfide
mineral and the performance of each can be calculated.
Further, in many cases, the use of all the methods in combination is warranted, allowing a
method that draws on the strengths of the data from various methods for obtaining mineral
assays. Suitable programs are needed for execution of the necessary calculations to produce
a combined set of mineral assays.
It has been observed that operating sites with both traditional assaying facilities for elements and
recently acquired assaying facilities for minerals generally do not merge the two sources of assay data
well to maximise the benefit to the site.
Method 3 relies on the elemental assays, which are very reliable but require assumptions
for conversion to mineral assays, which are of various levels of reliability. As an example,
consider a simple ore containing lead (only as galena), pyrite, a small amount of copper (only
as chalcopyrite) and various non-sulfide gangue minerals including talc.
Clearly, the lead and copper assays can be converted to galena and chalcopyrite assays,
preferably by using the measured stoichiometry for galena and chalcopyrite in that ore.
If sulfur only existed in the galena, chalcopyrite and pyrite, the sulfur assay could be corrected
for sulfur in the galena and chalcopyrite, and the corrected sulfur assay converted to a pyrite
assay, preferably using the measured stoichiometry for pyrite in that ore. By subtracting the
mineral assays for galena, pyrite and chalcopyrite from 100 per cent, a useful estimate of the
non-sulfide gangue assay would be obtained. If a substantial and variable proportion of the
magnesium in the ore existed in non-talc minerals, conversion of magnesium assays to talc
assays may provide unreliable information on the talc. In such circumstances, a combination
of elemental assays that are converted to mineral assays and directly measured mineral assays
for the talc (eg by X-ray diffraction) could be devised for that particular ore.

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 BILL JOHNSON

Obtaining mineral recoveries with introduction of the recalculated feed

After calculation of the solid balance, obtaining the recovery (the distribution of a mineral,
or element, between the concentrate and tailing streams for a separator) becomes a simple
calculation. It is recommended that the recovery is calculated with respect to the recalculated
feed when the raw assays (Table 1a) are used (ie no statistical adjustment of the assays to
provide ‘smoothed’ or internally consistent assays has occurred).
The solid balance was calculated using the method shown for the feed, concentrate and
tailing assays of mineral A, the only mineral for which there was a large difference between
the feed and tailing assays. Using the symbols in Figure 2, the two-product equation and
noting the feed flow rate is 1000 t/h of dry solid:
-
a = f t
F c-t
10.2 - 1.2
=
81.3 - 1.2
= 0.112
` a = 0.112 # 1000
= 112 t/h

As a result, a mineral balance must also exist for mineral A (see the same flow rates for
mineral A in the actual feed and recalculated feed (from summation of flows of mineral A in
the products) in Table 1b).
However, for minerals B and C, it is very unlikely that an exact mineral balance will
exist using the observed assays for minerals B and C and the solid balance calculated from
mineral A. In Table 1b, the different flow rates of minerals B and C are shown for the actual
feed and for the recalculated feed (defined as the sum of the flow rates in the concentrate
and tailing). The recovery values for minerals B and C can be expressed with respect to the

TABLE 1A
Raw mineral assays for a separator with two products.
Feed Concentrate Tailing
Mineral A 10.2 81.3 1.2
Mineral B 19.7 11.6 21.6
Mineral C 70.1 7.1 77.2
Total 100 100 100

Feed Tailing

F F –
t/h solid t/h solid

Concentrate
 t/h solid
FIG 2 – Illustration of the symbols for solid flow for a separator producing two products.

68 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

TABLE 1B
Summary of flow rates and recoveries.
Feed Recalculated Concentrate Tailing Recoveryb Recoveryc
(t/h) feeda (t/h) (t/h) (t/h) (%) (%)
Mineral A 102 102 91 11 89.2 89.2
Mineral B 197 205 13 192 6.6 6.3
Mineral C 701 693 8 685 1.1 1.2
Solid 1000 1000 112 888 11.2 11.2
a. Sum of mineral flow rates in concentrate and tailing.
b. With respect to actual feed.
c. With respect to recalculated feed.

recalculated or the actual feed. It is recommended that the recovery value is calculated with
respect to the recalculated feed because:
•• the resulting recovery value is less affected by sampling and assay errors existing in the
data, particularly for minerals with higher flow rates in the concentrate than the tailing
•• the values are bounded between zero per cent and 100 per cent
•• a consistent approach is provided.
There are several practical advantages in obtaining the recovery of minerals, aside from the
previously stated observation that, because minerals are being separated, logic dictates that
mineral data are the most relevant.
When metallurgical data are analysed on the basis of elements, some or all of the solid in
the non-sulfide gangue category may be ignored. Further, knowledge of an ore’s behaviour
via minerals allows ready calculation of the effects from changing ore head grade, assuming
all other properties remain fixed. Because this approach requires a knowledge of the
stoichiometry of each mineral and because the concentrations of minor and trace elements
in the lattice of each mineral should also be found in detailed analyses, more complete
information on the real limits to a separation can be obtained, based on the properties of the
minerals. For example, most sphalerite contains some iron in solid solution and the mineral
marmatite reflects naturally occurring zinc sulfide with very high levels of iron.

CALCULATION OF RECOVERY-SIZE DATA

The calculation of recovery values for each mineral for a bank in the previous section specifies
the behaviour of each mineral but, if some values are abnormal or if there is an economic
imperative to improve the recovery value in some size fractions, there is no direct clue to
the mechanism by which the gangue mineral was recovered or the valuable mineral was not
recovered. The first step towards determining the clues is to obtain recovery values for all the
minerals in all size fractions and to summarise the information for all the minerals (and also
water) in a graph of mineral recovery (y-axis) plotted with the mid-point of each size fraction
using a logarithmic scale (x-axis).
The key steps in generating this information are now listed, noting that item 4b will not be
required in many cases:
1. Deciding if there is sufficient quality in the mass balance calculated from the original
survey to warrant generation of more detailed data.
2a. Selection of the sizing method(s).

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 BILL JOHNSON

2b. Sizing of the samples.

3. Specification of any grouping of size fractions before assaying to lower costs, ensuring
consistent grouping of size fractions for each group of samples involved in a particular
bank or plant section. (This extends to a consistent approach to the size fractions combined
at or near the boundaries of sizing methods based on different principles, eg screening
(sizing method based on physical dimensions) and cyclosizing (sizing method based on
hydraulic size), for example.)
4a. Specification of the elemental assays to be obtained and submission of the size fractions
to the assay laboratory after pulverising the relatively coarse fractions to provide a
low fundamental error (see the appendix) in sampling a very small mass for chemical
analysis. For each stream, a ‘head’ sample (unsized) should be submitted for checking
consistency of the assays on the size fractions.
4b. Specification of the mineral assays to be obtained and submission of the size fractions
to an automated electron microscope, eg QEMSCAN or MLA. (The size fractions would
often also be required for measurement of liberation data and would therefore not be
pulverised; however, it is possible that the objective would be obtaining only mineral
assays in certain circumstances.)
A number of checking steps are required during the procedure, particularly with the sizing
step (2b) and the internal consistency of the assays. These are now discussed.
After each sizing is completed, the size distribution should be graphed to detect any
irregularities in the shape of the curve, which may indicate experimental errors. Further,
the position of the curve, ie its coarseness or fineness should be compared with the typical
range of values for that stream. If the sizing is outside the expected range, further checking
is needed.
For samples with elemental assays on the size fractions, the first check is to calculate the
head grade for the sample by using the size distribution and the assay for each size fraction.
The consistency between this value and the head grade for the sample (assayed at the same
time as the size fractions) needs to be checked. Further, these two values for the head grade
of the sample should be compared with the value obtained for the sample when the survey
was conducted and assayed initially. For samples with mineral assays on the size fractions,
the equivalent checks should be performed.
After checking the integrity of the data, a system is needed for processing the data to provide
useful information on the recovery values for each mineral in each size fraction. The concept
of the recalculated feed remains relevant for the sized data.
Initially, consider sized data for the simplest situation, ie two output streams and one input.
The following two options exist for processing the data when there is no size reduction inside
the section considered:
1a. use the solid balance established with the original survey data to calculate the flow rate
for each mineral in each size fraction in the recalculated feed (by summing the flow
rates of each mineral in the concentrate and tailing), and compare each value with the
observed value for the feed stream
1b. calculate the recovery value for each mineral in each size fraction with respect to its flow
rate in the recalculated feed
2a. use a data smoothing program to adjust the assays statistically and provide balanced
data for each mineral in each size fraction

70 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

2b. calculate the recovery value for each mineral in each size fraction, noting that the
recovery values with respect to the actual feed and recalculated feed will be the same
because the data were adjusted statistically to provide internally consistent assays in 2a.
When there is size reduction inside the section considered, it is only possible to employ
methods 1a and 1b for the recovery calculation for each mineral in each size fraction, there
being no basis for data smoothing. It is also relatively common that no sized data exist for
the feed stream. This can arise because a sampling point did not exist or the available sample
was not selected for sizing. In this case, the recoveries can only be calculated by use of the
recalculated feed.
The next step, which allows interpretation of the recovery-size information more readily,
is to summarise the information in a graph of mineral recovery (y-axis) and the mid-point of
the size fraction (x-axis) using a logarithmic scale on the x-axis. All the minerals should be
plotted on the one graph for a given processing stage and the values for the mid-points on the
x-axis should reflect the specific gravity of the minerals when the sizing device operates on
the basis of hydraulic equivalents such as for a cyclosizer, its predecessor (infrasizer) or for
sizings by beaker decantation. When the sizing is obtained by sieving, the mid-points for all
minerals will be the same.
To fully appreciate recovery-size data for minerals, the flow rates of each mineral in each
size fraction in the recalculated/actual feed also need to be reviewed. The values for mineral
recovery are key indicators of metallurgical performance but the practical and economic
significance of the recovery values depends on the quantity of each mineral in each size
fraction on which the recovery value acts. While it is less common to include this information
in the recovery-size curves, this can be done by way of a histogram along the base of the
recovery-size curve. Alternatively, tables or other means may be devised to allow convenient
recognition of this important information.

INTERPRETATION OF RECOVERY-SIZE CURVES

The hydrophobic mineral
The position and shape of the recovery-size (log scale) curves have metallurgical significance
for liberated valuable and gangue minerals from the sequence of subprocesses in the pulp
zone, which are particle/bubble collision and adhesion, followed by successful transportation
through the pulp zone. Detachment of a particle from a bubble can be caused by turbulence
during the transportation step. The next necessary step is successful transportation through
the froth zone. Survey methods now exist for examination of the recovery of the hydrophobic
and other minerals across the froth zone as discussed in a following section.
Particle/bubble collision depends on physical properties of the particles (eg particle diameter
and density) and the system (eg level of turbulence and bubble size). The chemical surface
properties of the particles (particularly their hydrophobicity) and bubbles are dominant in the
particle/bubble adhesion step and remain important for a successful transportation step, ie the
avoidance of detachment. Appropriate settings for both the physical and chemical properties
of the particles and the system are important to minimise detachment; low turbulence and high
hydrophobicity are required to minimise detachment. Hence, the position and shape of the
resulting recovery-size (log scale) curves are related to the physical and chemical properties
of the system through their effect on the subprocesses in the pulp zone for liberated particles.
For technical and economic reasons, complete liberation of all minerals is not possible.
Hence, comments in this section that referred only to liberated particles have to be tempered

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 71

 BILL JOHNSON

with the superimposed effects from incomplete liberation, which affect all size fractions,
but which typically affect the less liberated coarse size fractions to the greatest extent for
a given ore. It must be noted that by obtaining liberation data as a next step the effects of
this complication can be understood for a given ore. This avoids having full reliance on
deductions from recovery-size graphs, particularly for an ore whose liberation characteristics
are not well known.
It is also assumed that a particle that reports to a given size fraction in the recovery-size
curves existed in that size fraction in the flotation process. The existence of a fully dispersed
pulp is therefore assumed.
It is useful to summarise the general form of some basic relationships (Pyke, Fornasiero and
Ralston, 2003) between the efficiency of each subprocess in the pulp zone and particle diameter
(Figure 3). Figure 3 arises from ongoing investigations at the Ian Wark Research Institute. The
authors used the following equation to describe the collection or capture efficiency (Ecoll) for a
particle and bubble in terms of the efficiencies of the subprocesses in the pulp zone:

Ecoll = EcEaEs
where:
Ec = collision efficiency
Ea = adhesion efficiency
Es = stability efficiency
For each of the efficiencies in the subprocesses (Ec , Ea and Es), Pyke, Fornasiero and Ralston
(2003) provided equations relating them to properties of the flotation system.
For the particle/bubble collision step, there is a direct relationship between collision
efficiency and size (see Figure 3). This arises because small particles approaching a bubble
tend to be swept along the stream-lines around bubbles while larger particles with higher

FIG 3 – Calculated relationships between collision efficiency Ec, adhesion or attachment efficiency Ea and stability efficiency
Es and particle diameter dp, and the resulting calculated relationship between the first-order rate constant k and particle
diameter dp for the pulp zone, where cases a, b and c are for advancing contact angles of 50°, 65° and 80° respectively.*
* Reprinted from J Colloid and Interfacial Science, Vol 265, B Pyke, D Fornasiero and J Ralston, Bubble particle
heterocoagulation under turbulent conditions, pp 141–151, Copyright (2003), with permission from Elsevier.

72 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

momentum have an increased ability to cross the stream-lines and complete a collision. This
inability to cross stream-lines means that the probability is low for small particles to approach
a bubble with sufficient proximity for a collision to have occurred, ie with sufficient proximity
for the adhesion process to commence. For a particle of a given diameter, its momentum and
its ability to cross the stream-lines is increased if it has a higher density.
The second subprocess (known as adhesion or attachment) commences after a particle and
bubble come into close contact. Pyke, Fornasiero and Ralston (2003) described the approach
of the particle and the bubble:
Should they approach quite closely, within the range of attractive surface forces, the intervening
liquid film between the bubble and particle will drain, leading to a critical thickness at which
rupture occurs. Movement of the three-phase contact line (the boundary between the solid
particle surface, receding liquid phase, and advancing gas phase) then occurs, until a stable
wetting perimeter is established.
There is an inverse relationship between the adhesion efficiency and particle diameter
(Figure 3), noting that this subprocess is referred to as attachment in the reference (Pyke,
Fornasiero and Ralston, 2003). Small particles slide more slowly over the surface of a bubble
as they are ‘protected’ due to their low diameter by existing in the more slowly moving
boundary region of the water phase near the surface of the bubble. The lower sliding velocity
for smaller particles allows a greater time for the adhesion subprocess to be successful, ie for
the actual contact time between the particle and the bubble to exceed the needed contact time
for adhesion, known as the induction time.
Similarly, for the transportation step in the pulp zone, there is also an inverse relationship
between the stability efficiency and particle diameter (Figure 3). Small particles are subjected
to lower forces of detachment and have a higher probability of successful transportation as a
particle/bubble aggregate to the base of the froth phase.
In Figure 3, Pyke, Fornasiero and Ralston (2003) provided the summation of the relationships
for the three described subprocesses by calculating the relationship between the first-order
rate constant (k) and particle diameter for the hydrophobic mineral for a set of conditions.
This calculation involved the use of typical parameters for the induction time.
The first-order rate constant (k) for a mineral is closely related to its recovery (see section
entitled Process Analysis with Down-the-Bank Flotation Data) and summarises the propensity
for the flotation process for a mineral to proceed in the pulp region for a set of conditions. The
rate constant for the pulp region is linked to the efficiencies in the three subprocesses by the
following equation (Pyke, Fornasiero and Ralston, 2003):

k = z Nb Ec Ea Es
where:
z = frequency of particle bubble collision
Nb = number of bubbles per unit volume
It can be seen that the relationship between the rate constant and particle diameter in the
example has a maximum as a result of the interaction of the direct relationship between
efficiency and particle diameter for the collision subprocess and the two indirect relationships
discussed for the adhesion and transportation subprocesses. In some cases, a small plateau
region may result from the interactions of the three relationships. The importance of a high
particle hydrophobicity in the adhesion subprocess and in avoiding detachment in the

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 73

 BILL JOHNSON

transportation subprocess is highlighted in Figure 3 where calculated outcomes are provided

for contact angles of 50, 65 and 80 degrees.
For convenience of presentation and interpretation, industrial recovery-size data are
graphed with a logarithmic scale for the particle size on the x-axis. This step spreads the
values for particle diameter conveniently, as for plotting sizing distribution data.

The hydrophilic minerals

The entrainment mechanism is a non-selective physical mechanism for transfer of minerals
from the pulp zone to the concentrate launder. The entrainment mechanism does act on
all minerals – both hydrophilic and hydrophobic – because it is a non-selective physical
mechanism. It will be discussed principally in terms of the hydrophilic minerals because the
mechanism provides a much higher proportion of the total recovery of these minerals. For the
finest size fractions, the entrainment mechanism can be the sole recovery mechanism for the
non-sulfide gangue minerals in some ores.
The pattern of behaviour of hydrophilic particles of various sizes in the froth phase is better
described through knowledge of the entrainment mechanism. Throughout a perfectly mixed
pulp zone, hydrophilic particles of all sizes exist at a uniform concentration in each unit of
water in the pulp zone. These particles are subject to hydraulic classification in the froth
region because the water in the froth region must contain a representative sample of the
hydrophilic particles when the water enters the froth. In a conventional flotation machine, it
must be noted that water from the pulp zone is the only source of water for the froth zone;
such water is essential for a stable froth zone.
Knowledge of the water recovery assists in interpretation of the relationship between the
recovery of unwanted minerals (usually gangue sulfide minerals and non-sulfide gangue
minerals) and particle diameter (log scale). With the value for water recovery for a bank, it can
be seen if the entrainment mechanism explains all the recovery of the gangue minerals or only
a portion. This is possible because it is observed that the recovery of liberated, hydrophilic
gangue in the 0–10 µm region is 0.8 of the value for the water recovery (Lynch et al, 1981).
If the water recovery were ten per cent, a normal flotation system would exhibit a recovery
of eight per cent in the 0–10 µm fraction for a hydrophilic gangue mineral (specific gravity of
2.7) from the entrainment mechanism.
It can be visualised that, for a perfectly mixed pulp zone of a conventional flotation machine,
the recovery of ten per cent of the water would result in recovery of ten per cent of the
0–10 µm liberated non-sulfide gangue by this non-selective physical mechanism if there was
no drainage of this mineral in the froth region. In this situation, the entrainment efficiency
value would be 1.0. In real flotation systems, the observed entrainment efficiency factor is 0.8
for the 0–10 µm fraction for siliceous non-sulfide gangue.
The entrainment efficiency value for a size fraction can be defined formally:
Entrainment efficiency value for size i (ENTi) =
(Mass of free gangue per unit mass water) Con
(Mass of free gangue per unit mass of water) Top of pulp

The entrainment efficiency value for size i has been called the classification function
(Johnson, 1972) or the classification vector (Lynch et al, 1981). It is commonly described by
the term ENTi in the present literature and the topic was reviewed by Johnson (2005). Typical
values for ENTi for a range of size fractions of siliceous non-sulfide gangue are provided in

74 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

Table 2. On a sized basis, the simplest mathematical depiction of entrainment is a series of

entrainment efficiency values approaching unity for the fine sizes and which approach zero
for sizes exceeding 50 µm. If a gangue mineral has an elevated specific gravity, its value can
be determined to establish if lower values for ENTi are required for that system.
The following relationship can be demonstrated from the definition of the entrainment
efficiency factor (Lynch et al, 1981) for the first-order rate constant (ki) of a mineral in size
fraction i being recovered by entrainment:
ki = ENTi kw
where:
kw = the first-order rate constant for water recovered in the concentrate
For plant survey data, one method to obtain the values for ENTi for a non-sulfide gangue
mineral for a cell or grouping of cells is by use of the ki values for the various size fractions
and the value for kw. The values for ENTi can be obtained by an approximate but convenient
method based on recovery values. Both methods can also be used for laboratory batch data:
k R
ENTi = kwi . R i
w
where:
Ri = recovery values for various size fractions for a cell or grouping of cells for a mineral
Rw = recovery value for water for a cell or grouping of cells for a mineral
The recovery of gangue mineral by entrainment in a conventional flotation process results
in a lowering of the concentrate grade. However, in a reverse flotation process, the principal
mineral subjected to entrainment is the valuable mineral, resulting in a decrease in the
recovery of the valuable mineral, ie a serious process weakness is caused by the entrainment
mechanism. An example of a reverse flotation process is the recovery of silicate minerals from
iron-bearing minerals where the iron assay of the pulp is approaching the target required
for sale. For both conventional and reverse flotation processes, the extent of entrainment in
a single stage of processing can be lowered by technology where the water derived from the
pulp region and containing the entrained particles is replaced by water added to the froth
region. The added water, which must not contain solids, must be correctly distributed and
sufficient for provision of the water reporting to the concentrate. Some cells are designed with
deep froths, eg column and Jameson cells to facilitate the described water addition.

Review
To understand the behaviour of a particular ore, there is often a benefit from observing its
flotation behaviour in the absence of collector but with a normal frother addition (and possibly
depressant addition). The benefit can be increased if the recovery-size behaviour is obtained
for the recovered minerals. Minerals that display normal flotation through the particle/bubble
collision sequence in the absence of collector can be readily recognised (recovery values in
some size fractions considerably larger than water recovery) and the size fractions in which

TABLE 2
Values for entrainment efficiency factors (ENTi) for siliceous non-sulfide gangue (Lynch et al, 1981).
Size fraction (µm)
-11 -16 +11 -23 +16 -33 +23 -44 +33 -75 +44 +75
Entrainment efficiency 0.83 0.44 0.24 0.11 0.04 0.03 0.0

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 75

 BILL JOHNSON

this occurs can be readily identified (Johnson and Jowett, 1982). Minerals that display this
behaviour can be valuable sulfides, non-valuable sulfides and non-sulfide gangue (eg talc).
Hydrocarbons present during ore formation and which remain associated with a portion of
one mineral (eg pyrite with a rimming of hydrocarbons) can cause this behaviour (Croxford,
Draper and Harraway, 1961).
As a result of the various mechanisms for flotation and the steps involved in each mechanism,
recovery-size curves for the valuable mineral being recovered by flotation adopt a general form
with many variations, of which a few are demonstrated in Figure 4. It is given that the curves
were observed after high residence times, ie their position and shape were changing only very
slowly with additional residence time. For the valuable mineral in all graphs, two scenarios
(Johnson, 2006) are shown for the fine fractions. In scenario 1, the diminished recoveries are
typical of those arising from deficiencies in the collision subprocess. In scenario 2, the more
greatly diminished recoveries result from an additional effect beyond the collision deficiency
likely to result from an imbalance in the ratio of adsorbed hydrophobic/hydrophilic species
on the valuable mineral.
For the minerals for which recovery is not being sought, an extremely wide range of
positions and shapes exist (Figure 4). For the hypothetical fully liberated feed, the following
are demonstrated:
•• entrained liberated non-sulfide gangue (cases A, C and E)
•• entrained and hydrophobic, liberated sulfide gangue due to collector adsorption (case C)
•• entrained and naturally hydrophobic liberated sulfide gangue (case E).
For the realistic cases (B, D and F) with an imperfectly liberated feed, cases are shown with
increased recoveries of sulfide and non-sulfide gangue due to their recovery in composites,
along with lower recovery of coarse valuable mineral due to the lower hydrophobicity of
composite particles containing some valuable mineral. In case B, two examples are given for
the relationship between non-sulfide gangue recovery and size (log scale); no examples for
sulfide gangue are given in case B or case A.

ADDITION OF LIBERATION DATA TO RECOVERY-SIZE DATA

The addition of liberation data to recovery-size data eliminates the need for deductions and
inferences about the state of liberation of a mineral in given size fraction of a given product.
For a new ore or for an ore that is unfamiliar to a metallurgist, the collection of liberation data
in initial phases of the work can increase confidence in the interpretation of recovery-size
data for the ore in question such that less liberation data may be required in further stages of
experimental work on the same ore.
Liberation data have been collected traditionally on size fractions and there may be a lower
limit to the size fraction from the flotation process that can be examined, arising from the
physics of the method employed (Jones, 1987). For techniques based on optical microscopy
or generation of X-rays by electron microscopy, different reasons exist for the lower limit, but
the value is typically in the region of 5 µm, sometimes slightly lower. A limit may not exist
if a different method with different capabilities is useable for a given ore, eg one based on
backscattered electrons. For a given ore and measurement system, it is necessary to establish
if the finest fraction can be measured reliably. Size fractions submitted for liberation analysis
must not have been pulverised.
For a given size fraction in a separation with one concentrate and one tailing, the liberation
data can be used in two complementary ways. For the concentrate, the liberation state of

76 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

Fully liberated feed Typical feed

(All minerals 100% liberated) (Liberation of valuables >80%)
(Liberation of other minerals 70–90%)

Case A Case B
100
100 100
100

9090 9090
8080 8080
7070 7070

Recovery (%)
Recovery (%)

6060 6060
Recovery (%)

Recovery (%)
5050 5050
4040 4040
3030 3030
2020 2020
Water recovery (10%) Water recovery (10%)
1010 1010
10 10
11 1010
100
100
11 10
10
100
100

log Size (um) log Size (um)

log Size (μm) log Size (μm)

Case C Case D
100
100 100
100

9090 9090
8080 8080
7070 7070
Recovery (%)
Recovery (%)

6060 6060
Recovery (%)

Recovery (%)

5050 5050
4040 4040
3030 3030
2020 2020
Water recovery (10%) Water recovery (10%)
1010 1010
11
0 1 0

1 1010
100
100 11 1010
100
100

log Size (um) log Size (um)

log Size (μm) log Size (μm)

Case E Case F
100
100
100
100

90
90 9090
80
80 8080
70 7070
Recovery (%)
Recovery (%)

70

60 6060
Recovery (%)
Recovery (%)

60

50 50 5050
40
40 4040

30 30 3030
20
20
2020
Water recovery (10%)
Water recovery (10%)
10
10 1010
10 10
11 10
10
100
100 11 10
10
100
100

log Size (um)

log Size (um)
log Size (μm) log Size (μm)

Valuable mineral (Scenario 1) – ‘collision effect’ for fine valuables

Valuable mineral (Scenario 2) – additional deleterious effect beyond ‘collision effect’ for fine valuables

Non-sulfide gangue (Case 1)

Non-sulfide gangue (Case 2) – lowered contribution from recovery in composites with valuable mineral
compared to case 1
Sulfide gangue

FIG 4 – Examples of some mineral recovery – particle diameter (log scale) curves for a feed with
perfect liberation (cases A, C, E) and for a feed with acceptable liberation (cases B, D, F) for which
recovery of unwanted minerals in composites becomes a possible mechanism.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 77

 BILL JOHNSON

the unwanted minerals can be recognised, providing strong clues to their mechanism of
recovery. Equally, the liberation state of the valuable mineral is determined. If significant
losses of valuable minerals in composites are observed, corrective steps involving grinding or
regrinding may be assessed.
Liberation data allow the flow rate of each mineral in each size fraction of each product
(obtained from the recovery-size (log scale) level of analysis) to be distributed between a
number of categories (typically from five to ten). The performance of the various categories
becomes the basis of the next level of analysis.
Liberation data for a mineral are supplied in one of two basic forms. The traditional point
counting method with use of an optical microscope provides liberation data in the general
format as shown in Table 3 for a size fraction. Examples of graphs derived from this type of
data are given in Figures 5, 7, 8 and 9.
Automated scanning electron microscopes can also provide the data in the point counting
format illustrated in Table 3. The data from these devices are also commonly supplied in
another format based on the percentage of the mineral of interest in each category. An example
is shown in Table 4. An example of a graph derived from this type of data is given in Figure 6.
In the type of data indicated in Table 4, some grouping of the original data has been
performed. Typically, the data are provided with increments of ten per cent from category to
category; in practice, some grouping of the higher quality classes is often used while narrow
classes are employed for the very important lower quality composites, as shown in Figure 6.
The reader is reminded that several calculation steps, as described in preceding sections
of this chapter, are the necessary precursors to incorporation of liberation data. These steps
are listed:
1. Calculation of the mass or solid balance for the circuit. The water balance should also be
calculated.
2. Use of size distributions and assays for the size fractions of the concentrate and tailing
(as the minimum relevant streams), along with the solid flows from item 1, to calculate
the flow rates of minerals in each size fraction of the concentrate and tailing. The mineral
assays for each size fraction may be from conversion of elemental assays to minerals

TABLE 3
Example of some point count data for sphalerite in one size fraction.
Liberation data (categories)
% Liberated % in binary composite with listed minerals % in ternary
Galena Iron sulfide Non-sulfide gangue compositesa
% in each category 60 16 4 11 9
a. Includes other multiphase composites, eg quaternaries.

TABLE 4
Example of second form of liberation data for sphalerite in a size fraction.
Liberation data (% of mineral of interest defined in each category)
100 90–100 70–90 50–70 30–50 20–30 10–20 0.1–10
Percentage in category 61.2 30.4 4.1 2.1 1.1 0.4 0.4 0.3

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

100

90

80

70

60
Recovery (%)

Total Sphalerite
50 Liberated Sphalerite
Binary with Galena
40 Binary with Iron Sulfide
Binary with NSG
Ternaries
30

20

10

0
1 10 100
Particle Diameter (µm - log scale)

FIG 5 – Relationship between total sphalerite recovery and particle diameter (µm – log scale) for data
from the recovery-size level of analysis and from the recovery-size-liberation level of analysis illustrating
the recovery of the following sphalerite liberation categories in a sphalerite rougher – liberated, binaries
with galena, binaries with iron sulfide, binaries with non-sulfide gangue (NSG) and ternaries.

100

90

80
Copper Sulfide Recovery (%)

70 100
100‐80
60
80‐60
50
60‐40
40
40‐25
30 25‐15
20 15‐5
10 5‐0

0
1 10 100 1000
Particle Diameter (µm ‐ log scale)
FIG 6 – Relationship between copper sulfide rougher recovery and particle diameter (µm – log scale) for data at the
recovery-size-liberation level of analysis, showing the performance of a range of volume per cent classes for copper sulfide
(data from one rougher bank of the Phu Kham operation, provided with the kind permission of Pan Aust Limited).

assays, from modal analyses of the size fractions by an automated electron microscope or
by other means.
3. Calculation of the recovery of each mineral in each size fraction with respect to the
recalculated feed.
Steps 2 and 3 represent the calculations required for graphing the mineral recovery – particle
size (log scale) curves as discussed in earlier sections. The next level of analysis (liberation

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 79

 BILL JOHNSON

level) is now discussed. An example in the literature with the same methodology can also be
reviewed (Johnson, 1987).
To provide an example of the type of calculations required for the liberation level of analysis,
some sphalerite liberation data for a single selected size fraction are presented for a system
with such data for the concentrate and tailing only. In Table 5, the calculations for one size
fraction of one mineral are illustrated.
The flow rate of sphalerite in the concentrate and tailing were 6188.2 and 1155.9 kg/h
respectively. These flow rates (column A) were multiplied by each liberation value (each
divided by 100) in the five columns labelled as B to distribute the mineral flow rates amongst
the various liberation categories (columns labelled as C).
The recalculated feed is obtained in the table by summation of the flow rates in each
liberation category. In a further step, the distribution of sphalerite between the concentrate
and tailing in each liberation category is calculated (see values in brackets). In other words,
the recovery of mineral in each liberation category has been calculated with respect to the
recalculated feed.
Although the calculations are straightforward, the presentation of the calculated quantities
is more difficult for the listed reasons:
•• there is interest in information on the feed, concentrate and tailing streams
•• there are many size fractions and minerals
•• there are many liberation categories of relevance.
For compactness in some examples of presentation methods, data are used for a bank
where only four size fractions encompass all the solid in the concentrate and tailing. The first
presentation uses tables only (see Table 6). This table provides the flow rates and recoveries
for all the minerals in the various liberation categories and size fractions in the concentrate.
This table is particularly valuable for recognition of the major sources of gangue dilution in
the concentrate.
Therefore, the dominant flow rates for the gangue minerals (>200 kg/h) in the concentrate
have been highlighted. In reading the flow rates for minerals in a typical binary in Table 6, the

TABLE 5
Example of processing of point count form of some sphalerite liberation data for one size fraction.
Product Mineral Liberation data (B) Mineral flow in categories (kg/h) (C)
flow Liberated % in binaries with Tern Liberated Binaries with Tern
(kg/h) category category
Galena Iron NSG Galena Iron NSG
(A)
sulfide sulfide
Concentrate 6188.2 75.6 5.1 12.2 2.4 4.6 4678.3 315.6 755.0 148.5 284.7
(97.0) (90.4) (73.0) (54.8) (33.2)
Tailing 1155.9 12.7 2.9 24.2 10.6 49.6 146.8 33.5 279.7 122.5 573.3
(3.0) (9.6) (27.0) (45.2) (66.8)
Recalculated 7344.1 65.7 4.8 14.1 3.7 11.7 4825.1 349.1 1034.7 271.0 858.0
feed (100.0) (100.0) (100.0) (100.0) (100.0)
Notes: Tern = category containing ternary and quaternary composites. NSG = non-sulfide gangue.
Recalculated feed = recalculated feed from summation of flows in concentrate and tailing as shown in columns labelled as (A) and (C).
Liberation values for each category in the row ‘Recalculated feed’ and in columns labelled as (B) calculated using the flow rates for the recalculated
feed in columns labelled as (C) and the total flow rate of sphalerite (7344.1 kg/h) in column (A).

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

TABLE 6
Listing of flow rates (kg/h) and recoveries for sphalerite, galena, iron sulfide and non-sulfide gangue
in the various liberation categories and size fractions for a zinc rougher. All gangue mineral flow rates
>200 kg/h have been highlighted to indicate the dominant gangue mineral flow rates.
Mineral Liberated Galena Sphalerite Iron sulfide NSG Ternary Size fraction*
(Flow in binary with)
Flow rate of mineral in all liberation categories in concentrate
Galena 0.6 - 61.1 0.0 108.3 117.8
Sphalerite 1199.3 858.5 - 281.8 180.2 756.9
+38 µm
Iron sulfide 43.4 0.0 117.8 - 0.0 256.4
NSG 84.5 65.2 297.6 71.3 - 362.8
Galena 3.9 - 61.8 10.8 25.5 127.8
Sphalerite 4678.3 315.6 - 755.0 148.5 284.7
-38 µm +11 µm
Iron sulfide 266.5 13.1 339.1 - 13.9 139.1
NSG 214.3 0.0 267.2 80.7 - 641.6
Galena 7.0 - 11.0 1.3 4.4 4.7
Sphalerite 1336.7 29.4 - 29.4 63.3 13.3
-11 µm +8 µm
Iron sulfide 116.9 3.5 46.4 - 18.9 0.0
NSG 143.9 12.4 87.5 43.7 - 0.0
Galena 56.5 - 89.3 10.3 35.6 37.9
Sphalerite 5978.3 131.7 - 131.7 283.1 59.3
-8 µm
Iron sulfide 575.3 17.4 228.3 - 93.2 0.0
NSG 1206.4 103.8 733.5 366.7 - 0.0
Recovery of mineral in all liberation categories in concentrate
Galena # - # 0.0 12.9 6.9
Sphalerite 80.5 92.3 - 39.1 9.9 19.9
+38 µm
Iron sulfide 1.6 0.0 13.5 - 0.0 5.0
NSG 0.2 2.8 12.7 0.3 - 2.6
Galena # - 79.3 20.0 12.9 29.4
Sphalerite 97.0 90.4 - 73.0 54.8 33.2
-38 µm +11 µm
Iron sulfide 3.3 10.5 31.0 - 1.0 11.1
NSG 0.9 0.0 33.1 1.9 - 29.6
Galena # - # # 9.1 24.2
Sphalerite 92.4 # - 66.5 63.3 44.1
-11 µm +8 µm
Iron sulfide 7.2 # 37.3 - 12.3 ##
NSG 2.5 28.1 58.0 8.2 - ##
Galena # - # # 5.3 15.1
Sphalerite 74.6 # - 32.5 29.4 16.0
-8 µm
Iron sulfide 5.0 # 29.0 - 8.8 ##
NSG 2.0 24.3 53.2 6.9 - ##
Notes: NSG = non-sulfide gangue; = gangue flow >200 kg/h; # = insufficient observations of this category in tailing for reliable value;
## = insufficient observations of this category in concentrate for reliable value. * Values are for sphalerite.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 81

 BILL JOHNSON

reader is reminded of the following example for the sphalerite/iron sulfide binary (+38 µm
fraction): 281.8 kg/h of sphalerite and 117.8 kg/h of iron sulfide. The table also provides the
recovery values for all the categories in the various size fractions.
The recovery values are particularly valuable for examination of metallurgical behaviour of
the various liberation categories of the valuable mineral in the concentrate. The recovery values
represent the metallurgical performance for the valuable mineral in the category. However, it
must be noted that the significance of a high or low recovery value for the valuable mineral in
a category depends also on its flow rate in the feed. For example, a category with a high flow
rate in the feed and a metallurgical recovery of 95 per cent may result in a much higher flow
rate of valuable mineral to the tailing than another category with a low flow rate in the feed
and a low metallurgical recovery of 20 per cent.
Some recovery values have not been entered in Table 6. In collecting data from a standard
number of particles, the number of observations in some liberation categories may be too
small to provide reliable recovery values. For example, galena was present in the tailing in
small amounts only and no observations existed for some liberation categories in the tailing,
implicating a recovery of 100 per cent. A second phase of data collection recording only
information on a selected mineral (in this case for galena) in some liberation categories is
required in such circumstances.
The graph of recovery-particle diameter (log scale) for the valuable mineral can be updated
with the additional liberation categories for the valuable mineral as shown in Figure 5, where
the curve for sphalerite contained six data points. With the grouping of size fractions, the
curves for the various liberation categories contained four size fractions in this example. It can
be noted that the curve for liberated sphalerite displayed higher recoveries than for the overall
sphalerite curve. Further, the points available for sphalerite-galena binaries were in a similar
region to the liberated sphalerite because both the galena and sphalerite were hydrophobic in
these binary particles. For the other liberation categories containing sphalerite in composites
with less hydrophobic unwanted minerals, lower recoveries were observed in general. Similar
patterns of behaviour are often observed in data sets of this type.
For examination of rougher data for the valuable mineral, particularly where the rougher
tailing is directed to the final tailing, an informative type of graph utilising volume per cent
classes for the valuable mineral is illustrated in Figure 6. This type of graph is based on data of
the type discussed earlier and shown in Table 4. Figure 6 illustrates clearly the deterioration
in the recovery of the copper sulfide-bearing particles for larger and lower quality composite
particles with respect to their volume per cent of copper sulfides.
Figures 7 and 8 demonstrate the use of simple effective bar charts for illustrating process
weaknesses for sized liberation data. Figure 7 illustrates the flows of a gangue mineral in
various occurrences (liberated and several types of composites) in a concentrate. Figure 8
illustrates the flows of a valuable mineral in various occurrences (liberated and several
types of composites) in a tailing. The use of simple effective methods in reporting and in
presentations is an important aspect of communicating the findings from data at the mineral
recovery-size-liberation level of analysis.
Graphical presentations can be extended to three-dimensional graphs (with axes of size
fraction / liberation category / measure of quantity) of the types listed:
1. distribution of a selected mineral in the feed, concentrate or tailing
2. flow rate of a selected mineral in the feed, concentrate or tailing

82 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

3000

Ternary
2500 Binary with Iron Sulfide Gangue
Non‐Sulfide Gangue Flow (kg/hr) Binary with Sphalerite
Binary with Galena
2000
Liberated

1500

1000

500

0
F7 F6 Size Fraction ‐38um +F5 +38um

FIG 7 – Simple and clear method for illustrating the flows of one gangue mineral (non-sulfide gangue) in various
occurrences in various size fractions of a concentrate (F7 = -10 µm, F6 = -14 +10 µm and -38 µm +F5 = -38 +14 µm).

6000

Ternary
5000 Binary with Non‐Sulfide Gangue
Binary with Iron Sulfide
Binary with Galena
4000
Sphalerite Flow (kg/hr)

Liberated

3000

2000

1000

0
F7 F6 Size Fraction ‐38um +F5 +38um

FIG 8 – Simple and clear method for illustrating the flows of the valuable mineral (sphalerite) in various occurrences
in various size fractions of a tailing (F7 = -8 µm, F6 = -11 +8 µm and -38 µm +F5 = -38 +11 µm).

3. recovery values for a selected mineral (often the valuable mineral) in the concentrate or
tailing.
The types of graphs in item 1 are demonstrated in Figure 9 because their structure is difficult
to explain without an actual demonstration. However, the graph types in items 2 and 3
are not demonstrated because their structure is straightforward. The graph type in item 2
is suitable for demonstrating how each gangue mineral is diluting a concentrate and also
for demonstrating the flow rate of the valuable mineral in each category and size fraction

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 83

 BILL JOHNSON

A
100
Recalculated Zinc Rougher Feed 90
80
Distribution of Sphalerite in

70
60
50
40
30
20 Total
Ternaries
10 Sphalerite in Binaries with NSG
Sphalerite in Binaries with Iron Sulfide
0 Sphalerite in Binaries with Galena
Liberated Sphalerite

Size Fraction

B
100
90
Distribution of Sphalerite in Zinc

respect to Recalculated Zinc

80
Rougher Concentrate (with

70
60
Rougher Feed)

50
40
30
20 Total
Ternaries
10 Sphalerite in Binaries with NSG
Sphalerite in Binaries with Iron Sulfide
0 Sphalerite in Binaries with Galena
Liberated Sphalerite

Size Fraction

C
100
90
Recalculated Zinc Rougher Feed)
Distribution of Sphalerite in Zinc
Rougher Tailing (with respect to

80
70
60
50
40
30
20 Total
Ternaries
10 Sphalerite in Binaries with NSG
Sphalerite in Binaries with Iron Sulfide
0 Sphalerite in Binaries with Galena
Liberated Sphalerite

Size Fraction
FIG 9 – Examples of usage of three-dimensional graphs with axes of size
fraction/liberation: (A) recalculated feed, (B) concentrate, (C) tailing.

in the tailing. It can be noted that items 2 and 3 effectively represent a means of graphical
presentation of the type of data presented in tabular form in Table 6.
For non-sulfide and sulfide gangue minerals in each size fraction, liberation data can be
used to determine the contribution from both liberated particles and composites (often with

84 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

the valuable minerals) to their recovery. For fine-grained ores, recovery of non-sulfide and
gangue minerals in composites can continue to be significant in the fine fractions. For non-
sulfide gangue minerals, the data for the liberated form in each size fraction is the relevant
form for analysis of the contribution from entrainment. For sulfide gangue minerals and
certain non-sulfide gangue minerals such as talc, the recovery values for the liberated form in
each size fraction will be from entrainment, which can be estimated from the water recovery
and ENTi values, and any additional contribution from its recovery due to its hydrophobicity.
In some unusual systems, the values for ENTi for the liberated non-sulfide gangue can be
greater than 1.0 for the finest fraction and continue to exceed greatly the expected values for
ENTi in the intermediate and coarse size fractions. Entrapment is the term for this additional
mechanism ‘beyond entrainment’, which can arise from steric hindrance in the regions in
the froth phase containing solid particles and water, causing restrictions on the drainage of
liberated gangue. One example from Vianna (2004) is discussed in Johnson (2005).
Liberation data can also be used to identify the extent of liberation achieved at each grinding
or regrinding stage at the commencement or within a processing circuit. This information
can be obtained by including samples of the combined feed and product for a grinding or
regrinding circuit; such use of liberation data is extremely informative but is rarely used in
the industry. Measurement of the liberation values for the minerals in each size fraction of
the feed and product allows the overall liberation value for minerals in each stream to be
calculated. For each mineral, the increase in liberation across the grinding circuit is calculated
by difference. The method for calculating the liberation value within a given stream is
illustrated in Table 7.
The taking of a few extra samples in a plant survey may allow more reliable quantification
of the changes in liberation at size reduction steps. For example, to improve the quality of
the data, it is preferable that a single combined feed sample and a single product sample
be taken for an overall regrinding system, which often will contain a mill for size reduction
and a classification device. It is advisable that a survey plan is reviewed for the directness by
which liberation data may ultimately be obtained. In other words, the technical viability of a
‘liberation survey’ within the larger plant or circuit survey needs to be addressed separately
in the planning steps. Equivalent samples can be taken in pilot plant work and in laboratory
batch or cycle tests involving regrinding.
Historically, metallurgists have often sought to determine the benefits of regrinding by
examination of the separation results (often using the flotation process) with various levels
of regrinding. Particularly for regrinding to fine sizes, it is much safer to establish initially
if the regrinding step is causing a significant increase in the liberation level of the valuable
mineral and the gangue minerals. If a significant increase in liberation is measured, the necessary
conviction is provided to seek conversion of the increase in liberation into an increase in performance of
the following separation. Such increases in performance may not emerge after initial cursory separation
tests, even if a significant improvement in liberation is resulting from the regrinding. Optimisation of
the chemical conditions during regrinding and the following flotation separation may require many
months of tests for some systems.
The data from two-dimensional mounts may overestimate the levels of liberation of each
mineral because a two-dimensional intersection of a particle may, by chance, occur in one
mineral only, even if there is more than one mineral in the particle (Jones, 1987). This issue
is well known from the area of stereology. From the examination of liberated and composite
particles from real ores in the current literature on this stereological issue, there is no need

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 85

 BILL JOHNSON

TABLE 7
Calculation method for the total liberation of a mineral in a given stream.
Column 1 Column 2 Column 3
Size Mineral flow Liberation value Flow of liberated mineral
-105 µm +53 µm 5 20 1
-53 µm +CS2 8 25 2
-CS2 +CS3 10 40 4
-CS3 +CS4 10 60 6
-CS4 +CS5 10 75 7.5
-CS5 +CS6 20 80 16
-CS6 +CS7 37 80* 29.6
Total 100 → A 66.1 → B
Input information:
Column 1 – Flow of mineral in each size fraction (from size distribution and assays)
Column 2 – Liberation value for mineral in size fraction
The liberation value is calculated as:
B # 100
A
ie 66.1 # 100 = 66.1%
100
This is simply the weighted average of the liberation values in Column 2.
Note: in this example, observations could not be made on the CS7 fraction. The liberation value for this size
fraction (denoted by *) was assumed to equal the value for the C6 fraction because the liberation values had
essentially reached a plateau region.

for a stereological correction of 2D liberation data, or only a minor need. This finding applies
to real ores, which produce complex composite particles with a wide range of compositions
from very low quality to high quality with respect to the valuable mineral, and which produce
liberated particles of the valuable mineral along with barren particles containing no valuable
mineral. Hence, uncorrected two-dimensional data may be used with caution and with other
checks to improve understanding of the process for the listed reasons.
Firstly, in calculation of the recovery values for liberation-based species in Table 6, there may
be correction factors (a and b) needed to the flow rates in the numerator and denominator of
the following equation:

% Re covery = a # flow rate in conc # 100

a # flow rate in conc + b # flow rate in tailing

In percentage terms, the magnitude of the correction factor (slightly less than or equal to 1)
for the tailing flow rate (b) may differ from the correction factor for the concentrate flow rate
(a), ie b does not equal a. However, because the direction of the correction must be the same for
both the numerator and denominator, there is at least partial cancellation of the stereological
effect. When the flow rate for the concentrate in the equation is very large compared to the
flow rate for the tailing, the cancellation of the stereological effect is more complete.
Secondly, if a metallurgist is suspicious of the flow rates in Table 6 provided by uncorrected
liberation data, it is possible with care and patience to section a given set of particles in a

86 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

briquette at various levels to obtain, for practical purposes, three-dimensional liberation data.
Note that this step is a possibility for particularly unusual circumstances or when very high
confidence is required in the liberation data.
Thirdly, the liberation level (two-dimensional basis) for the valuable mineral(s) in a process
feed is used to judge if the sizing of the feed is at a value where an acceptable separation
could be expected. On a two-dimensional basis, the guidelines shown in Table 8 can be used
in process engineering where all the liberation is occurring in a grinding circuit at the start of
the circuit, ie no regrinding exists inside the flotation circuit. With liberation data converted
from 2D to 3D values, a new set of slightly different boundaries may exist.
Of course, obtaining a high level of liberation does not guarantee an efficient separation as
the appropriate settings for the process variables must also be obtained. For an efficient froth
flotation separation, both a high level of liberation and suitable settings for the physical and
chemical variables in the process are needed.
In porphyry copper circuits, liberation levels for the copper minerals may sometimes be less
than 50 per cent in the rougher feed. However, the regrinding steps in the circuit must raise
the liberation level of the copper minerals such that the guidelines in Table 8 are achieved for
the recalculated feed (summation of the final concentrate(s) and tailing(s)). This applies to
other circuits with major regrinding and liberation steps in the flotation circuit.
For an ore with multiple valuable minerals reporting to a single concentrate, it is necessary
to consider the liberation of the combined valuable minerals in the feed or recalculated feed in
conjunction with the guidelines in Table 8. For example, for an ore containing several copper
sulfide minerals, the liberation of the combined copper sulfides should be calculated because
its value will exceed the values for the individual copper sulfides; a particle containing only
chalcopyrite and bornite is a liberated copper sulfide particle.
The use of liberation data in conjunction with recovery-size data can be employed in
existing plants for surveys, monthly or yearly composite samples on feed and products, or
for samples from supporting laboratory or pilot plant development work. Plotting of the level
of liberation of the valuable mineral(s) in the recalculated feed of a concentrator versus time
(monthly or quarterly) has been demonstrated to be very useful in understanding declines
and monitoring improvements in plant performance (Young et al, 1997). Equally, for a new
deposit, the technique can be applied to laboratory test work and pilot plant surveys as a part
of flow sheet development and optimisation.

THE ROLE OF SURFACE AND SOLUTION ANALYSES FOR ORGANIC AND INORGANIC SPECIES
The use of recovery-size data in conjunction with liberation data will sometimes reveal
the recovery of a liberated gangue mineral in quantities that indicate it was recovered due

TABLE 8
The maximum potential quality of separation possible at various liberation levels (two-dimensional data)
for the flotation feed (circuit without regrinding) or the recalculated feed (circuit with regrinding).
Liberation level (%) (2D data) Potential quality of separation
>90% Very high, extremely efficient separation possible
80% to 90% High, very efficient separation possible
70 to 80% Sound, moderate separation possible
<70% Poor, inadequate separation only possible

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 87

 BILL JOHNSON

to hydrophobicity imparted by unintentionally adsorbed collector, possibly assisted by

activating metal ion adsorption. It cannot be explained solely by entrainment as the recovery
value is much greater than the yardstick provided by the water recovery and the entrainment
efficiency factors, and there is no evidence of recovery of the mineral (beyond entrainment
levels) in tests with frother but without collector.
Further, for the valuable mineral, there may be cases of unexpectedly low recovery of the
liberated valuable mineral, typically in the finest size fractions. In principle, further clues to
the causes of these two types of process weakness can be sought by examination of surfaces.
For the surface of the valuable mineral, an unacceptable ratio between collector based
hydrophobic and detrimental hydrophilic species (derived from the system) may be found
by analysis for organic and inorganic species.
Such surface analysis provides an additional fourth level in the system for process analysis.
However, the surfaces that are analysed must reflect their condition in the real process.
Therefore, additional samples that may be used for surface analysis must be taken at the
time of the survey. Alternatively, for an initial survey, the samples can be processed to obtain
recovery-size and liberation data and to recognise weaknesses. A decision can then be made
if surface analysis is warranted and a new survey taken for both recovery-size/liberation data
with separate samples for surface analysis.
The minerals in the samples for surface analysis must retain their properties from the
process pulp. Therefore, samples that have been dried and possibly sized as part of a normal
survey procedure are of no use. Samples that have not been specially taken and handled will
provide misleading surface analyses because of desorption of key species or the introduction
of artifacts on the surface. The correct handling of samples for surface analysis will depend
on the requirements of the surface analysis facility but may include protection of the sample
at low temperature (low reaction rates) and under nitrogen (absence of oxidising agent).
A method has been developed that uses classical chemical methods (Rumball and Richmond,
1996) to assess the aqueous phase and then to reassess the aqueous phase after a complexing
agent, ethylenediaminetetra-acetic acid (EDTA), has been used to return cations existing as
hydrophilic debris (for example metal hydroxides) and possibly other forms on the surfaces
of minerals to the aqueous phase. The increase in concentration of each cation is related to the
quantity existing on the surfaces of minerals. Hence, general information is provided as the
method cannot indicate the minerals on which the debris was deposited in greatest surface
concentration.
Surface analysis of particular minerals by instrumental methods with a strong focusing
ability is required to provide such information (see Chapter 9). However, the EDTA method
will indicate the relative increase in the quantity of precipitated species from the start of the
circuit to the exit points (Chapter 7). The increase in the extent of oxidation in the circuit can
be established by a relatively simple method.

INCLUSION OF FROTH RECOVERY IN SURVEYS

An industrial flotation machine contains two distinct regions – the pulp and froth zones.
Traditional flotation surveys seek to obtain the combined performance of the two regions,
ie an overall mass balance. Until recently, there has been no practical way of establishing a
separate mass balance for each of the two zones as part of a plant survey. With collection of
data from new types of measuring/sampling devices (see Chapter 6), the establishment of a
separate mass balance for the two zones is now possible.

88 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

The froth recovery Rf of a mineral in a size fraction is defined as the ‘fraction of particles
attached to bubbles entering the froth phase that are collected in the concentrate launder’
(Vianna, 2004) and this term is included in the modelling framework for the first-order rate
constant (k) for the overall process (combined pulp and froth regions) as used at the Julius
Kruttschnitt Mineral Research Centre:
k = P Sb Rf
where:
P = mineral floatability in pulp region
Sb = bubble surface area flux
Rf = froth recovery
The key additional step requires a device for capturing and measuring the upward flow
rate of minerals in particles attached to bubbles at the top of the pulp zone, just before the
bubbles enter the froth region; other related data gathering steps are required to obtain the
froth recovery for a given cell in a plant. A plant metallurgist can now request froth recovery
measurements on all or selected cells in a plant as part of a plant survey.
The obtaining of the froth recovery across the froth region is relevant for both conventional
flotation machines (including tank cells) and cells with water addition to the froth region.
Novel measuring devices (Seaman, 2006) for determining the transfer or flow rate of
attached particles at the top of the pulp region at steady state during the survey have the
advantage that there is no disruption to the plant. Some other methods require alteration of
the froth height after the survey and collection of data for the cell in question at each froth
height. Methods that require such disruption to the plant are also time consuming and are
much less practical.
Froth stability and therefore froth recovery (Rf) are believed to depend on factors such as
frother type and concentration and particle properties such as size, number, hydrophobicity
and shape. The role of particle hydrophobicity is of particular interest because two recent
studies have shown there is a maximum in the relationship between froth recovery and
hydrophobicity (Ata, Ahmed and Jameson, 2003; Schwarz and Grano, 2005). These findings
corroborate broadly with earlier more fundamental findings reported by Dippenaar
(1982). While increases in hydrophobicity assist the subprocesses of adhesion and stable
transportation in the pulp zone, such increases may only assist in the froth region up to an
intermediate hydrophobicity, indicated by a contact angle in the region 60 to 70 degrees.

PROCESS ANALYSIS WITH DOWN-THE-BANK FLOTATION DATA

Down-the-bank industrial flotation data can be presented and analysed in two forms:
1. cumulative metallurgical performance along the bank via cumulative grade/cumulative
recovery curves for the valuable mineral or element and one method for presenting the
associated selectivity curves for the sulfide and non-sulfide gangue minerals (see example
in Figure 10)
2. kinetic data (fraction remaining (log scale) versus nominal residence time) for the valuable
and other minerals (see examples in Figure 12).
Equivalent data can also be obtained from batch laboratory flotation tests. Alternative
graphs for kinetic data, instead of the method in item 2, eg mineral recovery versus time or
fraction remaining versus time (all with linear scales), are much less useful for interpretation
of kinetic data.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 89

 BILL JOHNSON

Cumulative Grade
of Valuables (%)
of Sulfide Gangue (%)
Cumulative Recovery
of Non-sulfide Gangue (%)
Cumulative Recovery

FIG 10 – Analysis of down-the-bank flotation data for a single rougher or cleaner bank using
the grade recovery curve for the valuables and selectivity curves for each gangue mineral.

Another example of cumulative metallurgical performance via cumulative grade/

cumulative recovery curves for the valuable mineral is given in Figure 11 for a three-stage
closed circuit cleaning system. Two types of graphs are shown. Information on the magnitude
of each circulating load of valuable mineral (and its assay relative to the stream it joins) is
incorporated in the more complete version located at the base of Figure 11.
The behaviour of each mineral may be described by Equation 3 for the laboratory batch
flotation or by Equation 4 for a series of isolated and perfectly mixed plant cells. These
equations were used to generate the points that are plotted in Figure 12:

90 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

1 2 3 4 5 6 7 8
Rougher First Cleaner First Cleaner A
Concentrate Tailing
A
B
8 7 6 5 4 3 2 1 C

Second Cleaner

D
1 2 3 4 5 6 7 8
Major Water Addition Third Cleaner
(for dilution cleaning)

Third Cleaner Concentrate

45
1 B
40 1-3
Cumulative Grade of Valuable Element (%)

1-2 1-5
35 1-4 1-7 Combined Third Cleaner Concentrate
1 1-6 1-8
30 1-3
1-2 1-5
25 1 1-4 1-6
1-7 Combined Second Cleaner Concentrate
20 1-2
1-3 1-4 1-5 1-8
15 1-6 Combined First Cleaner Concentrate
1-7
10 1-8
5
Rougher Concentrate
0
0.00 20.00 40.00 60.00 80.00 100.00 120.00
Cumulative Recovery of Valuable Element (%)

45
1
1-3
C
40
1-5
1-2
Cumulative Grade of Valuable Element (%)

1-4 1-6
35
1-7 Combined Third Cleaner Concentrate
1
1-8
30 1-3 1-4
1-2 1-5 Combined Second Cleaner Concentrate
25 1-7
1-6
1
Second Cleaner Feed (C+D)
20 1-8
1-2 1-3 1-6
1-4 1-5
15
1-7 Combined First Cleaner Concentrate (C)
1-8
10

5
First Cleaner Feed (A+B)

0 Rougher Concentrate (A)

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.00 110.00 120.00
Cumulative Recovery of Valuable Element (%)

FIG 11 – Examination of down-the-bank flotation data for three stages of closed-circuit dilution cleaning using grade recovery curves
for the valuable element using a straightforward method and a more advanced method. (A) Three-stage closed circuit cleaning system
referred to in (B) and (C). (B) Grade recovery curve of valuable element in cleaning system. (C) More complete grade recovery curves
for valuable element in cleaning system (providing additional information on magnitude and grade of circulating loads of valuables).

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 91

 BILL JOHNSON

(i) Batch flotation process (ii) Series of perfectly mixed plant cells
Time (min)
Case 1 Nominal Residence Time (min)
0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 25 30 35 40 45
1 1

Case 1 Case 1
Fraction remaining

Fraction remaining
0.1 0.1
Case 1 Case 1

0.01 0.01

Time (min)
Cases 2 and 3 Nominal Residence Time (min)
0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 25 30 35 40 45
1 1
Case 2 Case 2
Case 3 Case 3
Fraction remaining

Fraction remaining

Case 2 Case 2
0.1 0.1
Case 3 Case 3

0.01 0.01

kf (min-1) ks (min-1) km (min-1) Φs Φm Comment

Case 1 0.2 0 0 0 0 High rate constant for all valuables (one component)
Case 2 0.2 0.01 0 0.3 0 High rate constant for 70% of all valuables (two components)
Case 3 0.2 0.01 0.08 0.2 0.1 High rate constant for 70% of all valuables (three
components) and 10% with a medium rate constant

FIG 12 – Demonstration of various relationships between fraction remaining for the valuable
mineral (log scale) and (i) time (min) for a batch process and (ii) nominal residence time (min)
for a series of perfectly mixed plant cells and with various rate constant components.

Fraction Remaining = (1 - z s - z m) e -k ft + z se -kst + z me -kmt (3)

Fraction Remaining = (1 - z s - z m) 1 + zs 1 + zm 1 (4)

(1 + k f m) N (1 + ks m) N (1 + km m) N

where:
kf, ks, km = first order rate constant for high, low and medium rate constant components
(min-1)
ϕs, ϕm = fraction of component with low or medium rate constant
t = time for batch operation
λ = nominal residence time for each of the N continuous cells in series for continuous
operation
The behaviour of each mineral may be expressed in kinetic terms where the standard graph
(Figure 12) is the fraction or percentage remaining in the bank (log scale) on the y-axis and
nominal residence time (average residence time per cell multiplied by the number of cells to

92 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

that point in the bank) on the x-axis for plant data. For batch laboratory tests, the cumulative
flotation time is employed on the x-axis. Such relationships for the batch and plant cases
allow recognition of the kinetic components, which describe the behaviour of each mineral
in the bank. The number of kinetic components, the first-order rate constant of each and the
proportion of the mineral with that rate constant value can be determined. Such graphs can
be on an overall, unsized basis or they can be used for minerals or elements in size fractions.
It must be emphasised that the rate constant components can only be determined from
data with progressive values for fraction remaining and residence time. If the relationship
between mineral recovery and particle diameter (log scale) has been determined along with
the residence time at the end of a bank or a batch flotation stage, without progressive data on
reaching the overall performance for the stage, a single rate constant value can be calculated
for that mineral. The rate constant calculated by this method will represent a weighted average
of more than one rate constant component in many cases. While the single rate constant value
can be useful for some purposes, its limitations must also be recognised.
Some examples are provided in Figure 12. In the simplest case in Figure 12, the graph of
fraction remaining (log scale) versus time for a single rate constant is depicted, providing a
straight-line relationship. This case is followed by an example where the kinetic behaviour
with two, quite different values (high and low) for the rate constant is depicted. In this case,
two components existed for the mineral. It can be noted that a closely related case with two
components exists when the low rate constant is a non-recoverable component with a rate
constant of zero min-1 (this case is not illustrated in Figure 12). A third case is also depicted in
Figure 12 with three components, ie three quite different values (high, low and medium) for
the rate constant.
By comparing the batch and continuous cell examples (left and right-hand side of Figure 12,
respectively), it can be seen that a higher value for the fraction remaining (ie lower recovery)
exists at a given residence time for a given set of rate constants for the plant cells. By comparing
cases 2 and 3 and noting the apparent similarity of the fraction remaining (log scale) and
residence time relationships, it can be surmised that there may be difficulty in accepting the
existence of the third component, ie a fit deemed acceptable may still be obtained using the
equation in the form with two rate constant components.
Valuable liberated mineral with a medium rate constant will be recovered in a rougher
section with adequate installed residence time. The diminished rate constant component of
the valuables (medium or even lower rate constant) may reflect solely the deficiencies of
fine particles in the collision subprocess, or it may reflect an additional issue arising from an
imbalance in hydrophilic and hydrophobic species on the surface of the component. Such
liberated valuable mineral would be expected to report to the final concentrate on the basis
of its liberation state. However, the medium rate constant valuable mineral may have more
difficulty in being sufficiently competitive during conventional cleaning for the majority of it
to report to a high-grade final concentrate.
The design of laboratory batch rougher or cleaner tests with collection of a series of
concentrates also allows collection of traditional cumulative concentrate grade/cumulative
concentrate recovery curves and kinetic data as just described for a bank in a plant. The
usefulness of such data depends on the times selected for collection of each concentrate in a
laboratory batch test.
For both laboratory and plant processes, it is advisable to have many data points at the
commencement of a stage to allow checking for anomalous behaviour because the process was

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 93

 BILL JOHNSON

galena 50
grade % galena grade /recovery

40
4

30
10
10
mnulative flotation times ��
20

10

galena recovery %

□---
sphalerifl! 80
recovery¾
60
sp"11erite selectivity
/
/;if
40
0/
20 /

galena recovery %

iron iron sulfide selectivi ty

sulfide
recovery%3
20
10
galena recovery %
non
sulfide 30 non sulfide gangue selectivity
gangue
recovery%20
10
galena recovery %
10 20 30 40 SO 60 70 80 90 100
0 Zinc Sulfate 0.0 kg/t, pH 8.5 o Zinc Sulfate 2.0 kg/t, pH 8.5
FIG 13 – Example of comparison of results of laboratory batch tests using the grade recovery curve
for galena and selectivity curves for the unwanted minerals (sphalerite, iron sulfide and non-sulfide gangue)*.
*Reprinted from Minerals Engineering, Vol 1, Edition 2, S R Grano, J Ralston and N W Johnson, Characterization and treatment of heavy
medium slimes in the Mount Isa Mines lead-zinc concentrator, pp 137–150, Copyright (1988), with permission from Elsevier.

allowed to commence before the feed was fully prepared. It is also often useful to survey the
last cell individually to obtain directly the concentrate grade for the final cell. For a laboratory
batch test, a separate concentrate for a short time at the end of the test is the equivalent.
Experience with surveying improves a metallurgist’s judgement on the appropriate level of
detail in down-the-bank data collection.
Down-the-bank data can be collected for a series of bank surveys or laboratory tests with
changed conditions for each test. An example is given in Figure 13 (Grano, Ralston and

94 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

Johnson, 1988), which applies the graphing method in Figure 10. The following points can be
made in establishing the changes that occurred in the performance of each mineral for each
survey or laboratory test:
•• A graph of cumulative grade/cumulative recovery for the valuable element or mineral
provides a summary of the performance of the bank and indicates the trade-off between
grade and recovery in each portion of the bank. The graph does not allow analysis of
changes in the behaviour of the unwanted minerals when a series of tests is being compared.
•• A convenient method for analysis of changes in behaviour of the unwanted minerals
is the use of selectivity curves. There is more than one method for plotting selectivity
curves. A common feature of all methods is that the recovery of each unwanted mineral
(or an equivalent measure) is plotted against the recovery of the valuable mineral in a
series of graphs.
•• From the use of selectivity curves of the type illustrated in Figures 10 and 13, changes in
behaviour of the other minerals relative to the valuable mineral can be easily recognised.
These changes in conjunction with changes in the flotation rate constant of the valuable
mineral itself can be used to understand the origins of changes in position of a series of
grade-recovery curves for the valuable mineral.
•• The selectivity curves shown in Figure 13 are legitimate for convenient comparison of the
recovery of each gangue mineral at a given recovery for the valuable mineral, the primary
purpose of the described analysis. (However, for considering a single test in isolation, this
type of selectivity curve is not legitimate for evaluating changes in selectivity between the
valuable mineral and gangue mineral under examination from the commencement to the
end of the test. For this purpose on a single test, the logarithm of the recovery value for
both the valuable mineral and the gangue mineral in question must be plotted. A straight-
line relationship indicates no change in selectivity along the bank or during the batch test.)
The set of curves in Figure 13 shows that the selectivity of sphalerite relative to galena was
improved clearly with the use of zinc sulfate. The reagent also caused a slight decrease in
selectivity of iron sulfide and non-sulfide gangue relative to the galena. From Figure 13 alone,
no discussion is possible on changes in selectivity between the galena and each unwanted
mineral during each test.

USE OF SUMMARY GRAPHS WITH LIMITS IMPOSED BY LIBERATION

The sections in this chapter have described analysis methods for the separation that has
taken place in a laboratory batch process, a pilot plant or a full-scale plant. Strengths and
weaknesses of the separation can be recognised and targets for process improvement can
be identified. In addition, a different perspective on the obtained separation can be reached
by comparing the observed performance with the best achievable performance based on
the level of liberation of the valuable mineral(s) in the relevant feed. Only those particles
containing some valuable mineral are considered and, in effect, a queue is produced in
which the liberated particles form the start of the queue, and composite particles containing
the valuable mineral follow and are ranked in terms of decreasing quality of the composite
particles. This approach is shown schematically in Box 5 for a size fraction. The theoretical
performance curve assumes that no liberated gangue minerals reach the concentrate and
that gangue mineral can only reach the concentrate in composite particles with the valuable
mineral, that is, the imperfect liberation of the valuable mineral in the feed is accepted and
a perfect mineral separation is assumed. The theoretical performance curve in Box 5 is
expressed as a grade-recovery curve for the valuable mineral in the process and is obtained

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 95

 BILL JOHNSON

by summing the liberation information from all size fractions in the feed. Some laboratories
use the measured two-dimensional liberation data to construct the theoretical grade recovery
curve; other laboratories use three-dimensional liberation data from conversion of the two-
dimensional liberation data. Comparisons of the observed and theoretical performance for
each size fraction can also be obtained.
The physical meaning of key points on the theoretical grade recovery curve is provided in
Box 5.
For the feed information, liberation data for a new orebody or deposit, or the feed to a plant
or a bank in a plant could be used. In some cases, the liberation data for a recalculated feed

Consider the listed particles as separator feed (note: darkened mineral is the valuable mineral – V):
Liberated (group 1–40% of V) High quality composites (group 2–30% of V)

Medium quality composites (group 3–20% of V) Low quality composites (group 4–10% of V)

Particles containing no valuable mineral (group 5)

Construction using additional liberation information:

• Point B – % of valuable mineral that is liberated in group 1 (40%) and its grade
• Point C – % of valuable mineral in groups 1+2 (70%) and its cumulative grade
• Point D – % of valuable mineral in groups 1+2+3 (90%) and its cumulative grade
• Point E – % of valuable mineral in groups 1+2+3+4 (100%) and its cumulative grade.
Step 1 Step 2

100 MAXIMUM 100 MAXIMUM

POSSIBLE POSSIBLE
mineral/element in concentrate (%)
CUMULATIVE GRADE of valuable

B C B C
CUMULATIVE GRADE of valuable

90
CONCENTRATE 90
CONCENTRATE
D GRADE (100%) D GRADE (100%)
mineral in concentrate (%)

80 80

70 70
THEORETICAL GRADE-RECOVERY
60
E 60
CURVE FOR VALUABLE MINERAL E
50
THEORETICAL GRADE-RECOVERY 50

40 CURVE FOR VALUABLE MINERAL 40

30 30

20 20
THEORETICAL GRADE-RECOVERY
A FEED GRADE OF CURVE FOR VALUABLE ELEMENT A FEED GRADE OF
10 VALUABLE 10 VALUABLE
MINERAL (10%) 0
MINERAL (10%)
0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

CUMULATIVE RECOVERY of valuable mineral in concentrate (%) CUMULATIVE RECOVERY of valuable mineral/element in
concentrate (%)

group 1 group 1
group 1+2 group 1+2
group 1+2+3 group 1+2+3
group 1+2+3+4 group 1+2+3+4

BOX 5 – Illustration of the concepts in construction of a theoretical grade recovery curve for separation of a valuable mineral
(dark phase) based on the group of particles in a size fraction of the feed to the separation (step 1). The theoretical grade recovery
curve for the valuable element in the valuable mineral is included (step 2) based on the stoichiometry of the valuable mineral.

96 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

must be used to calculate the relevant theoretical performance curve. This situation would
arise for a number of reasons:
•• for a bank, liberation data on the concentrate(s) and tailing only were obtained for a bank,
possibly to reduce costs
•• for a total plant or section of a plant, grinding or regrinding existed within the section
and hence a ‘feed’ sample would not represent the total achieved liberation, unlike the
summed concentrate(s) and tailing (ie the recalculated feed), which would represent the
total achieved liberation
•• for a laboratory batch separation, only the concentrate(s) and tailing exist for that particular
sample tested.
As a further step, bands can be indicated between the actual and theoretical performance
curves to indicate the various sources of inefficiency from unwanted minerals. Examples are
the contribution of each liberated sulfide gangue mineral, each liberated non-sulfide gangue
mineral and composite particles containing no valuable mineral (all mentioned categories
contain no valuable mineral and were not included in construction of the theoretical grade
recovery curve) to creation of the difference in position for both the actual and theoretical
performance curves. The non-recovery of liberated valuable mineral can be another
contributor, by ‘pushing’ the observed grade recovery curve to the left.

GENERAL OUTCOMES OF THE ANALYSIS – MAGNITUDES OF SIGNIFICANT

PROCESS WEAKNESSES AND SOLUTIONS TO THE WEAKNESSES
The type of process analysis sequence described in the preceding sections provides
information on the magnitude of weaknesses in the process in the fine, intermediate and
coarse size fractions. An example of a weakness is a community of particles, typically in either
the fine, intermediate or coarse fractions, which has reported to the wrong product and which
has a similar liberation state, eg fine liberated valuable mineral reporting to the final tailing.
Such information cannot be obtained from non-sized data.
In general terms, the weaknesses in a process exist in one or more of the following categories:
•• valuable mineral reporting to the wrong product (tailing or incorrect concentrate)
•• gangue mineral(s) diluting a concentrate.
Examples of weaknesses are losses of valuable mineral to the tailing in low quality
composites, due to insufficient liberation of the ore in the grinding and regrinding stages,
or recovery of a liberated sulfide gangue mineral in a concentrate due to its accidental
activation (a process chemistry issue that may require the use of surface analysis for full
diagnosis). The misreporting of liberated valuable mineral to the wrong concentrate or the
tailing is another example.
Further, the magnitude of the significant weaknesses can be determined from such data,
leading to a ranking of the importance of the weaknesses.
From the diagnoses of the mechanisms causing the weaknesses, solutions to the weaknesses
can be developed. Test work is usually required at this stage. From a combination of the
magnitude of the weaknesses, the capital and/or operating cost of the corrective action in the
plant, along with the probability of success of the solution, the most prospective corrective
actions can be selected and implemented in the plant.
Ongoing collection of further sized/liberation data can be used to monitor the change in
process performance resulting from implementation of process improvements.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 97

 BILL JOHNSON

ACKNOWLEDGEMENT
The important contribution of Suzanne Munro (Mineralurgy Pty Ltd/Mineralis) in
preparation of diagrams and of other aspects for the content in this chapter is acknowledged
with gratitude.

REFERENCES
Ata, S, Ahmed, N and Jameson, G, 2003. A study of bubble coalescence in flotation froths, Int J Miner
Process, 72:255–266.
Croxford, N J W, Draper, N and Harraway, D H, 1961. Some aspects of the carbonaceous fraction of
Mount Isa lead concentrate, The AusIMM Proceedings, 197:149–161.
Dippenaar, A, 1982. The destabilization of froth by solids, 1. The mechanism of film rupture, Int J Miner
Process, 9:1–14.
Grano, S R, Ralston, J and Johnson, N W, 1988. Characterization and treatment of heavy medium
slimes in the Mount Isa Mines lead-zinc concentrator, Minerals Engineering, 1(2):137–150.
Johnson, N W, 1972. The flotation behaviour of some chalcopyrite ores, PhD thesis, The University of
Queensland.
Johnson, N W, 1987. Application of kinetics and liberation data to analysis of an industrial flotation
process, CIM Bulletin, 80(899):113–117.
Johnson, N W, 2005. A review of the entrainment mechanism and its modelling in industrial flotation
processes, in Proceedings Centenary of Flotation Symposium, pp 487–496 (The Australasian Institute of
Mining and Metallurgy: Melbourne).
Johnson, N W, 2006. Liberated 0 - 10 µm particles from sulphide ores, their production and separation
– recent developments and future needs, Minerals Engineering, 19:666–674.
Johnson, N W and Jowett, A, 1982. Comparison of lead primary rougher behaviour of several Mount
Isa lead zinc ores, in Proceedings Mill Operators’ Conference, pp 271–285 (The Australasian Institute of
Mining and Metallurgy: Melbourne).
Jones, M P, 1987. Applied Mineralogy – A Quantitative Approach (Graham and Trotman: London).
Lynch, A J, Johnson, N W, Manlapig, E V and Thorne, C G, 1981. Mineral and Coal Flotation Circuits –
Their Simulation and Control (Elsevier: Amsterdam).
Pyke, B, Fornasiero, D and Ralston, J, 2003. Bubble particle heterocoagulation under turbulent
conditions, J Colloid and Interfacial Science, 265:141–151.
Restarick, C J, 1976. Pulp sampling techniques for steady state assessment of mineral concentrators, in
Proceedings Sampling Symposium, pp 161–168 (The Australasian Institute of Mining and Metallurgy:
Melbourne).
Rumball, J A and Richmond, G D, 1996. Measurement of oxidation in a base metal flotation circuit by
selective leaching with EDTA, Int J Miner Process, 48:1–20.
Schwarz, S and Grano, S, 2005. Effect of particle hydrophobicity on particle and water transport across
a flotation froth, Colloids and Surfaces, A: Physiochem Eng Aspects, 256:157–164.
Seaman, D, 2006. Selective transport of attached particles across the froth phase, PhD thesis, The
University of Queensland.
Vianna, S M, 2004. The effect of particle size, collector coverage and liberation on the floatability of
galena particles in an ore, PhD thesis, The University of Queensland.
Young, M F, Pease, J D, Johnson, N W and Munro, P D, 1997. Developments in milling practice at the
lead/zinc concentrator of Mount Isa Mines Limited from 1990, in Proceedings Sixth Mill Operators’
Conference, pp 3–12 (The Australasian Institute of Mining and Metallurgy: Melbourne).

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

Appendix – Two aspects of sampling

CALCULATION OF MINIMUM SAMPLE MASS
The purpose of this portion of the appendix is to describe a means for calculation of a
minimum mass of sample required from a much larger population to allow a specified,
acceptable statistical error for the properties of the sample relative to the properties of the
population. Errors are introduced at all steps in the chain of events associated with obtaining
the sample, starting with its initial sampling from the process stream, its later handling/
size reduction/subsampling and the following chemical or other analysis of the subsample.
Various types of error can be recognised at each of the steps.
To assist this discussion, the concepts of a correct sample and a representative sample will
now be described. François-Bongarçon and Gy (2002a) recently discussed sample correctness:
A sample is said to be ‘correct’ when any fragment in the lot to be sampled has the same
probability of being selected in the sample as any other one.
For a sample to be representative (François-Bongarçon and Gy, 2002a), it must satisfy the
preceding statement of correctness (to ensure no bias exists in the sample) and, additionally,
it must have an acceptably small variance (to ensure the sample is sufficiently reproducible).
One type of error (fundamental sampling error) connected with the heterogeneity of the
particles in the population being sampled is now described because of its importance in
calculation of the minimum mass of sample required. François-Bongarçon and Gy (2002a)
described the heterogeneity of the particles (the shape, density and liberation state of each
particle being examples) in the population as the ‘natural, constitutive heterogeneity’ of the
population of particles.
To calculate the minimum mass ms for a sample from a flowing stream with steady properties
at a specified fundamental sampling relative variance s2FSE, the following equation developed
by Gy (1982) must be used:
ms = Cd3a2/s2FSE
where:
C = the sampling constant of the material being sampled for a particular particle size and
component of interest (depends on all the relevant properties of the set of particles
submitted to sampling)
d = nominal top size of the material (cm)
a = fractional concentration of the material of interest
For a specified fundamental variance, it can be observed that particle size has a dominating
effect on the required minimum sample size, while the properties of the set of particles
(expressed via the sampling constant C) and the fractional concentration of the mineral of
interest (a) play a role. The sampling constant C is given by:
C = clfg
where:
c = mineralogical composition factor (defined in a following equation)
l = liberation factor (d1/d)b where d1 is the nominal top size at which complete liberation
occurs and parameter b is determined for the system by experiment (François-
Bongarçon and Gy, 2002b)

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 99

 BILL JOHNSON

f = particle shape factor (often taken as 0.5)

g = size range factor (0.25 to 1.0 as shown in Table A1)
The size range factor g can be estimated from the ratio of the nominal top size d to the
lower size limit d’ (size corresponding to approximately five per cent undersize) as listed in
Table A1.
The mineralogical composition factor c is calculated from:
c = (1-a)[(1-a)ρ1 + a ρ2]/a
where:
ρ1 = density of the particles of the mineral of interest (g/ml)
ρ2 = density of the other mineral(s) (g/ml)
The liberation factor (l), which contributes to the sampling constant C, was defined earlier
as (d1/d)b. The ratio d1/d is 1.0 (its maximum value) when the mineral of interest is fully
liberated and d becomes equal to d1. The liberation value (l) remains equal to 1.0 irrespective
of the value for parameter b when the mineral of interest is fully liberated. It can be noted
that a larger sample mass is required to ensure a specified s2FSE when the population is fully
liberated, due to its increased heterogeneity.
The setting of d1/d to 1.0 when the value for d1 is not known for the mineral of interest is a
convenient conservative assumption under some circumstances. The calculated sample mass
becomes larger than the true value and may be quite misleading for coarse and, in reality,
poorly liberated solid (d>>d1) which is being sampled.
Consider a chalcopyrite ore that has the following properties (fully liberated (l = 1) with a top
size of 200 µm and containing two per cent chalcopyrite (a = 0.02)). The following calculations
can be performed using the previously described method (Gy, 1982), where the density of the
chalcopyrite is 4.2 g/ml and the density of the combined gangue is 2.6 g/ml, and assuming the
fundamental error for chalcopyrite does not exceed 0.06 per cent chalcopyrite (sFSE = 0.0006).
c = (1-a)[(1-a) ρ1 + a ρ2]/a
= (1 - 0.02)[(1 - 0.02) × 4.2 + 0.02 × 2.6]/0.02
= 204.2
C = clfg
= 204.2 × 1 × 0.5 × 0.25
= 25.5
ms = Cd3a2/s2FSE
= 25.5 × (0.02)3 × (0.02)2/(0.0006)2
= 0.23 g

TABLE A1
Guidance for selection of size range factor (g).
Description of size range Value for d/d' Resulting value for g
Broad >4 0.25
Medium breadth 2 to 4 0.50
Narrow <2 0.75
Uniform 1 1.00

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

The calculation can be repeated for coarser streams with the same particle properties. For
streams with top sizes (d) of 0.2, 2.0 and 20 cm associated with grinding and crushing circuits,
the calculated values for ms increase to 23 g, 2269 g and 226 889 g respectively (assuming d1
is 0.02 cm and letting parameter b equal 1.0). For the coarser solid in grinding circuits and
particularly in crushing circuits, care is therefore required such that sufficient sample mass
is obtained to ensure a given fundamental error is not exceeded. For each stream in crushing
and grinding circuits, the appropriate calculations for the sample size must be performed
using the real properties of the particles in the population being sampled.
To comply with sample correctness as discussed earlier, one aspect is that the width of the
parallel opening of the sampler must be commensurate with the top size of the particles in
the stream. Large particles must not have a lower probability than smaller particles entering
the sample because of interference with their motion. Standards exist for the key dimensions
of the samplers in such cases. Further, the samplers must be emptied in a way that ensures all
particles irrespective of their size or density are removed from the sampling device or system
and continue to be part of the sample.
The equation for ms can be expressed with the fundamental error as the unknown. Holmes
(1992) noted that:
… a fundamental characteristic of s2FSE is that it diminishes very quickly when d is reduced
and not so quickly when ms is increased. However, it can never be eliminated no matter what
crushing and homogenisation procedures are used, although for fine flotation concentrates it is
negligible when the sample mass exceeds about 100 g.
In collection of samples from a flotation circuit with several rounds of sampling and using
conventional types of samplers, the resulting sample mass is usually unavoidably in the
region of 500 g (or larger). Hence, as dictated by the use of conventional sampling devices in a
flotation circuit, the sample mass tends to be in a region where the value for the fundamental
error is at acceptable low values.
To obtain an assay for a sample or a size fraction, a very small mass (typically 0.25 g to 1 g)
has to be sampled from a much larger mass of dry solid in the laboratory. The fundamental
error for this step can also be calculated using the equation from Gy (1982) as described earlier.
If the fundamental error is unacceptably high, the sample or size fraction can be pulverised to
lower the top size, and greatly lower the mass of sample providing an acceptable fundamental
error. Of course, if a property that is affected by size reduction (eg liberation state) is to be
measured, this approach cannot be taken.
For a particular operation, it is clearly more effective to obtain a plant feed sample from the
flotation circuit feed, rather than the coarser grinding circuit feed or the even coarser crushing
circuit feed. For a given sampling error, the minimum mass of the required sample is much
smaller for the flotation circuit feed and cost savings result from handling of the smaller
sample, aside from the convenience. In collecting a sample, a large number of frequent
correctly executed sampling events with collection of the same small sample weight in each
sampling event is superior to a small number of infrequent correctly executed sampling
events, which produces the same final sample weight.
Some additional sources of information on sampling principles can be accessed (Weiss,
1985; Birnbaum, 1992).

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 BILL JOHNSON

LIP SAMPLING
The remainder of the appendix describes the lip sampling procedure, which provides various
types of data:
1. a reliable sizing and assay of the solid being recovered at the lip
2. a reliable value for the per cent solid of the pulp being recovered at the lip
3. an estimate of the solid flow rate passing over the lip.
To satisfy requirements 1 and 2, the sampler should be moved at right angles to the lip
across the full width of the cell lip at constant speed to intercept the discharging froth. The
speed should be selected to ensure that overflowing of the sampler is not possible and to
ensure that uninhibited entry of the discharging froth into the sampler is possible during
the sampling. Such lip samplers have typically the following dimensions: width 9 cm, height
30 cm and length 20 cm. The method was described by Restarick (1976).
To satisfy requirement 3, the time for which the sampler was intercepting the stream has to
be recorded. Therefore, the lip sampling procedure is performed using a crew of two people
with one recording the sampling times. The following points can be noted:
•• The requirements for the starting and finishing points in the movement of the lip sampler
are illustrated in Figure A1. These starting and finishing points arise because of the
requirement for determination of the solid flow rate per unit width of the sampler as
expressed in Equation A1:
Total weight (g) 3600 Lip width (mm)
TPH Solid = # # (A1)
Total time (sec) 106 Cutter width (mm)
That is, the full width of the sampler must be collecting sample during all the timing
period. (This requirement differs subtly from the correct sampling motion of starting and
finishing the sampler’s motion outside the flowing concentrate.)
•• The time taken for the sampler to intercept the concentrate stream has to be approximately
the same for each traverse to obtain reliable estimates of the solid flow rate.
•• For a group of cells being sampled together, the time taken for the sampler to intercept the
concentrate stream for each cell also has to be approximately the same for each traverse

Lip Width

Cell

Cell Discharge Lip

Starting Finishing
Position Position

Cutter Width
FIG A1 – Illustration of the lip sampling technique as described in the appendix for one cell. The lip
sampler is positioned under the lip from which concentrate is discharging in this plan view.

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 CHAPTER 2 | EXISTING METHODS FOR PROCESS ANALYSIS

of each cell. Initially, all the cells in the grouping have to be considered in selection of the
required time for the group of cells.
For obtaining the solid flow rate, the details of the correct lip sampling procedure for a
single cell are illustrated in Figure A1, and Equation A1 for conversion of the measurements
of the total mass of collected solid and the total sampling time (for all traverses on the various
rounds of sampling) was provided earlier. The total mass of collected solid divided by
the total sampling time is effectively the observed flow rate of solid per unit width of the
sampler. Movement of the sampler across the cell width at fixed velocity allows this value
to be averaged across the entire concentrate flow. In Equation A1, the ratio lip width/cutter
width then allows scaling up of the observed flow rate of solid per unit width of the sampler
to the full width of the cell lip.
To this point, all the discussion of lip sampling to obtain the solid flow rate has been based
on movement of the lip sampler across the cell lip at right-angles at fixed speed as indicated
in Figure A1. This movement of the sampler addresses any variations in concentrate assay
and flow rate across the full width of the lip. For a cell in good mechanical condition, such
variations are usually minimal.
However, given the large size and shape of some cells, the existence of floor grating over
the top of the cells, the design and maintenance of the cell lips or the existence of water pipes/
sprays or other obstacles in the launder, it is not possible to move the lip sampler across the
entire lip width or a portion of the lip. In this situation, an estimate of the observed flow rate
of solid per unit width of the sampler can be obtained by placing the sampler in one or more
fixed positions where a portion of the cell lip is accessible. The observed value can then be
scaled up to the full length of the cell lip.
Large tank cells can be one example of the described situation for several reasons:
•• the existence of relatively inaccessible external and internal launders and sometimes cross
launders
•• the existence of floor grating over the top of cells with possibly some small trapdoors for
access.
For sampling a single cell, the discharge of concentrate into the various types of launders
may have to be treated as separate but parallel sampling steps for that cell. It is also worth
noting that, depending on the overall sampling scheme, the objective from sampling a single
unit cell may be a sample of the combined concentrate for analysis without the need for an
estimate of the solid flow rate. While such an objective appears less onerous, timing of the
concentrate collection with the sampler in various fixed positions may still be required.
For example, taking a cell with one internal launder and one external launder, if the
concentrate discharging to the internal launder happened to be at a higher flow rate per unit
length of the lip than for the external launder, its assay may differ from the concentrate at an
external launder for the same cell. To obtain the assay of the combined concentrate for the
entire cell, two approaches could be taken:
1. The same lip sampling time for the concentrate discharging into the internal and external
launders could be used as the basis for a concentrate sample representing the entire
concentrate.
2. The assays for the solid at the internal and external launders along with the flow rate
estimate of each could be used to calculate the assay for the combined concentrate.
(Clearly, it is preferable that the plant designer provides a sampling point to enable

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 103

 BILL JOHNSON

sampling of the entire concentrate from all launders at a single point, to obtain the
overall assay of the stream.)
It can be noted that timing and recording of the lip sampling times would assist in correct
execution of approach 1 even though obtaining a value for the lip tonnage is not the objective.
Further, timing and recording of the lip sampling times at the internal and external launders
is an integral part of execution of approach 2.

REFERENCES
Birnbaum, P M, 1992. An evaluation of sampling errors in a mineral concentrator, in Proceedings Sampling
Practices in the Mineral Industry, pp 49–58 (The Australasian Institute of Mining and Metallurgy:
Melbourne).
François-Bongarçon, D and Gy, P, 2002a. Critical aspects of sampling in mills and plants: a guide to
understanding sampling audits, J S Afr Inst Min Metal, Nov/Dec, pp 481–484.
François-Bongarçon, D and Gy, P, 2002b. The most common error in applying ‘Gy’s Formula’ in the
theory of mineral sampling, and the history of the liberation factor, J S Afr Inst Min Metal, Nov/Dec,
pp 475–479.
Gy, P M, 1982. Sampling of Particulate Materials – Theory and Practice, second edition (Elsevier: Amsterdam).
Holmes, R J, 1992. Sampling of mineral process streams, in Proceedings Sampling Practices in the Mineral
Industry, pp 33-37 (The Australasian Institute of Mining and Metallurgy: Melbourne).
Restarick, C J, 1976. Pulp sampling techniques for steady state assessment of mineral concentrators, in
Proceedings Sampling Symposium, pp 161–168 (The Australasian Institute of Mining and Metallurgy:
Melbourne).
Weiss, N L, 1985. SME Mineral Processing Handbook (Society of Mining Engineers, American Institute of
Mining, Metallurgical, and Petroleum Engineers: New York).

104 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 Return to contents

CHAPTER 3
Mass balancing flotation data
Rob Morrison

ABSTRACT
A flotation circuit survey will typically produce a substantial volume of data – usually as
metal assays and flow rates.
In general, these measured data will not be consistent around any separation unit or junction
within the circuit. A fair assessment of circuit performance requires a set of numerically
consistent data. Otherwise key performance indicators (KPIs), such as recovery in each
section, will depend on which measured values are chosen as the basis of the calculation.
Generating a set of self-consistent data provides a basis for a single set of KPIs. The set of
self-consistent data should in some way be a ‘best estimate’ of the state of the circuit during
the survey.
This chapter discusses strategies for selection of flow measurement and sampling points.
Various ways of estimating measurement accuracy are considered. Lastly, some calculation
methods are described. These are supported by some simple examples.

INTRODUCTION
The basis of mass balancing is that all measurements are subject to statistical variation. If we
could make each measurement (sample, assay or flow rate) many times, the results would
have a spread of values. In practice, we can typically only afford to take a few replicate
samples at each measurement point. If we have some knowledge of the degree of variation
expected in each measurement, we can analyse all the data together to try to find a best
estimate of the mass balance. Data that is self-consistent with this mass balance can be used
to assess and compare performance and as the basis of mathematical models of the process.
The mass balancing process can also incorporate redundant data to produce not only mass
split factors but a further estimate of how well that mass split is defined. The ‘traditional’
approach, using a two-product formula based on a single assay, will also produce an estimate
of the mass split. However, it provides no estimate of the accuracy of that mass split and
therefore provides at best a poor basis for decision-making.

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 ROB MORRISON

Note that these techniques are not at all new. The first general purpose system is due to
Wiegel (1972) who developed the original MATBAL code. This chapter focuses on how to
attack the simpler cases using spreadsheet technology.
The other key factor is that the flow sheet being balanced must be operating in reasonable
‘balance’ during the measurement period; that is, operating at as close as possible to steady
state for both flow rates and separation processes. Otherwise, the fundamental assumption
that ‘what goes in is equal to what goes out’ is not justified.

Objectives
We wish to produce sets of self-consistent data to suit a range of measurement strategies to
characterise the performance of a flotation circuit or a part of it and to generate estimates of
the self-consistency of the data and of the accuracy of the flow rate measurements.
For the general case we can express these objectives in mathematical terms as three types
of data:
1. xi is a measurement of some sort – assay, flow rate, size fraction, liberated mineral fraction,
etc. These values are generally not self-consistent.
2. x*i is the true (unknown) value of the measured quantity. We can estimate this value at
various levels of accuracy but can never know it exactly. These values are self-consistent.
V i is an adjusted value of xi that satisfies all constraints, that is, is self-consistent and is in
3. x
some way a best estimate of the true value.
Hence, we can define an adjustment Δi of each measurement as:
Δi = (xi - xU i)

The simplest way to find a ‘best’ set of adjusted data is to find a strategy that minimises the
sum of squares (SSQ) of the adjustments. However, this strategy does not take any account
of how well (or badly) a measurement may be defined. The estimated or measured standard
deviation of each measurement σi provides us with an estimate of how well each piece of
data is defined. Hence, a better criterion for minimisation is a sum of squares where each
adjustment is divided (or weighted) by our estimate of the standard deviation of its associated
measurement.
SSQ = ∑ (Δi)

The weighted sum of squares (WSSQ) is the sum of squares of the adjustments where
‘weighted’ means that the adjustment is scaled in terms of the expected variation of that data.

Di 2
WSSQ = / f p
i
vi

It is also necessary that the adjusted values satisfy all flow sheet and summation constraints.
That is, what goes in is equal to what comes out and the various kinds of assays and subassays
add up to one or to the assay in the next level of measurements.

ACCURACY CONSIDERATIONS
We can estimate the standard deviation (‘sd’ or error for short) σi from experience or from
repeated sampling and assaying or repeated measurements against a known standard.
In practice this means taking five to ten replicate samples at several key points within a circuit

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

and subjecting all of them to the same sample preparation and assaying process that you
intend to use in the actual test work. The formula for sampling variance or standard error
then provides an estimate of standard deviation at each measurement point:

v 2x = / _x - x i / (n - 1)
i
2

x= / x / n – the mean of the n measurements.

i
i

Strictly speaking, the standard deviation refers to the complete distribution (which we can
never measure completely) while the standard error is the same property (the square root of
the variance) of the sampling distribution (which we can measure). However, the two terms
are often used interchangeably.
There are some suggestions in the examples for sd estimation based on experience, but it is
usually worth doing some repeatability testing to obtain actual estimates.
In general, this does not mean doing a full sampling tree (AS 2884.4-1997 Heavy mineral
sand concentrates – sampling moving streams) to split the errors into their components.
If you cannot reduce process and assaying variability to less than a few per cent (relative),
there is very little point in carrying out detailed test work as the results will mean very little.
If in general the measurement variations are small, then the required adjustments will also
be small and be drawn from the same population of differences. Therefore, we expect the
average value of (xi - xU i) / σi to be about equal to one and, as a consequence, the WSSQ to be
roughly similar to the number of measurements. However, each time we apply a flow sheet
or a summation constraint, we lose one degree of freedom. This reduces the expected value of
the WSSQ by one. Hence, we now have a quite general way of looking at data quality. If the
WSSQ is of the same order as the number of measurements, our data is likely to be suitable
for further analysis.
A note of caution: if you have taken multiple data sets, a few of these may balance well
by pure chance and still be nonsense. Balances that are self-consistent by chance are rarely
sensible in terms of other criteria such as the size by recovery response.
The WSSQ can also be used to provide an estimate of the standard deviation of each calculated
result xU i. If a small change in xi (or of a flow rate estimate) causes a large change in the sum of
squares, then xU i is well defined. If it causes no change, then it is not defined at all. This property
is particularly useful for checking whether calculated flow rates are well defined.
The formal name for this rule is the ‘propagation of variance’. An alternative approach is
to apply some artificial (random) variation to each measured value and solve the problem
many times. This is called a Monte Carlo method. The variation in results provides an
estimate of the variation that might be expected from a single experiment and analysis if
repeated many times.
This overall approach is usually called the ‘minimisation of weighted squared errors’ or,
simply, ‘least squares’. If for some reason the measured values are drawn from a highly
asymmetric probability distribution, outlying values may cause biases in the calculations.
An alternative approach to finding xU i is to use what are called ‘maximum likelihood methods’.
For measurement and analysis of flotation data, the probability distributions are sufficiently
symmetrical for least squares methods to be quite adequate.

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 ROB MORRISON

THE SIMPLEST CASE

The simplest case is also the most common and warrants quite extensive consideration.
Consider a single separator (or node) that has a feed stream of flow rate A, a product
stream of flow rate B and a reject stream of flow rate C (Figure 1). This single node case might
represent a complete flotation circuit or a single flotation cell. Each stream is sampled and
measured for n assays where i is an index for each type of assay. For stream A we have assays
a1, a2 .. …an. For stream B we have assays b1, b2.. …bn and so on. Note that these assays may
be any self-consistent, additive property – size or specific gravity fractions can also be used.
Per cent solids is not suitable as an assay but can be used if converted to per cent water. This
is because per cent solids is based on the total stream flow of ore and water while the other
assays are percentages of the solid phase only.
We also have some knowledge of (by repeated measurements or experience) the standard
deviations for flow rates (σA, σB, σC) and assays σa1, σb1, σc1 and so on. We could tackle the
problem directly but there are advantages in considering flow splits first and then looking at
assay data adjustment.
For the ‘true’ data (designated by a *):

A* = B*+ C* and A * ai* = B * bi* + C * ci* for all of i.

where:
A, B and C are the total solids flow rate in each stream
ai, bi and ci refer to a series of assays in each of those streams
For the simplest possible solution we would like to solve for a single variable and the best
way to do this is to consider the flow split as the ratio of B/A flowing into product stream B,
which we will call ‘beta’ or β.

B* = b * A* and C * = (1 - b *) A*

b * = ai* - b * bi* - (1 - b) * ci*

b * = _ai* - ci*i / _bi* - ci*i

This equation for β* offers the useful insight that, even with perfect data, this method is not
going to work for splitters where we can expect: ai = bi = ci to within measurement variation.
For this case β* is undefined as zero/zero, which is not zero but undefined. Beware of flow
split estimates that are only based on experimental noise. If the flow split is defined to any
reasonable degree, then the splitter is functioning as some kind of separator, which is not
usually desirable. This general approach also works for measured data and provides a useful
way to do an initial evaluation of a set of data.

A B

C
FIG 1 – The simplest case is a single node that represents any process with one input and two outputs.

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

We can set up the preliminary balance around our separator in MS Excel following the
general structure shown in Table 1. A spreadsheet containing some real data from a section of
a flotation circuit is shown in Table 2.
From the measured flow rate of copper cleaner concentrate, the mass split to concentrate
(beta) should be about one per cent. Note that 890 kg/h is not too difficult to measure as the
flow is only about 15 kg/min.
The estimates of mass split due to the change in each assay vary from 30 per cent to
-66.7 per cent, but perfect data should generate identical values that would be the same as the
perfect mass split.
The calculated mass split based on the copper assays is almost exactly one per cent. The
split based on the silver assay is 1.5 per cent. In each of these cases, the process strongly
concentrates the mineral containing that element.
Our estimate of beta is the ratio of two differences. If these differences are small compared
with the accuracy of measurement, then the ratio will be poorly defined – as it is here.

TABLE 1
Example of a preliminary balance set up around the separator in MS Excel.
Feed Product Reject (ai - ci) (bi - ci) Beta
assay assay assay (ai - ci)/(bi -ci)
A B C
Flows
Assayi
Assay 1 ' ' '
Assay 2 ' ' '
Assay 3 ' ' '
…
Assay n

TABLE 2
Spreadsheet containing some real data from a section of a flotation circuit.
Stream Float feed Cu clnr conc Cu rghr tail
(A) (B) (C)
Measured t/h 87.90 0.89
Relative flow 1 Beta (1-Beta) Beta for
each assay
ai bi ci (ai - ci) (bi - ci) (ai - ci)/(bi - ci)
Measured Pb (%) 4.02 4.07 4.04 -0.02 0.03 -0.667
Measured Zn (%) 15.80 7.80 15.50 0.30 -7.70 -0.039
Measured Cu (%) 0.43 22.40 0.20 0.23 22.20 0.010
Measured Fe (%) 14.30 16.10 13.50 0.80 2.60 0.308
Measured Au (g/t) 1.05 47.50 0.94 0.11 46.56 0.002
Measured Ag (g/t) 142 3023 97 45.00 2926.00 0.015

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 ROB MORRISON

If the differences are large compared with the accuracy of sampling and assay, then the ratio
should be well defined. This is almost certainly not the case for the lead assays, where both
concentrate and tailing assays exceed the feed value.
It is also clear that zinc is being rejected from the concentrate and that the zinc grade of the
tailings is apparently reduced as a result. A more reasonable possibility is that the zinc assay
of the tails is higher than that in the feed, but our measurement accuracy is insufficient to
demonstrate this effect.
The absolute value of an assay is also important. One gram per tonne is 0.0001 per cent or
one per cent is 10 000 ppm. Hence, the silver assays are really 0.0142 per cent, 0.3032 per cent
and 0.0097 per cent.
The gold assays are two orders of magnitude smaller again and the mass split of 0.2 per cent
is a reflection of good sampling and assaying at those concentrations.

Error models
There are some useful generic ways to ‘estimate’ likely measurement errors based on assay
magnitude. The most popular method is to assume a constant relative (or per cent) error. This
approach implies that the best defined values would be the tailings assays for gold and silver
and is plainly nonsense.
The next commonly used approach is to assume that the expected error is constant or
(usually) one. This simplifies the arithmetic and is a more sensible estimate. The larger assays
are now assumed to have the smallest relative error.
The JKMRC approach is to measure the error distribution through repeated sampling or to
use a well-proven heuristic; that is, a rule that should behave in a sensible manner. This rule
is often attributed to Bill Whiten, who disclaims ownership.
We assume that for assays (or size fractions) in the per cent range that the minimum sd
is 0.1 per cent (absolute) and that for assays greater than nine per cent the absolute sd is
one per cent. In between those two limits, the sd is 0.1 plus 0.1 times the assay value. Hence,
the relative error at a measured value of 0.1 per cent is 200 per cent. The relative error at an
assay value of ten per cent is also ten per cent.
At a measured value of 0.5 per cent, the absolute error is 0.1 plus 0.05 per cent or 30 per cent
relative. Some people refer to this as a ‘two-term’ error model, where 0.1 is the fixed error and
0.1 is the fractional error between zero and nine per cent. Another term is a ‘one over x’ model
because the relative error curve has much the same shape as that function.
If the analysis method used is very different, we can expect the error models to change.
For example, the fire assays typically used for precious metals should be intrinsically more
accurate at ppm values than standard techniques such as X-ray fluorescence (XRF) and
atomic absorption spectroscopy (AAS) for base metals in the per cent ranges would be at ppm
values. The reason for this is that the assaying technique itself uses some preconcentration
before measurement.

THE METHOD OF ‘MASS FLOW ERRORS’

If we switch to measured values in the component balance equation, we can expect a measured
‘mass flow error’ for each assay (or size fraction) measured:
Di = ai - bbi - (1 - b) ci

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

Note that only one β value is required for all the n assays and that Δi should be zero for
perfect data. Hence, a process that makes a large difference to the stream assays will have a
better-defined flow split than one that only makes a small difference, such as a final cleaner
or scavenger bank. Similarly, if a splitter is working well, it is essential to measure or estimate
its flow split as mass balancing will not be helpful.
Transposing and simplifying, we get for each component:
D i = (a i - c i) - b (b i - c i)
If we square both sides and sum up all the components:

/D = 7(ai - ci) - b (bi - ci)A

2
SSQ = 2
i
i

We might reasonably expect the value of β that minimises SSQ to be a reasonable estimate
of β*, which we can call bU .
As for the first case, this can use a quite generic spreadsheet format as shown in Table 3.
Set up this spreadsheet as shown in Table 4. Then work through it with estimates of β of 0,
0.005, 0.01, 0.02, 0.1, 1.0, as we know from the measured flow rate that the mass split is about
one per cent.
The gold assays have been divided by 100 and the silver assays by 1000 to bring them closer
to per cent values. (As an exercise, check out the minima with the unadjusted values.) If your
set-up is correct, the SSQ should go from 0.783 at 0.0 to 550 at 1.0 with a minimum value of
0.742 at 0.01.
It is also a useful exercise to tabulate β and plot it against SSQ as shown in Figure 2. This
graph shows a well-defined minima at β is approximately 0.01. It is well defined because
making a small change (±0.005) in β makes a ±10 per cent change in the SSQ. However, it is
necessary to plot the log of the SSQ to be able to see the minima.
Go through the β sequence again and watch how the SSQ or (Δi)2 for each assay varies. They
do not all have a minimum at the same value of β. How should we decide which value of β
to use? Obviously, the value that has the most accurately measured data should dominate.

TABLE 3
Generic structure of a spreadsheet balance around a single node using the method of mass flow errors.
Estimated beta Initial estimate
Feed Product Reject (ai - ci) Β*(bi - ci) Δi Δi2
assay assay assay
Measured A B C
Flows
Assayi
Assay 1 ' ' '
Assay 2 ' ' '
Assay 3 ' ' '
Assay 4
…
Assay n
Total SSQ =

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 ROB MORRISON

TABLE 4
An example of the method of mass flow errors.
Estimated beta = 0.0036 A B C
Stream Float feed Cu clnr con Cu rghr tail
Measured t/h 87.90 0.89
Relative flow 1.000 0.004 0.996 Delta Delta squared
ai bi ci ai - β* bi - (1-β) *ci
Measured Pb (%) 4.02 4.07 4.04 -0.020 0.000
Measured Zn (%) 15.80 7.80 15.50 0.328 0.108
Measured Cu (%) 0.43 22.40 0.20 0.149 0.022
Measured Fe (%) 14.30 16.10 13.50 0.790 0.625
Measured Au (g/t) 0.0105 0.475 0.0094 -0.012 0.000
Measured Ag (g/t) 0.142 3.023 0.097 0.020 0.000
SSQ = 0.759

100

10
Log of SSQ

SSQ

1
0 0.05 0.1 0.15 0.2 0.25 0.3

0.1
Estimated Beta

FIG 2 – Log of the sum of squared errors at a range of estimates of the mass split – beta.

Let us first consider the case where each of the minima is quite similar. Clearly the weighting
will have very little effect on the value of the flow split. In this case, there is little room for
debate about the value of the flow split.
In general, it will be more useful to derive an estimate of the standard deviation of the flow
split error based on our measured standard deviations. This estimate can be used to ‘weight’
the contribution of each flow split error to the sum of squares that is to be minimised.

Di 7a i - bb i - (1 - b) c iA
vD i = vD i

The rule for ‘propagation of variance’ is that the variance of a function is the sum of the
product of the variance of each input parameter and the square of its partial derivative – see
Deming (1938) or almost any statistics reference.
Dropping the i for the moment:
2D 2 2D 2 2D 2
v 2D = : 2a D (v 2a) + : 2b D (v b2) + : 2c D (v c2)

= v a2 + b 2 v b2 + (1 - b) 2 v c2

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

If we add some additional columns to our spreadsheet, we can derive a weighted sum of
squares WSSQ of the mass flow errors (Table 5).
As before, run through in increments of 0.001 for β from 0.00 to 0.02 and watch how the
minima change. For the first case, assume the sd of each assay is one. For the second case
assume they are each five per cent of the assay value. For the third case, assume ten per cent.
If your spreadsheet is right, the unit weighting case will look quite like the original but be
driven by the larger assay values. For the second and third cases, the smallest assays will
dominate. Neither seems very sensible and we will consider a better balanced approach in
the section on error models.

Arriving at a single numerical solution

For the examples in MS Excel, the built-in minimiser called Solver provides a very simple
solution: designate SSQ (or WSSQ) as the target for minimisation and beta as the variable that
can be adjusted. Run Solver. The result should be instantaneous.

AN ANALYTICAL SOLUTION
In the prehistoric days before PCs and Solver, a simple analytical solution was very useful.
Recalling some high school calculus, if we wish to find the minimum (or maximum) of a
function, we take the first derivative with respect to the variable of interest and set the result
to zero.
SSQ = 7(ai - ci) - b (bi - ci)A
/ 2

dSSQ
db
=2 / 7(a - c ) - b (b - c )A(b - c )
i
i i i i i i

0= / 7(a - c ) (b - c ) - b (b - c ) A
i i i i i i
2

b=
/ (a - c ) (b - c )
i i i i

/ (b - c ) i i
2

This is an interesting result. When ai = bi = ci, it is also undefined. The assays with the largest
difference will dominate each sum. Hence, the target of the separation process (for example,
copper in a copper circuit) provides the best defined balance.
As for the earlier cases, this approach is easy to set up in a spreadsheet. We already have
columns of (ai - bi) and (bi - ci) in the first example. Hence, we only need to add a column
each for their product and the second term squared. Divide the sums of these columns for an
analytical estimate of beta as shown in Table 6.

TABLE 5
Additional columns required for Table 3 to include a weighted sum of squares (WSSQ).
σa σb σc β2 (1 - β)2 D 2i

WSSQ =

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 ROB MORRISON

TABLE 6
Spreadsheet balance including the analytical solution for the ‘best fit’ mass split.
Data A B C
Flotation feed Cu cleaner conc Cu rougher tail
t/h 87.90 0.89
1 0.010 0.990 Analytical Estimate
ai bi ci (ai - ci) (bi - ci) (ai - ci)*(bi - ci) (bi - ci)2
Pb (%) 4.02 4.07 4.04 -0.02 0.03 -0.001 0.001
Zn (%) 15.80 7.80 15.50 0.30 -7.70 -2.310 59.290
Cu (%) 0.43 22.40 0.20 0.23 22.20 5.106 492.840
Fe (%) 14.30 16.10 13.50 0.80 2.60 2.080 6.760
Au (g/t)/100 0.001 0.475 0.009 -0.01 0.47 -0.004 0.217
Ag (g/t)/1000 0.142 3.023 0.097 0.05 2.93 0.132 8.561
Sum 5.003 567.669
Beta 0.008813553

ESTIMATING THE ACCURACY OF THE FLOW SPLIT

We can also estimate the variance of the residual errors at the best fit value of beta.
v D2 = / D / (n - 1)2
i
i

The accuracy with which the flow split is defined depends on how rapidly the SSQ increases
as we move away (in either direction) from the best fit value of beta. Once again from high
school calculus, we recall that the curvature of a function is its second derivative:
2SSQ
2b
= / ((a - c ) (b - c )) - / (b - c )
i i i i i i
2

i i

2 2 SSQ
2b 2
=- / (b - c ) i i
2

i
Hence:
v D2 = v 2b / (b - c ) i i
2

In the Excel case, Solver does not provide this value for parameters but we can easily change
beta by ±1 per cent and note the change on the sum of squares to test for a well-defined value.

THE MONTE CARLO APPROACH

An alternative approach is to add some random variation to the input data, run Solver (or
better our analytical formula) many times and consider the results as a mean and standard
deviation for beta. There are some specialist add-ons for MS Excel for this purpose; however,
for a simple case like this, a Monte Carlo investigation is not too difficult.
You can set up the process as a macro (or a Visual Basic Application program) or set the
spreadsheet to manual calculation and do a little manual accumulation. The latter is probably
more useful for understanding the process. You can automate it with a macro as an exercise.
We will use the same original data block and try the formula solution method.

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The Excel function RAND() draws a value from a calculated random distribution between
zero and one. We can scale the range of values between ‘min’ and ‘max’ by multiplying by
((max-min) + min). This generates a uniform distribution of random values between min and
max. However, what we actually need is a random set of variations drawn from a probability
distribution similar to the distribution we were sampling by making measurements or taking
samples. This is a little trickier than it sounds at first.
If we consider the cumulative (or integral) form of any probability distribution, by definition,
it will start at zero and end at one. Hence, we need the value of our cumulative distribution that
corresponds to each random value between zero and one. This is the inverse of the probability
distribution. This will work well most of the time, but it is worth remembering that the normal
distribution extends from negative to positive infinity. Most chemists will not accept this range
of variation and will simply not report numbers that are statistically possible but not plausible.
If we reduce the range of possible random values to say 0.025 to 0.975, then the inverse values
will lie between about plus and minus two standard deviations of the mean value.
To test out this process, set up four blocks of similar structure as shown in Table 7. The first
one is the measured data block. The second one is the block of estimated standard deviations.
The third one is our scaled random number. The last one is the block of perturbed data,
which we can use to rerun our balance (and other calculations) to generate an estimated
range of variation.

TABLE 7
Spreadsheet example of a Monte Carlo analysis.
Measured Data A B C
Stream Flotation feed Cu cleaner conc Cu rougher tail
Measured t/h 87.90 0.89
Relative flow 1 0.010 0.990
ai bi ci
Measured Pb (%) 4.02 4.07 4.04
Measured Zn (%) 15.80 7.80 15.50
Measured Cu (%) 0.43 22.40 0.20
Measured Fe (%) 14.30 16.10 13.50
Measured Au (g/t)/100 0.001 0.475 0.009
Measured Ag (g/t)/1000 0.142 3.023 0.097
Standard deviation Model A B C
Stream Flotation feed Cu cleaner conc Cu rougher tail
Standard deviations t/h 4.40 0.04 5%
ai bi ci
Standard deviations Pb (%) 0.50 0.51 0.50 0.1 +10% Or 1 if > 9
Standard deviations Zn (%) 1.00 0.88 1.00 0.1 +10% Or 1 if > 9
Standard deviations Cu (%) 0.14 1.00 0.12 0.1 +10% Or 1 if > 9
Standard deviations Fe (%) 1.00 1.00 1.00 0.1 +10% Or 1 if > 9
Standard deviations Au (g/t)/100 0.050 0.050 0.050 0.05
Random values RAND – min 0.025 RAND – max 0.975

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 ROB MORRISON

TABLE 7 cont ...

Est beta = 0.008713 A B C
Stream Flotation feed Cu cleaner conc Cu rougher tail
Measured t/h 0.25 0.28
ai bi Ci
Synthetic Pb (%) 0.47 0.30 0.84
Synthetic Zn (%) 0.44 0.94 0.82
Synthetic Cu (%) 0.79 0.84 0.97
Synthetic Fe (%) 0.07 0.54 0.53
Synthetic Au (g/t)/100 0.70 0.12 0.80
Synthetic Ag (g/t)/1000 0.95 0.06 0.41

Synthetic Data A B C
Stream Flotation Cu cleaner Cu rougher
feed conc tail
Measured t/h 80.67 0.90 Analytical Estimate
ai bi ci (ai - ci) (bi - ci) (ai - ci)* (bi - ci)2
(bi - ci)
Synthetic Pb (%) 3.51 3.54 3.61 -0.10 -0.07 0.008 0.006
Synthetic Zn (%) 15.13 9.12 16.04 -0.91 -6.92 6.277 47.819
Synthetic Cu (%) 0.37 22.19 0.17 0.20 22.02 4.403 484.766
Synthetic Fe (%) 13.13 16.24 12.57 0.56 3.67 2.060 13.460
Synthetic Au (g/t)/100 0.02 0.52 0.00 0.02 0.52 0.010 0.267
Synthetic Ag (g/t)/1000 0.18 2.98 0.11 0.07 2.87 0.207 8.243
Sum 12.964 554.560
Beta 0.023377

Each time the sheet is executed (press F9 to force a recalculation), this process will
generate an equally likely ‘plausible’ set of synthetic data, which our formula will then
solve for beta. After each run, jot down the resulting beta. If you edit the spreadsheet, it will
generate another value unless you switch to manual recalculation (Tools/Options/Manual
Recalculation).
In addition to the scaled RAND() function, you will need to use the NORMAL.INV (inverse
x, mean of x and sd) function to generate a deviation to add to the measured value. An
example is shown in Table 7.
Do as many runs as you like – but no less than ten. Now use the mean and sd functions
(AVERAGE(Range) and STDEV.S(Range)) with your row of β values as the argument. If the
mean is very different from your original W
b , there is a problem in the spreadsheet. The sd of
the synthetic betas provides an estimate of the sd of the calculated beta. Some mass balance
programs only provide this way of estimating how well the balance is defined for the balanced
flow rates.

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

GENERATING NUMERICALLY ‘EXACT’ DATA FOR FURTHER ANALYSIS

Given that we now have estimates of the flow split and its accuracy, we can consider various
ways to generate an ‘exact’ data set.

Reconstitution
If the flow split is well defined, adding the reject and concentrate together in the flow split
ratio has much to recommend it. If the weighted sum estimate of the feed assays is within
±1 standard deviations of the feed measurement, this realisation will be quite adequate for
further analysis. In practice, we can insert a single column to the right of the feed column
and add β times the concentrate plus (1 - β) times the tailing assay. Note that the summation
constraints are satisfied (Table 8). This strategy has the advantage that two thirds of our
numbers are exactly the ones that we measured.

Data adjustment
Persons of a statistical bent will favour least squares adjustment of all of the assays. This does
lead us back towards the general case, so it is useful as an exercise. We can start with the unit
weighted case. Recall that:
Di = ai - bbi - (1 - b ) ci

If we want an exact solution, we need some strategy to apportion Δi across the measured
assays. Strictly speaking, we should use the best fit value of beta, W
b . However, as we are
W
going to do a combined minimisation a little later using b it is probably confusing. Some
possible simple solutions are to divide delta by three or to proportion delta according to
the flow in each stream. The mathematically preferred approach is to minimise the required
adjustment in some way – and the sum of squares is a good general approach. Let Δa, Δb and
Δc be the minimum adjustments and omit the i – as we can consider each assay as a separate
case. Our adjusted data must balance if:
0 = (i - Da) - b (b - D b) - (1 - b) (c - Dc)

TABLE 8
A self-consistent data set generated by reconstituting products at the best fit mass split.
Data A B C
Flotation feed Reconstituted feed Cu cleaner conc Cu rougher tail
t/h 87.90 0.89
Beta 1 0.0088 0.991
ai bi ci
Pb (%) 4.02 4.040 4.07 4.04
Zn (%) 15.80 15.432 7.80 15.50
Cu (%) 0.43 0.396 22.40 0.20
Fe (%) 14.30 13.523 16.10 13.50
Au (g/t)/100 0.001 0.014 0.475 0.009
Ag (g/t)/1000 0.142 0.123 3.023 0.097

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 ROB MORRISON

And be subject to the constraint that:

D = Da - bD b - (1 - b) Dc

SSQ = (Da) 2 + (D b) 2 + (Dc) 2

We can use a Lagrange multiplier λ to impose the constraint by setting the constraint
equation to zero and adding it to the SSQ. This is called a ‘modified’ sum of squares. We then
minimise each adjustment and λ as well.
SSQ = (Da) 2 + (D b) 2 + (Dc) 2 - 2m (- D + Da - bDb - (1 - b) Dc)

Then:
2SSQ
= 2Da - 2m = 0
2Da
2SSQ
= 2bDb + 2mb = 0
2Db
2SSQ
= 2Dc + 2m (1 - b) = 0
2Dc
2SSQ
= 2 (- D + Da - bDb - (1 - b) Dc) = 0
2m

We can drop all of the ‘2’s:

Da = m
Db = - bm
Dc = - (1 - b) m
and substitute into the last equation:
b = m + b 2 m + (1 - b) 2 m
or:
m = D/ (1 + b 2 + (1 - b) 2)

As we already know the value of β and Δ for each assay, we can easily calculate a set of
adjustments. For this case, the adjustment is proportional to the flow of that component (assay)
in each stream. Table 9 shows the adjusted data and a check that it actually does add up.
Examining the adjusted values for lead and zinc shows that in this case it would be very
difficult to distinguish the likely change in the tailings assays as a result of the concentrate
assays; that is, the difference imposed by the process. By way of contrast, copper, iron and
silver are all changed significantly.
If we wish to scale each adjustment by its own standard deviation, the solution is quite
similar (subject to the same constraints as before):
WSSQ = (Da/ va) 2 + (Db/ vb) 2 + (Dc/ vc) 2
2WSSQ
= 2Da/ va - 2m = 0 or Da = mva
2Da
2WSSQ 2Db
= + 2mb = 0 or Db = - mbvb
2Db vb

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

TABLE 9
A self-consistent set of adjusted data generated by minimising the sum of squares of the required adjustments.
Beta 0.008813553 A B C 1.982528
Stream Flotation Cu cleaner Cu rougher
feed conc tail
Measured t/h 87.90 0.89
Relative flow 1 0.010 0.990 Check Beta
aI bi ci Delta Lambda Delta Check
Adjusted Pb (%) 4.03 4.07 4.03 -0.0203 -0.01 0 0.008814
Adjusted Zn (%) 15.61 7.80 15.68 0.3679 0.19 0 0.008814
Adjusted Cu (%) 0.41 22.40 0.22 0.0343 0.02 0 0.008814
Adjusted Fe (%) 13.91 16.10 13.89 0.7771 0.39 0 0.008814
Adjusted Au (g/t)/100 0.01 0.47 0.003 -0.0125 -0.01 0 0.008814
Adjusted Ag (g/t)/1000 0.13 3.02 0.11 0.0192 0.01 0 0.008814

2WSSQ 2Dc
= + 2 (1 - b) m = 0
2Dc vc
2WSSQ
= 2 (- D + Da - bDb - (1 - b) Dc)
2m
Da = mva
Db = - bmvb
Dc = (1 - b) mvc

D = mv a + b 2 mv b + (1 - b) 2 mv c

m = D/ _v a + b 2 v b + (1 - b) 2 v ci

As before, we know β and the sd for each assay.

Each set of assays has its own Lagrange multiplier, as shown in Table 10. The adjustments
that are shown are based on the sd estimates provided in the Monte Carlo example.
Assuming there is a reasonable quantity of gangue, the total assay summation constraint
can be satisfied by difference for each stream. That is, work out the assays of interest and
calculate the gangue by subtraction from 100 per cent.
It is interesting to note that even though the Lagrange multipliers have changed
considerably, the adjusted data is essentially identical with the unweighted case. If there were
real differences in the estimated flow splits (not simply measurement noise), the assay with
the smallest relative sds would dominate the flow split.
A note on Lagrange multipliers: these are named after their inventor. Possibly a more
instructive name would be ‘unknown’ multipliers. We are seeking a solution where each of
the first derivatives is equal to zero and the required constraints are also satisfied. Hence, the
multiplier is always one result from a set of simultaneous equations. The technique is very
unusual in that it is easier to use than to understand intuitively. See Boas (1966) for a clear
and detailed explanation.

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 ROB MORRISON

TABLE 10
A self-consistent set of adjusted data generated by minimising the sum of squares
of the adjustments weighted by the sd estimates from the Monte Carlo example.
Beta 0.010778355 A B C
Stream Flotation Cu cleaner Cu rougher
feed conc tail
Measured t/h 87.90 0.89
Relative flow 1 0.010 0.990 Check Beta
ai bi ci Delta Lambda Delta Check
Weighted adj Pb (%) 4.03 4.07 4.03 -0.0203 -0.02 0 0.010778
Weighted adj Zn (%) 15.61 7.80 15.69 0.3830 0.19 0 0.010778
Weighted adj Cu (%) 0.44 22.40 0.20 -0.0093 -0.04 0 0.010778
Weighted adj Fe (%) 13.91 16.10 13.89 0.7720 0.39 0 0.010778
Weighted adj Au (g/t)/100 0.01 0.47 0.003 -0.0134 -0.14 0 0.010778
Weighted adj Ag (g/t)/1000 0.14 3.02 0.10 0.0135 0.14 0 0.010778
adj – adjustment.

A FIRST PASS AT A MORE GENERAL SOLUTION

We can also see from the above analysis that a single flow split generates a full set of weighted
assay adjustments. The analytical solution is more complex and requires two steps to get to
an answer. However, if we make the weighted sum of squares for all assays the minimisation
objective for Solver and let Solver adjust the value of the flow split, we can achieve a simple
version of the general solution. If you also have measured flow rates and estimates of their sds,
they can easily be added to this solution. The weighted sum of squares of assay adjustments
plus flow rate adjustments now becomes the objective to minimise.
For this data set, the results are shown in Table 11. The flow split estimate changes from
0.0088 to 0.0108 and the weighted SSQ changes from 0.5138 to 0.4514. Whether either change
represents a ‘genuine’ improvement is not a very useful debate.
For reasonably self-consistent data, the results of each of these methods will be very
similar. For less well-defined data, the results will be dominated by the assays with the
largest differences (usually what the circuit is trying to separate) and the smallest standard
deviations.

ELEMENTS VERSUS MINERALS

The flotation process will usually be dependent on mineral composition, not assay composition.
If an element appears only in one mineral, it will not matter if you use elements or minerals.
For example, lead is often only present in galena. Many other cases are not so clear cut. For
example, iron can be present in chalcopyrite, pyrite, phyrrhotite and iron silicates – or in
varying proportions in sphalerite. If we have consistent assay ratios, we can convert our
assays into equivalent minerals and use the mineral assays for balancing. This will often give
results that are better defined and easier to understand – and are more suitable for modelling.
In this case, we might consider converting the copper to chalcopyrite and the remaining iron
to pyrite or phyrrhotite. However, this task is left as an exercise. In some cases, such as several
species of copper minerals or a variable Zn:Fe ratio in sphalerite, quantitative mineralogy will

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

TABLE 11
A mass balance that combines the search for the best fit mass split with the minimised weighted assay adjustments.
Adjusted Beta 0.0107783 A B C
Weighted Stream Flotation Cu cleaner Cu rougher
feed conc tail
Data Measured t/h 87.90 0.89
ai bi ci Delta Lambda Delta
Pb (%) Wtd adj Pb (%) 4.03 4.07 4.03 -0.0203 -0.02 0
Zn (%) Wtd adj Zn (%) 15.61 7.80 15.69 0.3830 0.19 0
Cu (%) Wtd adj Cu (%) 0.44 22.40 0.20 -0.0093 -0.04 0
Fe (%) Wtd adj Fe (%) 13.91 16.10 13.89 0.7720 0.39 0
Au (g/t) Wtd adj Au (g/t)/100 0.01 0.47 0.003 -0.0134 -0.14 0
Ag (g/t) Wtd adj Ag (g/t)/1000 0.14 3.02 0.10 0.0135 0.14 0
Adjustments A B C
Stream Flotation Cu cleaner Cu rougher
feed conc tail
Measured t/h 87.90 0.89 Weighted
ai bi ci SSQ
Pb (%) Wtd adj Pb (%) -0.02 0.000 0.02 0.0008
Zn (%) Wtd adj Zn (%) 0.19 -0.002 -0.19 0.0741
Cu (%) Wtd adj Cu (%) -0.04 0.000 0.04 0.0025
Fe (%) Wtd adj Fe (%) 0.39 -0.004 -0.39 0.3012
Au (g/t) Wtd adj Au (g/t)/100 -0.14 0.001 0.13 0.0361
Ag (g/t) Wtd adj Ag (g/t)/1000 0.14 -0.001 -0.13 0.0366
WTDSSQ 0.4514

become essential – each elemental assay will generate a flow split estimate, but they will not
define mineral behaviour.

PRACTICAL APPLICATION – SINGLE LEVEL BALANCING

Now that the various approaches to balances have been covered, we can consider some
common cases before starting on multilevel balances. Four typical strategies for data
collection are:
1. the complete circuit
2. block level, eg cleaners or scavengers
3. bank level – combined feed, concentrate(s) and reject
4. down-the-bank data.

Case 1 – the complete circuit

The complete circuit can usually be considered as a single two-product separator. There will
often be metal accounting samplers available. Flow rates will often be known – at least for
the circuit feed rate – from a (hopefully) well-calibrated weightometer. Because the complete
circuit maximises the differences in assays, the balance should be well defined. If it is not, it

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 ROB MORRISON

will be essential to refine your sampling and assaying techniques before attempting more
detailed test work.

Case 2 – block level

Block level will often be covered by the two-product case; however, it is worth reviewing the
feed, rougher, scavenger case as it is also very common. This case comes in two versions –
one with four samples and one with five. Each case does have an analytical solution, but they
can also be set up as mass flow errors in each component for a straight-forward solution in
MS Excel.
For the first case we only have one node. We retain the idea that beta is the flow split into
stream B and add gamma for the flow split into stream C, as shown in Figure 3:
D i = a i - bb i - cc i - (1 - b - c) d i

SSQ = /D i
2

As stream E is not measured for this case, we can use Solver to find ‘best fit’ values of β
and γ. Similarly, we can use Solver to find the minimum squared data adjustments subject to
the condition that the adjusted data add up to zero at the specified values of β and γ. As before,
the adjustments can be weighted by their estimated standard deviations. However, tackling
the complete problem in Solver will rapidly exceed the maximum number of constraints
available with the add-in version. Various expanded versions are available for purchase.
Note:
•• You will need at least two independent assays to solve this balance at all as there are two
unknowns.
•• If stream C is a middlings stream with similar composition to the feed stream, the flow rate
in stream C is not defined. Almost any flow measurement estimate (including a ‘calibrated
eyeball’) will be more useful than the result of the balance.
For the second configuration (in which E is measured) there are two separations or nodes.
Hence, we need two error equations:
D1i = ai - bbi - (1 - b) ei

D2i = (1 - b) ei - cci - (1 - b - c) di

SSQ = / 7(D1 ) i
2
+ (D2i) 2A
i

This case is also quite straightforward to set up for Solver – with or without weighting the
errors. As before, if your data is accurate and self-consistent, there is much to recommend
simple reconstitution to generate a self-consistent set of data for further analysis. However,

A E D

B C
FIG 3 – A two-node, rougher scavenger circuit.

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

it is also fairly straightforward to do a least squares adjustment one assay at a time. We will
work through the second case as it has two constraints.
For each value of i, we wish to minimise:

SSQ = Da 2 + Db 2 + Dc 2 + Dd 2 + De 2
subject to:
D1 = Da - bDb - (1 - b) De
and:
D2 = (1 - b) De - cDc - (1 - b - c) Dd

That is, minimise the modified sum of squares:

SSQ + 2m1 (D1 - Da - bDb - (1 - b) De)

+ 2m 2 (D2 - (1 - b) De - (1 - b - c) Dd - cDc)

2SSQ / 2Da = 2Da - 2m1 = 0

/ 2Db = 2Db - 2m1 b = 0

/ 2Dc = 2Dc + m 2 2c = 0

/ 2Dd = 2Dd - 2m1 (1 - b - c) = 0

/ 2De = 2De - 2m 2 (1 - b) = 0

We can express λ2 in terms of λ1:

m 2 = (De - m1 (1 - b)) / (1 - b)

m 2 = De / (1 - b) - m1

and calculate both Lagrange multipliers. This gives a direct solution for each adjustment.
As before, we can extend this to a direct solution of the minimum sum of squared adjustments
or of weighted squared adjustments.
The following set of data in Table 12 can be used as an exercise.

Case 3 – bank level

The ‘simplest case’ considered earlier is applicable to bank level sampling and analysis for
combined feed, concentrate and reject. A more detailed case is considered in the next case.

Case 4 – down-the-bank data

For a more detailed analysis, we may wish to sample the froth from each cell. We can either
take samples of the product of each cell and a pulp sample between each cell or take timed
lip samples of each concentrate and a feed and a tailings sample. Hopefully a combined
concentrate will also be available.

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 ROB MORRISON

TABLE 12
Measured assay data for the circuit shown in Figure 3.
Stream ID Pb (%) Zn (%) Cu (%) Fe (%)
Measured assay Measured assay Measured assay Measured assay
Pb rougher feed A 11.89 24.02 0.25 11.14
Pb rougher conc B 20.20 30.10 0.31 9.10
Pb rougher tail E 1.25 16.60 0.16 13.50
Pb scavenger conc C 8.20 39.80 0.37 11.70
Pb scavenger tail D 0.51 14.60 0.14 13.70

This problem provides a different kind of constraint. We have an estimate of the ratios of the
flow rate from each cell but we do not know the total flow rate. We may or may not know the
total assay of the concentrate. An analytical solution for this multiconcentrate plus each cell
tail was developed by the author and published in Chapter 7 of Lynch (1977). It is outlined in
Figure 4. The data from that example are shown in Table 13.
The flow ratios to A2, A3 can be designated as alpha 2, alpha 3 and so on. The solution is a
somewhat complicated matrix inversion:
Rm11 m12 0 0 VW SRa2VW RSx1VW
S
Sm21 m22 m23 0 W Sa3W S 0 W
S 0 m32 m33 m34W $ S W = S 0 W
S W Sa4W S W
S0 0 m43 m44W Sa5W Sx4W
T X T X T X
Each of the ‘m’ and ‘x’ terms is a sum of differences of assays. When a circuit reaches this
level of complexity it is recommended that the user switch to a more general approach or to
a commercial package.
The flow ratio case is better suited to a numerical approach. If we have measured flow rates,
fi, f2 →fm we can assume that they will be related to the total functional flow rate by some ratio
t. Hence, our node equation becomes:
D1 = a - bb - (1 - b) c

D2 = bb - t (f1conc1 + f2 conc2 + f3conc3 ff)

or if we cannot measure b, we simply substitute:

tb /f j
conc j l for βb.
j

TABLE 13
Measured assay data for the circuit shown in Figure 4.*
A1 A2 A3 A4 A5 B1 B2 B3 B4 B5
Copper 3.03 1.0 1.15 0.75 0.52 21.2 22.5 17.1 9.7 15.5
Iron 8.2 7.1 6.4 6.0 5.7 23.8 25.9 23.4 20.2 21.4
Sulfur 6.5 5.3 4.4 3.8 3.3 26.5 29.2 25.9 20.8 23.0
Insoluble 46.6 49.0 51.0 51.8 52.8 14.4 11.4 18.4 27.6 21.6
* Reprinted from Mineral Crushing and Grinding Circuits, A J Lynch, 350 p, Copyright (1977), with permission from Elsevier.

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

In either case, we are solving the original problem for the flow weighted average of the
concentrate assays and this will usually be a good first step to see if the lip sample data
are reasonably self-consistent. If they are, weighted addition and reconciliation should be
adequate for further analysis. Alternatively, a similar constrained least squares adjustment
can be used – either weighted or unweighted.

SELECTION OF MEASUREMENT POINTS

Now that we have considered a range of flow sheets, we can deduce some useful rules. If we
wish to use assays to define flow splits, we need to use either very accurate sampling and
assaying or survey around a separation process (or a series of separations), which will make
a large difference to the assays. Hence, the flow split around a rougher section or a complete
circuit will usually be well defined by feed, product and tailing assays.
Conversely, the flow split across cleaner and scavenger sections (and splitters!) will often be
poorly defined by those assays. For all of these cases, flow measurements are essential. There
is usually a good case for sampling and flow measurement across a complete circuit – even
though the study objective may only be measurement of a single section.

ANALYSIS OF MORE COMPLEX CIRCUITS

The methods that have been described so far can also be applied to more complex circuits.
At this point, it is also worth commenting that several flow sheet mass balancers (using
these principles) are available commercially (JKSimMet, JKMBal, JKSimFloat, BilMat). Some
websites that provide more detail are referenced at the end of this chapter. For more complex
flow sheets, an ‘off-the-shelf’ solution has much to recommend it – lest all the time available for
data analysis be spent trying to manufacture a balance. A useful compromise is a spreadsheet
offered by Luttrell (2004).
It is also possible to use a general purpose, constrained minimisation routine to solve
the general problem, but the sheer number of adjustments and constraints make this an
ineffective approach. Dividing the problem into flow rates estimation followed by assay
adjustment makes it much more tractable; however, we do need samples and assays from all
streams to be able to use this approach.
The most important step towards a general solution is to convert the measurement flow
sheet into a connection matrix. A connection matrix usually counts streams in columns and
nodes in rows. Where a stream flows into a node, the matrix value is set to +1. Where a stream
flows out of a node, the value is -1. All other values are set to zero. Table 14 is for the multi-
concentrate example shown in Figure 4. ‘B’ streams are set in order at six to ten and the zeros
are omitted for clarity.
The advantage of this approach is that we can use matrix arithmetic to express flow
component errors and constraints in quite general (and very compact) fashion. If we have
a vector of calculated flow rates where f1 is the flow in stream 1 and so on, then any self-
consistent set of flow rates must satisfy:
[C] . [ f ] = [0]
where:
C is the connection matrix for the flow sheet

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 ROB MORRISON

TABLE 14
Connection matrix for the circuit shown in Figure 4. Note that ‘B’ streams
are numbered 6 to 10 and zeros are omitted for clarity.
Nodes Streams
1 2 3 4 5 6 7 8 9 10
1 1 -1 -1
2 1 -1 -1
3 1 -1 -1
4 1 -1 -1
5 1 1 1 1 -1

A1 A2 A3 A4 A5

B1 B2 B3 B4

B5
FIG 4 – A typical ‘down-the-bank’ equivalent circuit for detailed sampling.*
* Reprinted from Mineral Crushing and Grinding Circuits, A J Lynch, 350 p, Copyright (1977), with permission from Elsevier.

Similarly, each assay times its stream flow rate times the relevant stream/node entry in
the connection matrix will generate a vector of mass flow errors. Hence, we can call [Ci] a
connection matrix where each row is multiplied by assay type i, then:
[Ci] . f = Δi for each assay i.
As MS Excel has a built-in function for matrix multiplication, it is straightforward to set up
a spreadsheet to define constraints and the SSQ of mass flow errors for each assay type. The
product of the Connection Matrix (Table 14) and the copper assay matrix is shown in Table 15.
The best fit solution for all flows (based on f1 = 100) is shown with the copper SSQ (Table 16).
The best fit flow rates can be based on any one or any combination of assays by including
its SSQ in the target for Solver to minimise. Weighting and sensitivity estimates can be added
in much the same way as for the single node case. Once the best fit flow rates have been
established, we can use a similar strategy to find each set of data adjustments. In this case, the
adjustments become the parameters for Solver, the SSQ of the adjustments is the target for

TABLE 15
Product of the Connection Matrix (Table 14) and the copper assay matrix.
Nodes Streams
1 2 3 4 5 6 7 8 9 10
1 3.03 -1 0 0 0 -21.2 0 0 0 0
2 0 1 -1.15 0 0 0 -22.5 0 0 0
3 0 0 1.15 -0.75 0 0 0 -17.1 0 0
4 0 0 0 0.75 -0.52 0 0 0 -9.7 0
5 0 0 0 0 0 21.2 22.5 17.1 9.7 -15.5

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

minimisation and our connection matrix multiplied by the flow rate of the selected component
must be constrained to zero. The results for copper are shown in Table 17, followed by the
constraints in Table 18, which are near enough to zero.

TABLE 16
Best fit flow rate solution for all flows (based on f1 = 100) is shown with the copper SSQ.
Flows Estimates Matrix product SQD
1 100 64.4250163 4150.58
2 93.13985 -78.0880874 6097.74
3 90.13671 3.37058247 11.3608
4 88.13768 -11.8850601 141.254
5 84.63477 43.0064029 1849.5
6 6.860148
7 3.003143 SSQ
8 1.999028 12250.5
9 3.502911
10 15.36523

TABLE 17
Comparison of adjusted and measured copper assay data.
Stream 1 2 3 4 5 6 7 8 9 10
Adjustment -0.091 0.664 -0.166 -0.125 -0.250 -0.949 -0.437 -0.287 -0.498 2.139
Adjustment squared 0.008 0.440 0.028 0.016 0.062 0.900 0.191 0.082 0.248 4.576
Adjusted Cu 2.939 1.664 0.984 0.625 0.270 20.251 22.063 16.813 9.202 17.639
Measured 3.030 1.000 1.150 0.750 0.520 21.200 22.500 17.100 9.700 15.500
Total SSQ 6.552

TABLE 18
Best fit flow rate and constraint residuals around each
node of the balance. The residuals are effectively zero.
Flows Estimates Matrix product
1 100 -3.7E-14
2 93.13985 6.35E-14
3 90.13671 -1.5E-14
4 88.13768 -2.1E-14
5 84.63477 1.78E-15
6 6.860148
7 3.003143
8 1.999028
9 3.502911
10 15.36523

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 ROB MORRISON

MULTI-DIMENSIONAL BALANCES (SIZE BY ASSAY)

For detailed performance analysis, size by assay (or size by mineral) measurements will often
be of interest as particle composition (and degree of liberation) and size underlie flotation
performance.
A major problem is that the coarse end of the size distribution is often in short supply. This
makes accurate assaying or mineralogical measurement difficult. To overcome this problem,
you can take multiple composite assays or simply wet screen some additional sample cuts
to obtain a substantial mass of ‘coarse end’ sample. The definition of ‘coarse’ will vary with
different circuits. Larger than the 90 per cent passing size is usually a reasonable definition.
The first test for size by assay data is to see if it is self-consistent within the sample itself. To
do this, simply add the assays for each size fraction weighted by the mass fraction for each
size fraction and see if the total assay resembles the measured total assay for that stream. If it
does not, your sampling and analysis methods need to be examined in detail.
Assuming that the weighted sum of the fractional assays does agree reasonably with the
measured total assays, we can now do a beta estimate for each total assay and each size
fraction using the formula developed in the section ‘Accuracy considerations’ or by using
Solver as in the section ‘The simplest case’.
As detailed in the section ‘Estimating the accuracy of the flow split’, we can reconstitute
product and reject in the mass split with the products. This strategy may require a little
more explanation. After the best fit mass split (beta) has been estimated, convert the product
into component flow rates by multiplying the concentrate size fraction by each assay (and
the gangue fraction as 100 – sum of all assays). Do the same for the reject using (1 – the flow
split) and add each component to generate each size fraction of the reconstituted feed. Next
divide the assay component flows in each size fraction by the fraction total to convert them
back to assays.
As in our earlier example, if the reconstituted results are reasonably similar to the measured,
the reconstituted results will usually be suitable for recovery calculations and modelling.
A more quantitative way to check is to see if the reconstituted size fractions and assays are
within the expected variation of the measured feed data. As in the simpler one-dimensional
case, two thirds of the measured numbers are included in the data set for analysis.
For this many data points, a plot of measured (x) against reconstituted (y) is a quick visual
check for agreement (Figure 5). The data is from the example shown in Table 19.

100.00

Pb
Zn
10.00
Cu
Fe

1.00
0.10 1.00 10.00 100.00

0.10
FIG 5 – Parity graph comparing measured total assays for each metal in each stream
with those based on reconstitution of the assays for each size fraction of each stream.

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

TABLE 19
Measured sizes, total assays and assays reconstituted from size fraction assays based on samples taken from zinc circuit.
Measured data A B C
Sizing Wt % Wt % Wt %
ai - ci bi - ci Beta (ai - ci) * (bi - ci) (bi - ci)2 Beta bar
+75 20.85 11.87 18.48 2.36 -6.61 -0.3571 -15.623 43.746
+53 12.46 15.73 8.58 3.88 7.16 0.5424 27.770 51.197
+38 11.53 14.22 7.07 4.46 7.15 0.6242 31.910 51.124
-38 55.17 58.18 65.87 -10.71 -7.69 1.3920 82.343 59.155
Totals 126.400 205.222 0.616
Pb 0.59 1.19 0.39 0.20 0.80 0.2438 0.156 0.640
Zn 15.34 59.41 0.86 14.48 58.55 0.2472 847.511 3428.103
Cu 0.15 0.29 0.10 0.05 0.19 0.2368 0.009 0.036
Fe 13.70 5.38 16.44 -2.74 -11.06 0.2477 30.304 122.324
Rem 70.24 33.73 82.21 -11.98 -48.48 0.2470 580.548 2350.310
Recon totals 1458.528 5901.413 0.247
Pb 0.71 1.49 0.41 0.30 1.08 0.2801 0.326 1.163
Zn 15.43 57.50 1.10 14.32 56.40 0.2540 807.833 3180.405
Cu 0.14 0.34 0.12 0.02 0.22 0.0861 0.004 0.047
Fe 13.97 5.14 15.81 -1.84 -10.67 0.1729 19.668 113.755
Remainder 69.75 35.53 82.55 -12.80 -47.02 0.2722 601.971 2211.343
1429.802 5506.712 0.260
Overall 3014.731 11613.34 0.260

There are many more sophisticated approaches but they will not help very much with poor
data – other than to spread the problems across the data set and make them more difficult to
identify.
Note that for diagnostic purposes, you can do a balance for each within each size fraction to
see if the mass split within each size fraction is self-consistent. The mass split calculated this
way should be close to the mass split in the size fraction, which is the concentrate size fraction
multiplied by the overall mass split divided by the feed size fraction.
There are a range of mathematically complex ways to approach the general case (Hodouin
and Everel, 1980; Gay, 1999).

SIZE BY ASSAY EXAMPLE

As noted in the previous section, a good place to start is to check the reconstituted size fraction
assays against the measured total assay for each stream. Table 19 shows measured sizes, total
assays and assays reconstituted from size fraction assays based on samples taken from a zinc
circuit.
Table 19 also shows mass split calculations for each total component and for each group of
totals based on the formula developed earlier. The total assays and the reconstituted assays
are quite consistent and indicate a mass split to concentrate of about 25 per cent. However, the
splits based on size fractions are not consistent with each other or the assay estimates. It would

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 ROB MORRISON

be useful to investigate whether all of the size fractions are likely in error or a particular
one is at fault. We can investigate by applying the 25 per cent split to the concentrate size
distribution and the 75 per cent split to the tails.
This generates mass flows of 2.97 and 13.86 respectively. The mass split within each size
fraction can be estimated from the assays within that size fraction. Table 20 estimates the
+75 micron mass split as 0.144, which gives flow rates of 3.00 and 17.85 respectively.
This simple analysis suggests that the feed and concentrate are consistent with the assay
split but the tailings are not. Hence, investigating the collection and sample preparation for
the tailings stream would be a good idea before doing more test work.

Size by assay balance

Each size fraction can be thought of as a separate process (provided we use the same set of
sieves) and we can apply the strategies developed earlier to investigate self-consistency and
to find a minimum SSQ of assay adjustments. Table 20 shows an example for the +75 micron
samples.
There is quite a bit of scatter but the split for zinc is very well defined – as might be expected.
The next size fraction, +53 micron (Table 21), contains a little more mass, a lot more particles
and is much more self-consistent.
The minimum data adjustment strategy is equally applicable. Tables 20 and 21 show how
to set this up for one size fraction. Note the check sums in both directions. They do take up
some space but it is very important to ensure that the calculated data are complete and self-
consistent with respect to size and assays.
Note that the ‘remainder’ assays are calculated by subtracting the measured assays from
100 per cent. This removes a substantial number of constraints from the solution.
The weighting factor is (1 + β2 + (1 − β)2) as derived earlier.
The fully weighted case can be used in exactly the same way at the expense of more
complexity. For example, a beta value of 0.15963 gives a weighting factor of 1.73169. The
adjusted assays are shown in Table 22 and the corresponding table of adjustments is shown
in Table 23.

TABLE 20
Assay mass balance within the +75 micron size fraction.
Mass splits in size fractions
Measured data A B C
Sizing Wt % Wt % Wt% Component
+75 ai - ci bi - ci Beta (ai - ci) * (bi - ci) (bi - ci)2
Pb 0.60 1.30 0.40 0.20 0.90 0.222 0.180 0.810
Zn 8.90 55.20 1.50 7.40 53.70 0.138 397.380 2883.690
Cu 0.17 0.30 0.18 -0.02 0.12 -0.125 -0.002 0.014
Fe 7.90 5.00 7.60 0.30 -2.60 -0.115 -0.780 6.760
Rem 82.44 38.20 90.32 -7.88 -52.12 0.151 410.966 2716.494
Fraction total 100 100 100 807.7444 5607.768
Beta bar 0.144040

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

TABLE 21
Assay mass balance within the +53 micron size fraction.
Measured data A B C
Sizing Wt % Wt % Wt% Component
+53 ai - ci bi - ci Beta (ai - ci) * (bi - ci) (bi - ci)2
Pb 0.65 1.00 0.50 0.15 0.50 0.300 0.075 0.250
Zn 18.3 59.00 1.30 17.00 57.70 0.295 980.900 3329.290
Cu 0.23 0.35 0.20 0.03 0.15 0.200 0.005 0.023
Fe 17.8 4.80 25.40 -7.60 -20.60 0.369 156.560 424.360
Rem 63.02 34.85 72.60 -9.58 -37.75 0.254 361.645 1425.063
Fraction total 100 100 100 1499.184 5178.985
Beta bar 0.289474

TABLE 22
Adjusted assays for the +75 micron size fraction.
Adjusted A B C
Sizing Wt % Wt % Wt% Exp Check
+75 Delta Lambda Sum
Pb 0.57 1.31 0.43 0.06 0.03 0.000
Zn 9.58 55.09 0.93 -1.17 -0.68 0.000
Cu 0.18 0.30 0.16 -0.03 -0.02 0.000
Fe 7.49 5.07 7.95 0.72 0.41 0.000
Remainder 82.18 38.24 90.53 0.44 0.25 0.000
Fraction total 100.00 100.00 100.00

TABLE 23
Assay adjustments for the +75 micron size fraction.
SSQ A B C
Sizing Wt % Wt % Wt % Delta
+75 SSQ
Pb 0.03 -0.01 -0.03 0.00
Zn -0.68 0.11 0.57 0.79
Cu -0.02 0.00 0.02 0.00
Fe 0.41 -0.07 -0.35 0.30
Remainder 0.25 -0.04 -0.21 0.11
Fraction total SSQ 1.20

We can now generate a complete set of data adjustments within each size fraction (weighted
or not). To link the size fractions together and tie back to the total assays it is important to
realise that the mass split within each size fraction has to be identical for the size-fraction-based
calculation and the assay-based calculations. Hence, we can multiply each feed size fraction

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 ROB MORRISON

by that mass to generate a set of concentrate flows and by one minus that split to generate
a set of tailings size fraction flows and then convert the flow back to size distributions. This
strategy makes another set of constraints implicit.
The last constraint can be imposed by calculating one of the feed size fractions (usually the
fines) by difference. We can use the other feed size fractions and each of the size fraction split
factors as a set of parameters to minimise the total SSQ for all sets of data. One way to set
this up is shown in Table 24. The parameters to minimise are identified in bold font as are the
adjusted total assays.
This approach is somewhat tedious to set up but does provide a very detailed view of
the data. For example, the problem with the tailings size distribution identified earlier is
now very clear. That set of sizing data contributes more than half the SSQ. We can omit that
contribution and reminimise to see how much the results change. As might be expected, the
changes are mostly in the tailings size distribution but they are not very large. Hence, either
set of data would be similarly useful. However, it does suggest that taking samples optimised
for equi-probable selection is essential for this kind of work. That means cutting through the
stream to be sampled – and avoiding any kind of dip sampling.

TABLE 24
A simple spreadsheet strategy for a complete size by assay balance.
Calc size A B C B C
Flows Wt % Flow Flow Wt % Wt %
Adj A Adj B Adj C
+75 fit 18.89 3.02 15.87 11.81 21.31
+53 fit 13.05 3.74 9.31 14.63 12.50
+38 fit 12.08 3.76 8.31 14.74 11.16
-38 55.99 15.01 40.98 58.82 55.02
Totals 100.00 25.53 74.47 100.00 100.00
Size Splits
Beta 75 0.15963
Beta 53 0.28631
Beta 38 0.31148
Beta-38 0.26814
Adjusted Assays
Recon Flows A B C
Pb 69.76 38.14 31.62 0.698 1.494 0.425
Zn 1553.57 1468.72 84.85 15.536 57.540 1.139
Cu 16.84 8.54 8.30 0.168 0.334 0.111
Fe 1379.62 133.11 1246.51 13.796 5.215 16.737
Rem 6980.21 904.03 6076.18 69.802 35.417 81.587
Totals 10000.0 2552.54 7447.46 100.00 100.00 100.00

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

RECAP
The suggested analysis sequence follows the order of the chapter. Run a check around each
node using the method of mass flow errors detailed in earlier sections ‘The simplest case’ and
‘The method of mass flow errors’.
The formulae derived in the sections ‘An analytical solution’ and ‘Estimating the accuracy of
the flow split’ are useful for a quick check on the flow split and how well it is defined.
Where the data are very different in magnitude (ppm and per cent assays), it is usually
worth using weighted least squares for both the flow split and the data adjustments. If the
required data adjustments are large (more than ten per cent of the measurement) for more
than a few of the measurements, repeat the experiment. The total weighted sum of squares
should always be of the same order as the number of measurements, node by node or across
a complete circuit. Hence, it is worth examining each total by node and for each set of assays.
If the adjustments are small, there is a lot to be said for reconstituting concentrate and tailings
to generate a set of self-consistent data – at least two thirds of your numbers will be the ones
you measured.
Once you have checked each node for self-consistency, you can continue on to the multinode
balancing strategies outlined in the section on ‘Practical application – single level balancing’;
however, as the circuit becomes more complex, it is well worth considering a commercial
product.
The single node checks will often pinpoint measurement problems that may be concealed
by doing the complete balance first. Some commercial systems (such as JKSimMet) will let
you select each node – or a broader subset of the flow sheet – for a check balance.
Plotting measured data against adjusted data is a way of compressing a lot of data into a
single graph. It is also an excellent way of detecting bias. If all of the small assays are adjusted
upwards, there is likely a problem with low assay analyses.
For more complex data, such as size by assay or size by mineral, the same guidelines apply.
Consider the balance around each node with each size fraction before progressing on to total
assay balances across the circuit and then total size by assay balances across the circuit.
It is usually a poor strategy to attack the complete problem from the start as least squares
balancing can spread a single wrongly measured (or transcribed) piece of data across the
complete set. Such errors are much easier to identify and weed out in single node slices.
Keeping backup splits of samples allows for reassaying of dubious values when the rest of
the set are self-consistent.
For mineral-based analysis (MLA or Q*S) be aware of the number of particles or sections
that contribute to your measurement. Low number errors follow the Poisson distribution and
even 100 sections will have a relative sd of ten per cent.
Overall, try to use a systematic approach, starting at the node level and working across the
circuit as you test each data point for its actual contribution to the balance. While we may
never be able to know the ‘true’ value, careful measurement and analysis will produce data
that can provide a sound basis for flotation modelling and for decision-making.

CONCLUSIONS
The techniques outlined in this chapter provide a reasonably simple yet quite powerful
approach to analysis of flotation data. Using a spreadsheet for the process avoids capital
outlay but like all spreadsheet activity requires extreme care in checking and including checks

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 ROB MORRISON

on constraints. While setting up these spreadsheets is a good way to learn about the analysis
process, they will not generally transfer between users.
For shared use – or anything at all complex – investing in one of the commercial, flow-
sheet-based products has much to recommend it. Some relevant product websites are listed
at the end of this chapter. Compared with even a very optimistic estimate of the true cost of
professional labour, the cost of commercially available mass balancing systems is really very
reasonable. A few days of time saved would pay for most of them.
Unless you are quite an expert user, building your own spreadsheets for more than the single
node cases is a high-risk endeavour. Using someone else’s spreadsheet is an excellent way to
generate a misleading analysis as the subsequent users do not know what modifications have
been made by others. If you are obliged to use a spreadsheet, the author strongly recommends
that you also use it to generate checks for self-consistency of your calculated or adjusted data
and graphs of all measured and adjusted data.
The well documented and secured spreadsheet offered by Luttrell (2004) may be a workable
compromise in some cases as it should not be subject to unauthorised and undocumented
‘improvements’.

ACKNOWLEDGEMENTS
Except as otherwise noted the data used for the examples in this chapter were provided
by Dr Chris Greet. The author gratefully acknowledges permission granted by the Elsevier
Scientific Publishing Company to reproduce Figure 7.8 and Table 7-IV from Lynch (1977).

REFERENCES
Boas, M L, 1966. Mathematical Methods in the Physical Sciences (Wiley).
Deming, W E, 1938. Statistical Adjustment of Data (Dover).
Gay, S L, 1999. Avoiding the zero-flow solution in mass-balance equations, Transactions of the Institutions
of Mining and Metallurgy, Mineral Processing and Extractive Metallurgy, 108:C121–126.
Hodouin, D and Everel, M D, 1980. A hierarchical procedure for adjustment and material balancing of
mineral processing data, International Journal of Mineral Processing, 7:91–116.
Luttrell, G H, 2004. Reconciliation of excess circuit data using spreadsheet tools, Coal Preparation,
24:35–52.
Lynch, A J, 1977. Mineral Crushing and Grinding Circuits, 340 p (Elsevier: Amsterdam).
Standards Australia, 1997. AS 2884.1-1997 Heavy mineral sand concentrates – sampling moving streams.
Wiegel, R L, 1972. Advances in mineral processing material balances, Canadian Metallurgical Quarterly,
11:413–419.

FURTHER READING
Montgomery, D C, Runger, G C and Hubele, N F, 2000. Engineering Statistics, second edition (Wiley).
Morrison, R D, 1991. Material balance techniques, in Evaluation and Optimization of Metallurgical
Performance, pp 209–218 (American Institute of Mining, Metallurgical, and Petroleum Engineers:
Denver).
Morrison, R D (ed), 2008. An Introduction to Metal Balancing and Reconciliation (Julius Kruttschnitt
Mineral Research Centre: Brisbane).

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 CHAPTER 3 | MASS BALANCING FLOTATION DATA

Morrison, R D and Richardson, J M, 1991. JKMBal – the mass balancing system, in Proceedings Second
Canadian Conference on Computer Applications for the Mineral Industry (CAMI ‘91), volume 1, pp 275–
286, Vancouver, September.
Napier-Munn, T J, 2014. Statistical Methods for Mineral Engineers: How to Design Experiments and Analyse
Data (Julius Kruttschnitt Mineral Research Centre: Brisbane).
Wills, B A and Napier-Munn, T J, 2006. Mineral Processing Technology, chapter 3 and associated
spreadsheet examples (Elsevier).

USEFUL WEBSITES
BilMat: <http://www.tpt.com/bilmat>.
JKSimMet, JKMBal, JKSimFloat: <http://www.jktech.com.au>.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 135

 Return to contents

CHAPTER 4
A practical guide to some aspects of
mineralogy that affect flotation
Alan R Butcher

ABSTRACT
This chapter is designed to introduce some of the basic aspects of mineralogy that can
influence flotation behaviour, with particular emphasis on sulfide flotation. Since the
invention of flotation in the early 1900s, the minerals industry has continued to refine and
continuously improve the many and varied chemical reagents and flotation cell technologies
during this period, yet it is only in the last decade or so that the role of mineralogy has truly
been realised as another important component in the better understanding of the flotation
separation process.
Most of the information required by mineral processing engineers involved in flotation
can now be provided by geologists and mineralogists using well-established optical, X-ray,
laser and electron-microbeam technologies. Metallurgically-relevant observations for
flotation processing applications can be made at any time during the life of a mine, from
first exploration drill core, which can flag-up problematic minerals and textures, through the
start-up phases of a mine, to full production, which can allow fine tuning of a concentrator
to produce acceptable grades and recovery. Finally, mineralogy can be used to optimise
recycling and/or disposal of tailings during the closure phase of the mining life cycle.
An understanding of the geological context, mineral assemblage and textures of an ore is
absolutely key to understanding its potential amenability to the flotation process. Equally
important is the measurement of sizes, composition, locking and liberation, and flotation
behaviour of particles as they pass through a circuit from blasting, crushing, grinding,
flotation to final concentration, using the appropriate mineralogical techniques, at the right
scale of observation.
This chapter will review the many and varied mineralogical techniques currently available,
and will guide the reader through when and where to use them. Examples will be drawn
from case studies that illustrate how mineralogy has allowed for a better understanding and
improvement in the flotation process on a range of ore types.

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 ALAN R BUTCHER

INTRODUCTION
An understanding of the geological context, mineral assemblage and texture of an ore is
absolutely key to efficient and effective unlocking and concentration of ore minerals during
blasting, crushing, grinding and flotation. Whilst this opening statement might appear
somewhat obvious to an experienced process mineralogist, it is seldom appreciated by
geologists, let alone by mining and minerals engineers. Let us explore why this is so.
The reasons for this are not always clear, or even logical, but experience has shown that it is
due in part to one or more of the following factors:
•• Historical – in the past, only mining of high-grade ores or easy-to-process ores was practised
and, generally speaking, these did not require strong geological input. In fact, in some of
the early mines, a geologist, let alone a mineralogist, may not even have been on staff.
•• Managerial – mineralogy is typically only considered and commissioned during the
exploration, feasibility and start-up stages, as part of due diligence exercises. It is not that
common for a mine manager to agree to regular mineralogical audits once an operation is
up and running, except of course when grade and recovery drop below acceptable limits.
Also, mining geologists rarely make it to mine manager level where they can influence
behaviour patterns in such matters.
•• Financial – there is real perception (which is also sometimes based on truth) that mineralogy
is costly, requires expensive equipment and involves highly qualified personnel who
write not particularly timely and relevant reports, which are all too often full of jargon,
and serve only to alienate the very audience for which they were intended.
Of course, the modern mining industry is quite different. Gone are the days where one could
choose to mine only the near-surface, high-grade, easy-to-process ores. With volatile metal
prices, heightened expectations from shareholders and unprecedented industrial growth
from China and India, the race is on to extract as much as possible from the earth to keep
up with demand. This must, of course, take place in a world where the awareness of human
safety and the environmental footprint of mining are coming under ever-increasing scrutiny.
All of these factors are challenging the viability of companies and mining operations every
day as we move to a world where mining lower-grade, more-difficult-to-process resources
will be the norm.
Given that our mantra as professionals involved in the earth resources industry could
be to ‘Take apart what Mother Nature has put together. Safely … with due regard for the
environment … and economically’, we really need to make effective use of the armoury
available to us to succeed in this combat exercise.
The science of mineralogy, and in particular that area of mineralogy dedicated to the
application of mineralogical information to mineral processing and smelting in order to
improve understanding, solve problems and improve efficiency of extraction, commonly
referred to as Process Mineralogy, is one such effective weapon in our mining armoury on
which we can draw. There is no doubt that process mineralogy, when used judiciously,
can make a major difference to a mining operation. In the author’s opinion, this was first
brought to the world’s attention in a seminal paper by Henley (1983), although many
others followed shortly thereafter (Hiemstra, 1984; Petruk, 1984; Baum et al, 1989). A text
book by Petruk attempts to pull together his experiences as a process mineralogist and is
a good source of case studies (Petruk, 2000). More recently, the Julius Kruttschnitt Mineral
Research Centre (JKMRC) has published a monograph on process mineralogy that contains

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 CHAPTER 4 | A PRACTICAL GUIDE TO SOME ASPECTS OF MINERALOGY THAT AFFECT FLOTATION

a number of case studies for a range of commodities, with chapters written by domain
experts (Becker, Wightman and Evans, 2016).
Before we move on, let us consider a hypothetical, but typical situation, which hopefully
will keep the sceptics interested and the novices alert.
The situation involves an ore type from the Eureka Concentrator. It needs investigating
because it is new. Routine assaying by the geologists in the mine suggests this ore type
contains a three weight per cent copper head grade, similar to all existing production ores.
The temptation is to go ahead, mine and crush the ore, and hope for the best. You might be
lucky. But a quick inspection of the ore by a mineralogist can immediately establish if the
copper is deporting to the usual phases (say sulfides), at the same grain size (which affects
grind size) and in the same host gangue (which affects flotation conditions) as the production
ore. If conditions are the same, fine. If they have changed, you could have saved yourself a lot
of expensive experimentation, not to mention embarrassment.
Mineral processing plants process minerals, and for mostly practical reasons, it is
accepted that conditions are often based on chemical assays rather than on mineralogical
information. Hopefully, your opinion on the use of mineralogy will change after reading
through this chapter.

BACKGROUND TO ORE DEPOSITS

It is necessary at this point to introduce a number of technical terms commonly used to
describe ore deposits, the minerals that make them up, and the textures that affect processing,
all with special reference to flotation behaviour.

Basic classification of deposit types

Believe it or not, it is helpful to know the geological context of a mine, especially where
mineralogical work is required to be carried out. This is undoubtedly satisfying from an
intellectual viewpoint. But more importantly, geologists need to do this all the time so that
they can conjure up a mental 3D image of the deposit on which they are working. It helps
us see things to scale, in some cases, put things back in order of formation and, ultimately,
allows us to rationalise and categorise the apparent anarchy we find in nature.
Ores are no different to any other rocks – they simply have an economic value and are
defined as a mineral or aggregate of minerals that form a rock which can be mined at a profit. They
can therefore be classified, like everything else in earth sciences, into conveniently simplified
categories. There are classifications that are based on simple criteria, such as the minerals or
metals contained (Pb-Zn, Cu-Au, PGM, etc). Better still, we can describe the structure of the
deposit in terms of its shape or size (basin, pluton, diatreme, vein, fault, etc), its relationship to
the host rocks, and the rocks that enclose or contain the deposit (for example, stratabound,
stratiform, volcanic-hosted, sedimentary-hosted, etc).
Of less use, is to classify a deposit according to the geological processes that combined
to form the deposit (or genesis). Why? Because most deposits are old, some very old, and
whose formation has not been witnessed by geologists today. We therefore have to rely on
interpretation alone, and given that there is considerable debate among geologists as to the
exact mode of formation of most mineral deposits, this is not a good classification in isolation.
So, in summary, it is best to stick to features that can be agreed on, such as the physical
description of the deposit. And even though no two mineral deposits are exactly alike, most
of them fall into a clear category. Each category often conveniently coincides with a generally

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 ALAN R BUTCHER

accepted hypothesis as to how the mineral deposit formed. So we typically end up with a
physically descriptive classification that includes a descriptor of how the deposit formed.
Once one understands that certain ore types produce distinctive mineral assemblages and
textures (and geologists are trained to know this), then it is easier to focus on issues that are of
specific interest. Figures 1 and 2 summarise some of the basic ore deposit types and structures
likely to be encountered by the professional minerals engineer. For a more thorough review,
the interested reader is referred to Guilbert and Park, 1986; Evans, 1993; Roberts and Sheahan,
1988; Eckstrand, 1984; Peters, 1978 and McKinstry, 1948.

FIG 1 – Summary diagram illustrating the main types of ore deposit, classified
according to mode of origin, host-rock and commodity, with real examples.

Mineralisation

Stratiform Stratabound

Vein-hosted Fault-hosted

• Exploration methods

• Mining method

• Sampling Strategies

Disseminated Replacement

FIG 2 – Cartoons to illustrate how the geological structure of an orebody controls how you explore for it, how you mine it and how
you sample it. Here, six typical types are presented. Black is mineral or ore of interest. No scale (after Butcher and Trudu, 1999).

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Take, for example, the deposit on which Eureka Mine is positioned. We know at the most
basic level that it is a polymetallic sulfide ore, and is mined underground. Armed with just this
information, an experienced geologist and process mineralogist can mentally map this to
be most likely a sediment-hosted, volcanogenic massive sulfide deposit, with an economic
mineral assemblage of sphalerite (Zn), galena (Pb), chalcopyrite (Cu).
With more information (such as age, geographic locality, geological model, tectonic history,
historical company reports), a mental checklist can be immediately created, and forms the basis
on which the mineralogist starts his or her campaign. It may include the following: look for
oxidation effects of sulfides; watch for grain size reduction if metamorphosed; look for talc
if sheared; check for more than one type of sphalerite; etc. More on this later in the chapter.

BASIC ORE TEXTURES

Once the macro-features (km-m) of an ore deposit have been established, it is then necessary to
concentrate on the meso- (m-cm) and micro-features (cm-mm-µm). It is at these scales we start
to gain valuable insights into which minerals make up the ore and how they all fit together to
form what is known as the texture. This is the area of study known as petrography.
A comprehensive study of ore deposit textures is beyond the scope of this chapter but the
interested reader is referred to the following texts for further details: Petruk, 2000; Craig and
Vaughan, 1994, and an excellent web-based atlas (Ixer and Duller, 1998), as well as the recent
creation of a virtual microscope (https://www.virtualmicroscope.org/about). Of particular
interest to flotation are the following basic types of textures. Starting at the most basic level
(Figure 3), an ore texture can be evaluated as to whether it is equigranular or inequigranular.
Milling strategies for the two extreme ores will be quite different.
On a more complex level (Figure 4), it is crucial to ascertain how the economic minerals
occur: if they are present as rims, disseminated inclusions (or exsolutions), or as interstitial
Equigranular
Inequigranular

Ore mineral

FIG 3 – Cartoons to illustrate the basics of ore textures, with special reference to flotation. At the simplest
level, ores can be considered either equigranular (all grains same size) or inequigranular (not all same size).
The mineral of interest is shown in black. Grain boundaries are straight or gently curved. No scale.

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 ALAN R BUTCHER

phases – as this will control breakage mechanisms during blasting, crushing and grinding
(intragranular versus intergranular), and will make it either relatively easy, or difficult (or
impossible) to liberate and float effectively. It is not uncommon for an ore to have multiple
textural deportments for the element of particular interest (see Figure 5).
Finally, and for completeness, a further concept is now introduced. It was mentioned above
that orebodies are generally contained within old rocks. Practically, this means that they have
been around long enough to experience post-formation modification, which can take one of many
forms (metamorphism, deformation, oxidation and weathering, to name a few). Sometimes
these so-called secondary processes can overprint or obliterate those that developed at the
time the deposit formed (so-called primary features). Metamorphism, for example, is generally
bad news for the metallurgist as it often involves growth of new (and unwanted) minerals

Rims Inclusions

Interstitial Disseminated

Exsolved Laminated

FIG 4 – Further cartoons illustrating complex ore textures, with special reference to those which affect
liberation and flotation performance. Mineral of economic interest shown in black. No scale.

FIG 5 – One major outcome of a textural analysis of an ore is to ascertain the deportment of elements of economic
interest. In this case, the element of interest, shown in black (say copper) occurs as: chalcopyrite intergrown with
pyrite (upper left); chalcopyrite blebs included within sphalerite (upper right); discrete native copper (centre);
chalcocite rimming pyrite (bottom left); bornite inclusions within silicate (bottom right); and native copper within
a cross-cutting vein (bottom left to top right). Scale: width 10–100 microns (after Butcher and Trudu, 1999).

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(such as mica, talc, graphite, serpentine, etc), which have an annoying habit of floating along
with the ore minerals to contaminate the concentrate – referred to here as menace minerals.
Deformation can lead to fracturing of the ore, recrystallisation and grain-size reduction, which
can change the comminution behaviour of an ore in a negative way (production of slimes).
Oxidation and weathering, however, can be both good and bad for a minerals engineer – it
can either upgrade (laterites, gossans) or downgrade (silcretes, calcretes and regoliths) the ore
depending on which process is dominant.
Figure 6 attempts to simplify what is obviously a very complex concept. The main point
being made here is that it is the job of the process mineralogist to: identify the presence of
these processes; then unravel them; and finally, understand how each one may impact on the
physical and chemical processing of the ore under investigation, and report these results in a
clear, easy to understand and practical way to the metallurgist.

THE CONCEPT OF LIBERATION

Now that we have revealed that ore deposits form in different ways, and that resulting mineral
assemblages and ore textures, to a large extent, reflect that heritage, we need to briefly review
what we mean by liberation from a mineralogical perspective.
This is quite important, as mineralogists often get asked to provide an estimate of liberation
or to estimate optimal grind sizes in their reports.

Fresh ore Surface Oxidation Hydrothermal Alteration Metamorphism

Ore minerals

Pristine Ground Water Heat & geofluids Heat, pressure & fluids

FIG 6 – Cartoon illustrating some of the processes which are known to affect ores after initial formation. The
fate of three pristine ore textures is considered (one equigranular and two inequigranular), which undergo
progressively more aggressive modification from left to right (oxidation, hydrothermal alteration to metamorphism).
The job of the process mineralogist is to identify the presence of these processes, unravel them and understand
how each one may impact on the physical and chemical processing of the ore under investigation.

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 ALAN R BUTCHER

Liberation is best studied, estimated and quantified in mineral agglomerates (rock

particles). Particles are typically examined in 2D sections, and this is achieved by setting
them in epoxy resin blocks and exposing their cross-sectional geometry by combinations of
cutting, grinding and polishing.
Examination of images of particles allows for the classification of each particle in terms of
whether it is ‘pure’, ‘barren’ or ‘locked’. This classification of particles is based on the volume
of the mineral of interest in each particle.
The concept can be illustrated with a cartoon in the same idealised format as we have seen
previously. Figure 7 shows how a complexly-textured ore (as viewed, for example, in thin-
section), and one that is essentially equigranular, starts to liberate the mineral of interest at
particle diameters of around 70 microns. The degree of liberation can be quantified using a
variety of optical and scanning electron microscope (SEM)-based image analysis techniques.
For a complete background to the theory of liberation, please refer to Barbery (1991), and
for further background on how automated SEM images can be used to derive knowledge of
particle behaviour in processing, see Sutherland et al (1988); Sutherland, Wilkie and Johnson,
(1989) and Spencer and Sutherland (2000).

A REVIEW OF MINERALOGICAL METHODS AVAILABLE

There are a bewildering number of techniques available to determine the mineralogical
and metallurgical behaviour of particles (of differing sizes) as they pass through a mineral
processing circuit from blasting, crushing, grinding and flotation through to final concentration
and disposal, in terms of their particle size and shape, composition, locking and liberation
characteristics and flotation behaviour.
The following is an essential guide to the main techniques, which briefly covers each
technique and provides when-and-where-to-use-it advice.

Hand-specimen analysis
Every self-respecting geologist and mineralogist should be able to gain information from
examination of materials in hand-specimen, using the naked eye or aided only by a hand

FIG 7 – Cartoon illustrating the effect of particle size reduction and increasing liberation from a complex, equigranular, ore texture,
where the mineral of economic interest is shown in black. Note that even the finest particle sizes still contain locked particles.

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lens, a scratch plate and a bottle of acid. However, once materials become reduced in size
to the point where they are barely visible to the naked eye, other techniques clearly need
to be used.

Optical techniques
This probably still remains the most widely used technique worldwide, and not surprisingly,
it has been around almost as long as the science of geology. It turns out that cleverly designed
combinations of reflected and transmitted light sources, in both polarised and unpolarised states,
allow minerals to be identified by their characteristic optical behaviour, especially when
viewed under magnification on a petrographic polarising microscope. Ore minerals (such
as sulfides, precious metals and oxides) are best viewed in reflected light as they tend to
be opaque, whereas gangue phases (such as silicates, carbonates and phosphates) are best
examined in transmitted light as they are often translucent. Sample presentation normally
takes the form of polished sections or petrographic thin-sections, although loose grains can also
be usefully observed with a basic stereo microscope. Apart from the identification of minerals,
the modal mineralogy of a sample can be determined by point counting. Textures can be
observed and recorded photographically (photomicrographs) and typically are used to
augment reports and illustrate features of the sample. A useful text on this topic is by Gribble
and Hall (1992).
In each case, optical techniques obviously require a competent person to operate the
microscope and make meaningful observations, typically a graduate in geological sciences
with a few years of relevant experience. Great microscopists, however, are a greying
workforce and continue to be in serious decline and good microscopists are getting harder
to find. It is becoming more and more difficult to encourage young graduates to move into
optical mineralogy. Automation of phase identification, modal point counting and texture
analysis goes some way to redress this situation (see Clemex Technologies Inc, 2009; Carl
Zeiss Microscopy, 2018).
A clear advantage of this method is that, in the right hands, a quick (and often relatively
cheap) prognosis can be obtained for both unbroken ore as well as particulates. And while that
might be good enough, like all techniques, it must be used judiciously, and in combination
with other methodologies.

X-ray beam techniques

A commonly used technique to assess a sample for the relative abundance of minerals present
is by a method that utilises the unique diffraction properties of minerals when subjected
to a primary X-ray beam, the so-called X-ray diffraction method or XRD for short. XRD is
particularly useful when trying to establish the nature of an unknown material, or tracking
the presence of an undesirable phase in a sample. It can be used to gain both semi-quantitative
and quantitative phase data.
XRD is a very powerful analysis technique for distinguishing certain mineral groups such
as the Clay Group (montmorillonite, illite, kaolinite), the Serpentine Group (lizardite, talc)
and certain polymorphs (minerals with exactly the same composition but differing only in
their crystal structure, such as rutile-anatase, quartz-coesite), or distinguishing minerals
with similar, but not exactly the same compositions (hematite-geothite-magnetite) or optical
behaviour. As it is a bulk method of analysis, it cannot provide information on particle shape,
size or internal texture.

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 ALAN R BUTCHER

In certain situations, it can be a relatively quick and inexpensive method to solve a problem.
It is best used, however, in combination with other mineral techniques.
XRD, of course, is not to be confused with X-ray fluorescence spectrometry (XRFS), which
is another established X-ray beam technique, but unlike XRD, provides whole-rock chemical
data. It is most commonly used for grade determination (say, Fe-, Pb- and Zn-content of ores,
Ti-contents of mineral sands, P-content of iron ores, etc). Latest scanning XRFs now have the
capability of creating both elemental and mineral maps, on drill cores and particle mounts
(Bruker, 2018).
An emerging area of imaging and analysis is X-ray computed tomography – known in
short form as either X-CT, micro-X-CT, or nano-CT – depending on the size of the sample
to be analysed and the voxel resolution required. Although commonly used in the oil
industry, typically on drill cores, it is finding more application within mining, especially
with regards to understanding ore textures (Sayab et al, 2017) and 3D liberation (Garcia, Lin
and Miller, 2009).

Electron beam techniques

The technology that has most revolutionised mineralogical investigation over the past 50
years or so has been that based on the utilisation of signals generated as a result of interaction
between a highly focused electron beam and geomaterials. As soon as scanning electron
microscopes (SEM) and later electron probe micro-analysers (EPMA) were introduced, they found
immediate appeal among geologists, mineralogists and materials scientists. Effectively non-
destructive, and with the ability to image, analyse and quantify a range of earth materials
(both unbroken rocks and particulates), they remain at the forefront of mineral analysis for
the earth resources industry today.
The underlying principles are common to all systems. Electron-induced, secondary X-ray,
energy dispersive spectrometry (EDS) can be used to qualitatively and quantitatively determine
the composition of a phase under the electron beam. Secondary electrons (SE), along with
backscattered electrons (BSE) and cathodoluminescence, all of which are simultaneously generated
along with the secondary X-rays, can be used to gain insights into other aspects such as sample
topography, composition and crystal defects. EPMA systems (and some SEM systems) have
both EDS and wavelength dispersive spectrometers fitted (WDS – for increased sensitivity using
a particular crystal to tune into a suite of elements). The electron beam can be used in both a
scanning or point-and-shoot mode.
A number of research groups around the world have attempted to automate SEMs and
EPMAs (King and Schneider, 1993; Schneider and Neumann, 2004; Jones, 1984, 1987). The
Australian systems succeeded in being widely adopted by the global minerals industry
(Gottlieb et al, 2000; Baum, Lotter and Whittaker, 2004; Gu, 2003). A particular strength of
an automated SEM system is that it removes some operator strain, tedium and repeatability
issues arising from manual SEM work.
CSIRO developed a system known as quantitative evaluation of minerals by scanning electron
microscopy (QEM*SEM) in the early 1980s (Grant et al, 1977; Miller, Reid and Zuiderwyk,
1982), which was used extensively by industry through ownership of their own systems as
well as through a bureau service offered by CSIRO. That was followed by a later product of
QEM*SEM technology, known as QEMSCAN®, which is a completely automated solution
from sample preparation through analysis to data reporting (Pirrie et al, 2004).

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The University of Queensland, through the JKMRC, developed an alternative technology

with similar objectives in terms of automation. Known as the Mineral Liberation Analyser
(MLA), it began in 1997 (Keith, 1998; Dou, 1998), and was offered as a bureau service from
1999 (Gu, 2003). Both QEMSCAN® and MLA are now owned by ThermoFisherScientific,
formerly FEI. For a useful summary of method developments up until 2015, the interested
reader is referred to a useful summary compiled by Sandmann (2015).
With market penetration developing at a pace, other SEM and EDS technology providers
have since entered into the automated mineralogy segment, and at the time of writing,
the following systems are available: Mineralogic, RoqSCAN and MinSCAN (Carl Zeiss,
2018); TIMA (Tescan, 2018); AMICS and Esprit (Bruker, 2018); AZtech and INCA (Oxford
Instruments, 2018); MAPS Mineralogy (ThermoFisherScientific, 2018).

Other techniques
Other technologies used by mineralogists include those that utilise proton beams, ion beams,
laser beams and infra-red and near infrared beams. A proton microprobe is ideal for mapping
ultra-trace elements within minerals. An example application at Eureka Mine would be to
examine the galena by PIXE to ascertain if silver was present in solid solution (Goodall and
Scales, 2006; Goodall, Scales and Butcher, 2005). A secondary ion mass spectrometer (SIMS)
can be used for accurately measuring invisible gold in sulfides – gold that is not possible to
see with SEM or EPMA microbeams as it is in solid solution (Vaughan and Corrans, 1977).
Fine grinding is not an option for this texture, but leaching could be.
Logging of cores, chips and powders for mineralogical composition can now be undertaken
using scanners that utilise near infrared radiation, which is phase specific. This is ideal for
on-site situations where rapid (near real-time) bulk mineralogical information is required to
troubleshoot processing problems or predict required conditions of operation as ores and
products pass along conveyors (Huntington, 2006; Shreeve et al, 2017).

APPLICATION OF MINERALOGY TO FLOTATION INTRODUCTION

Flotation isn’t about flotation cells. It is about minerals. Liberating the right minerals in
the right place, with the minimum of grinding power. Preparing the surfaces for maximum
selectivity for valuable minerals against gangue. Minimizing entrainment. Responding to the
needs of different size fractions. Doing all this at minimum cost, using the least new equipment
possible. Understanding the economics of the operation. And making the whole circuit work
together, simple, responsive and operable (Xstrata Technology, 2005).
This quote appeared within the conference proceedings of the 2005 Centenary of Flotation
Symposium held in Australia, which celebrated, as the name suggests, 100 years since the
introduction of flotation. It encapsulates many of the concepts introduced so far, which is
why it is reproduced here in full. Flotation, in fact, was developed because the ores in Broken
Hill, Australia were too fine to be separated efficiently by gravity (Figure 8).
We now move on to consider the practical application of all this know-how, particularly
the role of mineralogy, in the better understanding of the flotation separation process, with
respect to the Eureka Mine.
Let us imagine, therefore, that we have been set a mineralogical task to try and understand
why the metal recoveries at the Eureka concentrator are low despite the grades being
acceptable.

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 ALAN R BUTCHER

FIG 8 – Optical photomicrographs, taken using a digital camera attached to a reflected polarising
petrographic microscope, of processed particles from an Australian lead–zinc operation (McArthur River),
which contain textures that historically would have been too fine for conventional flotation, and now require
combinations of staged and fine-grinding methods to separate the galena and sphalerite.

Methodology
First up, we need decent primary samples to examine. These must be representative of the
problem we are trying to fix. A good starting point is to always organise for the collection of
a feed, concentrate and tail for each of the main saleable products. Experience has shown that
you might need to involve all relevant personnel in all key areas of the mines’ activity in the
sampling, and to make them aware of the common pitfalls and problems in sampling mineral
processing plants (many of these issues are covered in this book in other chapters, and by
other publications, for example Annels (1991)). Sampling a dynamic system such as a mineral
processing plant, where crushing throughputs can be in the region of 100 kt/d, is certainly a
challenging exercise. Results of any kind always need to be viewed with this in mind.
Next, we need to create secondary samples from the primary samples, using appropriate
methods, which normally take the form of one or more of the following, all of which are
familiar to the metallurgist: cone and quartering, splitting, riffling, sieving, cyclosising and
de-sliming. From these secondary samples, we are then able to produce genuine replicate
aliquots, which can be used for all mineralogy and allied testing and analysis (assaying,
etc). Typically, these aliquots then get made into a number of products depending on what
happens next. Polished thin-sections and polished blocks are best as these can be used for
optical work, SEM and EPMA work, as well as automated SEM techniques.

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Then, we need to generate quality petrographic information from the prepared products.
A typical checklist that most mineralogists might run through when examining samples
could look something like the following:
•• complete inventory of all known mineral phases present (Figure 9)
•• detailed modal analysis for major minerals (>5 per cent), minor phases (>1 per cent –
<5 per cent) and trace phases (<1 per cent)
•• textural information on both gangue and ore minerals, which includes:
•• grain size estimates (used to determine optimum liberation grain sizes and predict or
prevent problems such as poor liberation, over-grinding of the valuables, production
of slimes)
•• mineral associations (important for optimising the separation process, say galena from
sphalerite, chalcopyrite from sphalerite)
•• grain boundary relationships (curved, straight or irregular boundaries will affect behaviour
during crushing and grinding as this imparts preferential breakage mechanisms – for
example along or across boundaries)
•• elemental deportment information (important for tracking how metals behave during
processing; covered by Figure 5)
•• photomicrographs of typical textures.
All of the above can be generated manually from careful traditional optical-SEM-EPMA
interactive analysis. Automated techniques have enabled this type of information to be
collected and reported in a fast, robust, operator independent, time-efficient and scalable
manner.

Ore Type Example Valuable Example Problem Gangue

PGM PGM, Ni-sulfides Talc, pyroxene
Copper sulfide Chalcopyrite Pyrite, Fe-oxides, silicates
Nickel sulfide Pentlandite Pyrrhotite, talc
Pb-Zn Galena, sphalerite Pyrite, pyrrhotite, marcasite, carbonates
Gold Gold, electrum Pyrite, arsenopyrite, Fe-oxides, quartz

Ore Crusher Grinding & Classification Separation Product

Waste
Typical Process Overview

chalcopyrite – fast floating; pyrrhotite – slow floating depressants for carbonates and talc

naturally hydrophobic minerals float

FIG 9 – Summary diagram to show how different ores, classified by the main ore minerals, have quite different gangue phases.

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 ALAN R BUTCHER

EXAMPLE CASE STUDIES

Introduction
For mineralogy to add value to a mining operation, one really needs to acquire consistently
meaningful mineralogical data over a significant period of time (weeks, months, years). If a
well-performing ore is properly characterised it is much easier to troubleshoot problems in
an under-performing ore because there is a benchmark against which to compare it. Without
a good day, it is difficult to diagnose what went wrong on the bad day.
This section covers two examples where mineralogical data collected by the author has
been turned into information and knowledge, and then action has been taken based on that
knowledge to realise the value. The examples have been simplified and modified so as to be
relevant to the present text. A summary of information typically acquired is summarised in
Figure 10.

Case study 1 – finding the optimal grind size

Following measurement of crushed drill cores as part of an ongoing ore characterisation
exercise for a new orebody at Eureka Mine, it was found that there was a distinct bi-modal
distribution to the grain size distribution for galena (Figure 11). This flagged the possibility of
whether a two-stage grinding process could be implemented. When the same distribution for
sphalerite was considered, however, it was found that this displayed a normal distribution
(Figure 12).

Mineralogical Data
Roughers  Liberation
 Particle size
 Particle composition
Cleaners  Particle surface area
 Problematic particles
 Penalty elements
Re-grind Mill  Mineral associations

Metallurgical Implications
• Reagent regime
Scavengers • Surface preparation
• Residence time
• Mechanical entrainment
• Flash flotation options
• Staged grinding
• Grinding media
FIG 10 – Idealised view of what mineralogical data can be extracted from samples taken from a mineral
processing circuit, and the implications these data may have on metallurgical behaviour and practices.

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Lead-zinc Galena
deposit
-

+
2

6
0

0
/

0
+

0
/

/
+

+
2

5
0

4
5

5
6

0
G a l e n a B i - S i z e D i s t r i b u t i o n

FIG 11 – An image grid of galena-containing particles (red) from crushed drill core, organised by galena grain-size estimate,
as measured by a QEMSCAN® and plotted using iExplorer™. The distribution shows a distinct bi-modal pattern.

Lead-zinc Sphalerite
deposit
-

+
2

6
0

0
/+

/+

0
+

0
/+

/+

/
+

+
2

5
0

4
5

5
6

S p h a le r it e S i z e D i s t r ib u t i o n M T G A

FIG 12 – An image grid of sphalerite-containing particles (blue) from crushed drill core, organised by sphalerite grain‑size
estimate, as measured by a QEMSCAN® and plotted using iExplorer™. The graph shows a normal distribution.

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 ALAN R BUTCHER

Answer
Given that a two-stage grinding circuit was not possible at Eureka, an optimal grind size of
212/+106 microns was trialled during bench-scale grinding tests, and was found to achieve
the required grade and recovery.

Case study 2 – tracking down reason for penalty elements

After a few months of excellent results and acceptable concentrator performance, a crisis
hit Eureka Mine. The levels of iron in the final zinc concentrate reached unacceptable levels.
Mineralogy was used to establish the source of the iron.

Answer
Historic samples taken on a good day were compared with those containing high iron contents.
The results showed that Fe deports to both pyrite and Fe-rich sphalerite. Both phases were
more abundant in the final concentrate that had higher Fe-content (Figure 13).

Case study 3 – understanding locking relationships

A re-evaluation of the locking characteristics of particles within the lead circuit was initiated
following a managerial decision to set new grade and recovery targets at the Eureka
Concentrator. In order to undertake this, a feed sample was collected and analysed on a size-
by-size basis. The results revealed that the locking characteristics are complex (Figure 14).
Galena is locked with sphalerite, as expected, but also with Fe-sulfides and non-sulfide
gangue (NSG), which are problematic from a contamination perspective.

Fe-Sphalerite

Low Fe- Concentrate

Sphalerite

Pyrite
High Fe-Concentrate
CS2 CS3+4 CS5 CS2 CS3+4 CS5
100

90

80

70

60

50

40

30

20

10

Based on more than 1000 grains/fraction

FIG 13 – Comparison of samples from the final zinc concentrate, good and bad, in terms of Fe-content.
It illustrates that when iron increases, it is due to increases in both Fe-sphalerite and pyrite.

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Background
Fe Sulfides
Sphalerite
Galena
Other Sulfides
NSG

FIG 14 – Image grid of particles from a feed sample, sorted according to the size fraction from which they were
measured, and according to the texture they exhibit. The results show that the locking characteristics of galena are quite
complex and involve: locking with sphalerite (high- and low-grade ternary), Fe-sulfide, non-sulfide gangue (NSG).
Both barren and fully liberated particles are also present. Measured on QEMSCAN® and plotted using iExplorer™.

Answer
Finer grinding of the feed ore is perhaps suggested. This will liberate the composite particles.
Installation of secondary grinding equipment might be the solution, such as stirred mills,
which will help reduce particle size to the required liberation size range. Bench-scale testing
could validate this theory.

CONCLUDING REMARKS
It is the hope of the author that, after having gone through this chapter, the reader will take
something away of interest, and most importantly, something of use, which can be directly
applied to their everyday work.
No one expects or wants minerals engineers to become mineralogists or geologists – far
from it. What the author encourages, however, is that metallurgists, like geologists, mining
engineers and environmentalists, should take some of the responsibility for developing a
culture of cross-pollination of professional skill areas within the modern minerals industry.
Mineralogy is clearly useful when applied in the correct way. Rocks contain secrets that
traditionally only geologists and mineralogists have been able to unlock. With the advent of

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 ALAN R BUTCHER

more companies adopting automated mineralogical techniques, it is clear that mineralogy is

experiencing a revival, if not a renaissance, and it is allowing minerals engineers insights that
were previously just not possible.
Finally, ‘to measure is to know’ as Lord Kelvin, the famous English scientist, once remarked.
If you do not understand your inputs and your outputs, then you cannot hope to optimise the
overall process, whatever it is.

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 Return to contents

CHAPTER 5
Some troublesome sulfide
and non-sulfide minerals
Bill Johnson and Peter Munro

ABSTRACT
The abundance of each mineral in an ore sample allows early recognition of likely problems in
development of a processing circuit for a new orebody or in improvement of the performance
of an existing processing circuit.
This chapter discusses various aspects of the properties of selected valuable sulfide minerals
which affect the ease of preparation of a concentrate of marketable grade suitable for safe
transportation.
This chapter also reviews the properties of two common sulfide gangue minerals (pyrite and
pyrrhotite) that are known to cause processing problems. Troublesome non-sulfide gangue
minerals are also reviewed, eg those displaying hydrophobicity, those prone to causing
penalty payments for the concentrate and those with unusual or troublesome properties.

INTRODUCTION
Quantitative data on the percentage by weight of each valuable and gangue mineral present
in an ore is one type of data that is mandatory before commencement of the development of
a processing circuit. Such mineral abundance data allow early recognition of likely issues in
development of a processing circuit:
•• problems in both the preparation of a concentrate of marketable grade and its transportation
and sale, due to solid solution series, the presence in the valuable minerals of elements
incurring a penalty or the presence of elements affecting its fitness for safe transport
•• recognition of sulfide gangue minerals with some properties causing processing problems
and other properties that may provide a basis for process solutions
•• recognition of non-sulfide gangue minerals known to be hydrophobic in other ores, non-
sulfide gangue minerals containing elements incurring a penalty and non-sulfide gangue
minerals with unusual properties that cause processing problems.

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 BILL JOHNSON AND PETER MUNRO

SULFIDE VALUABLE MINERALS

Sphalerite (ZnS)/marmatite (Zn,FeS) partial solid solution series
Why can sphalerite/marmatite be troublesome? Sphalerite containing elevated concentrations of
iron, manganese and/or cadmium, ie marmatite limits the achievable zinc concentrate grade
because, as examples, the fully liberated marmatite may only contain 50.0 per cent Zn, or less.
Impact on feasibility study/existing flotation plant: Production of a commercial grade zinc
concentrate either may not be possible, or possible only at a prohibitively low zinc recovery.
Before a feasibility study, the type of sphalerite/marmatite in a deposit must be determined
and its variation over the deposit must be determined during the study. Deposits with
low levels of substitution of the zinc ion have an advantage because less storage space is
required for waste species removed during downstream processing of the concentrate to
produce zinc metal.
Solution: The properties of the valuable mineral can’t be changed. There is no plant solution.
Sphalerite (ZnS) contains 67.1 per cent by weight zinc and 32.9 per cent sulfur. However,
this mineral usually has some substitution of zinc ions by iron ions, forming a partial solid
solution series. The extent of substitution of zinc by iron is dependent on the temperature and
chemistry of the environment during ore formation (Klein, 2002). When the iron content in
sphalerite rises, marmatite (Zn,FeS) is the name given to the mineral. Its iron content can be
as high as 26 per cent by weight.
In addition to the substitution by iron ions, zinc ions in sphalerite are substituted by
manganese and cadmium ions with significant manganese substitution in some ores. An
example is given for the composition of one example of marmatite, expressed in terms of
atomic proportions: (Zn0.645Fe0.308Mn0.045Cd0.002)S (Klein, 2002). In this example, the marmatite
contains the following approximate contents for the cations (per cent by weight): 18.6 per cent
Fe, 2.7 per cent Mn, 0.3 per cent Cd and 45.5 per cent Zn.
The highest grade of zinc concentrate which could be produced from an ore containing this
marmatite would be a concentrate containing marmatite alone, ie containing 45.5 per cent
zinc. A concentrate grade of 45.5 per cent zinc would not be achievable in practice because
any industrial zinc concentrate will also contain some liberated gangue minerals and some
minerals in composites with the marmatite, because perfect liberation and perfect separation
are not possible. Typically, commercial zinc concentrates based on sphalerite/marmatite ores
contain 50 per cent to 55 per cent zinc by weight. Hence, the importance of understanding
the properties of the valuable mineral can be appreciated prior to embarking on circuit
development testing or improving the performance of an existing plant.
An example is given in Figure 1. If the marmatite contained slightly more than a combined
total of 12 per cent iron, manganese and other elements that substituted for zinc, the
production of a commercial zinc concentrate containing 52 per cent zinc by weight would
require that the concentrate contained only five per cent by weight of gangue minerals,
ie the valuable mineral would have to occupy 95 per cent by weight of the concentrate.
Commercial concentrates are rarely produced that contain 95 per cent valuable mineral by
weight. In contrast, if the marmatite/sphalerite contained a total of six per cent by weight for
iron and other elements that substituted for zinc, a concentrate containing 52 per cent zinc
by weight would allow the concentrate to contain 15 per cent by weight of gangue minerals,
ie the valuable mineral could occupy as little as 85 per cent by weight of the concentrate.

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 CHAPTER 5 | SOME TROUBLESOME SULFIDE AND NON-SULFIDE MINERALS

% Gangue Minerals Possible in Concentrate with 52% Zn 25

20

15

10

Typical Values in this Range

0
0 2 4 6 8 10 12 14 16
% of Fe + Other Elements in Solid Solution in Sphalerite/Marmatite Series

FIG 1 – Calculated relationship between the per cent by weight of gangue minerals that can be present in the
zinc concentrate while still producing a concentrate with 52 per cent by weight of zinc (y axis) and the per cent by
weight of Fe and other elements in solid solution in the sphalerite/marmatite solid solution series (x axis).

This is a realistic target because typical commercial zinc concentrates contain in the region
of 90 per cent valuable mineral by weight.

Tetrahedrite (Cu12Sb4S13)/tennantite (Cu12As4S13) solid solution series

Why can tetrahedrite/tennantite be troublesome? These copper minerals will raise the level of
Sb and As respectively in the concentrate, potentially making the concentrate unattractive
for sale.
Impact on feasibility study/existing flotation plant: Investigate the main minerals contributing
to the total Sb and As in the concentrate and repeat this for the valuable element, Ag. Establish
the distribution of tetrahedrite/tennantite and related minerals across the entire deposit.
Avoid the use of cyanide to maximise the recovery of silver-bearing forms of these minerals.
Solution: Direct all the concentrate to an extractive metallurgical process for removal of
Sb/As before sale, or separate the concentrate into high and low quality products, directing a
reduced tonnage of low quality product to the additional process before sale.
These two minerals have the same structure and form a complete solid solution series. Their
crystallographic and physical properties are so close that it is not possible to distinguish
between them by inspection (Klein, 2002). If these minerals represent a sufficient portion of
the copper in an ore, the resulting concentrate will be elevated in arsenic and/or antimony
and may exceed limits for sale.
The copper ions can be substituted by iron or zinc ions and less commonly by silver, lead and
mercury ions (Klein, 2002). Some iron is always present and silver-rich members of the solid
solution series can be important sources of silver in an ore and are referred to as freibergite.
An example is the zinc-lead-silver ore at the Mount Isa deposit where the silver content of the
freibergite was in the range 18 per cent to 35 per cent by weight with an average composition

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 BILL JOHNSON AND PETER MUNRO

of 26 per cent by weight (Riley, 1974, 1976; Knights and Patterson, 1988; Knights and Johnson,
2016). If freibergite contains a significant portion of the silver in an ore, the silver recovery
will be dictated by the liberation state of the freibergite and, for the non-liberated portion,
the behaviour of the mineral with which it occurs in composites. The composites with galena
(the lead mineral) will be recovered in the desired concentrate for silver, the lead concentrate,
while the composites with sphalerite (the zinc mineral) are likely to be recovered in the zinc
concentrate, which is less desirable commercially. The composites with iron sulfide gangue
minerals will be largely lost to the tailing.

Chalcocite (Cu2S)
Why can chalcocite be troublesome? Chalcocite oxidises rapidly and releases copper ions
which can have deleterious effects on some other minerals in the system, particularly pyrite,
pyrrhotite and sphalerite.
Impact on feasibility study/existing flotation plant: It is necessary to investigate the influence of
conditioning pH (from pH 5 to 11.5) and the use of NaHS in restoring the surface of oxidised
chalcocite to its original form just before the addition of collector for the flotation process.
In the flotation testing, it is necessary to obtain chalcocite recovery – size (log scale) curves
to compare the recovery obtained in the fine and intermediate size fractions ensuring that
the recovery of the chalcocite in the fine size fractions is maximised relative to that in the
intermediate fraction.
Solution: Use the findings from the described approach to testing to establish the necessary
chemical conditions for flotation of the chalcocite or its closely related minerals in the ore.
Chalcocite is one of the most important source minerals for copper. A well-known occurrence
of chalcocite is in the supergene enriched zone of sulfide deposits. Another is in iron oxide-
hosted copper-gold deposits where it occurs as a primary mineral in a well-defined zone, not
from supergene enrichment. An unusual property of chalcocite is that, with suitable values
for Eh and pH, it will oxidise rapidly, in minutes, to other copper sulfide phases and release
copper ions into the system which can have deleterious effects on the other minerals present
in the system.
The oxidation of chalcocite occurs through a series of non-stoichiometric copper sulfides as
shown in Table 1 (Woods, personal communication, 2015), based on copper sulfide phases
identified in the literature (Goble, 1985).
From Table 1, in conversion of chalcocite to djurleite, 1.5 per cent of the copper initially
present is released; in conversion of chalcocite to djurleite and then to digenite, a total of
10 per cent of the copper initially present is released. Eventually, 50 per cent of the copper is
released after moving from chalcocite (Cu2S) through the series of non-stoichiometric copper
sulphides to covellite (CuS), as dictated by the formulae of chalcocite and covellite. The values

TABLE 1
The oxidation of chalcocite (Cu2S) through a series of non-stoichiometric copper sulfides.
Copper sulfide Chalcocite Djurleite Digenite Anilite Geerite Spionkopite Yarrowite Covellite
phase
Formula Cu2S Cu1.97S Cu1.8S Cu1.75S Cu1.6S Cu1.4S Cu1.12S CuS
Copper released by
oxidation of Cu2S 0 1.5 10 12.5 20 30 40 50
(% of total in Cu2S)

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 CHAPTER 5 | SOME TROUBLESOME SULFIDE AND NON-SULFIDE MINERALS

for the released copper are based on conversion of all the chalcocite in the starting material,
ie both the surface and bulk chalcocite.
During the oxidation sequence in Table 1 through the non-stoichiometric copper sulfide
phases, the copper ions are very mobile in the bulk and surface regions of the phases.
In contrast, for the end point of the sequence, covellite, the copper ions are not mobile, ie it
has a ‘frozen’ lattice.
For the oxidation of chalcocite through the non-stoichiometric copper sulfide phases
to covellite, the thermodynamics of the direct conversion from chalcocite to covellite is
misleading and should not be considered (Woods, personal communication, 2015).
The copper which is released from the copper sulfide phases (ie not part of the non-
stoichiometric copper sulfide phases) may contribute to an acid soluble copper assay for a
sample containing nominally chalcocite.
For the Ok Tedi deposit, industrial experiences and supporting research work with chalcocite
(principally occurring as digenite in one orebody) were carefully documented (Orwe, Grano
and Lauder, 1997; Orwe, Grano and Lauder, 1998); for the Eh and pH conditions in the Ok
Tedi plant, the chalcocite was likely to be unstable, ie undergoing surface oxidation.
The authors studied the influence of conditioning pH and the use of NaHS in restoring
the surface of the oxidised chalcocite to its original form (Orwe, Grano and Lauder, 1998)
before introducing collector into the system for adsorption. However, surface re-oxidation
before the flotation process should be minimised. After exposure to oxidising conditions, the
authors found that fine particles of chalcocite (-10 µm) suffered greater adverse effects on
recovery when compared with the intermediate size fractions of the same mineral. The use of
NaHS minimised the collector required for flotation as it precipitated the hydrophilic metal
hydroxides, present at both the chalcocite surface and in solution, as a very insoluble metal
sulfide (Orwe, Grano and Lauder, 1997), because there are less hydrophilic species on the
chalcocite surface to lower the hydrophobicity conferred by the adsorbed collector.

Radioactive copper concentrate

Why can radioactive copper concentrate be troublesome? Some concentrates demonstrate
radioactivity levels that can approach or exceed the OH&S limit for safe transportation.
Impact on feasibility study/existing flotation plant: Investigate if there is a strong association
between the radioactivity sources and non-sulfide gangue in the concentrate. If the finding is
‘yes’, staged options exist in Solution.
Solution: Investigate the benefits of reduced entrainment of liberated non-sulfide gangue
(more dilute pulps in conventional flotation cells and/or use of cells designed for washed
froth cleaning) and, if necessary, the benefits from further regrinding to increase liberation of
non-sulfide gangue.
Some concentrates, most notably copper concentrates from iron oxide-hosted copper-gold
deposits, demonstrate radioactivity levels that can approach or exceed the OH&S limit for
safe transportation. It may be necessary for a plant to improve its process to increase the
margin between the actual value and the limit. The following five options can be considered
if there is a strong association between the radioactivity sources and the non-sulfide gangue
minerals in the concentrate:
1. process changes to improve the dilution cleaning in mechanical cells by employing more
dilute pulps, normally requiring an increase in the installed capacity of the cleaner cells

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 BILL JOHNSON AND PETER MUNRO

2. process changes to introduce washed froth cleaning technology or increase the proportion
of the concentrate produced by washed froth cleaning technology
3. process changes incorporating points 1 and 2
4. process changes to regrind to a finer size and increase the liberation of the non-sulfide
gangue
5. process changes incorporating point 4 and points 1 and/or 2.
In points 1, 2, 3 and 5, the process improvement lessens the contribution from recovery
by the entrainment mechanism of non-sulfide gangue containing sources of radioactivity.
If sufficient lowering of the radioactivity level is not achieved by these options, other methods
directed at the valuable sulfide mineral itself may be needed; such options are topics for
research projects at present and cannot be addressed here.

SULFIDE GANGUE MINERALS

Pyrite (FeS2)
Why can pyrite be troublesome? More than one form exists in some ores eg normal euhedral pyrite
and a second form in a framboidal texture. In addition to euhedral pyrite being inadvertently
recovered from collector adsorption or from copper ion activation and collector adsorption,
the framboidal pyrite can be naturally hydrophobic from a different mechanism (presence of
naturally occurring hydrocarbons during ore formation), lowering the concentrate grade at a
given recovery for the valuable mineral.
Impact on feasibility study/existing flotation plant: Use a standardised pre-flotation rougher test
in ore characterisation to assess the proportion of the pyrite displaying problematic natural
hydrophobicity; investigate the benefits from removal of a portion of this form of pyrite in a
pre-flotation step or by reverse cleaning. Investigate reduction of the hydrophobicity of this
form of pyrite with a high molecular weight organic depressant in cleaning, or in cleaning
and roughing. Avoid the use of grinding or regrinding stages with reducing conditions where
pyrite activation with Cu1+ will make the euhedral pyrite extremely difficult to depress.
Solution: Remove a portion of the naturally hydrophobic pyrite in a pre-flotation step
(rougher feed) or by reverse cleaning (final concentrate) and/or use a high molecular weight
organic depressant in cleaning, or in cleaning and roughing. Oxidation of the pyrite or a
depressant, metabisulfite (MBS), can be used to lower recovery of normal pyrite, from
inadvertent collector uptake.
Pyrite is the most common sulfide gangue mineral but there are some cases where the pyrite
or a portion of the pyrite with a different geological history is a carrier of a valuable element,
eg gold. It may also contain nickel and cobalt in small amounts. In addition, a complete solid
solution series can exist between pyrite and bravoite, (Fe,Ni)S2 (Klein, 2002).
Crystalline pyrite commonly occurs in deposits, sometimes described as euhedral pyrite.
However, the mineral can adopt other forms depending on the type of deposit and its
geological history; one or more of these forms can occur in addition to the euhedral pyrite.
Examples are pyrite with a colloform texture, a framboidal texture and as agglomerates
consisting of a set of juxtaposed small pyrite grains (McArthur, personal communication,
2018); pyrite in these forms can be important in ore processing as they may possess different
metallurgical properties from euhedral pyrite or be carriers of high levels of gold.
Base metal ores of the Carpentaria Inlier in northern Australia commonly have a portion of
the pyrite with a framboidal texture in addition to the dominant euhedral pyrite. The portion

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 CHAPTER 5 | SOME TROUBLESOME SULFIDE AND NON-SULFIDE MINERALS

with the framboidal texture represents a metallurgical problem in the copper and zinc-lead
ores at and close to Mount Isa (Croxford, Draper and Harraway, 1961) and for the zinc-
lead ores of other deposits in the Carpentaria Inlier (McArthur River, Century and Dugald
River). The spheroidal pyrite in the framboidal texture contains hydrocarbons derived from
bacteria at the time of ore formation. In these orebodies, the other minerals are affected only
slightly by the hydrocarbons in comparison with the spheroidal pyrite. The spheroidal pyrite
contains fine grains, typically 5–15 microns in diameter, and has the hydrocarbons existing on
its surfaces after breakage, causing this portion of the pyrite to display an intermediate level
of hydrophobicity (in the presence of frother and in the absence of collector) (Johnson and
Jowett, 1982). Dilution of the flotation concentrate occurs with this type of hydrophobic pyrite
in the feed as it is not affected by the variables used to control the euhedral pyrite in flotation.
This spheroidal pyrite is sometimes given the name ‘carbonaceous pyrite’; it is porous and
highly reactive.
Porous pyrite with high reactivity can also exist in some ores in a colloform texture which
results from hot metal bearing solutions contacting cold ocean water during ore formation,
conditions allowing little time for crystals to form. The pyrite formed has been described
(McArthur, personal communication, 2018) as the mineral melnikovite, a primitive pyrite.
Later recrystallisation results in voids, ie the porosity noted earlier. This component can be
a carrier of elevated levels of precious metals such as gold and it is important to understand
this occurrence.
Pyrite has a polymorph, marcasite, which can be present with pyrite in an ore, usually in
small amounts, marcasite being much less common than pyrite in general. Pyrite (specific
gravity 5.02) belongs in the cubic crystal system while marcasite (specific gravity 4.89) is
in the orthorhombic crystal system. Marcasite is less stable than pyrite, decomposing more
readily than pyrite into melanterite (FeSO4 7H2O).
For metallurgical characterisation of ores with a gangue mineral displaying moderate
hydrophobicity such as those with spheroidal pyrite in the Carpentaria Inlier, the direct
method is to use a standardised pre-flotation rougher test; this requires multiple staged
concentrates to be collected with frother as the necessary reagent in the test. It is necessary to
use the assay results on a mineral basis, not on an element basis; this requires an element assay
to mineral assay conversion system for the ore in question. For the ores in the Carpentaria
Inlier, the important pieces of information are listed:
•• pyrite head grade
•• percentage of the pyrite in the feed which is recovered in the pre-flotation test, ie that has
natural hydrophobicity (typically in the range ten per cent to 35 per cent).
The worst case is potentially an ore with a high pyrite head grade with a high percentage
of the pyrite displaying hydrophobicity as measured in the pre-flotation test. It is believed
that the distribution of the hydrocarbon is important in maximising the quantity of solid
displaying unwanted hydrophobicity, and may be more important than the quantity of
hydrocarbon in the feed.
Forbes, Smith and Vepsalainen (2018) compared the galvanic interaction of chalcopyrite with
two distinctly different types of pyrite recognised using several textural and electrochemical
characterisation methods. In flotation tests with the chalcopyrite and pyrite 1 and with the
chalcopyrite and pyrite 2 as the feed, the flotation response of the chalcopyrite was the same
but, for pyrites 1 and 2, the flotation response differed. This finding indicates that additional
characterisation methods for pyrite may need to be used in the future.

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 BILL JOHNSON AND PETER MUNRO

Pyrrhotite (Fe1-xS where 0 < × ≤ 0.125)

Why can pyrrhotite be troublesome? Pyrrhotite can be inadvertently recovered from collector
adsorption or from copper ion activation and collector adsorption, lowering the concentrate
grade at a given recovery for the valuable mineral. Naturally occurring pyrrhotites possess
a range of compositions and a wide range of properties, both magnetic properties and in the
flotation process.
Impact on feasibility study/existing flotation plant: The types of pyrrhotite in a deposit must be
determined and the variation in their relative amounts over the deposit must be determined
in the feasibility study.
Solution: Depending on the type of pyrrhotite diluting the concentrate, magnetic separation
using permanent magnet technology may allow its removal. For flotation separation options,
establish the recovery – size (log scale) graphs for the types of pyrrhotite present in the
ore to determine the potential usefulness of the flotation process in producing commercial
concentrate. Complexing agents diethylene triamine (DETA) and triethylene tetramine
(TETA) in conjunction with sodium sulfite will depress pyrrhotite activated by copper or
nickel ions (Kerr, 2002).
Pyrrhotite is usually considered as a sulfide gangue mineral. However, there are some cases
where this may not be the situation (Multani and Waters, 2017) and its recovery is sought:
•• pyrrhotite with platinum group elements in solid solution
•• pyrrhotite with discrete fine-grained platinum group elements
•• pyrrhotite with nickel in solid solution
•• pyrrhotite with very fine-grained disseminated pentlandite.
Pyrrhotite occurs in stability or phase diagrams in a complex narrow region between the
relevant end member minerals of troilite (FeS) and pyrite (FeS2) and close to the end member
troilite (FeS) (Klein, 2002). Unlike the varieties of pyrrhotite, troilite only contains ferrous iron
and has no vacancies in its structure. Pyrrhotites contain both ferrous and ferric iron and have
a deficiency of iron with respect to sulfur, and the varieties occurring at room temperature
possess a range of compositions (Fe7S8, Fe9S10, Fe10S11 and Fe11S12); the varieties of pyrrhotite
also possess a range of crystallographic forms. Hence, a wide range of properties for the
naturally occurring varieties of pyrrhotite can be anticipated and are observed in practice.
Because of the complexity of pyrrhotite and the importance of pyrrhotite in nickel sulfide
ores and for ores with the platinum group elements, research projects continue to expand
the understanding of the fundamental properties and processing properties of this mineral
(Becker, de Villiers and Bradshaw, 2010a, 2010b; Ekmekci et al, 2010; Multani and Waters,
2017).
Table 2 provides structural information for naturally occurring pyrrhotites, ie those
occurring at room temperature and their magnetic properties. In the naturally occurring
pyrrhotites, there is a range in the percentage of vacancies (Table 2), causing the pyrrhotite
composition to be in the range from Fe7S8 to Fe11S12.
The magnetic susceptibility of monoclinic pyrrhotite (Fe7S8) in Table 2 is sufficient for recovery
by magnetic separators using permanent magnets ie low intensity magnetic separators with
the lowest capital and operating costs. Among the common minerals, only magnetite has a
higher magnetic susceptibility than monoclinic pyrrhotite (Fe7S8). The other three varieties
of pyrrhotite in Table 2 display non-magnetic properties. Hence, there is a wide range of

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 CHAPTER 5 | SOME TROUBLESOME SULFIDE AND NON-SULFIDE MINERALS

TABLE 2
Data for naturally occurring pyrrhotites (from Multani and Waters, 2017).
Ideal Vacancy (%) Charge neutral Ideal atomic composition (%) Magnetic
composition formula Fe S properties
Fe11S12 8.3 Fe2 Fe9 S12
3+ 2+ 2-
47.83 52.17 Non-magnetic
Fe10S11 9.1 Fe23+Fe82+S112- 47.62 52.38 Non-magnetic
Fe9S10 10.0 Fe2 Fe7 S10
3+ 2+ 2-
47.37 52.63 Non-magnetic
Fe7S8 12.5 Fe2 Fe5 S8
3+ 2+ 2-
46.67 53.33 Magnetic

magnetic properties and the importance of understanding the types present in an orebody
and variation in the relative amounts of these types over the deposit can be recognised.
In the past, magnetic separators were common in processing ores in which pyrrhotite was
a gangue sulfide mineral and the varieties of pyrrhotite were directed into separate magnetic
and non-magnetic circuits (Table 2), based on their magnetic properties, and subjected to the
flotation process in independent circuits. More recently, operations have tended to eliminate
magnetic separation in the processing plants with the varieties of pyrrhotite being processed
in a single flotation circuit where it has been recognised that there is a wide range in flotation
properties for the varieties of pyrrhotite in real systems (Multani and Waters, 2017).
In the area of flotation properties, the focus has been on Fe7S8 pyrrhotite and Fe9S10 pyrrhotite,
being the most common and occurring together in intergrown mixtures in the ore texture.
It has been necessary to examine the recovery – size (log scale) graphs of each to understand
the differences in their behaviour in real systems. For Fe9S10 pyrrhotite, a recovery >60 per cent
is observed for the intermediate size fractions, while this is not the case for Fe7S8 pyrrhotite
which produces a poor response in the fine, intermediate and coarse size fractions (Multani
and Waters, 2017).

NON-SULFIDE GANGUE MINERALS

Introduction
Most of the non-sulfide gangue minerals considered in the following sections are from the
phyllosilicate category, well known for their troublesome properties in mineral processing
circuits. Klein (2002) uses four groupings within the phyllosilicates:
1. serpentine (antigorite, chrysotile and lizardite)
2. clay (kaolinite, talc and pyrophyllite)
3. mica (muscovite, phlogopite, biotite, lepidolite and margarite)
4. chlorite (chlorite).
Variations on this system are used by the authors of other texts but the system from Klein
(2002) is convenient for the following discussion of some non-sulfide gangue minerals. Any
ore that contains significant amounts of phyllosilicates is likely to display some difficult
processing properties. It is important that the phyllosilicate minerals are correctly identified
and verified by the use of multiple quantitative measurement techniques. Otherwise, incorrect
mineral identification will lead to inappropriate design of test work for a new deposit.
The minerals discussed in the following sections on non-sulfide gangue minerals have
been selected based on the importance of some phyllosilicates and some other non-sulfide
gangue minerals in process development in the experience of the authors. In the section

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 BILL JOHNSON AND PETER MUNRO

‘Clay Minerals in General’, brief reference is made to a recent publication (Grafe et al, 2017)
on clay minerals.

Non-sulfide gangue minerals contributing fluorine in the final concentrate

There are several non-sulfide gangue minerals which can contribute the undesirable penalty
element, fluorine, to the final concentrate:
•• fluorite (CaF2)
•• apatite (Ca5(PO4)3(F, Cl, OH))
•• sericite (KAl2(AlSi3O10)(OH)2 where F can substitute for OH).

Fluorite and apatite

Why can fluorite and apatite be troublesome? Fluorite and apatite can contribute the penalty
element, F, to the concentrate by the mechanisms of entrainment and in composites with the
valuable mineral.
Impact on feasibility study/existing flotation plant: Investigate the main minerals contributing
to the total F in the concentrate. If fluorite is one of the main minerals, staged options exist in
Solution.
Solution: Investigate the benefits of reduced entrainment of liberated non-sulfide gangue
(more dilute pulps in conventional flotation cells and/or use of cells designed for washed
froth cleaning) and, if necessary, the benefits from further regrinding to increase liberation of
the fluorite and apatite. High levels of fluorine in fluorite and apatite in a concentrate can be
removed by an acid leaching process in the presence of aluminium sulphate (Torrisi, 2001).
For fluorite, the situation is straight-forward with the fluorine occurring in the lattice of the
mineral.
For apatite, the fluorine, chlorine and the hydroxyl group can substitute for each other
giving the complete series (Klein, 2002) for which the end points are fluorapatite (Ca5(PO4)3F),
the most common, chlorapatite (Ca5(PO4)3Cl) and hydroxylapatite (Ca5(PO4)3(OH)).
If the dominant occurrences of fluorite and apatite in a concentrate are as composite
particles with the valuable mineral, additional regrinding will be needed to improve their
liberation and increase their rejection. If their dominant occurrences in the concentrate are
as fine liberated particles, sized process data should be analysed to confirm that the minerals
are behaving as expected for the entrainment mechanism. If entrainment is shown to be the
mechanism, its contribution will need to be lowered.

Sericite
Why can sericite be troublesome? Sericite can contribute the penalty element, F, to the concentrate
by the mechanisms of entrainment and in composites with the valuable mineral. Sericite,
a fine-grained member of the mica group, may be capable of interacting with the valuable
mineral, reducing the flotation rate of the valuable mineral.
Impact on feasibility study/existing flotation plant: Investigate the main minerals contributing
to the total F in the concentrate. If sericite is one of the main minerals, staged options exist
in Solution. Investigate if the sericite can adhere to the valuable mineral or interact with it in
other ways if the flotation rate of the liberated valuable mineral is observed to be diminished.
Solution: Investigate the benefits of reduced entrainment of liberated sericite (more dilute
pulps in conventional flotation cells and/or use of cells designed for washed froth cleaning)
and, if necessary, the benefits from further regrinding to increase sericite liberation.

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 CHAPTER 5 | SOME TROUBLESOME SULFIDE AND NON-SULFIDE MINERALS

Sericite has the composition of muscovite and it is the occurrence of muscovite in some
schistose rocks as fibrous aggregates of minute scales with a silky lustre that has resulted in
the use of the term, sericite (Klein, 2002). For muscovite and sericite, fluorine can substitute
in the locations normally occupied by the hydroxyl group. Various other elements can also
substitute to a limited extent in the locations occupied normally by potassium and aluminium.
For a particular ore, sericite can contribute to the total fluorine content of the final concentrate.
If the dominant occurrence of the sericite is in composite particles with the valuable mineral in
the concentrate, additional regrinding will be required to improve its liberation and increase
its rejection. If the dominant occurrence of sericite in the concentrate is in fine liberated
particles, steps will need to be taken to lower the contribution of the entrainment mechanism
in the recovery of sericite. As part of this procedure, process data should be analysed to
confirm that the sericite is reporting to the final concentrate in each size fraction as expected
from the entrainment mechanism.
Silvester et al (2011) noted that sericite has been viewed historically as a troublesome gangue
mineral. The authors also noted that it was possible to control its recovery by ‘judicial use of
dilution cleaning and/or froth washing’; this finding suggested that the sericite was being
recovered by the entrainment mechanism. For ore with elevated sericite content, it is therefore
important to establish if the liberated sericite follows the guidelines for entrainment in each
size fraction, noting that the sericite particles may possess an unusual shape.

Talc (Mg3Si4O10(OH)2) and pyrophyllite (Al2Si4O10(OH)2)

Why can talc and pyrophyllite be troublesome? These minerals have similar layered structures
which result in natural hydrophobicity (ie not induced by collector adsorption), causing
lowering of the final concentrate grade at a given recovery value for the valuable mineral.
These minerals are sometimes carriers of fluorine, by substitution for OH groups in the lattice.
Impact on feasibility study/existing flotation plant: Investigate reduction of natural
hydrophobicity with a high molecular weight organic depressant in cleaning, or in cleaning
and roughing. Investigate removal of a portion of these minerals in a pre-flotation step
(rougher feed) or by reverse cleaning (final concentrate). Use a standardised pre-flotation test
in ore characterisation.
Solution: Implement the most cost effective method for reducing the recovery of talc or
pyrophyllite.
Talc and pyrophyllite are non-sulfide gangue minerals which display natural hydrophobicity
(ie not induced by collector adsorption); these two minerals are discussed in terms of this
property. They are very closely related where the three divalent magnesium ions in talc
are replaced by two trivalent aluminium ions in pyrophyllite. Both minerals have a similar
layered structure and similar physical properties. The composition of talc varies depending
on its geological history while, in contrast, substitution of other elements in pyrophyllite are
minimal in comparison to talc.
These minerals cleave readily because weak bonding (van der Waals) exists between the
sheets containing strongly bonded silicate tetrahedra; it follows that the uncharged surfaces
of these sheets cannot interact well with water and that the surfaces of these sheets display
moderate hydrophobicity in a flotation process, in the absence of collector.
Liberated talc and pyrophyllite are recovered in roughing and cleaning to an extent greatly in
excess of those expected just from entrainment due to their natural hydrophobicity. Liberated
talc and pyrophyllite can be depressed with high molecular weight organic compounds

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 BILL JOHNSON AND PETER MUNRO

such as carboxy methyl cellulose (CMC), derivatives of guar gums, locust bean gums and
others where these reagents are added in cleaning and/or roughing. Additional approaches
to remove these minerals are a pre-flotation step preceding the rougher section and reverse
flotation of the final concentrate.
At the commencement of ore characterisation in laboratory testing of an ore, a standardised
pre-flotation rougher test should be used to evaluate the extent to which minerals in the feed,
including talc or pyrophyllite, are being recovered in quantities in excess of those expected
from entrainment. The pre-flotation test requires the use of frother and the absence of
collector; it is possible that a depressant for a gangue sulfide mineral may be used depending
on the system. A standardised pre-flotation rougher test as an ore characterisation method
was discussed earlier in the section on the mineral pyrite.
Both talc and pyrophyllite are industrial minerals which are often discussed together
because of their similarity (Tomaino, 2018).

Chrysotile (Mg3Si2O5(OH)4)
Why can chrysotile be troublesome? Chrysotile displays a positive surface charge at alkaline
pH values, causing it to adhere to the negatively charged valuable mineral in this pH region,
lowering the hydrophobicity and flotation rate of the valuable mineral and also lowering
concentrate grade. Additionally, it is fibrous, forming cylindrical tubes, and has an extremely
detrimental effect on pulp rheology. Its most common occurrence is in serpentinitic nickel
sulfide ores.
Impact on feasibility study/existing flotation plant: Investigate the use of depressants which
negate the positive surface charge on the chrysotile and investigate circuitry and conditions
which reduce its detrimental effects such as separate flotation of size fractions and the use of
very dilute pulps.
Solution: Implement the most cost effective methods for reducing the deleterious effects.
Most base metal sulfide ores are processed by froth flotation in the alkaline region.
Fortunately, most sulfide minerals (both valuable and gangue) and most non-sulfide gangue
minerals possess a negative surface potential in the alkaline region. This contributes to the
dispersion of the particles due to similarity of the sign of their surface charge.
An exception to the described situation is the mineral chrysotile (or closely related minerals)
which possesses a positive surface potential in the alkaline region and results in it adhering
to the other negatively charged particles, including the particles containing the valuable
mineral. This hydrophilic mineral which is adhering to the valuable mineral increases the
difficulty in obtaining a sufficiently hydrophobic surface on the valuable particles by collector
addition, thus reducing their flotation response.
Chrysotile is classified in the serpentine group of minerals (Klein, 2002), which contains
three common polymorphs: antigorite, lizardite and chrysotile. The occurrences of antigorite
and lizardite are commonly massive and fine grained while the occurrence of chrysotile is
fibrous, forming cylindrical tubes. Another deleterious effect from chrysotile’s structure is
that it has the most extreme effect on pulp rheology of all the clay minerals (Forbes, Ma and
Bruckard, 2017).
The recognition of chrysotile or closely related minerals in an ore from initial determination
of the ore’s mineral abundance data must be used to provide a warning of potential
metallurgical difficulties in process development. The most common occurrence of this

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 CHAPTER 5 | SOME TROUBLESOME SULFIDE AND NON-SULFIDE MINERALS

problem is with sulfide nickel ores with serpentine gangue minerals and for which the effect
of chrysotile is documented (Edwards, Kipkie and Agar, 1980).

Clay minerals in general

Clay minerals are known to cause detrimental effects in flotation and other processes before
and after it in processing circuits. This topic is very large and the following areas were covered
in a section of a recent publication (Forbes, Ma and Bruckard, 2017):
•• the role of entrainment of clay minerals into the concentrate in the recovered water derived
from the pulp region
•• the attachment of clay particles on the surface of valuable particles, reducing the
hydrophobicity of the valuable particles and lowering their recovery
•• the over-stabilisation of the froth region, reducing its effectiveness for upgrading
•• the detrimental effect on the rheological properties of the flotation slurry, causing poor gas
dispersion in cells from increased pulp viscosity, which also causes diminished bubble/
particle contact in flotation from decreased flotation cell turbulence.
The minerals included in the publication range from obvious candidates (kaolinite, smectite
and illite) to talc and serpentine minerals, including the fibrous mineral, chrysotile.

ACKNOWLEDGEMENT
The important contribution of Suzanne Munro (Mineralurgy Pty Ltd/Mineralis) in
preparation of diagrams and of other aspects for the content in this chapter is acknowledged
with gratitude.

REFERENCES
Becker, M, de Villiers, J and Bradshaw, D, 2010a. The mineralogy and crystallography of pyrrhotite
from selected nickel and PGE ore deposits, in Economic Geology, 105:1025–1037.
Becker, M, de Villiers, J and Bradshaw, D, 2010b. The flotation of magnetic and non-magnetic pyrrhotite
from selected nickel ore deposits, Mineral Engineering, 23:1045–1052.
Croxford, N W J, Draper, N and Harraway, D H, 1961. Some aspects of the carbonaceous fraction of
Mount Isa lead concentrate, The AusIMM Proceedings, 197:149–161.
Edwards, C, Kipkie, W and Agar, G, 1980. The effect of slime coatings of the serpentine minerals,
chrysotile and lizardite, on pentlandite flotation, International Journal of Mineral Processing, 7:33–42.
Ekmekci, Z, Becker, M, Bagci Tekes, E and Bradshaw, D, 2010. The relationship between the
electrochemical, mineralogical and flotation characteristics of pyrrhotite samples from different Ni
ores, Journal of Electroanalytical Chemistry, 647:133–143.
Forbes, E, Ma, M and Bruckard, W, 2017. Clay minerals in flotation and comminution operations, in
Clays in the Minerals Processing Value Chain (eds: M Grafe, C Klauber, A J McFarlane and D J Robinson),
pp 302–326 (Cambridge University Press).
Forbes, E, Smith L and Vepsalainen, M, 2018. Effect of pyrite type on the electrochemistry of
chalcopyrite/pyrite interactions, Physicochem Probl Miner Process, 54(4):1116–1129.
Goble, R J, 1985. The relationship between crystal structure, bonding and cell dimensions in the copper
sulfides, in Canadian Mineralogist, 23(1):61–76.
Grafe, M, Klauber, C, McFarlane, A J and Robinson, D J (eds), 2017. Clays in the Minerals Processing
Value Chain (Cambridge University Press).

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 BILL JOHNSON AND PETER MUNRO

Johnson, N W and Jowett, A, 1982. Comparison of lead primary rougher behaviour of several Mount
Isa lead zinc ores, in Proceedings Mill Operators’ Conference, pp 271–285 (The Australasian Institute of
Mining and Metallurgy: Melbourne).
Kerr, A, 2002. Overview of recent developments in flotation technology and plant practice for nickel
ores, in Proc of Minerals Processing Plant Design, Practice and Control Vol 1 (eds: A Mular, D Halbe and
D Barratt), pp 1142–1158 (Society for Mining, Metallurgy, and Exploration: Littleton).
Klein, C, 2002. Mineral Science (The 22nd Edition of the Manual of Mineral Science, after James D. Dana) (John
Wiley and Sons, Inc).
Knights, J G and Johnson, N W, 2016. Silver mineralogy and metallurgy of lead-zinc-silver deposits at
Mount Isa, in Process Mineralogy (Chapter 24) (eds: M Becker, E M Wightman and C L Evans), JKMRC
Monograph Series in Mining and Mineral Processing: No 6, pp 344–364 (SMI-JKMRC, The University
of Queensland).
Knights, J G and Patterson, D J, 1988. Process mineralogy of silver in lead-zinc-silver ores at Mount Isa,
Australia, in Proceedings International Conference ‘Silver-exploration, Mining and Treatment’, pp 101–110
(Institution of Mining and Metallurgy).
Multani, R S and Waters, K E, 2017. A review of the physicochemical properties and flotation of
pyrrhotite superstructures (4C – Fe7S8/ 5C – Fe9S10) in Ni-Cu sulphide mineral processing, in Canadian
Journal of Chemical Engineering, 96(5):1185–1206.
Orwe, D, Grano, S R and Lauder, D W, 1997. Chalcocite oxidation and its influence on fine copper
recovery at the Ok Tedi Concentrator, Papua New Guinea, in Proceedings Sixth Mill Operators’
Conference, pp 85–95 (The Australasian Institute of Mining and Metallurgy: Melbourne).
Orwe, D, Grano, S R and Lauder, D W, 1998. Increasing fine copper recovery at the Ok Tedi
Concentrator, Papua New Guinea, Minerals Engineering, 11(2):171–187.
Riley, J F, 1974. The tetrahedrite-freibergite series, with reference to the Mount Isa Pb-Zn-Ag Orebody,
Mineralium Deposita, 9:117–124.
Riley, J F, 1976. Silver mineralogy and its metallurgical significance at Mount Isa, Queensland, Australia,
in Transactions of the Institution of Mining and Metallurgy, 85:C102–C104.
Silvester, E J, Heyes, G W, Bruckard, W J and Woodcock, J T, 2011. The recovery of sericite in flotation
concentrates, Transactions of the Institutions of Mining and Metallurgy, 120:C10–C14.
Tomaino, G P, 2018. Talc and pyrophyllite, Mining Engineering, July, pp 86–89.
Torrisi, C, 2001. Leaching of fluorine bearing minerals from lead and zinc concentrates, Minerals
Engineering, 14(12):1637–1648.

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 Return to contents

CHAPTER 6
Characterisation measurements
in industrial flotation cells
Greg Harbort, Sarah Schwarz and Thu Nguyen

ABSTRACT
In recent years, a significant volume of research has focused on flotation machine parameters
and the impact they have on metallurgical performance. Technology has been developed as
part of the Australian Mineral Industries Research Association (AMIRA) P9 project, to conduct
characterisation measurements (such as gas dispersion and froth recovery) in industrial
flotation cells.
Gas dispersion measurements include gas hold-up, superficial gas velocity and bubble
size, and are a good indication of the hydrodynamics within the pulp phase. Each of these
measurements can be made in industrial-sized cells using specialised equipment developed
within the AMIRA P9 project. These measurements have been made in a wide range of type
and size of flotation cells throughout the world.
Various techniques have also been developed to indicate the efficiency of the froth phase,
known as froth recovery. These techniques range from physically changing the froth height,
through to performing mass balances across the froth phase, and collecting samples of the
material attached to the bubbles within the pulp phase.
This chapter discusses methods for obtaining these characterisation measurements, as well
as other necessary measurements within an industrial flotation plant environment. These
measurements can be used by plant metallurgists to analyse and improve the performance of
their flotation circuits.

INTRODUCTION
The range of flotation cell types and sizes in flotation plants has varied over the years,
from older circuits containing many small volume cells (<3 m3), through to newer circuits
containing smaller numbers of larger cells (>100 m3). The typical and/or optimum operating
conditions of flotation cells must be taken in context of the cell type and size. The following
lists the common types of cells currently in use in the flotation industry:
•• mechanical air-induced cells, eg Outotec, Metso, Bateman

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

•• self-aerated cells, eg Wemco

•• column
•• Jameson cells.
Each of these cell types has different operating conditions required to produce the optimum
metallurgical performance. Note that the performance of the cell is also dependent on the
characteristics of the slurry passing through, although this will be addressed in another
chapter.
For many years, plant metallurgists have been aware of the importance of air, agitation
and froth characteristics on the overall cell performance, but have not been able to quantify
the individual variables. Techniques have been developed in the last 20 years to measure
the gas dispersion properties and the performance of the froth phase. This has allowed
plant metallurgists to benchmark their cell operating conditions and identify potential
areas of improvement.
This chapter focuses on some of the measurement techniques available for characterising
the gas dispersion properties such as gas hold-up, superficial gas velocity and bubble size,
and the various techniques to characterise the froth performance, in terms of froth recovery.

GAS DISPERSION MEASUREMENTS

In simple terms, gas dispersion can be defined as how well the air entering a flotation cell is
dispersed throughout the cell. The gas dispersion conditions within a flotation cell directly
influence the flotation efficiency (Schubert and Bischofberger, 1978; Gorain, Franzidis and
Manlapig, 1995a) and can be characterised by measurements such as bubble size, gas velocity
and gas hold-up.

Bubble size
The bubble size within the pulp phase of a flotation cell significantly influences the efficiency
of particle-bubble contact and attachment. In general, smaller bubbles are more efficient for
smaller particles and larger bubbles are more suited for larger particles (Biswal, Reddy and
Bhaumik, 1994). Also, it has been acknowledged that smaller bubbles within the pulp phase
improve the flotation kinetics (Diaz-Penafiel and Dobby, 1994). While these points have
been in general knowledge for a while, the problem has been actually measuring the bubble
size in the pulp phase of industrial flotation cells. Many bubble measurement techniques
are available, consisting of either invasive or non-invasive techniques. The most common
technique developed to measure bubble size in industrial flotation cells currently is the
McGill bubble size analyser, due to its simplicity and robustness. This is discussed in detail in
the following sections, with other measurement devices discussed briefly, highlighting their
advantages and disadvantages.

McGill bubble size analyser

A bubble viewing device, to collect and image bubbles, was developed by Jameson and Allum
(1984) as part of the AMIRA P9 project. This approach has been progressively refined over the
years, leading to the McGill bubble size analyser, developed at McGill University in Canada.
A schematic of the McGill bubble size analyser (or ‘bubble viewer’) is given in Figure 1.
The McGill bubble size analyser consists of a sampling tube attached to a viewing chamber
with a window inclined at 15° from vertical. The sampling tube is immersed in the flotation
cell, with the bottom of the tube normally just below the pulp/froth interface in the quiescent

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

Window
Camera
Diffuser

Light source
Sample chamber

Sampling tube
Froth

Flotation cell

FIG 1 – Schematic of the McGill bubble size analyser and typical set-up.

zone. The set-up is filled with water dosed with enough frother to prevent bubble coalescence
in the tube. Bubbles from the flotation cell rise up through the sampling tube and slide up
the inclined window of the viewing chamber. The sloped window ensures a single layer
of bubbles passes through the image area, captured by a digital video camera. The light
source illuminates the image area, resulting in each bubble casting a shadow, which can be
detected by the software associated with the bubble viewer. Full details of the apparatus and
methodology can be found elsewhere (Chen, Gomez and Finch, 2001; Hernandez-Aguilar,
Gomez and Finch, 2002; Hernandez-Aguilar et al, 2004). Further refinements have since been
made to the apparatus, with LED lights operating from a battery and a digital still camera
used instead of a video camera. The probe is known as the Anglo Platinum Bubble Sizer, or
APBS and has been described in Taute and McClelland (2006).

Other bubble size measurement techniques

Extensive reviews of alternative bubble sizing techniques have been conducted by Rodrigues
and Rubio (2003) and Boyer, Duquenne and Wild (2002). Many of these are restricted to
laboratory use or limited to specific applications. Brief descriptions of these methods are
given below.

Alternative photographic techniques

Several alternative photographic techniques are in use for bubble size measurement. The
LTM-BSizer (Rodrigues and Rubio, 2003) is similar to the McGill bubble size analyser in terms
of equipment. It varies once bubbles have entered the viewing chamber where the bubbles are
decelerated and stopped prior to being photographed. Taking pictures through the wall of
a flotation machine is a frequently used bubble sizing technique that requires a see-through
section of wall and provides a bubble size image in the immediate vicinity of the wall. Laser
velocimetry uses a laser sheet to illuminate a slice of fluid within a flotation machine, which
can then be photographed and analysed.

Optical fibre and sensor probes

Optical needle probes are very thin, sharp ended probes, facing the bubble flow direction in
order to pierce bubbles. Infrared light beams are transmitted along the optic fibre to tips made
of quartz or sapphire and the difference in light transmittance when an individual bubble is

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

pierced is registered. They can be used in three-phase high air hold-up conditions (Magaud,
Souhar and Boisson, 2001). The most commonly used in industrial environments is the UCT
bubble probe (Figure 2) (Tucker et al, 1994). This analyser consists of a sampling system and
an optical/electronic detector system. The sampler enables incoming bubbles to be cleaned of
any attached particles before they enter the capillary, where they are deformed from spheres
to cylinders. The length of the bubbles is detected by a pair of optical sensors.

Conductivity probes
Conductivity probes register the variation in conductivity between bubbles and the
surrounding pulp. Immersion conductivity probes are also used and can measure bubble
size without extracting bubbles from the flotation machine (Sanaullah, Zaidi and Hills, 2001;
Wu et al, 2001).

Analysis of bubble sizes

Both the UCT bubble sizer and the McGill bubble viewer produce a bubble size distribution,
the average bubble diameter and the Sauter mean bubble diameter for each measurement.
The bubble size distributions can be compared on a normalised basis, as shown in Figure 3.
This figure shows that cells 2 and 3 had similar shaped bubble size distributions, with a
significantly different average bubble size compared to the other two cells in the circuit. This
indicates that cells 2 and 3 have a lot of similar smaller sized bubbles compared to cells 1
and 4, which have a large range of bubble sizes.

The atmosphere
Three-way valve
Flush water

Burette

The atmosphere Peristaltic

The atmosphere
Pump 1

Water reservoir
Photo-detector MPU timer Laptop
Capillary amplifier detector computer

Peristaltic
Plant water
Pump 2

Cleaning column Compressed air

The atmosphere

Pinch valve

FIG 2 – Schematic of the UCT bubble size analyser.

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

1.6

Normal distribution frequency (%

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0
0 1 2 3 4 5 6 7 8
Bubble diameter (mm)

Cell 1 Cell 2 Cell 3 Cell 4

FIG 3 – Normalised distribution of bubble sizes obtained from four cells within a flotation circuit.

The average bubble diameter is calculated from Equation 1 and the Sauter mean bubble
diameter is determined from Equation 2:
N
/d i
db = i=1
(1)
N

/d 3
i
d32 = i=1
(2)
/d 2
i
i=1

where:
di is the measured bubble diameter
N is the number of bubbles measured
Generally, the Sauter mean bubble diameter is quoted from these measurements, as this has
been shown to be a more accurate representation of the bubble size distribution. Currently
there is some debate about whether the ratio of the Sauter mean to the arithmetic mean should
also be quoted, to indicate the width of the bubble size distribution.

Typical bubble size ranges

Generally, Sauter mean bubble sizes range from 1.0 mm to 2.0 mm within mechanical cells,
with larger bubbles found in larger cells (>100 m3). Sauter mean bubble sizes within columns
are usually larger, 1.5 mm to 3.0 mm as the norm. Results of Sauter mean bubble sizes
measured in over 1000 cells are given in Figure 4.

Superficial gas velocity

Superficial gas velocity is a measure of the aeration ability of a cell and is directly related to
the flotation kinetics (Ahmed and Jameson, 1989). If the superficial gas velocity is too high,
however, the entrainment of gangue material into the froth phase may become excessive
and reduce the froth stability, as well as decrease the concentrate grade. Measuring the
superficial gas velocity at various locations across the cell cross-sectional area has been

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

30

Column, Jameson, Flash

25
Conventional cells

Frequency (%)
20

15

10

0
0.5 0.75
1 1.25
1.5 1.75
2 2.25
2.5 2.75
3 3.25
Bubble size (mm)
FIG 4 – Range of Sauter mean bubble size obtained in mechanical, column,
Jameson and Flash flotation cells (from Schwarz and Alexander, 2006).

shown to give a good indication of how well the air is dispersed in the cell (Gorain, Franzidis
and Manlapig, 1996). Superficial gas velocity can be measured by various means, ranging
from the air flowmeter readings through to sophisticated instruments, and these will be
discussed in this section.

Air flowmeter readings

For most air-induced mechanical cells, the air flow rate is controlled and recorded on the
control system. Using the flow rate recorded from the flowmeter, superficial gas velocity, Jg ,
can be calculated from Equation 3:
Q
Jg = (3)
A
where:
Q is the volumetric air flow rate
A is the cross-sectional area of the flotation cell
However, this method can be problematic if the flowmeters themselves are not correctly
calibrated, if the gas is not uniformly dispersed throughout the cell, or if the cells are self-
aerated (and hence no flow rate recorded). The following methods enable the gas velocity to
be measured accurately independent of the above conditions.

The JKMRC mechanical Jg probe

The mechanical Jg probe was developed at the Julius Kruttschnitt Mineral Research Centre
(JKMRC) as part of the AMIRA P9 project. A schematic of the probe is given in Figure 5.
The JKMRC Jg probe consists of a Perspex tube with a pneumatically controlled valve at
one end and water inlet and air release valves at the other end. The probe is lowered into
the flotation cell, generally just below the pulp/froth interface and filled with water. The air
release valve is closed to the atmosphere and the pinch valve at the bottom is opened to allow
gas from the cell to flow into the probe. This gas displaces the water within the probe at a
rate equal to the velocity flowing within the cell and is measured by the time required for the
water level to drop a predetermined distance. Corrections are made for pressure, based on

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

Water

Atmosphere

Compressed Air
Feed 3-way Valve
Mark 1

Mark 2

Perspex
Tube

Pinch
Valve
Nozzle

Tailings

FIG 5 – Schematic of JKMRC Jg probe and typical set-up.

the length of the probe and the distance the probe is immersed in the pulp phase. Full details
of the use and set-up of this probe can be found in Gorain, Franzidis and Manlapig (1996) and
Power, Franzidis and Manlapig (2000).

Worked example
Repeat measurements have been made using a Jg probe in a single location in a flotation cell.
The following is a list of the times taken for the water level to drop 20 cm: 14.0 s, 19.1 s, 17.7 s,
15.7 s, 14.8 s. The length of the probe from the bottom valve to the bottom line was 2.9 m
and the distance from the bottom valve to the top of the pulp phase was 1.2 m. Calculate the
average superficial gas velocity of this cell.

Calculations
The experimental Jg value can be obtained using the following equation:

Jg = L
t
where:
L is the distance between marks
t is the time taken for the water level to drop between the marks
This value is calculated for each measurement, for example:

Measurement 1: Jg = 20 = 1.43 cm/s

14.0
All measurements are averaged to give an experimental Jg value of 1.29 cm/s. The pressure
difference needs to be considered, as the measurement is taken within the pulp phase, at a
different height to the water level dropping.
The Anglo Platinum Bubble Sizer (APBS) also measures superficial gas velocity, using the
same concept as described for the JKMRC Jg probe. Measurements of time are recorded as
the water level drops known distances with corrections made for pressure and differences in
tube diameters.

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

McGill online Jg probe

As part of the ongoing research in the AMIRA P9 project, researchers at McGill University
have developed a probe to measure superficial gas velocity online in industrial environments.
The probe consists of two hollow plastic tubes that are placed just below the pulp/froth
interface (in the quiescent zone) similar to the JKMRC Jg probe. A typical arrangement is
shown in Figure 6.
The operating principle is based on the increase in pressure as the slurry in the first tube
(shown as P1) is pushed down due to the gas entering the probe from the flotation cell. There
is a linear relationship between pressure and time that can be related to the superficial gas
velocity. The second tube is monitored to account for changes in cell pulp level and the
pressure versus time relationship is subtracted from the relationship obtained from the first
tube. Repeated opening and closing of the valves enable continuous Jg measurements to be
obtained. An example of the output from this probe is given in Figure 7, with Equation 4 used
to calculate the superficial gas velocity:

3 3

-JVHQVRU 5HIHUHQFH

/
)/27$7,21
0$&+,1(

FIG 6 – Schematic of McGill online Jg probe and typical arrangement.

80

Changing slope P1 P1
PRESSURE (cm H2O)

60

Difference
40
Correct slope
P2 – level changes
20 P2

0
0 50 100 150
TIME (s)

FIG 7 – Output from the McGill online Jg probe.

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

1033 (2P - P0)

f p
tb dP
Jg = (4)
PL dt

where:
Po is the atmospheric pressure
PL is the pressure at the bottom of the tube, which changes as the level changes
tb is the density of the aerated pulp

Typical superficial gas velocity values

Superficial gas velocity tends to range widely depending on the operating philosophy of the
plant. In some instances, values of 0.1 cm/s have been recorded, while at the other extreme,
values greater than 3 cm/s have also been measured for mechanical flotation cells. In general,
values between 1.0 cm/s and 2.0 cm/s are considered reasonable. Where Jg is measured at
less than 1.0 cm/s, it is generally recommended to investigate increasing the airflow rate to
improve the recovery in the pulp phase. However, where Jg is higher than 3.0 cm/s, flooding
can occur, resulting in pulp being recovered in the concentrate launder. This indicates a
physical limit to increasing airflow rates, although the resulting effect on the froth phase
performance should also be investigated. As a guide, Jg measurements obtained from over
1000 flotation cells are displayed in Figure 8.

Gas hold-up
Gas hold-up measures the volume fraction of air contained within the pulp phase of the
flotation cell. Generally, increasing the gas content within the cell results in more bubbles per
unit volume and hence more available surface area for particle-bubble interactions to occur,
producing improved kinetics in the pulp phase (Ahmed and Jameson, 1989). However, there
is a maximum value of gas hold-up before the cell capacity is limited, resulting in reduced
residence time. Again, there are various measurement techniques available to measure both
overall and local gas hold-up values, and these are discussed in the following section.

25

Column, Jameson, Flash

20
Frequency (%)

Conventional cells

15

10

0
0.25 0.5
0.75 1 1.25 1.5
1.75 2 2.25 2.5
2.75 3
Superficial gas velocity (cm/s)
FIG 8 – Range of superficial gas velocity values obtained from conventional,
column, Jameson and Flash flotation cells (from Schwarz and Alexander, 2006).

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

Level change method

This method involves measuring the level of the pulp with gas flowing into the cell and then
measuring the pulp level when the gas is switched off. The change in pulp level is used to
calculate the volume of gas, εg, in the flotation cell, according to Equation 5:

f g = DH (5)
H
where:
ΔH is the change in pulp level after switching off the gas
H is the pulp level with gas
This method has the advantage that no specialised equipment is necessary and it also gives
the overall gas content within the whole flotation cell. However, it can often be quite difficult
to obtain the initial measurement of the pulp level with gas present in the cell.

The JKMRC gas hold-up probe

Probes were also developed to measure gas hold-up as part of the AMIRA P9 project both at
the JKMRC (this section) and at McGill University (following section). The JKMRC gas hold-
up probe is shown schematically in Figure 9 and is described in detail in Gorain, Franzidis
and Manlapig (1995b) and Power, Franzidis and Manlapig (2000). The early probes used
pinch valves operated by compressed air, while recent versions include mechanical swing
valves or spring valves.
This probe takes a sample of aerated slurry from just below the pulp/froth interface. The
probe consists of a vertical cylinder with either pneumatic or mechanical valves at the top
and bottom. The probe is lowered into the flotation cell and slurry is allowed to pass through
the probe for more than ten seconds. After this time, the top and bottom valves are rapidly
closed and the probe is lifted out of the flotation cell. The volume of the slurry collected, Vs,
is measured and compared with the known volume of the probe between the two valves, Vp.
The gas hold-up is calculated from Equation 6:
Vp - Vs
fg = (6)
Vp

This technique is simple and rapid, giving almost instantaneous results. However, the
results are for a localised region of the cell, and measurements must be repeated across the
cross-section of the flotation cell to give the average gas hold-up across the whole cell. It is
generally recommended that at least three measurements of gas hold-up are performed in
each location within the cell to ensure representative results.

Rubber tube Rubber tube

Plastic cylinder tube

Three-way valve
Air line
Compressed air

The atmosphere Pinch valve 1 Pinch valve 2

FIG 9 – Schematic of the JKMRC pneumatic gas hold-up probe.

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

Worked example
Repeat measurements have been made using a JKMRC gas hold-up probe. The volume of the
probe is 1070 ml. The following is a list of slurry volumes obtained from the same location in
the flotation cell: 1000 ml, 1010 ml and 1000 ml. Calculate the average gas hold-up from this
position within the flotation cell.

Calculation
Using Equation 6, the gas hold-up from the first measurement can be calculated as:

f g = 1070 - 1000 = 6.5%

1070
Similarly, the other measurements result in gas hold-up values of 5.6 per cent and
6.5 per cent, respectively. Averaging these gives an average gas hold-up value of that location
within the flotation cell of 6.2 per cent.

The McGill online gas hold-up probe

The McGill gas hold-up probe uses the differences in conductivity obtained from slurry and
gas. It consists of two tubes, with the arrangement shown in Figure 10.
The open cell measures the conductivity of the slurry with bubbles present, while the
siphon cell measures the conductivity of the slurry without any gas present. The gas hold-up
is calculated using Equation 7:
k
1- k
0

fg = s
k
(7)
1 + 0.5 k0
s

where:
ko is the specific conductivity of the slurry with bubbles present
ks is the specific conductivity of the slurry with no bubbles
Again, this technique produces gas hold-up values for a given location within the flotation
cell, and can be repeated across the cell to give the average overall gas hold-up. This technique
can also be used for continuous monitoring of the gas content within the cell.

Syphon cell
Open cell (slurry, no gas)

FIG 10 – Schematic and arrangement of the McGill online gas hold-up probe.

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

Other air hold-up measurement techniques

Pressure transducers
The use of pressure sensor measurements has been used for many years to determine the
pulp level in tanks. Dual sensors spaced a set vertical distance apart can also be used to
calculate the density of aerated pulp. Should the pulp density be known, this then allows the
air hold-up to be calculated. The average air hold-up can be calculated by sensors set into the
tank wall. Air hold-up at specific locations within the tank can be measured by non-intrusive
probes such as pitot tubes.

Ultrasonic techniques
Doppler ultrasonic probes have been used for many years for measuring liquid velocity
in pipes. Their use is based on the propagation of sound waves, generated within a piezo-
ceramic disc. Techniques can either rely on ultrasound transmittance through an aerated pulp
(Waniewski, Hunter and Brennen, 2001), or reflectance from bubble surfaces (Kulmyrzaev,
Cancelliere and McClements, 2000).

Acoustic emission
Acoustic emission techniques operate with a similar principle to the use of microphone
recordings to determine a grinding mill load. Pulp, with a specific air hold-up will generate a
unique acoustic signal that can be recorded through a hydrophone (Boyd and Varley, 2004).

Heat transfer anemometers

Heat transfer probes operate on the principle that the heat exchanged between an electrically
heated probe varies between that of the pulp and air contained within it. Knowing the heat
transfer coefficient between the probe and pulp/air allows the air hold-up fraction to be
calculated.

Light attenuation techniques

In the case of a clean aerated liquid, the light attenuation is a function of the interfacial
area of the air phase. A high intensity laser source is directed through the aerated liquid,
with received light being detected via a photomultiplier tube. The amount of light scatter is
proportional to the air hold-up (Aslan et al, 2006).

Radiation techniques
Radiation sources have for many years been in use for purposes of in-stream analysis. Gases,
liquids and solids have different adsorption coefficients of X-ray or γ-ray radiation or neutron
beam radiation. Radiation released by a radioactive source is passed through the phase being
evaluated. The attenuation of radiation can be related to the air hold-up (George et al, 2001).

Typical gas hold-up values

In general, gas hold-up varies between six per cent and 25 per cent for both mechanical and
column flotation cells (Power, Franzidis and Manlapig, 2000). However, in some instances
values of less than two per cent have been measured, indicating insufficient air introduced to
the cell. Values greater than 50 per cent have also been recorded, a possible indication of high
pulp viscosity. The range of values obtained can be seen in Figure 11.

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

45
40
Column, Jameson, Flash

Frequency (%)
35
30 Conventional cells
25
20
15
10
5
0
6 12 18
24 30 36
42 48 54
60 66 72
Air hold-up (%)

FIG 11 – Range of gas hold-up values obtained from conventional, column,

Jameson and Flash flotation cells (from Schwarz and Alexander, 2006).

Bubble surface area flux

The bubble surface area flux, Sb , combines the superficial gas velocity and bubble size to
give a measure of the rate of bubble surface area rising through a flotation cell per unit cross-
sectional area per unit time, according to Equation 8:
6 # Jg
Sb = (8)
db

There is a strong linear relationship between bubble surface area flux and recovery across
the pulp phase (Gorain, Franzidis and Manlapig, 1997).
The bubble surface area flux can also be estimated using impeller dimensions and speed as
well as particular properties of the pulp phase in an empirical relationship (Gorain, Franzidis
and Manlapig, 1999).
Also useful to note is that when treating the same type of ore, this linear relationship is
independent of impeller type, as shown in Figure 12. The slope of the relationship is related
to the floatability of the ore – with higher slopes indicating faster-floating material.
Typical bubble surface area flux values range from 30 s-1 to 70 s-1 for both mechanical and
column flotation cells, as shown in Figure 13.

0.8
Flotation Rate Constant (1/min)

0.7 Chile-X
Pipsa
0.6 Outokumpu
0.5
Dorr-Oliver

0.4

0.3

0.2
0.1
0
0 50 100 150 200 250
Bubble Surface Area Flux (m²/m² sec)

FIG 12 – Linear relationship between flotation kinetics in the pulp phase

and bubble surface area flux (from Gorain, Franzidis and Manlapig, 1997).

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

30

25 Column, Jameson, Flash

Frequency (%)
Conventional cells
20

15

10

0
10 20 30
40 50 60
70 80 90
100 110
120
-1
Bubble surface area flux (s )

FIG 13 – Range of bubble surface area flux values obtained from conventional,
column, Jameson and Flash flotation cells (from Schwarz and Alexander, 2006).

FROTH RECOVERY MEASUREMENTS

The main function of the froth phase in flotation is to transfer the particles attached to bubbles
from the pulp phase to the concentrate launder. Some bubbles with particles attached to them
may undergo coalescence in this region, leading to detachment of the most weakly attached
particles (Gourram-Badri, Conil and Morizot, 1997), which are usually gangue mineral
particles. There is then a subsequent upgrading of the concentrate because the detached
particles (which may contaminate the concentrate) will drain back to the pulp phase.
The effect of froth recovery on the overall cell recovery is significant. A particle may be
collected in the pulp phase and subsequently report to the froth phase. However, if the froth
recovery is low, the particle will probably not be recovered in the concentrate and drop back
to the pulp. This produces a decrease in the overall flotation recovery. In general, collection
zone (pulp phase) recovery varies from 60–99 per cent and froth phase recovery varies from
ten to 90 per cent (Savassi et al, 1997). Consequently, up to 50 per cent of the overall cell
recovery can be lost due to inefficiencies in the froth phase.
This section discusses three of the main techniques available to measure froth recovery, and
the advantages and disadvantages of each.

Froth residence time method

Many authors (Engelbrecht and Woodburn, 1975; Laplante, Toguri and Smith, 1983; Feteris,
Frew and Jowett, 1987; Vera, Franzidis and Manlapig, 1999) have calculated froth recovery
(Rf) from the ratio of the overall rate constant, k, to the collection zone rate constant, kc, via:

Rf = k (9)
kc

Various authors including Vera, Franzidis and Manlapig (1999) indicated the value for kc
by extrapolation of the overall rate constant (k) versus froth residence time (τf) graph to the
y-axis, where τf = 0 (the collection zone) (Feteris, Frew and Jowett, 1987; Gorain et al, 1998).
Froth residence time can be defined in several ways. The definition referred to in this chapter
is based on the concentrate flow rate. As such, the froth residence time is defined as (Mathe,
Harris and O’Connor, 2000):

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

Flotation rate constant (1/min)

0.25

0.2

0.15

0.1

0.05

0
0 20 40 60 80 100

Froth residence time (sec)

FIG 14 – Typical variation of flotation rate constant with froth residence time.

(1 - f g) Vfroth
FRT = (10)
Qconc

where:
εg is the gas hold-up in the froth phase
Vfroth is the volume of the froth phase
Qconc is the volumetric flow rate of the concentrate
By varying the froth residence time, through either varying froth height or airflow and
measuring recovery, a set of flotation rate constants at various froth residence times can be
calculated and plotted. A typical example of this is shown in Figure 14. From this graph
an estimated flotation rate constant (kc) of 0.13 min-1 is determined. At 20 seconds residence
time the flotation rate constant is approximately 0.05 min-1. Therefore, at 20 seconds froth
residence time the froth recovery will be 38.5 per cent.
In operations where the flotation circuit operates with flotation cells of various sizes an
adjustment based on the horizontal distance the froth travels to the concentrate launder may
be required. This is done by dividing the froth retention time by a typical cell length as shown
below; where τfs may be thought of as ‘specific’ froth residence time, which is independent
of cell size:

x fs = FRT (11)
L
where:
τfs = specific froth residence time (s/m)
L = perpendicular distance from impeller to launder (m)

Mass balance technique

The froth residence time method can result in significant disruption to operations, in order
to gain the required information. In order to overcome this, the mass balance technique was
developed (Alexander, Franzidis and Manlapig, 2003). This technique is based on several key
assumptions:
•• a froth sample can be generated that represents the grade of particles attached to bubbles
•• the average grade of particles attached to bubbles does not change over the froth phase
•• the grade of the tail sample is equivalent to the grade of particles that are entrained in the
water.

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

The technique is non-disruptive and involves taking samples of feed, concentrate, tail, froth
and air hold-up. These samples are assayed and a mass balance of attached and entrained
particles at various size fractions is conducted, as discussed below.
The air hold-up sample taken directly below the pulp/froth interface with the superficial
gas velocity measurement is also used to estimate the mass flow rate of attached particles
entering the froth phase, based on the following equation:
M ATT
Pulp
= 3.6 $ QAir $ BPulp (12)

where:
M ATT
Pulp
= mass flow rate of attached particles in the pulp zone
Qair = volumetric flow rate of air (m3/s)
BPulp = bubble load in the pulp phase (grams of solids/litre of air)
The volumetric flow rate of air can be measured directly in each cell or estimated using the
superficial gas velocity measurements across the cell cross-sectional area:
QAir = A $ Jg (13)

where:
Jg = superficial gas velocity (cm/s)
A = open area of cell (m2)
The bubble load is defined as the mass of attached solids per volume of air and involves
obtaining a sample using the air hold-up probe and using the assumptions outlined above.
Air bubbles (with particles attached) and pulp (with particles entrained) pass through the
air hold-up sampler in the open position. When the air hold-up probe is closed, the attached
particles become detached from the air bubbles and are included with the pulp containing
entrained particles and water. The volume of air and the mass and grade of the pulp sample
are noted. The bubble load can then be calculated using:
matt $ 1000
BPulp = (14)
V
where:
matt = mass of attached particles in the air hold-up probe (g)
V = volume of air measured in the air hold-up probe (ml)
The mass of attached particles in the air hold-up probe is estimated using the following
mass balance equation:
mtotal. $ (Gtotal - Gent)
matt = (15)
(Gatt - Gent)
where:
mtotal = total mass of particles in the air hold-up probe (g)
Gent = grade of entrained particles in the air hold-up probe
Gtotal = grade of all particles in the air hold-up probe
Gatt = grade of attached particles in the air hold-up probe
In order to calculate the mass of attached particles (matt), the grade of attached particles (Gatt)
is taken as that of the grade of the top of froth sample, while the grade of entrained particles

186 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

(Gent) is taken to be equivalent to the grade of the tailings. This is in accordance with the
assumptions made at the beginning of this section.
The estimate of the mass of attached particles in the air hold-up sample obtained from
Equation 15 can then be used to calculate the mass flow rate of attached particles into the
froth phase (Equation 12).
The mass flow rate of attached particles in the concentrate can be calculated using a similar
mass balance equation to Equation 15 applied to the concentrate sample:
mtotal
Conc
$ (Gtotal - Gent)
m att
conc
= (16)
(Gatt - Gent)
where:
m Att
Conc
= mass flow rate of attached particles in the concentrate stream (t/h)
mtotal
Conc
= mass flow rate of all particles in the concentrate stream (t/h)
Gent = grade of entrained particles in the concentrate
Gtotal = concentrate grade
Gatt = grade of attached particles in the concentrate
The froth recovery of attached particles can then be calculated using the following equation:
m Att
Conc
Rf = (17)
m Att
Pulp

where:
Rf = froth recovery of attached particles
m Conc
Att
= mass flow rate of attached particles in the concentrate stream (t/h)
m Pulp
Att
= mass flow rate of attached particles in the pulp (t/h)

Worked example
A flotation machine operates with an air rate of 396 m3/h treating a feed of 6.5 t/h solids. The
average air hold-up volume is 83.3 ml, giving an air hold-up of 7.79 per cent and the mass of
solids in the air hold-up probe is 28.3 g. The following zinc assays have been recorded: feed
– 11.05 per cent Zn; concentrate – 33.72 per cent Zn; tailing – 8.80 per cent Zn; air hold-up –
9.28 per cent Zn; froth – 36.1 per cent Zn. Calculate the froth recovery.

Calculations
The overall concentrate produced can be calculated either by concentrate measurements, or
from the two-product formula:
6.5 # (11.05 - 8.8)
mtotal
Conc
= = 0.59 t/h
(33.72 - 8.8)

The total mass of attached particles in the air hold-up probe is:
(9.28 - 8.8)
m att = 28.3 # = 0.50 g
(36.1 - 8.8)
The bubble load is:
B Pulp = 0.50 # 1000 = 6.00 kg/m 3 air
83.3

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

The mass of particles attached to bubbles entering the froth is:

M ATT
Pulp
= 3.6 # 396 # 6.00 = 8555 kg/h = 8.56 t/h

The froth recovery is:

R f = 0.59 # 100 = 6.9%
8.56

Bubble load measurement techniques

As discussed above, the mass of attached particles entering the froth is a critical measurement
in determining froth recovery. Seaman, Franzidis and Manlapig (2004) developed a new
technique to measure this, requiring a bubble load collection chamber suspended above the
froth phase as shown in Figure 15. The chamber has a sampling tube inserted into the pulp
that captures rising, mineral-laden bubbles. These bubbles rise through the tube where they
enter a collection chamber, burst and release the particles. The captured particles are weighed
and volume of air from the rising bubbles is measured to allow a bubble load to be calculated.

Comparison of different froth recovery techniques

The plant metallurgist will decide on the froth recovery measurement technique to be used.
The froth residence time method is relatively easy to perform, but requires many samples
(feed, concentrate and tails required at different froth heights with more than three froth
heights required to generate the relationship) and is disruptive to normal production.
The mass balance technique does not disrupt normal plant operation, and generates only five
samples per cell (feed, concentrate, tails, top of froth and air hold-up). The main disadvantage
of this method is requiring assays of the tails and air hold-up samples to be different enough
to perform the mass balance of attached and unattached particles in the air hold-up sample.
This has shown to be problematic in certain scavenging operations, although the technique
generally works well in roughing and cleaning duties.

FIG 15 – Arrangement of the bubble load device (from Seaman, Franzidis and Manlapig, 2004).

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

The bubble load technique is also non-invasive and generates only two samples per cell
(concentrate and bubble load sample). This technique is performed in conjunction with a
general survey to give the flow rates of the individual cell concentrate streams. There have
been some issues with the size of the sample collected, with long sampling periods sometimes
required to obtain enough sample for sizing analysis to be performed.
The bubble load device has been shown to give similar froth recovery measurements to
the mass balance technique, but significantly different results to the froth height or froth
residence time methods. This is mainly due to the different basis of calculations – the froth
residence time method is concerned with processes occurring within the froth phase only,
while the mass balance and bubble load techniques consider processes occurring at the pulp/
froth interface as well. The majority of bubble-particle detachment has been found to occur
at the pulp/froth interface, due to the sudden change in momentum of the bubble-particle
aggregates. Since the froth residence time method does not take this section of the flotation
system into account, the froth recovery measurements are routinely higher than for the same
cell and operating conditions using the other techniques. A comprehensive evaluation of
different froth recovery measurement techniques was given by Runge et al (2010).

OTHER PLANT MEASUREMENTS

In a mechanical flotation cell, the size of the bubbles generated is dependent on the impeller
design and cell operating variables like impeller speed and airflow rate (with chemical
conditions fixed). In general, the mean bubble size decreases with an increase in impeller
speed, whereas it increases with an increase in airflow rate (Gorain, Franzidis and Manlapig,
1995a, 1995b). The manner in which the mean bubble size changes depends on the air
dispersion capability of the impeller. Previous investigation has also shown that feed particle
size (P80) affects the rheological properties of slurry treated in the cell and therefore affects
bubble size (O’Connor, Randall and Goodall, 1990).
Since the Sb generated in a cell is dependent on bubble size, it is expected that Sb will also
depend on impeller speed, airflow rate, impeller design and the particle size of the feed to
the cell. In order to represent Sb mathematically in terms of these variables, irrespective of
impeller design and cell sizes, it is useful to convert these variables into more ‘general terms’.
Impeller peripheral speed (Ns) instead of impeller speed (N) and airflow rate per unit cell
cross-sectional area (Q/A) instead of airflow rate (Q) are suitable conversions that enable Sb
to be represented mathematically in terms of variables whose values are independent of cell
size and impeller design.
The production of Sb in flotation machines also depends on impeller design. Impeller
diameter in general increases with cell size and also varies from one design to another.
However, for a particular impeller type, the impeller aspect ratio (ratio of impeller height
to impeller diameter) is approximately the same irrespective of cell size. So, impeller aspect
ratio (As) can be considered as a suitable criterion to characterise impellers of different design
or type.
This can be expressed mathematically as:
Q c d e
Sb = a $ N sb $ b l $ A s $ P 80 (18)
A
where:
a, b, c, d and e are the parameters for the model

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

Standard units of the operating variables are used in the model viz m/s for Ns, cm/s for Q/A,
which in theory is equal to superficial gas velocity, dimensionless for As and microns for P80,
which is typically used to represent particle size in flotation operations.
A database of cell characterisation values for over 2500 flotation machines has been
developed at the Julius Kruttschnitt Mineral Research Centre (JKMRC) for flotation cells
of different sizes and designs operated using a variety of impeller types, and for industrial
scale cells on operating plants. Other substantial cell characterisation activities have also been
conducted by Metso Process Technology & Innovation, the Outotec Flotation Division and
the Mining and Metals Consulting division of Amec Foster Wheeler. Initial investigations
indicate that the same general form can be used for the Jameson cell, using jet velocity and
the downcomer diameter to orifice plate diameter ratio.

OPERATIONAL FACTORS AFFECTING GAS CHARACTERISTICS

A number of operational factors, sometimes out of the control of plant operators, can affect
cell characteristics and need to be monitored and corrected to optimise performance. These
factors, including changes in ore specific gravity, particle shape and feed per cent solids,
can often result in a series of complex interactions, as illustrated simply in Figure 16. They
can have both negative and positive effects on recovery, for example increasing viscosity
increases bubble size, reducing kinetics and recovery, while at the same time the increased
bubble size reduces air hold-up, reduces bubble loss to tailing, increases residence time and
hence increases recovery.

Rheology in mineral processing

The rheological behavior of mineral slurries is indicative of the level of inter-particle interaction
or aggregation. In simple terms, rheology or viscosity can be defined as resistance to flow. The
higher the viscosity of a suspension, the more difficult it is for a particle to move through it.

Decrease in
Particle Size Increase in
Bubble Loss to
Tailing
Decrease in
Solids SG Decrease in
Increase in Air
Hold-up Residence Time
Decrease in
Increase in Recovery
Viscosity Increase in
Decrease in
Bubble Size
Kinetic Rate

Increase in % Increase in
Solids Concentrate
Solids Loading

Increase in
Residence
Decrease in
Time Increase in
Volumentric
Flow Recovery
Decrease in
Bubble Loss to
Tailing
Decrease in Air
Hold-up
Decrease in Solids
Short Circuit to
Tailing

FIG 16 – Interactions of various factors on gas characteristics and their affect on recovery.

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

The viscosity of a non-Newtonian fluid (as in the case of mineral slurry) at a specified
point is referred to as ‘apparent viscosity’. The apparent viscosity of slurry depends on the
microscopic structures of suspended particles in the slurry and is a function of the volume
fraction of the solid, particle shape, particle interaction and the aggregation of the suspended
solid (Yoshida et al, 2013).
Rheology or viscosity has an important influence on the flotation process. However,
measuring the rheological behavior is difficult as particles tend to settle during measurement.
It has been shown that the measurement of froth rheology in situ can be done using the vane
rheometer but only at a limited vane head speed (Chao et al, 2015).

Per cent solids, ore specific gravity and viscosity

It is known that increasing viscosity results in a decrease in the turbulence intensity in the
flotation cell, causing an increase in bubble coalescence and bubble size (Kilickaplan, 2007;
Koh and Schwarz, 2008; Nesset, Zhang and Finch, 2012).
The viscosity of suspensions is a function of solids content. The viscosity at a high solid
concentration is governed by the solid packing fraction p; beyond this solid fraction
the dispersed particles lock into a rigid structure and flow ceases. For each particle size
distribution, and for each particle shape there is characteristic packing fraction, for example
the maximum packing fraction for hexagonally packed spheres is 0.74. The viscosity increases
dramatically when the fraction solids by volume, θ approaches p, as described in its simplest
form by the Einstein equation (Barnes, Hutton and Walters, 1989):
h = h w (1 + 2.5i) (19)

Two key determinants of pulp viscosity are the per cent solids by weight and the solids
specific gravity, as shown in Figure 17. If gangue changes from sulfide- or iron-dominant
gangue to siliceous gangue, the solids specific gravity decreases, resulting in an increase in
viscosity, which will alter gas characteristics.

Particle shape and viscosity

Particle asymmetry has a strong effect on the viscosity and maximum packing fraction and on
the concentration/viscosity relationship. Any deviation from spherical particles results in an

2.0
1.9
1.8
Viscosity (mPa.s)

1.7
1.6
1.5
1.4
1.3
1.2
1.1
1.0
0 10 20 30 40 50 60
% Solids (w/w)

Solids S.G. = 2.8 Solids S.G. = 4.5

FIG 17 – Relationship between per cent solids by weight and viscosity.

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 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

50

Viscosity (mPa.s) 40

30

20

10

10 20 30 40
Volume concentration (%)
Spheres Grains Discs Rods
FIG 18 – Effect of particle shape on viscosity (from Barnes, Hutton and Walters, 1989).

increase in viscosity for the same phase volume. Figure 18 (Barnes, Hutton and Walters, 1989)
details the effect of particle shape on viscosity for the following cases:
1. spheres – grinding via attrition mills such as the Vertimill® or IsaMill® generates essentially
spherical particles
2. grains – grinding via impact mills such as SAG mills, ball mills or rod mills generates
granular particles
3. discs – the presence of discs generally comes from material that breaks along plate lines
such as mica
4. rods represent the most severe particle shape to affect viscosity and can be fibrous, such
as asbestos.

Agglomerates and viscosity

The formation of agglomerates via particle attraction leads to a larger effective phase volume
than that of the individual particles. This results in an additional increase in the viscosity
over and above that expected from the phase volume of the individual particles. This effect
is typically observed in ultra-fine particles, such as clay, or following ultra-fine grinding, as
illustrated in Figure 19 (Barnes, Hutton and Walters, 1989).
Lime addition can also have a significant effect on viscosity, both through the formation of
flocs and above a pH of 9.5 via the precipitation of magnesium hydroxides in gelatinous form.
Since lime often contains magnesium, if the addition of lime is sufficient to raise the pH above
9.5, the magnesium content in the lime precipitates as Mg(OH)2.

Effect of per cent solids and viscosity on bubble size

Figures 20 and 21 (Amec Foster Wheeler database) illustrate the expected change in bubble
size caused by viscosity and pulp per cent solids variation in a massive sulfide zinc rougher
circuit, operating at a feed P80 of ~60 µm. In terms of the commonly measured pulp per cent
solids, an increase from 20 per cent w/w to 40 per cent w/w is expected to cause bubbles to
approximately double in diameter.

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

Particle
Diameter (um)
101 0.05

Average interparticle separation (nm)

0.10
0.50
103 1.00

102

101

100
Particle Coagulation Region
10‐1
0.1 0.2 0.3 0.4 0.5 0.6
Solids volume fraction
FIG 19 – Formation of agglomerates (from Barnes, Hutton and Walters, 1989).

1.8

1.6

1.4
Sauter mean bubble size (mm)

1.2

1.0

0.8

0.6

0.4

0.2

0.0
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8
Viscosity (mPa.s))

FIG 20 – Effect of viscosity on bubble size.

Effect of per cent on air hold-up

An increase in per cent solids also results in an increase in the drag forces acting on bubbles,
due to increased viscosity. This results in bubbles rising slower and an increase in air hold-
up in the flotation cell. The air held up reduces the effective volume of the flotation cell and
hence decreases the residence time. Figure 22 illustrates the effect of per cent solids on air
hold-up from data sourced from the Amec Foster Wheeler database. It should be noted that
the majority of this data was from duties with solid sg values between 3.0 and 3.5.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 193

 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

1.8

1.6

1.4
Sauter mean bubble size (mm)
1.2

1.0

0.8

0.6

0.4

0.2

0.0
0 10 20 30 40 50
% Solids (w/w)
FIG 21 – Effect of per cent solids on bubble size.

30
25
Air hold‐up (%)

20

15

10

0
0 10 20 30 40 50 60
Per cent solids (w/w)
FIG 22 – Effect of per cent solids on air hold-up.

Effect of volumetric pulp flow on air characteristics

Increases in volumetric flow have several effects on a flotation cell. One of these relates to
the effect of volumetric flow on air hold-up. Figure 23 illustrates the effect of bubble surface
area flux on air hold-up. The curves indicate a divergence generally between 25 per cent and
30 per cent air hold-up. At this point the aerated pulp transitions from a bubbly mixture flow
regime to a foam flow regime. The transition causes a number of effects:
1. Coalescence of bubbles increases dramatically and the Sb decreases. Further increases in
air do not result in an increase in Sb and the froth surface often ‘boils’.
2. Flooding of the cell may occur, that is the bubbles are not able to disengage from the
pulp and the air hold-up in the tailing stream is similar to the main pulp in the cell. Often
this occurs with very little visible evidence and is characterised by severe deterioration in
concentrate grade and recovery.

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 CHAPTER 6 | CHARACTERISATION MEASUREMENTS IN INDUSTRIAL FLOTATION CELLS

35

30

25
Air hold‐up (%) 20

15

10

0
0 50 100 150 200
Sb (s‐1)
JKTech Database Matiolo et al
FIG 23 – Effect of Sb on air hold-up.

Increases in volumetric pulp flow result in an increase in pulp superficial velocity, Jp, which
in turn changes the operating point where the transition to the foam flow regime occurs.
Figure 24 details the relationship at Jp values of 0.0 cm/s and 0.66 cm/s (Matiolo et al, 2011) and
1.5 cm/s (Amec Foster Wheeler database). Typically, once familiar with the issue, operators
will reduce air to prevent flooding. The loss in recovery from reduced kinetics is typically far
less than the loss due to cell flooding.

CONCLUSIONS
Measurement of gas dispersion characteristics in industrial flotation plant cells has aided
troubleshooting and identified problem areas such as worn impellers, non-uniform gas
dispersion, etc. Being able to measure these parameters quickly and relatively easily has
enabled plant metallurgists to make adjustments to their cell operation and improve the plant
performance significantly.
Measurement of the froth performance has indicated that most flotation cells operate at
reasonably low froth recovery, with a significant proportion of material that entered the froth

30

25
FOAM TRANSITION POINT
20
Air hold‐up (%)

15

10

0
0 20 40 60 80 100 120
Sb (s‐1)
Jp = 0.0 cm/s Jp = 0.66 cm/s Jp = 1.5 cm/s

FIG 24 – Effect of Sb and air hold-up on the foam transition point.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 195

 GREG HARBORT, SARAH SCHWARZ AND THU NGUYEN

phase dropping back down to the pulp phase. These measurements have also identified that
the processes within the froth phase are still relatively unknown, but quite significant in the
overall flotation cell performance.
While a great deal of flotation plant operation has developed based on experience and
instinct, it is envisaged that with the various techniques now available to measure critical
parameters within the flotation cells, plant metallurgists will have a greater understanding
of the flotation process. Once the process is better understood, there is a greater potential for
improving and operating the flotation cells at their optimum levels for the best metallurgical
performance possible.

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Wu, Q, Welter, K, McCreary, D and Reyes, J N, 2001. Theoretical studies on the design criteria of
double-sensor probe for the measurement of bubble velocity, Flow Measurement and Instrumentation,
12:43–51.
Yoshida, Y, Katsumoto, T, Taniguchi, S, Shimosaka, A, Shirakawa, Y and Hidaka, J, 2013. Prediction of
viscosity of slurry suspended fine particles using coupled DEM-DNS simulation, Chemical Engineering
Transactions, 32:2089–2094.

198 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

Return to contents

CHAPTER 7
Chemical measurements during plant
surveys and their interpretation
Stephen Grano

ABSTRACT
This chapter addresses simple chemical measurements and their interpretation in the
optimisation of base metal sulfide flotation plants. The measurements include pH, Eh,
dissolved oxygen, dissolved oxygen demand, extractable metals, and solution species. For
each measurement, the basic theory and practical examples of application are discussed.
Simple hydrolysis and Eh/pH diagrams are described which aid interpretation. The key
sampling points and methodology for chemical measurements during a plant survey are
outlined. The critical importance and method of correlating the laboratory conditions and
performance to the plant is discussed. Two practical case studies highlight the utility of these
chemical measurements for process troubleshooting are discussed.

INTRODUCTION
This chapter is divided into the following three sections:
1. chemical measurements during a plant survey
2. analysis and interpretation of these chemical measurements
3. two practical case studies that highlight the utility of these chemical measurements for
process troubleshooting.

CHEMICAL MEASUREMENTS DURING A PLANT SURVEY

In this section, basic chemical measurements taken during a typical plant survey will be
outlined. The chemical measurements include:
•• pH
•• Eh
•• dissolved oxygen
•• dissolved oxygen demand
•• ethylene diamine tetra-acetic acid (EDTA) extractable metal ions
•• solution ionic species.

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 STEPHEN GRANO

For each measurement type, a brief theoretical background will firstly be discussed. This
will then be followed by a brief discussion on the importance of the measurement, how the
measurement may be made, and some practical guidelines.
The combined measurements of Eh and pH will, to a significant extent, define the
thermodynamic stability of bulk species (Garrels and Christ, 1965). This is because most equilibria
are principally controlled by pH (eg hydrolysis) and Eh (eg oxidation/reduction). The other
important variable when considering the predominant equilibrium species is concentration
(eg the total metal ion or collector concentration in the system), though this parameter may
be very difficult to define and measure. However, the strict application of thermodynamic
equilibria is often not appropriate for reactions that have not come to equilibrium, or at a mineral
surface where the interfacial pH and concentrations may not be at their bulk solution values
(Woods, 1984). Putting aside these considerations, it is still very valuable to measure both pH
and Eh during plant surveys and to use these measurements to ‘predict’ species predominance
(Natarajan and Iwasaki, 1973a). Several examples are presented which show the utility of such
an approach. It is always important to measure both pH and Eh at key sample points, such as
the ball mill discharge, flotation feed and process water in a plant survey.

pH
This is the most common and easiest to measure of the chemical measurements. pH is
relatively easy to measure as it does not rely on particle contact with the electrode to ensure
an accurate measurement, unlike Eh, which does. The definition of pH is given below (Garrels
and Christ, 1965):
pH = -log [H+]

This definition is a formal one as it involves the activity of a single ion, a quantity that cannot
be measured directly. As a result, the measured pH is defined in terms of an operational
procedure. For all practical purposes, the measurement of pH is accomplished using an
electrochemical cell that consists of a glass electrode dipping into the solution, together with
a reference electrode to complete the circuit. The reference electrode is usually a mercury-
mercurous chloride (calomel) electrode in saturated KCl solution, connected to the solution to
be measured by a salt bridge of saturated KCl solution. The glass electrode consists of a glass
bulb containing an acid solution, and an inner electrode of fixed potential, usually Ag-AgCl,
to conduct electrons, into and out of solution. When the bulb is immersed in a solution, an
electrical potential is developed between the inner and outer solutions which is proportional
to log [H+] in the external solution. The reference electrode has a constant potential, whilst
that of the glass electrode will vary with [H+]. The overall cell may be represented as: glass
electrode, sol. x| KCl(sat.), AgCl (s); Ag (l).
The half-cell (electrode) potential of the glass electrode is given as:

E'x = C H + 2.303 RT log [H+]

F
ie
E'x = C H - 2.303 RT pH
F
where:
R = gas constant, 8.135 J K-1 mol-1
T = temperature in degrees Kelvin
F = Faraday’s constant, 9.684 × 104 C mol-1

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 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

The overall cell potential is given by the difference of the two-half cell potentials:

E x = E'x - E ref = C H - 2.303 RT pH - E ref

F
If a given experimental arrangement as represented by the above cell is used firstly to
determine the cell potential developed by a solution whose pH (pHx) is to be measured, and
then the test solution is replaced by a standard reference solution of assigned pH value, pHs,
the cell potential measured in the test solution, at the same temperature, is given by:

E x = C H - 2.303 RT pH x - E ref
F

Es = C H - 2.303 RT pHs - E ref

F
Subtracting these potentials and rearranging gives:
F (E x - Es)
pH x = pHs -
2.303 RT
This equation is the basis for the operational definition of pH. The pH is dependent upon
temperature. Thus, it is always important to measure the temperature of the pulp when
measuring the pH. Temperature will also affect the oxidation of minerals, decomposition
reactions, solubility of gases in the slurry, and precipitation from solution. For example, the
temperature of a ball mill discharge stream can be up to 70°C in some climates, which can
greatly accelerate interaction of thiol collectors with sulfur-oxy depressants (Sheldon and
Johnson, 1988) which may then affect flotation of the minerals (O’Connor, Dunne and Botelho
De Sousa, 1984).
Buffer solutions are available for calibrating the pH electrode which fix the values of Es and
pHs. The pH meter must be calibrated with buffer solutions at the same temperature as that of
the process solution to be measured. Most pH instruments have a temperature compensator
that can be adjusted to the temperature of the test solution. This adjustment will have the
effect of putting the correct value for the slope (ie 2.303 RT / F) into the pH meter. For a well-
calibrated pH electrode, the accuracy of the measurement can be ±0.01 pH units. However,
for slurry measurements it is usual to determine the pH at an accuracy ±0.2, or at best
±0.1 pH units. In general, electrode response to homogenous solutions is rapid, but between
readings the glass electrode should be rinsed several times with distilled water to remove
adsorbed ions. For pH measurement in slurries in industrial flotation cells the electrode
should be placed into the pulp through the froth so that the tip of the electrode is deep enough
to be covered with the pulp. Furthermore, using appropriate sampling equipment, transfer
the slurry to an empty bucket or vessel and while stirring, record the pH and compare the two
values. The reason this is done is to check if sampling and de-aerating the pulp changes the
pH appreciably which may occur in highly oxygen consuming environment.
The importance of pH in controlling the hydrolysis of metal ions is shown in Figure 1. If a
system contains 10-5 mol dm-3 of copper at pH 4, the predominant copper species will be
Cu2+ (aq) and CuCO3 (aq) in solution. Increasing the pH to 7 would give rise to the onset
of Cu(OH)2 (s) precipitation. By pH 8 - 8.5, virtually all the copper in the system will be
precipitated as Cu(OH)2 (s) with a small amount of CuCO3 (aq) and Cu2+ (aq) in solution.
The extent of metal ion precipitation in a particular system can be measured by extraction,
while the metal ions in solution can be measured by separating the solid phase from the
aqueous phase. These methods are discussed further below. It is very important to know

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 201

 STEPHEN GRANO

2+ 2+
Cu2(OH)2 Cu 4-
Cu(CO3 ) 3

-log Concentration / mol dm-3

0
-1
-2 Cu(OH) 2(s) 2-
Cu(CO 3 ) 2
-3
-4 +
Cu(OH)
-5
-6
CuCO3 (aq) 2-
-7 Cu(OH)4
2 4 6 8 10 12
pH
FIG 1 – Solubility diagram for the Cu (II)-H2O-CO2 system. [CO2]tot = 10-3 mol dm-3.

what species are in solution at specific points in the circuit. For example, a thickener overflow,
which contributes to the process water, containing 5 ppm of copper at pH 7, is sufficient to
inadvertently activate some sphalerite during galena flotation and increase contamination of
the lead concentrate by zinc, reducing also zinc recovery to the zinc concentrate.
Increasing the pH further will dissolve Cu(OH)2 (s) as Cu(CO3)32-. It is important to note that
Cu(OH)2 (s) will still be present in the system to pH values greater than ten, though equilibrium
considerations suggest it will be at a lower concentration. Because the Cu(OH)2 (s) is in
equilibrium with negatively charged species in solution, the zeta potential of the Cu(OH)2 (s)
will be negative at pH values greater than approximately 8–8.5 (pHiep). To dissolve copper
hydroxide it is necessary to decrease the pH to less than ~6, though this will depend on the total
concentration of copper in solution. Copper in solution may be derived from the oxidation
of copper minerals, which is dependent upon the pulp Eh, while hydrolysis of the copper is
pH dependent. The adsorption of copper and iron onto copper sulfide minerals controls their
flotation properties to a very large extent. An excellent case study of the effect of pH on iron
hydrolysis and the zeta potential of pyrite is given by Fornasiero, Eijt and Ralston (1992),
while the ensuing effect of pH on collector adsorption is discussed by Montalti, Fornasiero
and Ralston (1991). Kristall et al (1994) has described the influence of pH on the selective
dissolution of zinc hydroxide on sphalerite while leaving iron (III) hydroxide on pyrite intact
in a copper/zinc flotation plant.

Eh
The oxidation/reduction potential, Eh, is defined as the potential of a half-cell, referred to
the standard hydrogen halfcell, the potential of the standard halfcell being taken as zero at
all temperatures, by definition (Garrels and Christ, 1965). Oxidation/reduction potential is
measured with an electrode pair consisting of an inert electrode and a reference electrode.
The same reference electrode is used for most Eh measurements as for pH measurements –
the saturated calomel. The inert electrode used most commonly is bright platinum, although
gold electrodes are also used. The role of the calomel electrode is to supply a known potential
and to make electrical connection with the system to be measured. The inert electrode acts
as an electron acceptor or donor to the ions in the measured solution. When connected to the
calomel electrode, the platinum electrode can accept electrons from dissolved ionic species,

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 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

or it can give them up, depending upon whether the potential of the half-cell involving the
dissolved species is greater or less than that of the calomel reference electrode.
The half-cell reaction for every oxidation-reduction system can be written as:

Oxidised State + ne- = Reduced State

An example is:
Fe3+ + e- = Fe2+

The half-cell potential is given by:

[Oxidised state]
Eh = E o + RT ln
nF [Reduced state]
The reference electrode acts as a half-cell of constant potential (at a constant temperature)
and the overall cell potential is given by:

EMFcell = EhRed/Ox – Ehref

As an example, it is possible to calculate, using the Nernst equation, the theoretical potential
of the cell:
Pt (inert) | Fe3+ (aq) 0.01 M || Hg2Cl2 | Hg

| Fe2+ (aq) 0.001 M || KCl aq (sat) |

The two half-cell reactions and potentials are:

2Fe2+ (aq) = 2Fe3+ (aq) + 2e- EhFe2+, Fe3+

2Hg + 2Cl- (aq) = Hg2Cl2 + 2e- Ehref

Subtracting these two equations gives:

2Fe2+ (aq) + Hg2Cl2 = 2Fe3+ (aq) + 2Hg + 2Cl- (aq)

Ecell = EhFe2+, Fe3+ - Ehref

The value of Ehref is constant at a given temperature and pressure, and for the saturated
calomel cell (Hg2Cl2) at 25°C is 0.2444 v. The half-cell potential for the Fe2+, Fe3+ couple is
given by:
[Fe 3+] 2
Eh Fe2 + ,Fe3+ = EoFe2 + ,Fe3+ + 0.0592 ln
2 [Fe 2+] 2

EoFe2+, Fe3+ = 0.771 v, gives:

Eh Fe2 + ,Fe3+ = 0.771 + 0.0592 ln 0.01

0.001

EhFe2+, Fe3+ = 0.830 v

Therefore:
EMF cell = 0.830 - 0.244 = 0.586 v

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 203

 STEPHEN GRANO

The measured potential of an inert electrode will be close to the ‘reversible’ potential
calculated by the Nernst equation, provided:
•• All the species involved in the oxidation/reduction are in equilibrium.
•• The indicator electrode is truly an inert electrode and does not itself become oxidised or
reduced.
•• There is only one couple, which dominates the potential response. Often there are two or
more redox couples, such as the reduction of water, which may influence the potential.
In this case, the developed potential is referred to as a ‘mixed’ potential (Rand and
Woods, 1984; Natarajan and Iwasaki, 1974).
In Eh measurements most of the difficulties result from contamination of the platinum
electrode (Natarajan and Iwasaki, 1973b). It is useful to have two indicator or inert electrodes
set up with the same reference electrode to check for differences due to contamination.
Solutions containing sulfide ion often ‘poison’ Eh electrodes. Eh measurements under ideal
conditions are typically only reproducible to ±5 mV, while for measurements in slurries
it is only reproducible to ±10 mV. In slurries, the Eh will also depend upon contact of the
inert electrode with conducting particles of sulfide minerals (Rand and Woods, 1984). It is
important to maintain a reproducible technique to measure the Eh, which usually involves
rapid stirring of the pulp to ensure adequate particle contacting with the electrode.
The degree to which the oxidised species predominates over the reduced species depends
on the difference between the potential of the system (Eh) and the standard potential (Eo)
(Figure 2). Eo is the potential at which all species are at unit concentration. For single electron
transfer reactions (n = 1), if the potential is more than 60 mV greater than the Eo, then
90 per cent of the species considered will most likely be in their oxidised state (Figure 2),
assuming equilibrium has been achieved. If the potential is more than 60 mV less than the
Eo, then 90 per cent of the species considered will likely be in their reduced state (Figure 2),
again assuming equilibrium has been achieved. In the above case of the Fe2+, Fe3+ couple,
over 90 per cent of the iron is in the Fe3+ oxidation state at a potential 50 mV greater than the
standard half-cell potential.
For systems which are open to the atmosphere, the reduction of oxygen at the inert electrode
is very important. For example, slurry exiting a ball mill may be in a highly reducing state

100
90
80
70
n=1
% Oxidised

60
n=2
50
n=3
40
30
20
10 Eo
0
-120 -80 -40 0 40 80 120
Potential (mV) from Eo

FIG 2 – Degree of oxidation ([Oxid]/([Oxid]+[Red])) as a function of potential difference

from the standard potential, Eo, for reactions having n = 1, 2, or 3 electrons involved.

204 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

in situ of the pulp, but with sampling and stirring the Eh of the sample can increase due to the
introduction of air into the pulp. The Eh of the plant pulp can also increase through pumping,
cycloning and its introduction to flotation. The reduction of oxygen can be written as:

2H2O = O2 + 4H+ + 4e-

PO 2 [H +] 4
Eh = E o + 0.059 Log
4 [H 2 O] 2

Substituting -pH for [H+], the activity of pure water being unity, and with Eo = 1.23 v yields:

Eh = 1.23 - 0.059 pH + 0.059 Log PO 2

4
At a partial pressure of oxygen of one atmosphere, the PO2 term disappears. This equation
can be used to plot a line on an Eh-pH diagram for any chosen pressure of oxygen (Figure 3).
For potentials greater than the PO2 = 1 atm line (eg pH 10, Eh 1 v), water is not stable, and
oxygen will bubble out of solution. The Eh is dependent upon the partial pressure of oxygen
in the system. At very low potentials (eg pH 10, Eh – 0.7 v) water is not stable and hydrogen
will start to bubble out of solution.
It is useful to plot the measured values of pH and Eh, as shown in Figure 3, from a plant
survey or flotation test, or across different flotation tests under different conditions to isolate
whether a change in Eh is due to a change in pH or is due to a change in concentration of an
oxidising/reducing species (Johnson, 1988). For example, Grano, Johnson and Ralston (1997)
have measured the Eh of a laboratory mill discharge as a function of pH to demonstrate
that the pulp Eh becomes more oxidising with increasing soda ash addition (pH) to the mill.
This approach is discussed further in the first case study at the end of this paper, and in the
next section on the interpretation of chemical measurements. It is clear that it is also very
important to measure the dissolved oxygen in the pulp. This is discussed further below.

1.2
PO
1 2 =1
PO PH
0.8 2 =10 -2 2 =10 -41
0 .6

PH
Eh versus SHE (V)

0.6 PO 2 =10 -3
2= 10 -40 1.6

0.4 PO PH
2= 2 =10 -4
10 -40 1.6
0.2 PH
PO 2 =10 -1
2 =10 -8 1.6
3.1
0
PH
2 =1
-0.2

-0.4

-0.6

-0.8
0 2 4 6 8 10 12 14
pH

FIG 3 – Stability limits of water as a function of Eh and pH at 25°C. Contours

show partial pressure of oxygen and hydrogen at intermediate Eh values.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 205

 STEPHEN GRANO

Finally, it is possible to summarise the various redox and hydrolysis reactions for a system
in the form of an Eh/pH diagram (Figure 4 in the case of iron). In the case of vertical lines ‘A’
and ‘E’, these represent the equilibrium between Fe3+/Fe (OH)3 and Fe2+/Fe (OH)2, respectively.
These equilibriums are hydrolysis reactions only and so do not depend upon Eh, only pH.
In the case of horizontal lines ‘B’ and ‘C’, these represent the equilibrium between Fe3+/Fe2+
and Feo/Fe2+, respectively. These equilibria are redox reactions only and so do not depend
upon pH, only Eh. In the case of lines ‘D’, ‘F’ and ‘G’, these represent the equilibria between
Fe2+/Fe(OH)3, Fe(OH)2/Fe(OH)3 and Feo/Fe(OH)2, respectively. These equilibria involve both
redox and hydrolysis reactions and therefore have slopes which are neither simply horizontal
nor vertical. For the case of a ball mill discharge (Figure 4) in which there is oxidation of iron,
redox reactions involving this species will tend to dominate. This is reflected in the low Eh
(-200 mV, pH 7) of this stream. Fe is stable at low Eh values and will tend to decrease the Eh.
However, with pumping and cycloning, the introduction of air into the pulp raises the Eh at
the flotation feed sample point. This is because of:
•• the removal of the slurry away from reducing environment in the ball mill
•• the introduction of another electrochemical couple, O2/H2O.
It is possible to show that the Eh increase is not due to a change in pH over these two
sample points, as the Eh increases without any appreciable change in pH. The change
in Eh shows there must also be a change in the dissolved oxygen content of the pulp
(Figure 3). The initially depressed Eh in flotation, and changing Eh with aeration, have
consequences in flotation. Johnson, Jowett and Heyes (1982) have shown that the initial
flotation rate of the valuable mineral can be retarded due to the low Eh in the initial stages
of flotation. With aeration, the Eh increases above a critical value for collector adsorption.
This is a consequence of the Eh dependency of sulfide mineral flotation with thiol collectors
(Richardson and Walker, 1985).

Dissolved oxygen
Dissolved oxygen is the next most important variable to measure. However, its value in
a sampled pulp is often not at steady state. This is because of the continuous removal of
oxygen from the pulp due to mineral and media oxidation. The introduction of oxygen

1.5

‘A’
1 Fe 3+

‘B’ O2
‘D’ Fe (OH)3
0.5
Eh versus SHE (V)

Flotation
Fe 2+ Feed
0
H2 Ball Mill
‘F’
Discharge ‘E’
-0.5 Fe (OH)2
‘C’
Fe ‘G’
-1
0 2 4 6 8 10 12
pH

FIG 4 – Eh/pH diagram for the Fe system. [Fe]tot = 0.01 M. Also shown are values of Eh
and pH taken from an Australian gold mine. The stability limits of water are also shown.

206 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

in flotation systems raises the Eh of the pulps. Thus, when a sample is removed from a
pulp stream, the pulp is being taken away from the dynamic equilibrium which had been
established between the removal of oxygen in solution and the introduction of oxygen. In
some cases, it may be worthwhile to attempt to measure the dissolved oxygen (and Eh)
in situ of the pulp.
The dissolved oxygen electrode consists of a gold cathode and Ag/AgCl anode, placed
in an electrolyte solution. The solution is contained behind a plastic membrane, usually
polyethylene. A polarising potential of about 800 mV is applied between the two electrodes.
The gold electrode is placed close to the membrane and because of the polarising potential,
oxygen diffusing through the membrane will be reduced at the gold electrode:
O2 + 2H+ + 2e- = H2O2
The reduction of oxygen will produce a current through the electrode. A load thermistor
situated in the electrode itself converts this current into a voltage proportional to the oxygen
partial pressure. The thermistor has a temperature coefficient, which can compensate for
changes in ambient temperature, though this will depend upon the thickness and type of
plastic membrane. It is therefore always important to use the correct plastic membrane that is
matched to the particular electrode. In some ore systems containing galena or sphalerite and
large quantities of pyrrhotite, the critical variable appears to be dissolved oxygen, rather than
Eh, due to the oxidising influence of Fe3+ on Eh. In this case, collectors may be used which are
able to adsorb onto galena in a low oxygen environment (eg alkyl or aryl phosphinates), or
alternatively oxygen may be supplied to the pulp to oxidise pyrrhotite and increase the Eh,
allowing conventional xanthate collectors to be used.

Dissolved oxygen demand

The dissolved oxygen demand test (DO demand) has been used to determine the rate of
oxidation of minerals in pulps (Spira and Rosenblum, 1978). It is a useful in situ method that
provides information on the average oxidation state of the minerals. It is possible to construct
a device where the dissolved oxygen demand is measured in a separate vessel after a specific
purging period in a supply vessel. Alternatively, it is possible to conduct the dissolved oxygen
demand test in the one vessel. In this case, the demand measurement is conducted in the same
vessel after specific oxygen purging periods after which the oxygen supply is discontinued
and its depletion from the solution is measured.
As oxidation of the minerals and grinding media proceeds in the supply chamber, the rate
of oxygen removal from the pulp is reduced (Figure 5). With no initial oxygen purging, there
is a rapid depletion of oxygen from the initial value (~6.5 ppm) to virtually ‘nil’ oxygen in
solution (~0.8 ppm). With 120 minutes of oxygen purging there is slow depletion from the
initial value (~8 ppm), which then decreases to a non-zero value. This implies that the rate
of oxygen removal by oxidation at that stage is being balanced by oxygen being introduced
into the solution. When the oxygen purging gas is discontinued for the DO depletion stage
then that flow is discontinued and there is removal of oxygen from solution due to fixation on
minerals and media debris (rate k1), but also due to equilibria with the atmosphere (rate k2).
When the concentration of oxygen in the pulp is greater than the equilibrium value [O2]eqm,
oxygen is removed at a rate of -k2. When the concentration of oxygen in the pulp is less than
the equilibrium value, oxygen is dissolved into solution at a rate of k2. This analysis assumes
the rate of oxygen dissolution is equal to the rate of oxygen nucleation.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 207

 STEPHEN GRANO

O2 Concentration (ppm)
7

0
0 30 60 90 120 150 180
Aeration Time (minutes) in the Supply Chamber

FIG 5 – Dissolved oxygen concentration as a function of time, after oxygen purging the slurry for different periods of time. For
each determination of oxygen demand, the initial oxygen concentration was set to approximately 6–8 mg/L with air purging,
then the oxygen discontinued and the oxygen concentration measured with time. Slurry sample is grinding cyclone overflow.

d [O2] t
= - k1. [O2] t - k2. ([O2] t - [O2] eqm)
dt

d [O2] t
= - (k1 + k2) . [O2] t + k2. [O2] eqm
dt
Integration yields:
k2. [O2] eqm k2. [O2] eqm
[O2] t = + e[O2] o - o exp - (k1 + k2) t
(k1 + k2) (k1 + k2)
where:
[O2]o is the initial concentration of oxygen at t = 0 minutes when the oxygen purging gas is
turned off
[O2]eqm is the concentration of oxygen in the liquid when it is in equilibrium with the
atmosphere presented to it, having an approximate value of 8 mg/L when it is in
equilibrium with air
When k2 = 0 (ie the demand chamber is closed to the atmosphere) the oxygen concentration
is simply given by:
[O2]t = [O2]o exp − (k1)t

This equation has been used to fit the experimental data points shown in Figure 6, and the
value of rate constant k1 determined for the various amounts (ie purging time) of oxygen
delivered. It is possible to quantify the oxygen delivered with air delivery time in the
supply chamber by measuring the rate of oxygen dissolution in the liquid phase only at the
experimental temperature and pressure. The value of this rate constant is plotted against
time of air purging in the supply chamber (Figure 7). As the time increases, the rate of oxygen
depletion decreases. These experiments also show the effect of adding iron to the system.
Adding iron increases the oxygen demand of the slurry. The rate of decrease of oxygen
demand with aeration time is similar for the ore without iron and with iron, suggesting that
the rate of removal of oxygen is controlled by media oxidation.

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 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

4.0
PCO

First order rate constant (minutes-1)

3.5 No Fe

3.0 3kg/t Fe
6kg/t Fe
2.5
15kg/t Fe
2.0

1.5

1.0

0.5

0.0
0 20 40 60 80 100 120 140
Aeration time (minutes)

FIG 6 – Rate of oxygen removal from solution (k1) as a function of aeration time. The various experiments
are for a plant cyclone overflow (PCO), a sample of ore taken during the measurement of the PCO and
ground in a laboratory mill (no Fe), and with various addition of iron to the laboratory mill.

Conditioned
Reagents Rougher Feed
Process Process
Water Primary X X X
Water Cyclone O/F
Rougher
X Block

Primary
SAG Mill X X
Ball Mill X
SAG X Includes regrind
pump box and cyclone
Feed
Reagents
Regrind
Reagents Ball Mill
Reagents
X
Reagents
Process Water
X
Cleaner
Block
X
X = Sampling Point

FIG 7 – Typical points (X) for measuring pulp chemistry values in a flotation
plant, showing typical reagent and process water addition points.

Alternatively, in the absence of the oxygen demand equipment described, it is possible also
to measure the oxygen demand in a beaker. In this case the procedure is to carefully place a
sample into a plastic beaker from a process stream and stirring for two minutes during which
time the dissolved oxygen is recorded with time. The dissolved oxygen can be measured over
this period and the rate of depletion measured.

Ethylene diamine tetra-acetic acid (EDTA) extractable metal ions

Ethylene diamine tetra-acetic acid is a powerful chelating reagent. It can be used as a diagnostic
tool for the determination of the amount of oxidation products on the surface of sulfide
minerals (Kant, Rao and Finch, 1994; Rumball and Richmond, 1996). The very high stability
of EDTA-metal complexes can be explained in terms of the values of the formation constant,

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 209

 STEPHEN GRANO

K, for the complexes. This means that there is a strong driving force for the formation of metal
complexes with EDTA. Note that complexes of EDTA have an intermediate stability between
the sulfide and hydroxide. This means that the metal hydroxides adsorbed or precipitated
on the mineral surface will be dissolved with EDTA, but that EDTA will not dissolve the
unoxidised metal sulfide. This statement is true, provided that EDTA does not catalyse the
oxidation of the sulfide minerals. In this method, the slurry sample is first purged of oxygen
to reduce oxidation during the EDTA extraction stage. A prepurged solution of EDTA is then
added to the slurry to make an overall concentration of ~10-2 M. It is important that the EDTA
concentration be high enough to ensure the soluble species which can be complexed by EDTA
(eg calcium) do not consume EDTA, such that there is sufficient available to complex with the
products of surface oxidation. The amount of EDTA metal ions is determined by filtration and
measurement of the solution phase, with mass balancing. It is very important to quote the
EDTA extractable metal ions as both:
•• the concentration of EDTA-metal ions taking into account both sample dilution and metal
ions already in solution prior to extraction
•• the percentage EDTA-metal of the total metal in the head sample.

Solution ionic species

It is very important to measure the dissolved species as well as the precipitated species using
EDTA. This is because it aids in the correct calculation of EDTA-metal ions, and it is also a
useful measurement in its own right. At most alkaline pH values, metal ions precipitate and
so are usually only measurable by EDTA extraction. However, elements and species such
as Ca, Mg, Na, Cl, K, SO42-, SxOy2-(eg thiosulfate) species are all important. It is important to
measure the total dissolved solids (TDS) and to account for most of the species in solution
by mass balance. The heavy metal cations and others should be measured by filtration
(to 0.45 μm) and acidification by HCl to prevent precipitation after sampling. Woodcock and
Jones (1970a, 1970b) have conducted comprehensive pulp chemistry measurements in many
sulfide flotation plants. In the case of SxOy2- special preservation techniques are required to
prevent oxidation. It is also possible to measure carbonate, but this needs to be done in situ
as carbonate ion will equilibrate rapidly with the atmosphere. Other important species
include total organic carbon (TOC), which may be a measure of residual reagents in solution.
It is possible to measure the concentration of collector, frother and polymers in solution
using special techniques not normally available at sites, such as Uv-Vis absorbance. Jones
and Woodcock (1984) have reviewed the measurement and reaction pathways of xanthate
derivates in solution.

ANALYSIS AND INTERPRETATION OF SURVEY CHEMICAL DATA

In this section, a typical survey and key sample points for measurements are discussed.
The importance of assimilating laboratory conditions to plant conditions is also outlined.
Following this, a typical example of measurements taken from a plant and their interpretation
will be discussed.
A typical comprehensive plant survey should be organised in the following way:
1. Metallurgical sampling including sampling for per cent solids and solids composition (bulk
assays) at the block level (ie rougher block, cleaner block) and the cell-by-cell level. This
could also include the measurement of lip froth flows and froth recovery for specific cells
(eg froth recovery of scavenger cells is usually less than rougher cells).

210 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

2. Pulp chemical measurements and sampling, including pulp samples for bulk chemical
and surface analysis and process water samples. This could also include specialised
measurements for reagents in solution and at the mineral surface. It should always include
the measurement of all reagent flows during the survey.
3. Cell characterisation measurements, including superficial gas velocity, bubble size and
residence time distribution by tracer tests (eg an estimation of energy dissipation in the
cell should also be made (usually in the range of 1–10 w/kg of pulp).
4. Batch flotation tests on process streams for the purpose of correlating laboratory conditions
to the plant and/or to build a circuit model based on component floatability. The batch
flotation tests will determine the fractions of different floatability in the feed.
5. Sample of SAG feed and circuit water for the purpose of laboratory testing. This is not
often carried out in conventional plant surveys, but it is very useful for optimisation at
laboratory scale tests. Obtaining these samples allows the plant conditions to be mimicked
at laboratory scale in grinding and flotation experiments.
The following section will focus on aspects of items 2, 4 and 5 above.

Pulp chemical measurements during a typical plant survey

Key points for the pulp chemical measurements (pulp chemical survey) are shown in Figure 7.
It is very important to measure the primary ball mill discharge Eh and pH as this is usually
the point in the process where the Eh is at its lowest value. This point is important because
this will indicate the extent of media oxidation and the possibility of low Eh values during
collector conditioning and flotation. Low Eh values during flotation may retard the flotation
of minerals (Trahar, 1984). It may be difficult to measure the SAG mill discharge for reasons
of access and safety, though it can be useful to demonstrate the difference between the SAG
and primary ball mill chemical environments. This is very important for unit flotation stages
in the primary grinding circuit. It is interesting to note the pulp chemical change across the
primary ball mill by comparing the primary cyclone underflow to the primary ball mill
discharge. This has consequences in the matching of the laboratory conditions to the plant as
discussed further below.
The cyclone overflow should be separately measured from the ‘conditioned rougher feed’
due to the addition of reagents and aeration in cycloning and pumping from the primary ball
mill circuit to flotation feed. The ‘conditioned rougher feed’ is the feed presented to rougher
flotation with all reagents added (including frother), and should also be the focus of batch
flotation experiments during the survey. This is discussed further below. The regrind ball
mill discharge and regrind cyclone overflow should also be separately measured. If there are
any conditioning stages, such as pulp heating, pH adjustment, aeration or reagent additions
(eg CuSO4, SO2), the change in pulp chemistry across the conditioning stage should also be
measured. The utility of these measurements in solving processing problems is outlined in a
case study below on a zinc reverse process.
The circuit water should definitely be measured along with other key streams in the
process water circuit (eg tailings return water, make-up water, mine water, tailings thickener
overflow water, concentrate thickener overflow water, etc). As an example of the importance
of the process water samples, it has been found, for example, that copper emanating
from a thickener overflow stream (which contained [Cu] at 5 ppm at pH 7) inadvertently
activated some sphalerite in the lead circuit of a lead/zinc flotation plant. To minimise this
inadvertent copper activation, only tailings return water, which contained much lower levels
of copper (<0.5 ppm), was used as make-up water in the lead circuit. Another example of the

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 211

 STEPHEN GRANO

importance of water quality is the use of fresh water in the zinc cleaning stages of a lead/zinc
flotation plant to reduce lime consumption to achieve a set point pH value and, consequently,
improve selectivity between sphalerite and pyrite. The normal process water at this plant
is supersaturated in calcium sulfate (Grano et al, 1997), suggesting that calcium sulfate has
probably precipitated in the pulps. This has a pH buffering effect, meaning that higher lime
additions are required to achieve a set pH (~11), and that more calcium sulfate will precipitate
due to lime addition, a source of calcium. By using fresh water in the cleaning stages, lower
lime additions are required, and better selectivity is achieved. In the future, use of treated
water sources for special applications (eg cleaning, fine grinding) will likely become more
common. Another example is when thickeners are operated with dirty overflows and there is
residual polymeric flocculant adsorbed on the particles in the thickener overflow. This may
interfere with flotation due to the adsorption of these hydrophilic slime particles onto the
value mineral.
For block surveys, samples and measurements contrasting the products of the major
separation should also be undertaken. This includes those across the rougher block (ie rougher
concentrate, rougher tailing reporting to final tailing, and rougher feed) and cleaner block
(ie final concentrate, cleaner block tailing reporting to final tailing, and cleaner feed). EDTA
extractions and surface analysis samples (not discussed here) would contrast the oxidation
state of these streams. EDTA extraction and other simple measurements can be taken more
routinely and correlated to plant flotation performance. In general, the valuable metal in the
tailing streams has a greater proportion in an oxidised state than the valuable metal in the
concentrate streams, both extractions measured on a mass of metal basis when using the
EDTA technique. Sulfide flotation, under conventional conditions (eg without sulfidisation)
with thiol collectors, is always selective against oxidised forms. Changing oxidation levels in
the conditioned feed gives rise to changing recoveries in the plant.
It is very important to measure the reagent flows during the pulp chemical survey. This
should include all reagents and all addition points (eg collector stage added points, usually in
the scavengers, frothers – often overlooked in surveys, activators and depressants, including
any test reagents). The solution strength of the reagents should be noted, including taking a
sample for later analysis, and the reagents additions quoted as mls/min, g/t of total plant feed
and g/t of the specific process stream to which the reagents are added. This is very important
for any laboratory tests to be conducted on the sample of SAG feed collected during the
survey. A mass balance on reagents should be attempted, which may identify problems of,
for example, frother adsorption onto particles and high residual frother in the process tailings
and the continuing presence of frother in the process water (Tsatouhas, Vera and Grano, 2005).
The type of plant survey, which if comprehensive, should be the beginning point of any
optimisation program. It is important to undertake multiple, simpler block surveys at key
sample points, both before and after the comprehensive survey to establish plant stability and
the normal operating range of the plant. These simple surveys may be called quality control
surveys and are aligned to the comprehensive survey in their reporting. The quality control
surveys increase confidence that the comprehensive survey was conducted under conditions
which reflect the plant operating range at that time.

Correlating the laboratory conditions and performance to the plant

Correlating the laboratory conditions to the plant is extremely important if any optimisation
work is contemplated at laboratory scale (Pietrobon, Grano and Greet, 2004). Often laboratory
experiments are undertaken under conditions which are far removed from the plant (eg adding

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 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

lime in conditioning and not to the mill in the laboratory, while lime is added to the mill in the
plant). To be more confident about successfully transferring the results of laboratory studies
to plant scale it is, at least, necessary to mimic the plant pulp chemical conditions and particle
size distribution at laboratory scale. This has the advantage that it will focus the initial stages
of laboratory investigations onto the effect of simple parameters, which may be relatively
easy to manipulate at plant scale, and which may acutely affect plant performance. This could
include the effect of water quality or water source, grind pH, aeration and standard plant
reagent additions, etc. The procedure outlined below adds more confidence to the testing of
future ores, which may have not yet been processed through the plant.
During the comprehensive survey, a SAG mill feed sample is taken (Figure 8) and treated
in the normal way to produce samples suitable for laboratory flotation testing. Storage of the
crushed and riffled sample should aim to minimise oxidation, though subjecting the sample
to the same standard laboratory flotation conditions with storage time may examine this,
along with routine EDTA extractions. During the comprehensive survey, flotation tests on the
conditioned rougher feed should ideally be undertaken in triplicate under known conditions
of the physical variables, such as cell type and mechanism, gas flow rate (Jg), impellor speed,
scrape rate and bubble size. These same physical conditions would then be used in latter testing
of the SAG feed sample to ensure that differences from the plant to the laboratory are only due
to differences in the feed (properties) presented to the flotation cell. During the comprehensive
survey, a large sample of circuit water should also be collected and used in laboratory flotation
testing (Figure 8). However, circuit water samples may not be stable due to the continuing
oxidation of thio-salts and microbiological activity. In this case, a simulated circuit water
sample should be prepared based on the inorganic composition of the circuit water, matching
all the major constituents of the circuit water during the survey including the total dissolved
solids (TDS). Unfortunately, it is very difficult to match the organic components that may
include, for example, collector decomposition products, bacteria and residual polymer from
dewatering. Comparing these water types may be very informative as well. Also, removing

Ore
(SAG Feed)

Reagents Process Water Reagents

Plant Grinding Laboratory

Circuit Grinding

Reagents Reagents

Plant Conditioning Laboratory Conditioning

Plant Flotation Laboratory Flotation

Matching Conditions

FIG 8 – Procedure for assimilating the laboratory to the plant conditions of pulp chemistry.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 213

 STEPHEN GRANO

some, or all, of the organic components from the circuit water (eg by adsorption onto activated
carbon) may determine the effect of these components on flotation performance.
Once these samples have been collected and treated appropriately, the SAG feed,
water samples and reagents may be used at laboratory scale. Special mills are available
(eg Magotteaux Mill®, Greet et al, 2004) which allow the pH to be continuously controlled
during grinding. This may be important in matching the laboratory to the plant as the pH
of the feed to most plant primary ball mills (ie the cyclone underflow) is the same pH as the
plant ball mill discharge. Most batch mills have wide variations in pH from the beginning
of grinding to the end, with the mill discharge pH usually being set as the target pH value.
This special mill (Magotteaux Mill®) allows continuous purging with different gases during
grinding to ensure that the laboratory mill discharge Eh is at the same value as the plant ball
mill discharge. Gas purging during grinding and post-grinding can be very informative in
terms of optimisation. Once grinding is complete the slurry is conditioned with the same
reagents and at the same addition level as during the plant survey. Laboratory flotation is
then conducted under the same physical conditions as that in the laboratory flotation tests
conducted during the plant survey. With care it is possible to duplicate the same performance
in the flotation tests during the plant survey. Differences will highlight variables which subtly
affect plant performance. These may include:
•• grind pH
•• grind Eh
•• flotation pH
•• flotation Eh
•• water quality
•• pulp temperature
•• grinding media
•• reagent quality, etc.
The parameters which require matching between the laboratory and plant trials are shown
in Figure 9. As well as Eh and pH, the particle size distribution of the ore and individual
minerals need to be reasonably matched. If there are significant deviations in the mineral size
distribution, then it may be necessary to analyse the laboratory flotation behaviour for both
tests on the plant conditioned feed and the SAG mill feed on a size-by-size basis. This can
be advantageous in providing flotation performance by particle size. The dissolved oxygen
demand and EDTA extractable metal ions can also be matched. However, these parameters
are dependent upon Eh and pH of both the grinding and conditioning stages. Matching the
values of Eh and pH will go a significant way towards matching dissolved oxygen demand
and EDTA extractable metal ions, provided the SAG feed sample has not oxidised during
storage (Pietrobon, Grano and Greet, 2004). It is also important to match the Eh and pH of
the mill discharge separately from the flotation feed Eh and pH values. This is because the Eh
during grinding is usually much lower than the Eh during flotation. However, if the Eh during
grinding is not mimicked then the conditions during laboratory grinding may not be realistic.
The grind and flotation Eh and pH values should be considered separately in the study.

The Eh/pH stability (predominance) diagram – interpretation

To demonstrate the utility of undertaking simple pulp chemical measurements during a
plant survey, as well as the importance of correlating laboratory conditions to the plant, an
example is discussed for the remainder of this section. The example comes from a flotation

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 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

GRINDING FLOTATION

MILL FLOTATION FLOTATION

DISCHARGE FEED RESPONSE

P80 and -38microns pH mass and water rec.,

pH Eh grade and recovery
Eh O2 concentration of value and
other minerals.
O2 concentration O2 demand
EDTA ext. M+ ions

FIG 9 – Parameters that need to be matched from the plant to the laboratory.

plant which normally treats porphyry copper ore (ie copper in chalcocite and chalcopyrite
in igneous host rock), but for which the proportion of the run of mine (ROM) ore from
sulfide skarns is generally increasing throughout the remainder of the mine life. Sulfide
skarns emanate from the intrusion of the igneous into the country rock and generally
contain higher copper and gold concentrations, but also much higher pyrite and magnetite
contents (Orwe, Grano and Lauder, 1997). The flotation plant encountered problems when
treating feeds with high sulfide skarn content such as low copper recovery (<75 per cent) and
low final concentrate grade (<20 per cent Cu). Ore blending was only partially effective and
cannot be used in the latter stages of the mine life due to the preponderance of sulfide skarn.
The low concentrate grade was a consequence of both high pyrite recovery and low copper
recovery. The normal conditions in the plant (lime addition to SAG feed to pH 11–11.5 and
using a dithiophosphate collector in the primary ball mill) were inadequate in the flotation
separation of sulfide skarn ores. The copper-bearing minerals were adequately liberated
from gangue being ~80 per cent fully liberated, across all size ranges, at the normal grind
size of 150 μm in flotation feed. The level of copper mineral liberation was the same or
greater than for porphyry sulfide ores. The reason for the low copper concentrate grade and
recovery were related to pulp chemistry differences between the porphyry and sulfide skarn
ores, rather than differences in mineral liberation.
In the preceding section, the stability diagram of iron was discussed. The stability diagram
shows the thermodynamically most stable species (ie the species at the highest concentration)
at various Eh and pH values while assuming a certain total concentration of the species.
Attention will now turn to the Eh-pH diagram for the Cu-S-H2O system (Figure 10). The Eh/
pH measurements at the cyclone overflow from two plant surveys on a porphyry ore are also
shown (Orwe, Grano and Lauder, 1998). The principal copper-bearing sulfide minerals are
chalcocite and chalcopyrite. The normal pH for this plant is 11.5. The Eh/pH diagram shows
that chalcocite is only stable to approximately Eh 0 mV at pH 11, while above this Eh value
it may begin to oxidise. However, the Eh of the pulp at the cyclone overflow is +150 mV
(Survey 1), suggesting that chalcocite oxidation may occur. Oxidation was confirmed by
EDTA extraction and surface analysis (Orwe, Grano and Lauder, 1998). In this system, further
aeration of the pulp in flotation does not appreciably increase the Eh, suggesting that the pulp

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 215

 STEPHEN GRANO

800
O2
H2 O o
CuO + S
CuS + Cu S Plant
400 2-x Cyclone O/F
Survey 1

Eh / mV 0 Cu2 S Cu S + CuO
2-x
H2 O
Cu2 S Plant
H2
-400 Cyclone O/F
Survey 2
o o 2-
Cu + H 2S Cu + HS- Cu + S
-800
0 2 4 6 8 10 12 14
pH
FIG 10 – Plant cyclone overflow pulp potential (Eh) as a function of pH in plant surveys on porphyry ore blends (head grade
2.05 per cent Cu, 5.6 per cent S, Cu/S 0.37, six per cent pyrite) for Survey 1 without sulfidisation and Survey 2 with sulfidisation.

is fully aerated under these high pH conditions (ie DO is high and the DO demand of the
minerals and ore does not outweigh oxygen delivery to the pulp). In Survey 2, NaHS (~100 g/t)
was added to the plant cyclone overflow to achieve an Eh of -50 mV. This decreased the Eh of
the cyclone overflow as shown into the stability region of Cu2S (Jones and Woodcock, 1978).
Oxidation would be prevented while oxidation products on chalcocite (copper hydroxide)
would be reduced to a ‘Cu-S’ phase. With aeration in the plant flotation cells the Eh increases
to +150 mV, which is an acceptable value for collector adsorption onto chalcocite (assuming the
sulfidised chalcocite does not re-oxidise) (Trahar, 1984). Copper recovery increased with this
treatment though the extent of this increase depended upon copper mineralogy (chalcocite
oxidises more than chalcopyrite and so the effect is less marked for chalcopyrite dominated
feeds), the feed particle size (fine chalcocite is more oxidised than coarser chalcocite), the
sulfidisation potential and other factors.
Another example of the application of presenting pulp chemical data in an Eh/pH
representation is shown in Figure 11. Presenting data in this way gives order to the data as it
allows changes in Eh, which may have been caused by changes in pH, to be detected. In this
example, both plant and laboratory data are shown (Putubu, Grano and Morey, 2001). The
Eh and pH experimental values from plant surveys conducted in October (on predominantly
porphyry ore) and March (on predominantly skarn ore) 2000, are compared to laboratory
data for moderate (shown as 20/11/98 SAG feed) and high pyrite skarn feed types (shown
as PSM). The plant Eh and pH values for skarn ore (high pyrite) surveys are lower than the
porphyry ore survey, but also lower than the Eh values after laboratory grinding of skarn
samples. It should be noted that for high pyrite skarn ores, higher (~4 kg/t) than normal
(~1 kg/t) lime additions are required to achieve the target pH (11.5). In spite of the higher
lime additions, the pH value is often lower than the target pH for high pyrite skarns. This is
because of pyrite oxidation, which generates acid in solution.
In the latter cases, laboratory grinding at high pH causes adequate chalcopyrite recovery
and selectivity from a high pyrite feed (PSM). Surface oxidation of pyrite in the laboratory
experiments assists depression of copper activated pyrite and the promotion of chalcopyrite
recovery. Chalcopyrite recovery is increased due to increased collector adsorption on its
surface due to reduced collector adsorption onto pyrite. It is also useful to note that without
pH control, the pH levels of the pulps generally decrease with aeration conditioning

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 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

450
60
Aeration
30 O2
400 10
Time
H2O
60
30
350
Eh / mV

3 10 Aeration Laboratory Tests

Laboratory Pit Skarn Initial pH 10.0 Porphyry Plant
Time Surveys (Oct 2000)
Magnetite Ore
300 Natural pH 3 60
30
Laboratory 10
20/11/98 SAG Feed 3 Cell 15 Tail
Aeration
250 Natural pH
Time Flotation Feed
Laboratory Tests Ball Mill D/C
Initial pH 11.5
200
Skarn Plant
Surveys (March 2000) Cell 15 Tail
150 Flotation Feed
Ball Mill D/C

3 4 5 6 7 8 9 10 11 12 pH
20/11/98 SAG feed sample Pit Skarn Magnetite (PSM) sample
Head Grade 2.05% Cu, 5.6% S, Head Grade 1.59% Cu, 10.7% S
Cu/S 0.37, 6% Pyrite Cu/S 0.15, 17% Pyrite

FIG 11 – The pulp potential (Eh) as a function of pH in plant surveys on porphyry ore blends (17 October 2000) () and sulfide
skarn blends (March 2000) (), as well as for laboratory tests on 20 November 1998 SAG feed sample (head grade 2.05 per cent
Cu, 5.6 per cent S, Cu/S 0.37, six per cent pyrite) (open symbols) and on pit skarn magnetite (PSM) sample (head grade
1.59 per cent Cu, 10.7 per cent S, Cu/S 0.15, 17 per cent pyrite) (closed symbols) for aeration tests at different initial grind pH values
(~11.5, ~10 and natural pH). The numerical values are aeration times in minutes after grinding the ores in the laboratory.

(Figure 11). In the case of grinding at pH 11.5 and 10 this is accompanied by increases in
Eh, which may be accounted for by changes in pH through the oxygen/water equilibrium.
This is because with aeration, the pH/Eh relationship parallels the oxygen/water equilibrium.
However, in the case of grinding at natural pH, the Eh increases markedly after grinding
suggesting an increase in the dissolved oxygen content of the pulp with aeration. The pH/
Eh relationship does not parallel the oxygen/water equilibrium for test at natural pH. In this
case, the oxygen content of the pulp increases with aeration. In these laboratory experiments,
pyrite very quickly passivates at alkaline pH values. It is noted that the optimum potential
for chalcopyrite flotation occurs in the Eh range of 200 to 250 mV (SHE) (Trahar, 1984). When
the pyrite is not adequately passivated (at alkaline pH), the pyrite consumes oxygen (and
collector), which retards chalcopyrite flotation in this system.

Dissolved oxygen demand – interpretation

Continuing with this example, sulfide skarn ores show much higher dissolved oxygen
demand in the plant rougher cells than porphyry ores (Figure 12). The dissolved oxygen
demand is a function of surface oxidation state and exposure of sulfide minerals. The rate
of oxygen depletion from the pulp is an indication of the oxidation rate. The high dissolved
oxygen demand of sulfide skarn pulps is related to their high active pyrite content. Through
processing in the plant, the pyrite surfaces become progressively more oxidised, consuming
less oxygen (Figure 12). The porphyry ores consume oxygen to a much lower degree and
develop higher Eh values in the pulp for the same pH values. These factors combine to give
better chalcopyrite recovery from porphyry sulfide ores. It is important to note that the
copper rougher recovery during surveys on high pyrite skarn blends (March 2000) varied
dramatically between 60 and 80 per cent, while copper rougher recovery during surveys on
porphyry ore (October 2000) was between 80 and 85 per cent. The rapid passivation of sulfide

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 217

 STEPHEN GRANO

100

Dissolved Oxygen / %
Cell 15 Tail

80 Cell 9 Tail
Cell 3 Tail
60
Cell 15 Tail
Rougher Feed Cell 9 Tail
40
Cell 3 Tail
20 Rougher Feed
A B
0
0 0 30 60 90 120 0 30 60 90 120 Time / sec
Porphyry ore blend Sulfide skarn blends
17/10/2000; average for 15/3 to 21/3/2000;
Head Grade Head Grade
0.6% Cu, 1.2% S, Cu/S 0.5 ~1.2% Cu, ~4.0% S, ~Cu/S 0.3

FIG 12 – Dissolved oxygen concentration as a function of time (dissolved oxygen demand) after the discontinuation of
air purging for plant rougher streams in surveys on (A) porphyry ore blends (17 October 2000; head grade 0.6 per cent
Cu, 1.2 per cent S, Cu/S 0.5) and (B) sulfide skarn blends (average for 15–21 March 2000; head grade ~1.2 per cent Cu,
~4.0 per cent S, ~Cu/S 0.3). The acid soluble copper and Cu/S ratio is a very important parameter in porphyry sulfide ores.

minerals, most probably pyrite, at alkaline pH values and under laboratory grinding and
flotation conditions is demonstrated in Figure 13. The high pyrite skarn feed (PSM) requires
a longer aeration time to achieve complete oxidation and that grinding under alkaline
conditions is important for pyrite oxidation.
Following these plant surveys, flotation tests were performed on samples of SAG feed.
Attention turned to the effect of grind pH on copper recovery and selectivity against pyrite for
laboratory tests of SAG feed (Figure 14). For tests with lime addition after the mill (Figures 14a
and 14b), pyrite readily responds to collector addition in spite of lime addition to pH 11.5.
Under these conditions, copper shows lower recovery and rate. This flotation behaviour is
characteristic of problems encountered under normal plant conditions during treatment of
high pyrite skarn ores. In the plant it is not possible to increase collector addition to counter
low copper recovery due to the increased pyrite recovery when treating sulfide skarns under
normal plant conditions. Radically different results are obtained with lime addition to the
laboratory mill for pH values above ten (Figures 14c and 14d). In this case, pyrite recovery
is markedly decreased, and copper maximum recovery and rate greatly increased. It seems
clear that without appropriate control of the grinding environment, in particular grind pH
and grind Eh, pyrite activation ensues, and copper recovery is very low.
In terms of plant practice, it was recommended that lime addition be made to the primary
ball mill feed, as well as SAG feed, and that collector addition be made after the grinding
circuit. The objective here was to passivate, or oxidise, pyrite prior to collector addition so that
most of the collector would then be directed towards chalcopyrite, and not pyrite. It was also
recommended that further work should investigate stage-adding collector, not only for coarse
composite recovery, but also for pyrite control. The effect of using the first cell in flotation as an
aerator to passivate pyrite, prior to collector addition, also needed to be investigated for high
pyrite skarn feeds. Once conditions are established which ensure effective pyrite depression,
collector additions may then be generally increased, in accordance with the higher copper
grades of the sulfide skarn ores. It was also recommended that dissolved oxygen demand
and EDTA extraction should be used to monitor pyrite oxidation and copper activation, and

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 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

100
90 20/11/98 SAG Feed
80 Pit Skarn Magnetite Ore

Dissolved Oxygen / %
70
60
50 A
20/11/98 SAG Feed
90
Pit Skarn Magnetite Ore
80
70
Aeration
60
Time
50 B
30 min
90 10 min 20/11/98 SAG Feed
80 3 min
30 min
70
60 10 min Pit Skarn Magnetite Ore
50 C 3 min
40
0 20 40 60 80 100 120 Time / seconds
FIG 13 – Dissolved oxygen concentration as a function of time (dissolved oxygen demand) after the
discontinuation of air purging for laboratory tests on 20 November 1998 SAG feed sample (closed symbols)
and on pit skarn magnetite (PSM) sample (open symbols) for aeration tests at different initial grind pH values,
(A) 11.5, (B) 10 and (C) natural pH. Aeration times of three (Δ), ten (), and 30 () minutes shown.

6 30
pH 6.8
Pyrite Recovery / % Copper Grade / %

25
4 pH 7.5
20
pH 8 pH 9.3
15
pH 10 pH 10.6
2 10
pH 11 pH 11.5
A pH 11.5 5
C
0 0
80 40
60 30
40 20
Lime after mill Lime in mill
20 10
B D
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Copper Recovery / % Copper Recovery / %

FIG 14 – Copper grade/recovery relationship (A, C) and selectivity of copper against pyrite recovery (B, D) for
laboratory flotation tests on pit skarn magnetite (PSM) sample head grade 1.59 per cent Cu, 10.7 per cent S,
Cu/S 0.15, 17 per cent pyrite with d80 144 microns 30 g/t 7249 collector added after grinding and pH adjustment,
for tests with lime added after milling at natural pH (A, B) and for lime added to the mill (C, D).

this data correlated to plant performance. It was recommended that laboratory tests should
continue to focus on correlating laboratory conditions to the plant, while the effect of Eh,
controlled by gases in the mill and conditioning stages, should also be investigated. The
possibility of increasing the Eh from +170 mV to +230 mV during the treatment of high pyrite
sulfide skarn blends should also be investigated. Based on the plant Eh/pH relationship
(Figure 11), it is unlikely that simply increasing the pH to above 11.5 would be adequate to
achieve this desired increase in Eh.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 219

 STEPHEN GRANO

CASE STUDY – ZINC REVERSE PROCESS

This case study focuses on determining why a specific zinc reverse process did not operate
efficiently at pilot plant scale (Johnson and Munroe, 1988; Johnson, 1988). Separation in a
zinc reverse flotation process is achieved after conditioning with heat and sulfur dioxide.
These inputs cause depression of sphalerite and flotation of pyrite in a relatively high-cost
process (Broman, Hultqvist and Marklund, 1985). The zinc reverse process was practiced
at Brunswick Mining and Smelting (BMS) Corporation Limited in New Brunswick, Canada
(McTavish, 1980), and at Woodlawn Mines, New South Wales. The principal of the zinc
reverse process is to separate pyrite from a sphalerite-rich stream. The pyrite reports to the
concentrate launder while the sphalerite and minerals, such as non-sulfide gangue, report
to the tailings stream. It is important to note that even if complete chemical depression of
the sphalerite is achieved in the process, some fine free sphalerite will report to the pyrite
concentrate by entrainment and some sphalerite in composite particles with pyrite may also
be recovered by true flotation.
The principal attraction of the zinc reverse process is that the ratio of the pyrite rate
constant to the sphalerite rate constant is much higher than the equivalent ratio for
conventional sphalerite cleaning flotation. In other words, the zinc reverse process is a
much more powerful process for separating liberated sphalerite from pyrite compared with
conventional cleaning. In the zinc reverse process, the ratio of rate constants for pyrite to
sphalerite is 10:1 or greater, while for conventional cleaning the equivalent ratio is typically
1:3.5. Reverse flotation is usually applied to streams in which the non-sulfide gangue has
already been removed by prior conventional dilution cleaning. Removal of pyrite from
a zinc concentrate (46–50 per cent Zn) by the process results in a higher zinc grade (52–
54 per cent Zn). The removal of pyrite (and pyrrhotite, if present) typically lowers the iron
assay from 8–10 per cent to 6–7.5 per cent Fe.
The following discussion details results from an industrial zinc reverse process at BMS.
Further, results from a zinc reverse process operated at pilot scale on a zinc-rich stream at
Mount Isa Mines, Mt Isa, are presented (Johnson and Munroe, 1988). This latter process
did not operate efficiently. However, with careful measurement of the pulp chemistry and
with accompanying interpretation, the process was modified, and the separation efficiency
improved. A simplified circuit diagram for a primary zinc process at an industrial plant
is shown in Figure 15. Three stages of the process are identified as significant to the pulp
chemistry:
1. SO2 addition at 18°C
2. temperature elevation to 80°C
3. air addition to the flotation process at 75–80°C.
Collection of Eh/pH data from each process allowed quantification of the pulp chemistry
to an important degree. A typical plant result of the pulp chemistry from BMS is shown
in Figure 16, presented as an Eh-pH diagram. As discussed previously, this presentation
allows changes in Eh due to either pH changes (water/oxygen equilibria) or changes in
the oxidising/ reducing potential of the pulp to be discerned. In this example, the feed
to the zinc reverse process is the third cleaner concentrate, a stream already close to final
zinc concentrate Zn grade, but for which additional iron rejection was required. The sulfur
dioxide conditioning stage caused a large pH change and a large movement away from the
region of the experimental water/oxygen line (Figure 16). The movement was essentially
parallel to the pH axis and therefore away from the experimental water/oxygen line. For the

220 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

Zinc Concentrate

Pyrite Cleaner
Tailing (from
Pyrite Cleaner)
SO2 Conditioning

Heat Conditioning

Upgraded
Air Roughing Zinc Concentrate

Pyrite Rougher
Concentrate
(to Pyrite Cleaner)

FIG 15 – Simplified circuit diagram for the plant zinc reverse cleaning process.

400

300 22oC
SO2 Conditioning
Pulp Eh (mV)

200 Heating 18oC

25oC

100 Rougher 80oC

Flotation

-100
3 4 5 6 7 8 9 10 11 12

Pulp pH

FIG 16 – Pulp Eh-pH diagram for the plant zinc reverse cleaning (BMS).

heat conditioning stage, there was a considerable change towards more reducing conditions
in comparison to those after addition of sulfur dioxide (Figure 16). This change is easily
seen in the Eh-pH diagram because there was no complicating simultaneous large change
in pH. The main feature for the flotation stage with air was an increase in the Eh value.
Unlike the two previous process steps where the Eh values had moved further away from
the experimental water/oxygen line, the Eh values moved back towards the water/oxygen
line (Figure 18).
Attention will now turn to the pilot plant studies at Mt Isa lead/zinc concentrator (Johnson
and Munroe, 1988). At the commencement of the pilot plant testing of zinc reverse, only a
single pyrite rougher stage was used (ie no cleaning of the reverse concentrate), and the
feed to the reverse process typically assayed 23–24 per cent Zn. In this case, the zinc reverse
process was applied to a plant stream which contained high levels of slow floating sphalerite.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 221

 STEPHEN GRANO

This type of sphalerite is difficult to upgrade in conventional cleaning because of its small
flotation differential against gangue sulfide minerals. In reverse flotation, the rate constant
for the sphalerite in conventional cleaning is irrelevant, and therefore the reverse flotation
approach provides one possible solution to the problem of upgrading this type of sphalerite.
In the initial stage of the pilot plant study, the pyrite rougher stage only occasionally
performed to expectation, and it was apparent that it was insufficiently developed to
routinely maintain the expected daily result. The zinc grade was expected to increase by
0.8 units for each unit of zinc loss, but the observed increase was only approximately 0.38
(Table 1, large cells). However, surveys of Eh/pH values in the pyrite rougher bank and
conditioning stages provided very important clues to the cause of the inconsistent depression
of sphalerite (Figure 17). The data revealed a very large increase in Eh (~+200 mV) between
the last conditioner and the first cell of the pilot plant pyrite rougher bank (Figure 17,
unsuccessful process). This behaviour differed from the previously described behaviour for
plant processes where an Eh increase of only ~50 mV was observed for the entire pyrite
rougher flotation stage.
The large increase in Eh meant that even the first cell of the pyrite rougher was destroying
the deliberately created chemical environment in the conditioners. The pulp flowed a
horizontal distance of four meters by gravity from the last conditioner and the first cell, which
was completely enclosed from the atmosphere. It was reasoned that there was little scope
for accidentally raising the Eh during transportation through the pipe and that the oxygen
in the flotation cell was destroying the reducing environment created in the conditioners.
Therefore, a solution to the problem (at that time) was the use of smaller flotation cells with
weirs at intervals to lower exposure of the pulp to oxygen in the initial cells (Johnson and
Munroe, 1988). The use of weirs was necessary to eliminate any possibility of back mixing

TABLE 1
Summary of some daily metallurgical results for the pyrite rougher before and after changing the size of the cells in the pilot plant.
Cells Assays/zinc (%) Zinc recovery (%) Zinc grade Zinc grade increase
Feed Concentrate Tailing to concentrate increase (%) per unit zinc loss
Large 23.7 43.1 16.6 48.7 19.4 0.38
Small 21.9 49.7 10.1 67.6 27.8 0.86

400

28oC SO2 Conditioning 24oC

300
25oC
28oC
Pulp Eh (mV)

200 Cell 1 80oC (Start of roughing)

Cell 3 72oC (End of roughing)
Cell 1 80oC (Start of roughing)
100
Data for Unsuccessful Process
0 90oC Data for Successful Process
90oC (smaller cells with weirs)

-100
3 4 5 6 7 8 9 10 11 12
Pulp pH

FIG 17 – Pulp Eh-pH diagram for two configurations of the zinc reverse flotation process.

222 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

of comparatively aerated pulps from the latter cells (Johnson and Munroe, 1988). Another
possibility was to use nitrogen instead of air as the carrier gas in flotation.
A robust (ie a consistent performance irrespective of feed condition) process was obtained
at the expected level after the change to smaller cells with weirs (Table 1). Surveys of the
Eh/pH values of the new pyrite rougher bank showed that a much smaller increase in Eh
values (~100 mV) existed between the last conditioner and the first cell (Figure 17, successful
process). Further, the increase in Eh for the remainder of the pyrite rougher was quite
small, ~20 mV. The zinc concentrate (45–52 per cent Zn) from the pyrite rougher concentrate
typically assayed 6.5 - 8.5 per cent iron after successful removal of the pyrite. Later inclusion
of cleaning to the process improved its performance further. There is an indication that the Eh
in flotation should not exceed +150 mV to ensure depression of sphalerite in reverse flotation.
This work demonstrated the importance of measuring both Eh and pH to solve flotation
separation problems. It also suggested that on-line measurement of these variables may
provide a more stable and robust process. It was also speculated, though not examined,
that use of an inert gas (eg nitrogen) in flotation may benefit flotation by either improving
selectivity or reducing the need for pulp heating, which may improve the process economics.

CASE STUDY – MOLYBDENITE RECOVERY IN COPPER ROUGHER FLOTATION

This case study focuses on increasing molybdenite recovery in copper roughing stages.
Characteristically, in porphyry copper flotation plants, molybdenite exhibits lower recovery
than copper, in spite of molybdenite apparent natural hydrophobicity. Furthermore,
molybdenum recovery is highly variable. While copper recovery is usually between
80 per cent and 90 per cent, molybdenum recovery may range between 25 per cent and
85 per cent. Molybdenite recovery may vary significantly from operation to operation, and
also within different ore bodies in the same operation.
The highly variable flotation recovery of molybdenum may be a result of several factors all
related to the properties of the molybdenite (MoS2) mineral in the pulp chemical environment
which controls particle interactions and pulp rheology. The molybdenite crystal structure
consists of hexagonal layers of molybdenum atoms sandwiched between two layers of
sulfur atoms. These factors determine the flotation behaviour of molybdenite, which is a
combination of:
•• particle morphology (shape and size) in relation to the cell hydrodynamics controlled by
energy dissipation and slurry rheology (Ametov et al, 2008)
•• particle inherent hydrophobicity, an important factor controlled to a degree by the particle
face/edge ratio
•• particle-particle interactions between molybdenite and gangue minerals particularly for
slime generating skarn rock
•• particle recovery across the froth phase (Zanin et al, 2009).
Models of bubble-particle collection frequency and collision efficiency of abnormally shaped
molybdenite particles suggested that its flotation rate may be enhanced by either reduced
kinematic viscosity or increased energy dissipation. Additionally, the changing behaviour
of molybdenite with gangue mineral type suggest that slime coatings of gangue particles on
molybdenite may be important for some ore types.
A key issue is the appropriate percentage solids to operate copper rougher flotation to
maximise the recovery of both copper and molybdenite. In practice, as the feed throughput
is increased the percentage of solids in the plant flotation feed may also increase. Decreasing

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 223

 STEPHEN GRANO

the percentage of solids may have beneficial effects on molybdenite recovery due to a
number of mechanisms related to the factors outlined above. At least one is to reduce the
concentration of fine gangue particles which may potentially adsorb onto molybdenite.
The effect of percentage solids has been investigated in three different rougher flotation
circuits and as a function of particle size (Figure 18). Significant increases in molybdenite
recovery are noted, and are greatest in the coarse particle size fraction where molybdenite
losses are greatest, occurring in predominantly fully liberated form to 250 microns. This
effect is related to both reduced particle interactions, an effect related to ore type, and also
to increased particle-bubble collision efficiency and frequency at low percentage solids.
At lower percentage solids, the rheology of the medium is reduced increasing the effective
shear rate. Molybdenite recovery increases even though the cell residence time decreases
due to higher water additions.

CONCLUSIONS
This chapter has dealt with simple pulp chemical measurements which should be taken with
most plant surveys. The basic theory, interpretation and utility of these measurements are
demonstrated.

100
Reduced %solids
81% Mo Recovery
80 Across all Size Fractions

60
Normal %solids
71% Mo Recovery
40 Across all Size Fractions
Molybdenite Recovery / %

20
A
0
Reduced %solids
80 85% Mo Recovery
Across all Size Fractions
60
Normal %solids
40 73% Mo Recovery
Across all Size Fractions
20
B
0
Reduced %solids
85% Mo Recovery
80 Across all Size Fractions

60
Normal %solids
75% Mo Recovery
40 Across all Size Fractions

20 Particle Size
C / Microns
0
10 100 1000
FIG 18 – Molybdenite recovery as a function of particle size across three plant rougher:
(A) Plant A, (B) Plant B, (C) Plant C, for different per cent solids in the rougher flotation feed.

224 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 7 | CHEMICAL MEASUREMENTS DURING PLANT SURVEYS AND THEIR INTERPRETATION

REFERENCES
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molybdenite recovery in plant and batch laboratory cells in porphyry copper rougher flotation, in
Proceedings 24th International Mineral Processing Congress (IMPC), Beijing, 24–28 September, pp 1129–
1137.
Broman, P G, Hultqvist, J and Marklund, U, 1985. Experience from the use of SO2 to increase selectivity
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(ed: K S Forssberg), pp 277–291 (Elsevier: Stockholm).
Fornasiero, D, Eijt, V and Ralston, J, 1992. An electrochemical study of pyrite oxidation, Colloids
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Engineering, 10(1):17–39.
Grano, S R, Lauder, D W, Johnson, N W and Ralston, J, 1997. An investigation of galena recovery
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Mineral Processing and Extractive Metallurgy, 91:C32–C37.
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sulphide additions during laboratory flotation of oxidised ores, Transactions of the Institution of
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environment in sulphide mineral flotation, in Proceedings Principles of Mineral Flotation (The Wark
Symposium) (eds: M H Jones and J T Woodcock), pp 147–183 (The Australasian Institute of Mining and
Metallurgy: Melbourne).
Kant, C, Rao, S R and Finch, J A, 1994. Distribution of surface metal ions among the products of
chalcopyrite flotation, Minerals Engineering, 7(7):905–916.
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flotation in the Murchison Zinc concentrator, in Proceedings Fifth Mill Operators’ Conference, pp 171–
179 (The Australasian Institute of Mining and Metallurgy: Melbourne).
McTavish, S, 1980. Flotation practices at Brunswick Mining, CIM Bulletin, February, pp 115–120.
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adsorption of ethyl xanthate on pyrite, Journal of Colloid and Interface Science, 143:440–450.
Natarajan, K A and Iwasaki, J, 1973a. Practical implication of Eh measurements in sulfide flotation
circuits, Transactions of the American Institute of Mining, Metallurgical, and Petroleum Engineers (AIME),
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Natarajan, K A and Iwasaki, I, 1973b. Effect of poisoning of platinum electrodes on Eh measurements,
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Natarajan, K A and Iwasaki, I, 1974. Significance of mixed potentials in Eh measurements with Pt

electrodes, Transactions of the American Institute of Mining, Metallurgical, and Petroleum Engineers
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recovery at the Ok Tedi concentrator, Papua New Guinea, in Proceedings Fifth Mill Operators’ Conference,
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of the Elura lead circuit, Pasminco Australia Ltd, Minerals Engineering, 17(6):811–824.
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Tedi concentrator, Papua New Guinea, in Physicochemical Problems of Mineral Processing, 35:125–140.
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Mineral Processing, 13:29–42.
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Woods, R, 1984. Electrochemistry of sulphide flotation, in Principles of Mineral Flotation (The Wark
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 Return to contents

CHAPTER 8
Electrochemical aspects of
sulfide mineral flotation
Ronald Woods OAM

ABSTRACT
Flotation is considered from an electrochemical perspective. Electrode potential is a
determining parameter in recovery and can be monitored and controlled in the laboratory
and the plant. The underlying electrochemical science is reviewed and its application to plant
practice explored.

MECHANISM OF MINERAL/COLLECTOR INTERACTION

Towards the middle of the 20th century, the doyens of flotation theory were vigorously
debating the mechanism of the attachment of flotation collectors with sulfide minerals. Taggart,
Taylor and Knoll (1930) proposed that attachment occurred by reason of ‘chemical reactions
of well-recognized types’; thus, for example, xanthates would form lead xanthate on a galena
surface. Wark and Cox (1934) pointed out that the development of a finite contact angle on
sulfide surfaces can occur at lower collector concentrations than that of the solubility of the
metal-collector compound. Wark and Cox (1934) as well as Gaudin (1939) considered that the
attachment of a collector to a sulfide surface was best considered as adsorption. But Cook and
Nixon (1950) realised that adsorption of collector ions would lead to highly charged surfaces
and proposed that the adsorbed species is the acid form of the collector ion. Xanthic acids,
however, are unstable. Thus, there were three theories and each had difficulties; formation of
metal thiols didn’t fit thermodynamics, adsorption of ions didn’t fit charge requirements and
adsorption of thiol acids didn’t fit stability criteria.
A solution to this dilemma was provided by Nixon (1957). He had carried out research with
Cook on the theory of adsorption of the acid form of collectors before joining Melbourne
University and working in a department that was at the forefront of the development of
electrochemical mechanisms for metal corrosion. With his co-worker, Salamy, he saw another
way in which a neutral surface could be generated, based on corrosion science concepts. It
was proposed that ‘the troublesome electrons’ identified by the Cook school (Cook and Nixon,
1950) that would lead to excessive charge on the surface ‘are removed by a reaction with

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 227

 RONALD WOODS

oxygen’. That is, the interaction of thiol collectors with mineral surfaces comprises a mixed-
potential mechanism in which an anodic oxidation involving the collector transfers electrons
to the mineral and the simultaneous cathodic reduction of oxygen returns this charge to the
solution phase. Most sulfide minerals are semiconductors with high electronic conductivity
and hence can readily sustain such processes. Nixon (1957) suggested that ‘prominent
theories of flotation could be reconciled’ by the electrochemical approach. This is illustrated
in Figure 1, in which the requirement of a neutral surface species espoused by Cook (Cook
and Nixon, 1950) can be met in different ways. The anodic reaction can be adsorption as
proposed by Wark (Figure 1a). Also, it can be the formation of a metal thiol compound as
proposed by Taggart (Taggart, Taylor and Knoll, 1930). The latter process can occur as a single
step as in 1b, or through separate surface oxidation and ion exchange processes as shown in
1c and 1d. In addition, the anodic process can be the formation of the dithiolate as suggested
by Nixon (1957) and illustrated in 1e.
Each of these mechanism types has been identified experimentally and shown to occur in
flotation systems. They all impart hydrophobicity to mineral surfaces. Chemisorption is the
thermodynamically favoured reaction for most mineral/collector systems, which means it
occurs first. As will be shown later, it is sufficient, in itself, to induce efficient flotation.
Chemisorption involves bonding between collector molecules and metal atoms in the
mineral surface. The attachment of ethyl xanthate to a galena surface is illustrated in Figure 2.
The lower spheres are sulfur (white) and lead (black) atoms in the galena surface. The sulfur
atoms of the xanthate are smaller than those in the mineral because they have no ionic character.
The xanthate sulfurs are equally bonded to lead atoms in the mineral surface. This bonding
is similar to that occurring in lead xanthate molecules, but in chemisorption, the metal atoms
remain part of the mineral lattice. Various spectroscopic investigations have confirmed this
mode of attachment of xanthate to mineral surfaces (Buckley, Hope and Woods, 2003). With
collectors such as 2mercaptobenzothiazole and butylethoxycarbonylthiourea, bonding with
metal atoms in the mineral surface was found to occur through nitrogen atoms as well as
sulfur atoms (Goh et al, 2006; Hope et al, 2006).
The electrochemical mechanism has two important implications. First, the potential across
the mineral/solution interface will be an important parameter in determining flotation
recovery. Second, the reaction imparting floatability, the anodic process involving the
collector, is amenable to investigation using electrochemical techniques. From the viewpoint
of the flotation engineer, it is the former of these implications that is more important and this
attribute will be the focus of this chapter. Since the potential can be measured in flotation cells
in the laboratory and in flotation plants, it can provide the engineer with a diagnostic tool
for developing flotation strategies and for alleviating flotation problems. Nowadays, most
laboratories apply potential measurement to derive optimum flotation strategies for operation
in the plant. As pointed out by Hintikka and Leppinen (1995) ‘monitoring of potential with
noble metal electrodes is now almost routinely carried out in laboratory testwork and full-
scale processes’. The reader is referred to Chapter 7 in the present volume for information on
the practical aspects of measuring potentials in laboratory cells and in flotation plants. Early
examples of the application of potential measurements in developing flotation strategies are
those of Johnson (1988) at Mt Isa Mines in Queensland. More recent examples are those of
Leppinen, Hintikka and Kalapudas (1998), in which the influence of potential on flotation
separation in copper and zinc from complex sulfide ores was considered, and of Smith and
Bruckard (2007) and Smith, Davey and Bruckard (2012), in which flotation strategies for the

228 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

A 4X- + O2 + 2H2O 4Xods + 4OH- B 2X- + MS + 2O2 MX2 +SO42-

M X X- S MX2 X
-
S M
M X
S S MX2
M X M SO42-
e- S e- S MX2
M M
S SM
M
S 02 MS O2
M SM
MS
0H- OH

Anodic Anodic
X- Xods + e- 2X- + MS + 4H2O MX2 + SO42- + 8H+ + 8e-
Cathodic Cathodic
O2 + 2H2O + 4e- 4OH- O + 2H O + 4e-
2 2
4OH-

C MS + 4O2 MSO4 D MSO4 + 2X- MX2 + SO42-

S -
MSO4 S MX2 X
M H+ M
S MSO4 S MX2
M M
e- S MSO4 S MX2 SO42-
M M
S M S M
M S O4 M S
S M S M
OH-

Anodic
MS + 4H2O MSO4 + 8H+ + 8e-
Cathodic
O2 + 2H2O + 4e- 40H-

E 4X- +O2 + 2H2O 2X2 + 4OH-

M X X-
S I
M X
S X
e- M I
S X
M
O2
S
M
OH-

Anodic
2X- X2 + 2e-
Cathodic
O2 + 2H2O + 4e- 2OH-

FIG 1 – Schematic representation of the mixed potential mechanism for the interaction of thiol collectors (X-) with sulfide minerals
in which the anodic process is (A) chemisorption; (B) reaction to form a metal collector compound; (C and D) the reaction in (B)
occurring in two stages, (C) oxidation of the mineral and (D) ion exchange with the collector; and (E) formation of the dithiolate.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 229

 RONALD WOODS

Pb

S(Pbs)

S(xanthate)

O
H
FIG 2 – Schematic of the attachment of chemisorbed xanthate to a galena surface.

separation of copper-arsenic minerals such as tennantite and enargite from chalcopyrite and
bornite were developed.

ELECTROCHEMICAL POTENTIAL
The electrochemical potential is the driving force for processes in which electrons are
transferred between a conducting solid and species in solution. The web-based Electro­
chemical Dictionary (https://www.corrosion-doctors.org/Dictionary/Dictionary-E.htm) says
the electrical potential:
… is somewhat analogous to the difference in height in a waterfall that causes the water to fall,
or the difference in pressure in a pipeline that causes the gas to flow.
Electrode potentials are measured against a reference electrode and are often converted to
the standard hydrogen electrode (SHE) scale. For example, potentials measured against the
silver/silver chloride 3.5 mol dm3 potassium chloride reference electrode at 25°C require the
addition of 0.205 V to convert them to the SHE scale. Similarly, for the calomel electrode at
25°C, 0.244 V has to be added to make them the potential vs SHE. Potentials on the SHE scale
are often referred to as the Eh.
The equilibrium potential of an electrochemical process is the potential at which no overall
reaction can take place. As the potential is taken more positive than the equilibrium value,
an anodic oxidation reaction occurs, in which electrons are transferred from solution species
to the electrode. Conversely, as it is taken more negative, the reverse, a cathodic reduction
reaction takes place in which electrons are transferred from the electrode to solution species.
The potential is a mixed potential when it is determined by two or more different
electrochemical processes occurring on the same electrode surface. Mixed potential systems
are non-equilibrium systems and hence are determined by the kinetics of potential-
determining reactions as well as the thermodynamics. The situation in which two redox
couples are involved is illustrated in Figure 3.
E1 and E2 in Figure 3 are the reversible potentials of the two couples and correspond to
equilibrium between forward and back reactions for each of the couples in the absence of the
other. When both are present, the potential will take up a value at which the two processes
give equal and opposite currents so that the net charge transfer across the interface is zero.
This potential is the mixed potential. It can be seen that the system involves an anodic
oxidation and a cathodic reduction reaction proceeding at finite rates and hence an overall
chemical reaction is taking place.

230 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

Anodic
E2
E1

CURRENT
Mixed
potential
Cathodic Potential

FIG 3 – Schematic current-potential curves showing reversible potentials of

two redox couples and the mixed potential when both couples are present.

It should be pointed out that both processes that make up the mixed potential system can
proceed on a homogeneous surface. The surface is then acting both as a source and a sink for
electrons. On the other hand, a heterogeneous surface may have areas of different activity for
the individual processes and in this case the anodic and cathodic reactions occur on different
surface sites. The potential is the key parameter in determining whether the important
reaction can take place. It can be seen from Figure 3 that, for the oxidation of the species
characterised by E1 to take place, the potential must be greater than E1.
Mixed potential mechanisms are important in a range of reactions of metallurgical
interest, for example corrosion of metals, cementation (metal displacement) reactions,
hydrometallurgical processing, supergene alteration of sulfide orebodies, spontaneous
oxidation of sulfide minerals in transport and storage, as well as in sulfide mineral flotation.
The important potential determining flotation is that occurring across the mineral/solution
interface. It is generally measured by inserting a noble metal electrode into the pulp, in which
case it is often referred to as the pulp potential. It is presumed that sufficient mineral particles
contact the noble metal surface for the measured potential to be that of the mineral of interest.
The solution potential is often determined in metallurgical systems and is measured by a noble
metal electrode inserted into filtered solution. This is different from the potential across the
mineral/solution interface and may not relate to flotation recovery. Only when a very strong
redox couple is present in solution will the two potentials be the same and this is due to
the redox couple determining the potential of the indicator electrode as well as that of the
mineral/solution interface (Rand and Woods, 1984).

GALVANIC INTERACTIONS
It was pointed out above that a heterogeneous surface may have areas of different activity for
the individual processes in a mixed potential system and in this case the anodic and cathodic
reactions occur on different surface sites. When two dissimilar conducting solids are in contact,
it is possible for the anodic process to occur on one solid and the cathodic on the other. This
situation is utilised in corrosion prevention through cathodic protection of a metal structure
such as a ship or a bridge with a sacrificial anode composed of a more electrochemically
active metal such as magnesium. The manner in which this procedure operates is illustrated
in the schematic shown in Figure 4.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 231

 RONALD WOODS

Anodic
CURRENT

A
Potential
Cathodic

FIG 4 – Schematic of current/potential relationships explaining cathodic protection.

The solid anodic curve represents corrosion of a metal to form an ionic species or an oxide.
The solid cathodic line represents the reduction of oxygen derived from the atmosphere. The
mixed (corrosion) potential will be at A and it can be seen that corrosion will be proceeding
at the current flowing at point A. When a sacrificial anode is attached to the corroding metal,
oxidation of this metal occurs to give the dashed curve and the mixed potential now shifts to
B. It can be seen from Figure 4 that, at this potential, there is a negligible contribution to the
anodic current at the mixed potential from the metal to be protected. Thus, corrosion of the
structure of interest does not take place.
Similar galvanic interactions occur in mineral flotation systems. Grinding of sulfide ores is a
prime example. The grinding media galvanically protects the sulfide minerals in an ore from
oxidation that would impair interaction with a collector in the subsequent float cells. On the
other hand, oxidation of the grinding media results in iron oxy-hydroxy species that inhibit
flotation through coating the minerals of interest with a hydrophilic layer. Galvanic interaction
between grinding media and sulfide ores has been the subject of many investigations reported
in the literature, from those of Iwasaki and co-workers in the 1980s (Adam, Natarajan and
Iwasaki, 1984) to those today (for example Grano and Huang, 2006; Peng and Grano, 2010).
Similarly, sulfide minerals can undergo galvanic interaction with each other and this
can enhance oxidation of a mineral and affect selective flotation. For example, pyrite has a
relatively high rest potential and also strongly supports oxygen reduction (Biegler, Rand and
Woods, 1977). If a sulfide such as galena is in contact with pyrite in a flotation pulp, then
its oxidation is not only driven by oxygen reduction on itself, but also that on pyrite and,
consequently, is increased significantly. This can result in loss in flotation recovery. Again,
this phenomenon has been the subject of many investigations reported in the literature, from
the 1960s (Majima, 1969) to today (Mu, Peng and Lauten, 2018). Galvanic interaction between
sulfides can also promote spontaneous heating in mining, storage, shipping and disposal of
sulfide minerals (Payant et al, 2012).

ELECTROCHEMICAL INVESTIGATIVE TECHNIQUES

The most useful electrochemical technique for studying the interaction of collectors with
mineral surfaces has proved to be voltammetry. In this technique, the potential of an electrode
constructed from the mineral of interest is controlled with a potentiostat and the current
flowing through the electrode is recorded. The potential is scanned linearly in time traversing
regions in which no reaction occurs to those where collector adsorption takes place.

232 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

The range of sensitivity of current measuring techniques allows submonolayer formation to

be determined as well as that of multilayers. In cyclic voltammetry, the potential is reversed
at a selected value and the scan in the opposite direction allows electrochemical reactions of
products formed on the initial scan to also be explored.
An example of the application of cyclic voltammetry, that to investigate the interaction
of ethyl xanthate with galena, is shown in Figure 5 (Woods, 1971). The initial scan was
started at -0.5 V versus SHE and the potential was taken in the positive-going direction. The
anodic current peak that is seen at ~0 V was identified with chemisorption of a monolayer
of ethyl xanthate on the galena surface. This assignment was later substantiated by X-ray
photoelectron spectroscopy (XPS) (Shchukarev et al, 1994). The increase in anodic current
following the anodic peak arises from oxidation of the collector to lead ethyl xanthate and
diethyl dixanthogen. On the return scan, a cathodic current peak can be seen at ~ -0.3 V.
This peak results from reduction of the products of anodic oxidation back to galena and
ethyl xanthate. The area under a voltametric peaks is the charge passed in the electrochemical
process and, when the process is adsorption, gives a measure of surface coverage of xanthate
on the mineral surface. That for the anodic peak in Figure 5 was as expected for adsorption
of a monolayer.
For further studies of mineral/collector interaction using electron spectroscopic techniques
such as XPS, the reader is referred to Chapter 9 in the present volume.
Spectroelectrochemistry combines voltammetry with spectroscopy to understand
adsorption on surfaces. Of the optical spectroscopy methods that are relevant to
understanding flotation, surface-enhanced Raman spectroscopy (SERS) is the most
informative. Hope et al (2006) reviewed the work carried out at Griffith University on the
application of SERS to elucidate the interaction of flotation reagents with mineral surfaces.
They showed that, for each collector studied, adsorption on the mineral surface occurs

20 μA/cm2
Anodic
CURRENT

-0.4 0 0.4
Cathodic

POTENTIAL Eh

FIG 5 – Voltammograms for a galena electrode at pH 9.2; scan rate 10 mV s-1; ethyl
xanthate 9.5 × 10-3 mol dm-3 (solid line), 0 (dashed line) from Woods (1971).

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 233

 RONALD WOODS

via charge transfer to form a metal-sulfur bond and, in situations for which the reversible
potential of the formation of the bulk phase is known, at underpotentials, that is, at
potentials below the reversible value.
The electrochemical quartz crystal microbalance (EQCM) provides a means of studying
mass changes at the nanogram level and hence can detect chemisorption. Woods and Jeffrey
(2007) applied this technique to elucidate the interaction of the collector, ethyl xanthate,
with silver surfaces. The induced oscillations of the quartz crystal on which the electrode
material under investigation is deposited follow changes in the mass of the electrode and
hence measure adsorption. The oscillations follow changes in mass of the electrode and
hence measure adsorption. Slippage at the interface occurs when the surface is hydrophobic
but not when it is hydrophilic and hence the EQCM allows changes in wettability of the
surface to be determined.
The atomic force microscope (AFM) provides a means of probing surfaces at the atomic
level and hence can monitor adsorption. In a recent review of the application of AFM to
flotation, Xing et al (2018) pointed out that, in this technique, a sharp probe mounted near to
the end of a cantilever scans over the sample surface and provides a high-resolution three-
dimensional topographic image. In addition, the AFM tip can be used as a force sensor to
detect local properties such as adhesion, stiffness, charge etc.
Electrochemical impedance spectroscopy has also been applied to the study of flotation
collector adsorption on mineral surfaces (Ertekin, Pekmez and Ekmekci, 2016). Those authors
report that microflotation, induction time measurement and electrochemical methods were
used to measure adsorption of flotation reagents and to derive a proxy to correlate with
flotation behaviours of sulfide minerals.

FLOTATION RECOVERY AS A FUNCTION OF POTENTIAL

The mixed potential mechanism implies that flotation will not occur if the potential is below
the region in which a collector oxidation reaction can take place and, at potentials within
this region, flotation becomes possible. This mechanism was not generally accepted until
the 1980s after investigations had been carried out that demonstrated that flotation recovery
was, indeed, a function of potential. The early work in this area was carried out in the
CSIRO Divisions of Mineral Chemistry and Mineral and Process Engineering laboratories
in Melbourne (both now CSIRO Mineral Resources), the US Bureau of Mines in Avondale,
Maryland and Virginia Polytechnic Institute and State University. Thus, Gardner and Woods
(1973, 1977) at CSIRO designed a particulate bed electrode flotation cell, and applied it to
demonstrate that the flotation of galena and that of pyrite were potential-dependent and
obtained an estimate of the potential of onset of flotation.
Heyes and Trahar (1977, 1979), also at CSIRO, modified a Denver flotation cell to allow the
use of nitrogen as the carrier gas and the control of the potential of the mineral particles in
the flotation pulp through the regulated addition of redox reagents. They applied this system
to study the flotation of chalcocite with ethyl xanthate as a function of potential. At the US
Bureau of Mines in Avondale, Richardson et al (1984) and O’Dell et al (1984) determined the
potential dependence of the flotation of chalcocite with ethyl xanthate in which the potential
was controlled electrochemically. At Virginia Polytechnic Institute and State University,
Basilio, Pritzker and Yoon (1985) studied the same system using a Hallimond tube flotation
cell with chemical control of potential by the addition of redox reagents. The results of these
three groups are shown in Figure 6.

234 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

FIG 6 – Flotation recovery of chalcocite with ethyl xanthate as a function of potential: –– data from Richardson
et al (1984); –– curves from Heyes and Trahar (1979); dashed curve from Basilio, Pritzker and Yoon (1985).
Dotted curve is a cyclic voltammogram at 5 mV s-1 for a chalcocite bed electrode (O’Dell et al, 1984).

It can be seen from Figure 6 that flotation does not take place below ~ -0.2 V and that
efficient flotation occurs at ~0 V. It can also be seen that there is good agreement between the
three groups as to the potential of onset of flotation even though the experimental conditions
employed differed. The dotted curve is a voltammogram obtained with a chalcocite particle
bed electrode in the flotation cell used by Richardson et al (1984) to record their flotation
recovery data. The characteristics of the voltammogram are the same as that found with
electrodes made from single chalcocite specimens. The anodic peak at ~ -0.15 V arises from
the chemisorption of a monolayer of ethyl xanthate on the mineral surface, while the anodic
current above 0 V is due to interaction with the mineral to form copper(I) xanthate. It can
be seen that the onset of flotation occurs in the potential region of chemisorption, and that
efficient flotation still occurs when copper(I) xanthate is also formed.
As illustrated for galena in Figure 5 and chalcocite in Figure 6, chemisorbed xanthate occurs
before metal xanthate formation; that is, the chemisorbed collector is the thermodynamically
more favourable species. Furthermore, it is sufficient to induce flotation.
Figure 7 shows the flotation recovery/potential curves for chalcocite, bornite, chalcopyrite
and pyrite in the presence of ethyl xanthate reported by Richardson and Walker (1985). It can
be seen that, in each case, the mineral changed from a non-float to a float condition at a
characteristic potential. The potential of onset of flotation of pyrite is similar to that found by
Gardner and Woods (1973) with their particulate bed system.
Guy and Trahar (1984) applied their modified Denver flotation cell to the galena/ethyl
xanthate system. Flotation of galena from mixtures with quartz was found to be a function of
potential, but the potential dependence varied with the mode of pretreatment of the mineral
(Figure 8). The left-hand diagram in Figure 8 shows the potential dependence after grinding
the mineral in a ceramic or a stainless-steel mill and flotation is observed from the most
negative potential induced. When a mild-steel mill was used (middle diagram), negligible
flotation was observed below about 0 V. The difference between these two relationships
could be explained in terms of the redox conditions in the mill. In the ceramic and stainless-

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 235

 RONALD WOODS

100

FLOTATION RECOVERY (PCT)

80

60 Cu2s Cu2FeS4 CuFeS2 FeS2

40

20

0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
POTENTIAL (V vs SHE)
FIG 7 – Dependence of flotation recovery on conditioning potential; conditioning time
ten minutes; flotation time two minutes; pH 9.2; xanthate 1.44 × 10-5 mol dm-3 for Cu S and
(2 ± 0.1) × 10-5 mol dm-3 for the other minerals (from Richardson and Walker, 1985).
100 100 100

GALENA GALENA
RECOVERY PER CENT IN FIRST MINUTE

90 90 90
pH 8 pH 8
80 80 KEX 80 PPG 400
STEEL MILL KEX
70 70 ALCOHOL FROTHERS 70
STAINLESS STEEL MILL
GALENA
NO 2 S IN MILL
60 60 60
pH 8
PPG 400
50 KEX 50 50

40 40 40
CERAMIC MILL
STAINLESS STEEL MILL
30 30 30

SAMPLE 1
20 SAMPLE 2 20 20

10 10 10

0 0 0
-500 -400 -300 -200 -100 0 100 200 300 400 500 -500 -400 -300 -200 -100 0 100 200 300 400 500 -500 -400 -300 -200 -100 0 100 200 300 400 500

EPt (mV) EPt (mV) EPt (mV)

FIG 8 – Flotation recovery of galena in a modified Denver cell at pH 8 in the presence of

10 mg of ethyl xanthate for different pretreatment conditions from Guy and Trahar (1984).

steel mills, the mineral is free to oxidise by reaction with atmospheric oxygen, but the mild-
steel mill will provide cathodic protection and keep the mineral at a low potential. A similar
situation can be achieved by grinding in the presence of sodium sulfide. The right-hand
graph in Figure 8 shows the results obtained with a stainless-steel mill in the presence of
10-2 mol dm-3 sodium sulfide solution. It can be seen that the recovery/potential relationship
observed is similar to that for the mild-steel mill.
Figure 9 shows the correlation made by Guy and Trahar between their flotation recovery
data for galena in the presence of ethyl xanthate and the voltammetry of Woods (1971, 1972).
It can be seen that, for mineral ground under reducing conditions, the onset of flotation occurs
at the same potential as does the anodic peak due to chemisorbed xanthate (cf Figure 5).
When galena is pre-oxidised, some sulfur is lost from the surface as thiosulfate or sulfate.
Thus, when the potential is subsequently taken to low values, the oxidised surface species

236 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

100 100

90 RECOVERY 90

RECOVERY PER CENT IN FIRST MINUTE

80 60

CURRENT DENSITY (μA/cm2)

70 CURRENT 40

60 20
CURRENT
50 0
PREPARED IN
40 REDUCING -20
CONDITIONS
RECOVERY
30 PREPARED IN -40
REDUCING
20 CONDITIONS -60

10 -80

0 -100
-500 -300 -100 0 100 300 500
EPt (mV)

FIG 9 – Anodic current and flotation response of galena in the presence of ethyl xanthate
following preparation under reducing or oxidising conditions from Guy and Trahar (1985).

are reduced to lead metal on the surface. On the subsequent potential scan, an anodic peak is
observed that occurs at potentials expected for the reaction of lead with xanthate to form lead
xanthate. In the work of Guy and Trahar for mineral prepared under oxidising conditions, the
flotation correlates with the current peak and, in this case, lead xanthate would appear to be
the species inducing flotation. The flotation recovery increases significantly, however, when
the potential is in the region of chemisorption of xanthate on galena.
The potential dependence of the flotation of galena has also been determined in a pilot plant
operating with Mt Isa Mines lead/zinc ore (Johnson, Jowett and Heyes, 1982) using hydrazine
to adjust the potential and the results are shown in Figure 10.
Comparison of Figures 8–10 shows that the potential of onset of flotation in the pilot plant
is the same as that in the laboratory investigations in which the mineral was ground under
reducing conditions. Thus, such a pretreatment would appear to be the one most relevant to
flotation practice. It is interesting to note that flotation of galena was found to be initiated at
0.1 V in the particle bed electrode cell used by Gardner and Woods (1973).
Grano, Ralston and Smart (1990) also carried out studies on the potential dependence of the
flotation of galena from Mt Isa lead-zinc ore (Figure 11). It can be seen from the figure that
the recovery/potential relationship they obtained is similar to that in Figures 8–10. It can be
seen in Figures 8 and 9 that there is an upper as well as a lower potential limit of flotation
of galena and that it is independent of the pretreatment conditions. A similar upper limit of
flotation was observed for the flotation of chalcocite with ethyl xanthate (Heyes and Trahar,
1979; Basilio, Pritzker and Yoon, 1985). The results of Heyes and Trahar (1979) are shown in
Figure 12; note that this figure covers a wider potential range than that covered in Figure 6.
It can be seen from Figure 12 that the potential at which the upper flotation edge occurs varies
with change in pH. For both galena and chalcocite, the upper limit is close to the potential at
which the metal xanthate is known to oxidise to the metal oxide and diethyl dixanthogen, and
displays the expected pH dependence. Since dixanthogen is more hydrophobic than metal
xanthates, oxidation to this compound and a metal oxide would not, alone, be expected to

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 237

 RONALD WOODS

50

RECOVERY PER CENT IN FIRST CELL

MT ISA ORE
40 PILOT PLANT TEST

30

20

10

0
-500 -400 -300 -200 -100 0 100 200 300 400 500
EPt (mV)

FIG 10 – Flotation response of galena in Mt Isa lead/zinc ore as a function of potential

at pH 8.3 in the presence of ethyl xanthate (from Johnson, Jowett and Heyes, 1982).

100

EX-0.0 kg/t

80 EX-0.10 kg/t

EX-0.20 kg/t
RECOVERY %

60

40

20

-600 -400 -200 0 200 400 600

Eh (mV)
FIG 11 – Potential dependence of galena flotation from Mt Isa lead/zinc
ore with ethyl xanthate at pH 8.1 from Grano, Ralston and Smart (1990).

inhibit flotation. Oxidation of the mineral itself also occurs in the relevant potential range and
it is likely that, once the mineral surface is no longer passivated by a metal xanthate, oxidation
occurs to form significant quantities of metal oxide and this renders the surface hydrophilic.
Roos, Celis and Sudarsono (1990a) determined the potential dependence of the xanthate-
induced flotation of chalcopyrite and (1990b) of chalcocite and covellite. Onset of the flotation

238 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

100

RECOVERY PER CENT IN THE FIRST MINUTE

90

80

70

60

CHALCOCITE
50
KEX 7.6 mg/L
PPG 400
40
pH 11
pH 8
30

20

10

0
-600 -400 -300 -200 -100 0 100 200 300 400 500 600

PULP POTENTIAL (mV vs SHE)

FIG 12 – Flotation recovery of chalcocite with ethyl xanthate as a function of potential at pH 8 and 11 from Heyes and Trahar (1979).

of chalcopyrite and of chalcocite was found to occur at the potentials previously reported
by Richardson and Walker (1985). The threshold flotation potential for covellite was about
50 mV more positive than that for chalcocite under the same conditions. An anodic shift is to
be expected since the activity of copper in covellite is less than that in chalcocite.
Researchers at the Central South University, Changsha, China determined the potential at
which optimum flotation recovery of sulfide minerals occurs (Hu, Sun and Wang, 2009). They
then established ore grinding conditions and chemical compositions in the flotation pulp that
give rise to the derived optimum potential. This approach, which is referred to as ‘Original
Potential Control Flotation (OPCF)’, has been applied in a number of flotation plants and it
is reported (Hu, Sun and Wang, 2009) that improvements in recovery of target minerals is
significantly greater than with conventional procedures.

FLOTATION RECOVERY AS A FUNCTION OF COLLECTOR COVERAGE

Voltammetry provides a method of determining collector coverage as a function of potential
under analogous conditions to those used to determine flotation recovery. Figure 13 shows
flotation recovery and surface coverage of chemisorbed xanthate as a function of potential
for three mineral/collector systems. The flotation recoveries for galena/ethylxanthate in
Figure 13a are from Guy and Trahar (1984) for mineral ground under reducing conditions
and the surface coverage from Buckley and Woods (1991); data for the chalcocite/ethyl
xanthate in Figure 13b is from Woods, Young and Yoon (1990); the flotation recovery for
the chalcocite/diethyldithio- phosphate system is from Woods, Kim and Yoon (1993) and the
surface coverage from Buckley and Woods (1993).
It can be seen from Figure 13 that, for each system, significant flotation recovery is observed
at low thiol coverage, about 50 per cent recovery at a fractional coverage of <0.2, and maximum
recovery is achieved when there is about half a monolayer of chemisorbed collector molecules
on the mineral surface.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 239

 RONALD WOODS

A B 100 1.0
100 1.0
Flotational recovery / (%)

Flotational recovery / (%)

Surface coverage (%)

Surface coverage (%)

80 0.8
80 0.8

60 0.6 60 0.6

40 0.4 40 0.4

20 0.2 20 0.2

0 0 0.0
-0.3 -0.2 -0.1 0 0.1 0.2 -0.40 -0.30 -0.20 -0.10 0.00
Potential / V(vs SHE) Potential / V(vs SHE)
C
Flotational recovery / (%)

100 1.0

Surface coverage (%)

80 0.8
60 0.6
40 0.4
20 0.2
0 0.0
-0.4 -0.3 -0.2 -0.1 -0.0 0.1
Potential / V(vs SHE)

FIG 13 – Comparison of potential dependence of flotation recovery and collector coverage (A) galena/
ethyl xanthate, (B) chalcocite/ethyl xanthate, and (C) chalcocite diethyldithiophosphate.

THE POTENTIAL DEPENDENCE OF FLOTATION IN THE ABSENCE OF COLLECTORS

Some sulfide minerals, such as molybdenite and stibnite are naturally hydrophobic as a result
of cleavage occurring between planes of sulfur atoms held together only by Van der Waal’s
forces. Such surfaces do not have high affinity for polar water molecules and adhere readily
to air bubbles and hence the minerals display floatability in the absence of collectors. Other
sulfides float in the absence of collectors when exposed to mild oxidising conditions.
Heyes and Trahar (1977) showed the floatability of chalcopyrite in the absence of collectors
to depend on potential as shown in Figure 14. In these experiments, flotation was carried out
in their modified Denver cell using nitrogen as the carrier gas. The potential was controlled
by adding redox reagents (hypochlorite for oxidation and dithionite for reduction) and was
monitored with a platinum electrode inserted in the pulp. Gardner and Woods (1979) confirmed
the potential dependence of self-induced flotation of chalcopyrite using a Hallimond tube
cell in which the potential was controlled electrochemically. Luttrell and Yoon (1984) also
found the same potential dependence for the collectorless flotation of chalcopyrite using a
Hallimond tube cell with redox reagents for potential control.
It can be seen from Figure 14 that there is a good correlation between the potential of onset
of flotation and the commencement of the anodic current. The current arises from oxidation
of chalcopyrite to remove iron and leave an iron-deficient copper sulfide, which is considered
(Buckley and Woods, 1984; Buckley, Hamilton and Woods, 1985) to be responsible for flotation
in the absence of collectors.
Galena, pyrrhotite and pentlandite are also non-floating under reducing conditions and
floatable in the absence of collectors under oxidising conditions (Guy and Trahar, 1985; Healy

240 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

75 100

Anodic current (μA cm-2)

Flotation recovery (%)

80
50
60

40
25
20

0 0

-0.4 -0.2 0 0.2 0.4 0.6

Potential (V vs SHE)

FIG 14 – Potential dependence of flotation of chalcopyrite in the absence of collectors: — • — • — Heyes

and Trahar (1977); • • • • Luttrell and Yoon (1984); — — Gardner and Woods (1979). Anodic current on a
positive-going voltammogram from a chalcopyrite electrode –––––– Gardner and Woods (1979).

and Trahar, 1989). It was pointed out by Woods (1991) that the potentials reported by Healy
and Trahar for 50 per cent flotation recovery of these minerals in one minute correlated with
the equilibrium potentials for the oxidation of each mineral to form sulfur. This suggests that
the important species in the self-induced flotation of sulfides is a sulfur species similar to that
formed on chalcopyrite.
Attempts were made by Control International to exploit self-induced flotation commercially
in Arizona copper mines in the late 1980s (Arbiter and Gebhardt, 1992). Flotation recoveries
in the complete absence of collector failed, however, to match those achieved in conventional
practice and process development was terminated. A more optimistic application of
collectorless flotation of chalcopyrite was recently reported by Heyes (2007). A strategy to
separate chalcopyrite from chalcocite and bornite was developed based on work at CSIRO in
the late 1970s (Heyes and Trahar, 1977, 1979). Flotation in the absence of collectors produced
a concentrate that was predominantly chalcopyrite and the other copper sulfide minerals
were then floated following collector addition. This procedure was devised to maintain the
provision of a copper concentrate with a copper-sulfur ratio suitable for direct to blister
smelting technology as the chalcopyrite content of the ore is increased as a result of the mine
being converted from underground to open cut operation.
It should be pointed out that self-induced flotation will occur whenever the potential of the
mineral of interest is in the region of surface oxidation. Thus, self-induced flotation acts as a
complication in collector-induced flotation.
Flotation of sulfide minerals in the absence of conventional collectors also occurs in the
presence of sulfur(-II) species in solution (Hu, Sun and Wang, 2009).

ACTIVATION AND DEPRESSANT ACTION

The separation of one sulfide mineral from another in a complex ore depends on the ability to
selectively depress chosen components.
Consideration of flotation in terms of a mixed potential mechanism provides a means of
exploring the possible ways in which flotation can be enhanced or depressed. This will be
illustrated by a discussion of the curves presented in Figure 15.

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 RONALD WOODS

(b2)
(c)

Anodic
CURRENT

C
A
Potential
Cathodic

(b1)

FIG 15 – Schematic diagram showing the effect of various factors on the mixed potential of collector/oxygen systems.

The solid lines represent collector oxidation (anodic) and oxygen reduction (cathodic)
occurring at a mixed potential A. This system can be modified in the following ways:
•• The mixed potential can be shifted to B if the oxygen current can be decreased to give
curve b1, for example by adding a reagent such as sulfite that diminishes the oxygen
content. In this case the collector oxidation current becomes zero, no oxidised collector
species are formed, and flotation is depressed.
•• If the collector oxidation current is increased, that is, the curve becomes b2, the new mixed
potential B is characterised by greater currents and flotation will be enhanced. This can
be achieved by increasing the collector concentration or substituting a homologue of the
collector with a longer alkyl chain length.
•• If collector oxidation is inhibited such that the anodic wave becomes curve c, flotation
will be depressed. In this case, the mixed potential will be moved to point C, at which
value negligible collector is oxidised. The effect of cyanide in depressing pyrite, in which a
surface iron cyanide species is formed, is an example of this mechanism.
•• Flotation can be depressed by the addition of a species that oxidises at a lower potential
than that for the collector. Thus, if the additional reaction is represented by curve b2, the
mixed potential B, at which the rate of reaction is equal and opposite to oxygen reduction,
corresponds to zero collector oxidation and hence no flotation. The use of NaSH to depress
chalcopyrite in copper/moly plants follows this mechanism.
•• Flotation can also be depressed if the solution conditions are changed such that the mineral
oxidises in a potential region below that for the collector. That is, mineral oxidation
becomes represented by curve b2 and the mixed potential, again, involves negligible
collector oxidation. Change in pH can bring about this situation. Another example is the
action of cyanide on copper minerals in which situation oxidation of the mineral occurs
at lower potentials as a result of the formation of copper cyanide complexes in solution.
Each of the mechanisms discussed above have been confirmed by electrochemical
investigations. For example Castro and Larrondo (1981) validated the mechanism of the
depressant action of cyanide for chalcocite in the presence of propyl xanthate. These authors
correlated measurements of flotation recovery with the potential of a chalcocite electrode
in the solution. They found that depression of the mineral was accompanied by a decrease

242 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

in potential and the appearance of copper in solution. The dissolution of chalcocite to form
a copper cyanide complex ion shifted the potential below the region in which xanthate
reactions occur.

SELECTIVE FLOTATION RECOVERY AS A FUNCTION OF POTENTIAL

The early work on the potential dependence of flotation led researchers to assume that the
development of separation strategies from differences in recovery/potential relationships
established experimentally for individual minerals would be uncomplicated. Progress in
developing flotation schemes this way became constrained, however, by the finding (Guy
and Trahar, 1985; Gebhardt, Dewsnap and Richarson, 1985; Gebhardt and Richardson, 1987)
that the behaviour of mixtures could not be predicted unconditionally from single mineral
studies, due to mineral–mineral interaction. Nevertheless, flotation recovery of minerals in
pulps containing more than one sulfide mineral is still a function of potential. It is just that
deriving the potential dependence of minerals in mixtures may not be as straightforward
as assuming they are the sum of the responses of the individual components determined
separately.
Chander and Fuerstenau (1983) utilised the potential dependence of the flotation of
chalcocite with diethyl dithiophosphate (DTP) to develop an electrochemical strategy for
separating chalcocite from molybdenite. Chalcocite was found not to float with DTP at
potentials less than 0.0 V, but to float readily at potentials greater than 0.2 V. Molybdenite
displays natural hydrophobicity and its floatability is not affected by potential. Thus, this
sulfide can be selectively floated from chalcocite at negative potentials. It was found that
66 per cent of the molybdenite and only 14 per cent of the chalcocite floated from a 50:50
mixture of the two minerals at -1.2 V. When the potential was raised to 0.3 V, 100 per cent of
the chalcocite, and only 17 per cent of the molybdenite, floated. It was considered that the
apparent depression of molybdenite at positive potentials results primarily from competition
with the more hydrophobic constituent, chalcocite.
In recent years, a significant amount of research has been directed towards developing
strategies for the effective removal of arsenic-containing minerals from copper and nickel
ores prior to smelting since arsenic is a serious environmental hazard and causes problems
in the metal recovery processes. This results in ores containing arsenic to be subject to severe
penalties when being sold to smelters. The progress made in this area exemplifies what can
be achieved by taking into account the different potential dependence of flotation recovery of
sulfide minerals. In copper ores, arsenic occurs mainly as enargite (Cu3AsS4) and to a lesser
extent as tennantite (Cu12As4S13) and research has been carried out to remove these minerals
by selective flotation. For example, Castro, Balttierra and Hernández (2003) determined the
flotation response of enargite, chalcopyrite, chalcocite and pyrite and found (Figure 16) that
the only mineral that was not strongly depressed at high potentials was enargite. From these
studies, it was concluded that selective flotation of enargite from copper and iron sulfide
minerals is technically feasible by applying a pre-oxidation stage to depress copper and iron
minerals. This is consistent with the findings of Fornasiero, Fullston and Ralston (2001) that
selective oxidation with hydrogen peroxide allows the selective removal of enargite and
tennantite from chalcocite, covellite and chalcopyrite in mixed mineral systems.
Guo and Yen (2005) also studied the influence of potential on the flotation recovery of
enargite and chalcopyrite to assess the feasibility of enargite removal from a chalcopyrite
concentrate. Their results (Figure 17) showed that chalcopyrite begins to oxidise quickly at
a much lower potential than does enargite. Guo and Yen (2005) found that enargite could

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 RONALD WOODS

100

90

80

70 Enargite
Chalcopyrite
Recov ery, %

60 Pyrite
Chalcocite
50

40

30

20

10

0
280 300 320 340 360 380 400 420
Potential, m V (SHE)

FIG 16 – The effect of oxidation pre-treatment with hydrogen peroxide at pH 9.8 on the flotation recovery of energite,
chalcopyrite and pyrite with isopropyl xanthate at pH 6.8 (from Castro, Balttierra and Hernández, 2003).

100
90
80
70
Recovery (%)

60
50
40
30
20 Chalcopyrite
10 Enargite
0
-0.6 -0.4 -0.2 0 0.2 0.4 0.6

Potential (V vs SCE)
FIG 17 – Effect of potential on the flotation recovery of enargite and chalcopyrite at pH 10 in the
presence of 7 × 10-5 mol dm-3 potassium amyl xanthate (from Guo and Yen, 2005).

be floated efficiently at a potential higher than +0.2 V versus SCE (0.444 versus SHE), while
chalcopyrite was completely depressed at potentials higher than this value. Selective flotation
revealed that enargite can be successfully removed from chalcopyrite through controlling
the pulp potential in the range +0.2 to +0.55 V versus SCE, with the most effective separation
being achieved at 0.5 V (0.744 versus SHE). These authors noted that the flotation response of
enargite was greater in mineral mixtures with chalcopyrite than when floated alone. The work
of Guo and Yen illustrates that, although single mineral studies may not give precise data for
mixtures, they can be used to identify conditions for selective flotation in polymetallic ores.
Kaye (2006) reported that Leanne Smith (née Shannon) and co-workers of CSIRO, building
on the many years of experience in investigating the potential dependence of flotation at their

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 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

organisation, had developed a flotation process to separate the arsenic-containing components

from other copper sulfides in ores. By studying the flotation behaviour of individual minerals
as a function of potential, the CSIRO team identified several electrochemical windows
whereby it is possible to selectively float copper–arsenic minerals from other copper minerals.
The CSIRO flotation process is reported by Kaye (2006) to involve:
… some changes to existing chemicals used in the separation process as well as possible changes
to the flotation gas, such as the use of nitrogen instead of oxygen.
Unlike the flotation separation proposals put forward by Castro, Balttierra and Hernández
(2003) and by Guo and Yen (2005), it is not restricted to floating under highly oxidising
conditions.
CSIRO, in partnership with BHP Billiton, has drawn on its extensive databank of
experimental relationships between potential and flotation recovery of single minerals, to
develop a flotation strategy for the separation of enargite from other copper minerals in
the Tampakan copper–gold deposit in Mindanao, Philippines (Senior, Guy and Bruckard,
2006). The potential dependence of flotation recovery of enargite reported by these authors
is similar to that of Guo and Yen for amyl xanthate shown in Figure 17. The difference in the
flotation threshold for enargite and chalcopyrite was found to be greater, however, and it
was concluded that enargite could be floated from copper-iron sulfides such as chalcopyrite
at pH 8 to 11 at 0 V versus SHE. A conceptual flow sheet was devised using the addition of
redox reagents and variation in the flotation gas composition to control potential (Figure 18).
The first stage aims to exploit the difference in the onset of flotation for chalcocite and cuprite
from those of enargite and chalcopyrite (see Figures 7 and 17). The second stage seeks to
take advantage of the difference in the potential of onset of flotation of enargite and that of
copper-iron sulfides. Any chalcocite and cuprite not floated in stage 1 will follow the enargite
as the potential in the second stage is in the potential range for the efficient flotation of these
minerals. The third stage utilises the difference in the potential of the upper flotation edge
between enargite and chalcocite and cuprite (see Figures 12 and 17). It was reported in later
studies (Smith and Bruckard, 2007) that one of the separation methods proposed in the work
of Senior, Guy and Bruckard (2006) was successfully tested on Tampakan ore and enabled
the production of a copper concentrate with sufficiently low arsenic content to be sent to a
conventional smelter for copper metal production.
Smith and Bruckard (2007) showed that it is possible to selectively separate tennantite
from chalcopyrite and bornite in Northparkes copper–gold ore using pulp potential control.
The conceptual flow sheet developed to treat high-arsenic regions of the orebody involved
producing a bulk copper–arsenic concentrate using isopropyl xanthate and a dithiophosphate
as collector. A tennantite-rich concentrate was then obtained by floating at pH 12 and an Eh of
-120 mV using nitrogen as the carrier gas. A copper concentrate, constituting about 61 per cent
of the copper content of the ore, with low enough arsenic content to avoid smelter penalties,
could then be produced at pH 12 and the Eh generated by using air as the carrier gas.
Long, Peng and Bradshaw (2012) assessed the state-of-the-art of copper arsenic removal
from copper concentrates and affirmed that differential flotation with control of pulp potential
represents an effective option for reducing the arsenic content of copper concentrates.
Smith, Davey and Bruckard (2012) reported the results of selected case studies of the
application of pulp potential control to separate copper and arsenic. The procedure applied by
these authors involved controlled separations at high or low pulp potential regions exploiting
subtle differences in the flotation behaviour of the arsenic-bearing and non-arsenic-bearing

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 RONALD WOODS

Bulk Cu-As flotation concentrate

REGRIND IN BALL MILL AND

CYCLONE CIRCUIT

Reductant

FIRST FLOTATION STAGE

PH11, Eh - 125 mV (SHE)
Nitrogen atmosphere

Concentrate Tailing
(chalcolite +
cuprite) Air
bleed

SECOND FLOTATION STAGE

pH 11, Eh 0 mV (SHE)
Nitrogen atmosphere

Tailing Concentrate
(chalcopyrite) (enargite +
chalcocite +
cuprite)
PRODUCT 1

Air bleed

Oxidant

THIRD FLOTATION STAGE

pH 11, Eh +290 mV (SHE)
Air atmosphere

Tailing Concentrate
(chalcocite + (enargite)
cuprite

PRODUCT 3 PRODUCT 2

FIG 18 – Conceptional flow sheet for a Tampakan arsenic rejection circuit,

based on pulp potential effects from Senior, Guy and Bruckard (2006).

copper minerals at particular pulp potential windows. They showed that, for each ore
investigated, the identified procedure can produce a saleable low-arsenic copper concentrate,
which can be directly smelted without penalty, and a high-arsenic copper concentrate, which
will require further processing.
Smith, Davey and Bruckard (2012) reported that the pulp potential at which separation of
tennantite from chalcopyrite and bornite was possible with one of the ores tested was lower

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 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

than that expected from single mineral data, assuming that bornite behaves in a similar manner
to chalcopyrite The threshold potential for the flotation had been shifted about 100 mV SHE
in a more reducing direction. These authors considered a number of reasons for this shift in
the pulp potential, including that there was a difference in the potential dependence of the
flotation of bornite and chalcopyrite. Indeed, it can be seen from the findings of Richardson
and Walker (1985), shown in Figure 7, that the threshold potential for bornite is, indeed,
100 mV below that for chalcopyrite.
In a study of the treatment of copper/nickel ore from Sudbury, He et al (2008) found that
pentlandite recovery, and its selectivity against pyrrhotite, is considerably improved by
controlling pulp potential. In later work, Manouchehri, Lawson and Taylor (2010) applied the
Outotec Chena analyser (vide infra) to monitor pulp potential in the flotation of nickel ores
and were able to identify optimum conditions.
Lotter and Bradshaw (2010) reviewed the usage of mixtures of collectors in sulfide flotation
– both in the application and in research – in order to gain insights and prepare guidelines
for the development of a methodology for use in a predictive capacity. McFadzean, Mhlanga
and O'Connor (2013) reported that most collector mixtures achieved greater recoveries than
would be expected based on their additive performance alone. This synergistic behaviour
was most notable for mixtures of strong and weak collectors. Antagonistic behaviour was
noted for mixtures of two strong collectors.
Buckley et al (2017) utilised XPS to identify the species adsorbed on Cu sulfide ore minerals
from alkaline or near neutral solutions of different blends of the flotation collectors dibutyl
dithiophosphate (BDTP) and 2-mercaptobenzothiazole (MBT). Depending on the collector
concentration and pH, direct (albeit ex situ) surface chemical characterisation established
the adsorption of different species from a BDTP-MBT blend compared with sequential
conditioning in the individual collectors, and hence potentially different hydrophobicities.
The identity and coverage of each collector species depended on the relative concentration of
the two collectors in the blends investigated.

MONITORING POTENTIAL IN FLOTATION PRACTICE

Copper-moly flotation
The use of nitrogen to replace air in the copper/moly separation stage of flotation plants was
introduced in the mid-1980s in North and South American plants to minimise oxidation of
the sodium hydrosulfide (NaSH) used to depress copper sulfides. At the same time, sulfide
additions were monitored and controlled by the use of noble metal electrodes inserted in the
pulp. The electrode becomes coated with sulfur and then responds to hydrosulfide ions in
solution displaying the equilibrium potential of the HS-/S0 redox couple, which is given by
the Nernst equation (see: https://www.sciencedirect.com/topics/chemistry/nernst-equation):

E (V vs SHE) = -0.065 - 0.0295 pH - 0.295 log [HS-]

Thus, pH needs to be recorded as well as the potential of the redox electrode for proper
control of NaSH additions. In practice, redox potentials in flotation pulps are recorded with an
oxidation/reduction cycle (ORC) electrode, which contains a platinum redox electrode and an
internal reference electrode, which is usually silver/silver chloride. Commercial electrodes often
combine Eh and pH measurement in the same probe structure. If the redox potential is required
on the standard hydrogen scale, the measured value needs adjusting by adding 205 mV at 25°C
(vide supra). The correction at other temperatures is given by 205 - 0.77 (T - 25°C) mV.

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 RONALD WOODS

Aravena (1987) reported that NaSH consumption was reduced by 48 per cent with the
introduction of nitrogen at the Chuquicamata mine in Chile and a further saving of 21 per cent
was achieved when depressant additions were controlled by electrode measurements.
Meadows et al (2013) claimed that several of the larger copper projects recently built in the
Americas have included a molybdenum plant due to favourable market conditions, and that
these plants apply ORC electrodes to control depressant additions.

Controlled potential sulfidisation (CPS)

It is well established that oxidised lead and copper ores can be activated by treatment with
hydrosulfide ions. Jones and Woodcock (1978) proposed that sulfidisation of oxidised lead
and copper ores should be carried out under potential control to improve performance.
Controlling the potential during sulfidisation ensures that the oxide component of the ore
is sufficiently converted to sulfide for it to float, while the sulfide ions remaining in solution
are insufficient to depress subsequent flotation. In both CPS and copper/moly separation,
the electrode responds to solution species, although the solution species are responsible for
control of the potential of the mineral/solution interface. Jones and Woodcock suggested that
silver sulfide ion-selective electrodes be applied but this proved to be inappropriate in plant
practice and were replaced by noble metal electrodes (Jones, 1991).
Major improvement in performance results from the use of CPS compared with that
obtained with ‘slug’ addition of NaSH. In Australasia, CPS, marketed through AMDEL
laboratories, is being, or has been, applied at the Boddington, Cadia, Horseshoe, Mineral
Hill, North Parkes, Ok Tedi, Red Dome, Selwyn and Telfer mines for the treatment of copper/
gold ores containing reactive sulfides or mixed oxides and sulfides (Jones, 1991; Woodcock
and Hamilton, 1993; Woodcock, 1996, personal communication).
Mekhanobr in St Petersburg, Russia also marketed a CPS system and applied it in mines
in Europe and Asia for copper/moly separation and the flotation of oxidised lead–zinc and
copper ores (Mashevsky, 1992, personal communication).
Fuerstenau and co-workers (Herrera-Urbina, Sotillo and Fuerstenau, 1999) have also
concluded that the xanthate flotation of sulfidised, mixed oxide-sulfide ores may be controlled
by monitoring pulp potential.
Outokumpu Oy (now Outotec Oyj) suggested (Heimala and Jounela, 2000) that djurleite
(Cu1.96S) electrodes should be used for CPS flotation of oxidised copper and cobalt ores
with the potential controlled between -600 mV and -300 mV versus SCE, the optimum value
depending on mineral composition. These authors reported that effective mixing of NaSH
additions was important in achieving good grades and recoveries. Most CPS plants, however,
still employ a platinum redox (ORC) electrode for Eh measurement.
The CPS procedure is applied by a number of mines throughout the world. For example, in
addition to the mines identified above, it is used at Mutiny Gold’s flagship copper–gold project
in Western Australia to improve the flotation of oxide and carbonate copper mineral present in
the oxide and transition zones. It is used at MMG’s mine at Golden Grove in Western Australia
to treat oxide copper/gold ore. It is applied at Newmont’s Batu Hijau copper–gold mine in
Indonesia. It has also enhanced the recovery of oxide copper minerals at the Kanshansi mine
in Zambia, Africa’s largest copper mine (Chadwick, 2011; Corin et al, 2017).

Sulfide flotation plants

More challenging for the flotation engineer than controlling sulfide additions is the
monitoring and control of the potential of the mineral/solution interface across the full

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 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

range of flotation situations in order to enhance performance and maintain it at a high

level. A number of groups throughout the world have researched the concept of controlling
flotation plants through continuous measurement of potential in the pulp.
The questions to be answered before a control system can be made effective are:
•• How should the potential be measured?
•• How should the potential be adjusted?
As pointed out above, noble metal electrodes are appropriate for determining the
potential in systems in which a dominant redox couple determines the potential, such as
in monitoring NaSH additions. Such electrodes can also be used in conventional flotation
pulps for monitoring pulp potential; for example, Hecker et al (1999) applied platinum
electrodes for potential monitoring in the El Teniente Colon concentrator’s SAG line
feeding the copper flotation rougher circuit. However, the potential measured by a noble
metal electrode in a conventional pulp may not be that corresponding to a mineral/solution
interface of interest. Rand and Woods (1984) demonstrated that a platinum or gold electrode
could express a potential close to that of a galena electrode inserted into the same pulp
due to continued collision between the noble metal surface and galena particles. However,
this may not apply to complex ores, because different sulfide minerals in a pulp can be at
different potentials (Ruonala, Heimala and Jounela, 1997). Also, noble metal electrodes do
not always correspond to sulfide mineral potentials in dilute pulps, such as in the flotation
of platinum group metal ores (Buswell et al, 2002).
It would appear that the most appropriate method of determining the potential of each
sulfide mineral in the flotation of complex ores is to use electrodes composed of the individual
minerals being floated or depressed. However, the surface of the mineral electrodes will
continuously react with the collector and other constituents of the pulp and hence will not
continue to respond in the same manner as the freshly ground mineral particles of the same
composition in the flotation pulp. Outokumpu Oy has addressed this problem (Ruonala,
Heimala and Jounela, 1997) by regenerating sulfide mineral electrodes ‘by electricity or
ultrasound as well as by mechanical cleaning’. It is difficult to know to what extent these
treatments solve the problem, or if further research is required to develop techniques to
maintain the activity of sulfide mineral electrodes and ensure that the potential expressed is
the same as that of the particular mineral in the flotation pulp being monitored.
Adjustment of potential can be achieved by modifying the conditioning time or by
changing the composition of the pulp or flotation gas. It is interesting to note that Newmont
Technologies Ltd developed a process, N2TEC®, for the flotation of refractory gold ores that
employs nitrogen as the carrier gas. This process was proven at the Lone Tree mine and at the
Tonkin Springs gold project (Symmons et al, 1999). The use of nitrogen inhibits the oxidation
of arsenian pyrite in the ore (Dunne et al, 2009). Measuring pulp potential would appear to be
a useful method of monitoring such a process.
In most cases, the pulp chemistry that gives good flotation recovery has been established by
conventional methods, and only small changes in potential are required to maintain flotation
efficiency at the optimum level. A paper by Panayatov et al (2000) described technology for
direct potential control using electrodes inserted in the pulp, but regulating pulp chemistry
offers a simpler and more economic approach.
Outokumpu Oy in Finland has probably progressed further than any other company in
the application of potential measurement for flotation control and has introduced its OK-
PCF potential monitoring system in a number of its flotation plants. The system has been

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 RONALD WOODS

in operation at the Hitura nickel mine since 1984, at the Vammala nickel and Vihanti Cu/
Zn/Pb mines since 1988 and was installed at the Pyhasalmi Cu/Pb/Zn/FeS2 mine in the early
1990s. At Hitura, the replacement of pH control by potential control was reported to result in
an improvement in nickel recovery by up to two per cent depending on ore type (Ruonala,
Heimala and Jounela, 1997). At Vihanti, it was claimed that lime and collector consumption
has been decreased to one third of the values experienced prior to the installation of the OK-
PCF system. It is claimed that profitability has increased by ten to 20 per cent since potentials
have been monitored.
Outokumpu proposed the use of electrodes composed of synthetic or natural sulfide
minerals, usually of the composition being floated. For each valuable mineral, it is claimed
(Ruonala, Heimala and Jounela, 1997) that there may be one or more combinations of
variables for the most economic processing, and this requires integration of on-stream X-ray
fluorescence analysis, electrochemical potential measurements and collector concentrations.
Outokumpu insisted (Ruonala, Heimala and Jounela, 1997) that, because different sulfide
minerals can express different potentials in the same slurry, electrodes prepared from the
sulfide minerals present in the flotation pulp must be used to maximise separation and
recovery. The company marketed a plant audit procedure (Sotka et al, 2003; Oravainen
et al, 2005) that includes the measurement of potentials in the flotation plant with mineral
electrodes. The application of Outokumpu’s electrochemical knowledge would now appear
to be focused on its audit procedure rather than online control.
Outotec Oyj supplemented the Outokumpu flotation monitoring knowledge in 2007
through the acquisition of the Chena® (Chemistry Navigator) trademark from Liqum Oy
and then began to market the Chena® Electropotential Measurement System for monitoring
flotation circuits. This system was promoted by the company for use online to provide
flotation plant operators with potentials measured with a number of electrodes as well as
the pH and, together with assays from other on-stream analysers, suggested it could be used
for expert control of the circuit. Manouchehri, Lawson and Taylor (2010) used the Chena
system incorporating a range of metal and sulfide mineral electrodes to monitor changes in
pulp chemistry in a laboratory study of copper/nickel ore from Clarabelle, Sudbury, Canada.
These authors concluded that the Chena analyser ‘offers a possibility to control the flotation
characteristics of pentlandite and pyrrhotite through the understanding and optimising of the
pulp chemistry’. Manouchehri (2014) reported that, using the Outotec Chena analyser in the
treatment of pentlandie/pyrrhotite ores, the rest potential displayed by pentlandite electrodes
in low oxidising pulps is still high enough to allow the formation of dixanthogen and hence
promote nickel flotation. Controlling pulp potential at slightly lower values, pentlandite
recovery from pyrrhotite was still found to be satisfactory.
Etelapaa et al (2012) and Mashevsky et al (2012) proposed the application of a molybdenum
electrode to monitor Eh using the Outotec Chena system as they perceived problems with
the use of platinum. The role of an Eh electrode in monitoring flotation pulps is to act as
an inert probe that will adopt the mixed potential being expressed by the sulfide mineral
particles through multiple collisions. As pointed out above, Rand and Woods (1984)
demonstrated that platinum can operate in this way. In this regard, the problems Etelapaa
et al (2012) and Mashevsky et al (2012) perceived with the use of platinum for measuring
the relevant Eh value are not pertinent. Certainly, the replacement probe they adopted,
molybdenum, will not be inert; it will adopt the potential of the molybdenum/molybdenum
oxide couple at the pH of the pulp. Indeed, molybdenum electrodes have been shown to act
as pH probes (Nomura and Ujihira, 1987). The actual values, however, could be influenced

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 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

by other components of the pulp solution, but not the mineral content. Any correlations
found between flotation recovery and the potential displayed by a molybdenum electrode,
therefore, relate to pH rather than Eh.

CONCLUDING REMARKS
In this chapter, it has been shown that the electrochemical nature of the interaction of flotation
collectors with sulfide minerals is well established. Also, that combining electrochemical
methods with a range of spectroscopic techniques provides valuable detail on collector-
mineral interaction. Furthermore, monitoring of electrochemical parameters in flotation pulps
can identify optimum conditions that yield the highest concentrate grades and recoveries.
As pointed out above, the potential-dependence of the flotation of a sulfide mineral present
in a sulfide assemblage has been found to differ from that of the mineral on its own (see
above). It would be advantageous to have a better understanding of the mineral-mineral
interactions responsible for such differences.

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Appendix – General description of the oxidation of

sulfides and the consequences for the flotation process
Bill Johnson and Peter Munro

INTRODUCTION
Oxidation of the sulfide minerals proceeds throughout a flotation separation circuit, with a
measurable increase in the extent of oxidation from the commencement of roughing to the
end of flotation. This appendix provides an overview of the products from oxidation of the
sulfide minerals, both valuable and gangue, and shows how these products influence the
flotation process.

GENERAL DESCRIPTION OF THE OXIDATION OF SULFIDES

The chemical conditions in a flotation circuit for processing a sulfide ore are conducive for
ongoing oxidation of the sulfide minerals. Measurements show oxidation increases from the
beginning of roughing to the end of flotation. Each flotation cell provides well-mixed pulp
zones with air dispersed as bubbles and the contained oxygen is dissolved in the aqueous
phase providing a basis for oxidation of the sulfide minerals.
The simplest depiction of the oxidation of a sulfide mineral (MS) is under acid conditions
(Witika and Dobias, 1995):

MS = M2+ + S + 2e- (A1)

Equation A1 depicts the transfer of a metal cation from the surface of the sulfide mineral
and the retention of the cation in the aqueous phase. Normally, the conditions in a sulfide
flotation circuit are slightly or strongly alkaline. Under alkaline conditions, many metal
cations are no longer soluble because the solubility product for the hydroxide of the
metal cation (M(OH)2) is exceeded due to the increased hydroxide ion concentration in
the aqueous phase. Table A1 shows the pH value at which various metal hydroxides are
precipitated (Vogel, 1962). It can be seen that various metal ions, but not all, are precipitated
below or at pH 7 while others are precipitated in the slightly alkaline region.

TABLE A1
pH values for precipitation of various hydroxides (Vogel, 1962).
pH value Metal ion precipitated
3 Fe3+, Sn2+, Zr4+
4 Th4+
5 Al3+
6 Cu2+, Zn2+, Cr3+
7 Fe2+
8 Ni , Co2+, Cd2+
2+

9 Ag+, Hg2+, Mn2+

10 Mg2+

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 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

Hence, under alkaline conditions, the initial oxidation of a sulfide mineral (MS) in a flotation
circuit can be described by Equation A2 (Witika and Dobias, 1995):

MS + 2H2O = M(OH)2 + S + 2H+ + 2e- (A2)

Equation A2 introduces into Equation A1 the formation of the metal hydroxide, which is
retained in the system. In fact, the metal hydroxide precipitates can adhere on the surfaces
of the particles in the flotation pulp with process implications. Both Equations A1 and A2
show elemental sulfur (So), which is hydrophobic, as a product of oxidation. Its presence is
one explanation of the observed limited hydrophobicity of sulfides during initial oxidation,
another being the existence of a metal-deficient sulfide on the surface.
From flotation experiments, the following ranking (Trahar, 1984) was produced for the
floatability of the sulfide minerals from initial oxidation in the absence of collector (most
floatable minerals in the group on the left):
Chalcopyrite, Galena, Pyrrhotite, Pentlandite > Bornite > Chalcocite > Pyrite > Sphalerite
Ongoing oxidation in the alkaline region increases the quantity of hydrophilic hydroxide
precipitates on the surfaces, as shown in Equation A2, overriding the limited hydrophobicity
from initial oxidation.
Further oxidation under alkaline conditions of the sulfide mineral (MS), depleted in metal
cations on its surface, may lead to the production of oxy-sulfur species in the aqueous phase
(Witika and Dobias, 1995) according to Equation A3:

xS + yH2O = SxOy2- + 2yH+ + (2y – 2)e- (A3)

For the oxidation reactions involving the minerals in Equations A1, A2 and A3 to continue,
the electrons produced in Equations A1, A2 and A3 must be consumed; reactions of the
type in Equation A4 provide this. Note that such reactions can occur on pyrite and a high
pyrite feed grade causes greater oxidation of the other sulfide minerals. Sulfide oxidation is
electrochemical in nature from the combination of anodic (Equations A1 to A3) and cathodic
(Equation A4) reactions.

O2 + 2H2O + 4e- = 4OH- (A4)

An example is given of one anodic reaction for pyrite, the most widespread and abundant of
all sulfide minerals. This reaction (Equation A5) applies above pH 6.7 where Fe2+ is no longer
stable (Hiskey and Schlitt, 1982):

FeS2 + 11H2O = Fe(OH)3 + 2SO42- + 19H+ + 15e- (A5)

In Equation A5, the products from the iron and sulfur in the pyrite are insoluble iron
hydroxide and soluble sulfate, respectively, and these two products are of the type indicated
in the general Equations A2 and A3 for the metal iron and sulfur respectively. Importantly,
the generation of hydrogen ions in Equation A5 shows that the pH can be expected to move
in the acid direction as a result of the oxidation of pyrite and sulfide minerals in general.
Table A2 lists the rest potentials for six of the sulfide minerals for which a ranking was given
earlier for their floatability after initial oxidation, in the absence of collector. In general, the
minerals with low rest potentials, that is minerals more prone to oxidation showed high self-
induced floatability from greater formation of sulfur (So), as shown in Equations A1 and A2

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 BILL JOHNSON AND PETER MUNRO

TABLE A2
Rest potential values of sulfides and related behaviour for self-induced floatability (also known as collectorless or natural
floatability) and sodium-sulfide-induced floatability (modified from Hu, Sun and Wang, 2009 and Wills and Finch, 2016).
Mineral Rest potential Self-induced floatability Sodium-sulfide-induced
(volts, SHE) (no collector) floatability (no collector)
Pyrite (noblest) 0.66 Low High
Chalcopyrite 0.56
Sphalerite 0.46
Pentlandite 0.35
Pyrrhotite 0.31
Galena 0.28 High Low
SHE – standard hydrogen electrode as the reference electrode.

(Hu, Sun and Wang, 2009). In experiments, chalcopyrite displayed much higher self-induced
floatability than expected from its rest potential in Table A2.
Pyrite, the noblest mineral based on the rest potential values in Table A2, displayed low
self-induced floatability and, commensurately, it is observed to display high sodium sulfide
induced floatability (Hu, Sun and Wang, 2009), as indicated in Table A2, because it requires
assistance from the sodium sulfide by providing a potential source of sulfur (So).
From Table A2, sulfide mineral pairs with a large difference in rest potential are expected to
demonstrate a greater driving force for galvanic oxidation in flotation pulps, in comparison
with a pair with a small difference. The same approach is also taken in consideration of the
propensity for oxidation and dangerous self-heating to occur in sulfide mineral concentrates
under storage or during transport (Payant et al, 2012).

CONSEQUENCES FOR THE FLOTATION PROCESS

An outcome of the oxidation step for the ore minerals is that hydrophilic metal hydroxide
precipitates, referred to as oxy-hydroxides in the current literature, adhere to the surfaces of
the particles in the flotation process, including the valuable minerals that need to be made
hydrophobic. The presence of the adhering hydrophilic precipitates increases the difficulty
preparing a hydrophobic surface on the valuable mineral.
Figure A1 from Healy (1984) illustrates the situation schematically. It shows the relationship
between surface potential and pH for three examples of metal hydroxide precipitates, labelled
as Zn(OH)2, Cu(OH)2 and Mn(OH)2.
Figure A1 also shows the nature of the relationship for a typical sulfide mineral and a typical
non-sulfide gangue mineral. The typical relationship is a positive surface potential in the acid
region, declining and becoming negative also in the acid region, with the value becoming
more negative as neutral pH values approach and in the alkaline region.
In the closely related Figure A2, the solid lines in Figure A1 are replaced by broken lines
for ease of comparison. Figure A2 shows the effect of deposition of a colloidal precipitate of
Zn(OH)2 on the surface potential of both the sulfide and gangue minerals. In the region of
neutral and alkaline pulps, the following can be noted:
•• the surface properties of the two example minerals are completely changed from their
normal properties

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 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

SURFACE POTENTIAL
0 pH

Mn (OH)2
Cu (OH)2
Zn (OH)2 (s)

Sulfide
–
Gangue
FIG A1 – Schematic representation (Healy, 1984) of the variation of surface potential of a typical sulfide mineral and a typical
non-sulfide gangue mineral and of colloidal hydroxide precipitates of Zn(OH)2, Cu(OH)2 and Mn(OH)2. The typical relationship for
a sulfide and a non-sulfide mineral is a positive surface potential in the acid region with the potential declining and becoming
negative, while still in the acid region, with the value becoming more negative with neutral and alkaline pH values.

+
SURFACE POTENTIAL

Sulfide + Zinc

0 pH

Gangue + Zinc

FIG A2 – Schematic representation (Healy, 1984) of the effect of adsorption of a colloidal hydroxide
precipitate of Zn(OH)2 on the surfaces of a typical sulfide mineral and a typical non-sulfide gangue mineral.
Both minerals now show the behaviour of Zn(OH)2 in the region in which Zn(OH)2 forms. The solid lines in
Figure A1 are replaced by broken lines in Figure A2 for ease of comparison of the two related graphs.

•• the surface properties of the two example minerals adopt the properties of the precipitated
colloidal Zn(OH)2 and therefore the surface properties of the two example minerals
become similar
•• depending on the pH value, the example minerals have regions of both positive surface
potential and negative surface potential.
Oxidation of an iron or steel grinding media in grinding or regrinding in a flotation circuit
creates the same difficulty; the oxidation products from the grinding media provide a
potentially large source of hydrophilic species that adhere to the surfaces of the valuable
minerals and greatly increase the difficulty in preparing a hydrophobic surface on the

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 BILL JOHNSON AND PETER MUNRO

valuable mineral. It is useful to consider the relative magnitudes of the rest potentials for the
sulfide minerals (Table A2) with mild steel grinding media (Wills and Finch, 2016), noting the
large difference between the values for mild steel and galena:
(Noble end) Pyrite > Chalcopyrite > Sphalerite > Pentlandite >
Pyrrhotite > Galena >> Mild Steel (Active end)
The large difference in the rest potentials for mild steel and for the various sulfide minerals
indicates that there is large driving force for galvanic oxidation of the mild steel in grinding
systems, producing large quantities of iron species as detrimental hydrophilic hydroxides/
oxy-hydroxides adsorbed by particles in the system, as discussed earlier. Grinding balls
with elevated levels of chromium have a higher rest potential than mild steel and reduce the
driving force for galvanic oxidation in grinding systems, in comparison with mild steel balls.
Increasing the chromium content in the grinding balls heightens this effect by driving its rest
potential further from the value for mild steel.
Another outcome of the oxidation step for the ore minerals is that the released metal ions
are capable of interacting with, and altering the surfaces of the other sulfide and gangue
minerals in the flotation system. Some examples are:
•• Metal ions from oxidation of a valuable mineral in a copper circuit or a lead circuit will
transfer to other sulfide minerals and change their surfaces, for example uptake of copper
ions and lead ions on sphalerite in a copper circuit or a lead circuit, noting that alteration of
the sphalerite surface is only required in a zinc circuit that follows copper or lead circuits.
Premature unintentional activation of the sphalerite will cause losses of sphalerite because
it reports to the wrong concentrate.
•• Metal ions from oxidation of a valuable mineral in a copper circuit will activate gangue
sulfide minerals, for example copper ions will activate pyrrhotite and if present as Cu+
ions under reducing conditions, will activate pyrite. Unintentional activation of the pyrite
will cause dilution of the concentrate containing the valuable mineral.
As described earlier, the oxidation of a sulfide ore creates a large amount of hydrophilic
hydroxide/oxy-hydroxide species on the surfaces of all minerals, including the valuable
mineral. Collector must be selectively adsorbed on the valuable sulfide to produce surfaces
that are sufficiently hydrophobic for recovery by the flotation process. Hydrophobic
surfaces on the valuable sulfide must be obtained despite the presence of the described
hydrophilic species from various sources also on the surfaces. This uptake of collector is also
electrochemical in nature where the oxidation of the collector is the anodic reaction. For the
flotation metallurgist, the consequence is that the pulp potential (see earlier in this appendix)
will be an important parameter and must exceed a critical value to allow collector uptake; this
pulp potential is dependent on the mineral and the type of collector.
For some ores with a high head grade of iron sulfide minerals, that is pyrite and pyrrhotite,
it may be necessary to aerate the pulp extensively before rougher flotation to raise the pulp
potential to the critical value, allowing collector uptake. Even for ores with a low head grade
of iron sulfides, the head grade of iron sulfides in some internal streams being reground in the
flotation circuit may be quite high and pulp aeration after regrinding may also be required
to achieve the necessary pulp potential value, allowing uptake of collector prior to flotation
of the target sulfide mineral. The quantity of air or oxygen that needs to be supplied is a
property of the ore that can be determined in oxygen demand tests (see Chapter 7); this needs
to be known, because this property of iron sulfide minerals varies from deposit to deposit.

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 CHAPTER 8 | ELECTROCHEMICAL ASPECTS OF SULFIDE MINERAL FLOTATION

ACKNOWLEDGEMENT
The important contribution of Suzanne Munro (Mineralurgy Pty Ltd/Mineralis) in preparation
of diagrams and of other aspects for the content in this appendix is acknowledged with
gratitude.

REFERENCES
Healy, T W, 1984. Pulp chemistry, surface chemistry, and flotation, in Principles of Mineral Flotation – The
Wark Symposium (eds: M H Jones and J T Woodcock), pp 43–56 (The Australasian Institute of Mining
and Metallurgy: Melbourne).
Hiskey, J B and Schlitt, W J, 1982. Aqueous oxidation of pyrite, in Proceedings SME–SPE International
Solution Mining Symposium: Interfacing Technologies in Solution Mining (eds: W J Schlitt and J B Hiskey),
pp 55–74 (American Institute of Mining, Metallurgical, and Petroleum Engineers: Englewood).
Hu, Y, Sun, W and Wang, D, 2009. Electrochemistry of Flotation of Sulphide Minerals (Tsinghua University
Press and Springer).
Payant, R, Rosenblum, F, Nesset, J E and Finch, J A, 2012. Galvanic interaction in self-heating of
sulphide mixtures, CIM Journal, 3(2):169–177.
Trahar, W J, 1984. The influence of pulp potential in sulphide flotation, in Principles of Mineral Flotation
– The Wark Symposium (eds: M H Jones and J T Woodcock), pp 117–135 (The Australasian Institute of
Mining and Metallurgy: Melbourne).
Vogel, A I, 1962. A Text-book of Quantitative Inorganic Analysis, third edition (Longmans).
Wills, B A and Finch, J A, 2016. Mineral Processing Technology, eighth edition (Elsevier/B-H).
Witika, L K and Dobias, B, 1995. Electrochemistry of sulfide minerals, in Flotation Science and Engineering
(ed: K A Matis), pp 157–177 (Marcel Dekker, Inc).

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 Return to contents

CHAPTER 9
Surface chemical characterisation
for flotation plant optimisation
Alan Buckley*

ABSTRACT
The principal surface chemical characterisation techniques of relevance to the optimisation
of flotation plants will be described in this chapter. The main emphasis is on conventional
X-ray photoelectron spectroscopy (XPS), the most widely applied spectroscopy for obtaining
ex situ surface chemical analyses. The complementary information that can be obtained by
synchrotron XPS and by X-ray absorption spectroscopy is also described. Other important
ex situ characterisation techniques covered include static secondary ion mass spectrometry
and to a lesser extent, vibrational spectroscopy. General considerations for the preparation of
specimens for the ex situ techniques are discussed, including the relative merits of investigating
single particles rather than pulp specimens. Off-stream, but in situ (wet), surface chemical
characterisation techniques are outlined.

INTRODUCTION
As discussed in preceding chapters, the floatability of a particle in a flotation cell depends
on its hydrophobicity, and hence on its surface chemical composition. The separation of a
valuable ore component from gangue, or the selective flotation of one valuable component
relative to others, normally requires one component to be significantly more hydrophobic
than the other constituents (or the converse for reverse flotation). Thus, it can be important
to know the surface chemical composition of not only the component to be concentrated,
but also the other components or gangue that should report to the tails. Of course, flotation
has been an industrial process for more than a century, and for much of this period, surface
chemical characterisation of the particles in flotation pulps has not been carried out or even
feasible. Advances in flotation technology have usually arisen from empirical developments
rather than as a result of surface chemical knowledge. However, when a flotation process fails
to deliver the required recovery or grade, or when there is some other need to understand
flotation behaviour, then surface characterisation becomes not an option but a necessity.

* This chapter was revised by Alan Buckley, who sadly passed away in 2017, prior to the publication of this edition.

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 ALAN BUCKLEY

Most flotation plants process base metal ores, and most base metal ores comprise sulfide
minerals that can sometimes be partially oxidised. Accordingly, while emphasis will be
placed on sulfide minerals in this chapter, oxide minerals will be covered sufficiently to
illustrate the main surface characterisation differences for the two mineral types. Quite apart
from ‘industrial minerals’, oxide minerals can be important sources of metals as most rare
earth and actinide elements occur in ores predominantly in the form of oxides, carbonates or
phosphates. There is also an emphasis in this chapter on the surface chemical characterisation
of mineral specimens prepared in the laboratory expressly to help optimise generic flotation
plant circuits rather than on pulp samples to identify and solve plant-specific problems. The
latter approach will be covered briefly here but addressed more fully in the next chapter
where some case studies are described in detail. Regardless of whether the surface chemical
composition to be determined is that of mineral particles from a flotation plant or of a single
piece of mineral conditioned in a laboratory, the underlying principles of any characterisation
technique and its data interpretation will be the same.
The surface chemical composition of relevance in flotation systems is usually that of mineral
particles either bearing organic adsorbates, especially collectors, or being free of organic
adsorbates but altered by interaction with oxygen, added reagents other than collectors
such as activators, or normal constituents of flotation pulps such as metal ions. In the first
category, adsorbed collector coverage can range from the submonolayer of chemisorbed thiol
that is just sufficient to impart hydrophobicity to an unoxidised sulfide mineral particle, to a
multilayer of metal thiolate and/or of dithiolate. In the second category, the altered surface
can vary from one involving only the outermost atomic layer of the mineral lattice, such as
the interaction of Cu ions with pyrite (eg Wang, Forssberg and Bolin, 1989), to one involving
several atomic layers, such as the interaction of Cu ions with sphalerite (eg Finkelstein, 1997).
Thus, in both categories, the altered surface layer to be chemically characterised can vary in
thickness from one atomic layer (~0.2 nm) to several or even many atomic layers (typically
1–5 nm), notwithstanding the fact that it is only the outermost atomic layer that will have a
significant influence on the hydrophobicity. Characterisation of the former sometimes calls
for extreme surface sensitivity at the limit of available technology, while examination of the
latter is manageable using conventional laboratory surface analysis techniques such as X-ray
photoelectron spectroscopy (XPS). The advanced approaches, which usually require access
to major infrastructure such as a synchrotron, have become well-established for flotation
research in recent years, and are now at the stage that they should be considered for flotation
problem-solving when appropriate.
This chapter is concerned with the surface chemical nature of mineral particles, but readers
should be reminded that surface physical aspects, including microstructure and particle
shape, can also influence floatability. The chemical and physical aspects are often inextricably
linked when the crystal structure is particularly anisotropic. For example, the basal planes of
molybdenite have been shown, as anticipated, to have lower reactivity than the edges (Buckley
et al, 1995), and an analogous reactivity difference is expected for covellite. In these cases, the
particle size will influence the ratio of edges to basal planes, and hence the composition of
surfaces predominantly encountered by the bubbles in a flotation cell.

SURFACE CHEMICAL CHARACTERISATION – GENERAL CONSIDERATIONS

To a large extent, the surface chemical characterisation technique or techniques applied
in any given problem-solving situation will depend on the relevant altered surface layer
thickness, the feasibility of investigating samples that are truly representative of the particles
in the flotation environment under consideration, and the time scale in which the information

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

is needed. These general considerations will be addressed before specific characterisation

techniques are described in detail.
Sample selection is of crucial importance, and hence deserves serious attention. It goes
without saying that any flotation pulp sample for either bulk or surface characterisation must
be representative of the majority of particles in that part of the flotation cell or circuit under
investigation. The issues peculiar to surface chemical characterisation are those beyond
representative sampling to those that concern the preservation of the surface chemical
composition, until and during the actual characterisation measurements, without significant
inadvertent change. Ideally, surface characterisation would be carried out on-stream; that is,
while the mineral particles were in the flotation cell or circuit, as is the case for analysis of
some bulk properties. However, on-stream surface chemical characterisation is rarely feasible,
although it is achievable in principle with one or two of the in situ techniques described
towards the end of this chapter. In most cases the characterisation measurements must be
made off-stream, and very often ex situ (dry rather than wet) in which case the considerable
problem of sample preservation and handling after collection arises.

Flotation pulp samples

The collection and subsequent handling of industrial flotation pulp samples suitable for
meaningful surface chemical characterisation have been considered in detail by Smart
and co‑workers at the University of South Australia (Smart, 1991; Smart et al, 2003). Their
methodology involves the initial purging of the pulp sample with nitrogen or argon
within 15 min of collection to reduce dissolved oxygen levels from typically 8–40 ppm to
less than 0.1 ppm before sealing and freezing (within 30 min). Immediately before surface
characterisation, for example by XPS, the sample is thawed and, if necessary, deslimed by
several successive applications of a procedure which consists of shaking (but not ultrasonic
agitation), decanting of the supernatant solution containing the dispersed ultra-fine particles,
and replacement of this pulp solution immediately after filtering through a 0.1 μm filter.
A small quantity of the deslimed slurry is then inserted into the spectrometer on an electrically
conducting sample stub and the solution evaporated in the sample introduction chamber of
the spectrometer to achieve a vacuum of approximately 10-5 Pa within 10 min. Those workers
maintained that before the mineral particles are exposed to a non-aqueous environment by
evaporation of the solution, essentially all air has been removed from the chamber, thereby
minimising extraneous oxidation or other alteration of the surface of the particles. In
demonstrating the validity of the procedure, it was found that deposition of soluble species
on to the mineral particles is not usually a problem. In cases where it is a problem, the actual
pulp liquor is changed for a dilute solution having a similar pH and Eh, the latter being
established with sodium dithionite stabilised with sodium carbonate for reducing potentials
and with hydrogen peroxide for oxidising potentials. Cooling of specimens prepared in this
way to retain volatile surface species was also carried out, and water retention by the sample
was found not to be a problem, notwithstanding some complication of spectral interpretation
arising from different degrees of charge-shifting from different components in the specimen.
Surface characterisation of specimens handled using this procedure was shown to be valid
provided the storage time prior to analysis was less than three months (Smart, 1991).

Particles conditioned in simulated flotation pulps

One alternative to the surface characterisation of mineral particles from industrial or pilot
scale flotation feeds, concentrates and tailings is the study of ground mineral particles treated

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 ALAN BUCKLEY

under flotation-related conditions in the laboratory. Simulated flotation pulps prepared in

this way can be extremely useful for determining the effect of a particular variable, such
as Eh, that might be difficult to control even in a pilot plant. Another alternative is to move
further towards the laboratory environment by investigating the surface of single mineral
particles. This step might be taken in circuit design or to attempt to solve a plant problem that
potentially requires extremely fine control of reaction conditions, such as an initial surface
that is completely unoxidised or unaltered. The single mineral particle approach is the one
normally adopted in research when a generic flotation problem is being investigated. There
are many advantages of investigating either fracture or abraded single particle surfaces over
fine particle specimens, including better control or knowledge of the surface atomic plane
presented to the aqueous phase, better control of the electrical potential (and hence enhanced
spectral resolution for some techniques), better temperature control (and hence retention
of adsorbates), greater compatibility (less out-gassing) for those techniques that require the
specimen to be under ultra-high vacuum (UHV), easier mounting (anchoring) of the specimen
especially for those techniques for which the specimen does not remain horizontal, and a
‘flatter’ specimen surface for techniques where that is an advantage or a necessity (eg infrared
external reflection spectroscopy). It is important to note that the surface characterisation of
single mineral particles does not necessarily imply the study of systems containing only a
single mineral component. For example, if the selective separation of two sulfide minerals
(such as pentlandite and pyrrhotite) is being investigated, systems containing both minerals
should be included in those studied to allow for any interactions between the two sulfides
not already covered by the use of a relevant pulp liquor as the aqueous phase (Trahar, Senior
and Shannon, 1994). The possible influence of particle size on floatability must also be kept in
mind (Senior, Shannon and Trahar, 1994).
Apart from specimen mounting differences, the surface characterisation principles are
largely the same for both particles of floatable size and single piece specimens. The main
exception to the similarity in analysis approach arises in characterisation techniques involving
a variation of the angle between the specimen surface and either a source or a detector. In
such cases, care must be taken to minimise the typically ‘rough’ surface of a multi-particulate
specimen. For the UHV-based techniques, single piece specimens are normally held in place
on a conducting metal sample stub by means of metal screws or clips, or by UHV-compatible
double-sided adhesive C or Cu tape. Particulate specimens are usually either pressed into
pure indium foil or mounted on double-sided adhesive tape.

Single particle surface preparation

For research on single particle surfaces, a decision must be made on whether to use abraded
or fracture surfaces, or if possible, both. It is clear that for most sulfides, the chemical
composition of a surface abraded in air and washed free of swarf is different from (and
typically sulfur-rich relative to) that of a fracture surface. This does not mean that an abraded
surface is necessarily inferior, as because of the comminution processes commonly used, the
surface of mineral particles in a flotation pulp may be more closely represented by abraded
than fracture surfaces. Ideally, both abraded and fracture surfaces should be used in any
investigation; however, unless the problem being addressed appears to be one that might be
strongly influenced by any prior alteration of the surface, then it is more realistic to restrict
experiments to abraded surfaces only. There are a number of difficulties involved in the
use of fracture surfaces, including the acquisition of sufficient lump mineral of the desired
composition, the conchoidal fracture rather than cleavage along an ‘easy’ plane exhibited by
a majority of minerals, and the tendency to fracture along interfaces already weakened by

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

small inclusions of other phases or weathering products (although that in itself may be of
relevance in the flotation of some minerals). On the other hand, the main difficulty involved
in using abraded surfaces is the additional complexity introduced by the need to interpret
the observed behaviour of altered surfaces. Indeed, in order to obtain meaningful data, there
is sometimes the need to fracture surfaces under the flotation-related aqueous phase (eg
collector solution).

Extent of collector coverage

As noted above and in the previous chapter, flotation of an unoxidised sulfide mineral can be
induced if its particles are covered by less than a full monolayer of chemisorbed thiol collector,
with maximum recovery achieved with only about half a monolayer. Therefore, in practice,
only submonolayer coverage should be sought to minimise cost and optimise selectivity.
Ideally, multilayer coverage by a thiol collector should not arise in a flotation plant context,
but multilayer formation can sometimes be unavoidable if higher collector concentrations are
used because oxidised or highly variable ores are being processed. The principal multilayer
species of a collector such as sodium butyl xanthate (NaBX) that could potentially be adsorbed
would be the molecular metal thiolate (eg CuBX), the dithiolate (dixanthogen) and the
protonated thiol (HBX). Multilayer coverage does not necessarily lead to a recovery problem,
as adsorbed multilayer species of most thiol collectors do not significantly lower (or enhance)
the hydrophobicity achieved by full monolayer coverage. However, for some thiol collectors,
not all multilayer species are benign in this regard, so the identification of any adsorbed
multilayer species can be an important aspect of surface chemical characterisation. For this
reason, it is sometimes necessary to adopt specific strategies to differentiate monolayer and
multilayer collector species in the principal surface chemical characterisation techniques.
It should be noted that for some sulfide minerals, it is the dithiolate (eg dixanthogen) that
is believed to be the collector species primarily responsible for floatability. Also, the situation
with some oxide minerals and their collectors can be different from sulfide minerals and thiol
collectors. For example, with oxide Cu minerals and a collector such as n-octanohydroxamate,
multilayer patches of oligomeric Cu(I) hydroximate are believed to be the reason for the
high efficacy of that collector for those minerals (Hope et al, 2012). Accordingly, in practice,
hydroxamate collector concentrations are typically orders of magnitude higher than thiol
collector concentrations.

Ex situ surface chemical characterisation

Separation by flotation takes place in an aqueous medium, therefore it is legitimate to question
the general validity of surface characterisation effected in the absence of the aqueous phase
(ie ex situ), including under UHV. This is tantamount to questioning whether removal of the
pulp liquor and replacing it with an inert gaseous phase or UHV alters the surface chemical
composition of the mineral particles. There is substantial evidence to indicate that provided
precautions are taken to avoid loss of moderately volatile species such as dixanthogen from
the surface to a vacuum, removal of the aqueous phase in this way does not have a noticeable
effect on the surface chemical composition. This evidence includes the agreement of in situ
and ex situ surface enhanced Raman scattering (SERS) spectroscopic data, the agreement of
cyclic voltammograms determined before and after emersion, and the correlation of surface
composition and floatability (eg Zachwieja et al, 1989). The validity of ex situ characterisation
is logical, as it is likely that only strongly adsorbed collector species would contribute to
mineral particle hydrophobicity in the turbulent environment of a flotation cell, and such

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 ALAN BUCKLEY

strongly adsorbed species would be expected to survive at a surface subjected to rinsing,

drying and evacuation.
Photon beam damage, which may actually be damage caused mostly by electrons ejected by
photons of sufficient energy, can sometimes be a problem when intense sources such as lasers
or synchrotron X-ray beams are used; however, such damage is usually minor compared
with that caused by electron or ion beams. Accordingly, charged particle beams are rarely
used in surface chemical characterisation unless the technique is inherently destructive as in
secondary ion mass spectrometry (SIMS).

Characterisation of surfaces under UHV

The loss of moderately volatile species from the surface of mineral particles is a possibility
that must always be kept in mind when UHV-based surface characterisation techniques
are being used. Although not widely believed when first noted (Buckley and Woods, 1984),
the complete loss from a specimen surface of a low coverage of even elemental sulfur by
sublimation to an ultra-high vacuum is possible. Sublimation can be prevented by cooling
the specimen to well below ambient temperature with a flow of liquid nitrogen; however, all
condensable material in the vapour phase must be removed before cooling is commenced to
prevent its deposition on to the specimen surface. Removal of such material, including water
vapour, is usually effected by thorough flushing with dry nitrogen or argon in an insertion
chamber in a procedure similar to that described by Kartio et al (1992). The specimen must
continue to be maintained at a low temperature when transferred to the analysis chamber.
As an alternative to cooling, it is possible (although not common) to incorporate differential
pumping into some surface analysis equipment so that the local pressure near a specimen
can be maintained at ~1 mbar while the other parts of the equipment remain under UHV
(Shchukarev, 2006).

Time scale for surface chemical characterisation

For on-stream surface characterisation, essentially contemporaneous information is feasible
provided there is someone present with the expertise to interpret the raw data, or the data is
processed by an ‘intelligent system’. For off-stream surface chemical characterisation using
laboratory techniques, it is possible to obtain same-day information if the equipment is in a
corporate laboratory, or same-week information if an external service provider is involved.
For characterisation requiring a major facility such as a synchrotron, the waiting time is
usually much longer, as access to that facility is normally allocated several months in advance
on a competitive, peer-reviewed basis. However, most major mineral processing countries
(with the possible exception of those in Africa) already have, soon will have, or can readily
gain access to, a synchrotron. Well-established synchrotrons in the United States, Sweden,
Brazil, China, Russia, France, Canada and Australia are particularly important in this regard,
and several recently constructed synchrotrons have been justified on an economic and
scientific case that depended significantly on the minerals sector. Most synchrotrons welcome
approaches from the minerals industry, especially when analyses would be undertaken by an
experienced research provider. Beam access is typically at no cost to the user if the research can
be published in the open literature, but synchrotrons often have industry liaison personnel,
and affordable arrangements for beam access at short notice can usually be made for urgent
measurements. As explained later in this chapter, synchrotron radiation techniques will be
used increasingly for surface chemical characterisation of minerals because the X-ray energy
can be tuned to provide either maximum surface sensitivity (essential for advanced flotation

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

research and problem-solving) or maximum elemental sensitivity in electron spectroscopy,

and to enable complementary X-ray absorption spectroscopy.

The principal surface chemical characterisation techniques

The surface chemical characterisation techniques covered in this chapter are discussed from
the point of view of a minerals processing engineer. In particular, only generic and ‘need-to-
know’ details of the instrumentation are described, and the fundamentals of each technique
are presented in no greater depth than the ‘working knowledge’ level. In these two aspects,
then, some fine details may be glossed over, and subtleties ignored in the knowledge that
the cited references are available to redress any imbalance. By contrast, an attempt will be
made to treat interpretation of the data in most of its complexity, as proper data evaluation is
essential in the context of problem-solving or process optimisation, and it is always preferable
if a plant engineer and research provider can understand the same technological language.
The application to flotation research of some of the techniques described below has been
reviewed previously (eg Smart et al, 1998, 2003).

EX SITU SURFACE CHEMICAL CHARACTERISATION TECHNIQUES

X-ray photoelectron spectroscopy (XPS) and X-ray excited Auger electron spectroscopy (XAES)
It is appropriate to start with conventional XPS and to describe it in most detail, as this
spectroscopy is indisputably the ‘workhorse’ ex situ surface chemical characterisation
technique. XPS is widely applicable, and at least at a cursory level, the data are relatively
straightforward to interpret. Not surprisingly then, at least one electron spectrometer
is available in most major cities and large corporate laboratories where flotation research
is carried out, and the expertise to interpret the data is correspondingly well distributed.
Commercially manufactured instruments have been available since about 1970, and are now
at a mature stage of development. Nevertheless, in their standard form, these spectrometers
still do not have a glove box around the load lock and not all have the ability to cool a
specimen before evacuation in the load lock. Succinct descriptions of the fundamentals of,
and instrumentation for, XPS are available in surface analysis handbooks (eg Briggs and
Seah, 1990a) and in journals (eg Szalkowski, 1977; Chaney, 1987). There have been previous
reviews of the application of XPS to flotation research (eg Buckley, 1994); however, there have
been considerable advances in the area in recent years.

Principles of electron spectroscopy

Essentially, an electron spectrometer consists of a high-resolution electron energy analyser
to determine the energy distribution of electrons ejected from a specimen by an incident
monochromatic X-ray beam. A vacuum is required to ensure a sufficiently long inelastic mean
free path (IMFP) for the electrons to pass through the analyser and be detected, but so that
the vacuum quality is sufficiently high for the specimen surface to remain clean, the vacuum
is almost always an ultra-high vacuum. Thus, a spectrometer is based on a UHV system
typically constructed of non-magnetic stainless steel. An alternative arrangement in which
the local pressure for the specimen is ~1 mbar and differential pumping maintains UHV in
other parts of the spectrometer (Ruppender et al, 1990) has significant advantages as well
as some disadvantages but is not widely used and is not considered further in this chapter.
The photon source is usually of energy 1486.6 eV produced by X-rays from an aluminium
metal anode and rendered monochromatic by means of a quartz crystal monochromator.
Although of greater linewidth, non-monochromatised 1253.6 eV X-rays from a Mg anode

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 ALAN BUCKLEY

are also used, especially when Auger electron peaks interfere with photoelectron peaks
ejected by Al X-rays. The electron energy analyser is usually of hemispherical design with
~150 mm mean radius preceded by an electron lens and with a solid-state detector typically
consisting of either a number (usually three to ten) of individual channel electron multipliers,
or a multichannel plate. The specimen is inserted into the spectrometer via a load lock and
subsequently transferred to the analysis chamber where it is mounted on a manipulator of
some kind. An electron spectrum is normally obtained by maintaining a fixed pass energy
(eg 20 eV) for the hemispherical analyser, and incrementing a potential to retard the kinetic
energy of the emitted electrons to this pass energy value.
An X-ray photoelectron spectrum is a plot of the intensity of detected electrons as a function
of their kinetic energy. In most cases, it is the binding energy of the electrons from each
core level that is of primary interest; consequently, it is traditional to show the spectrum
abscissa as binding energy increasing from right to left, rather than kinetic energy (the actual
independent variable) increasing from left to right. The counter-current relationship between
kinetic energy and binding energy exists because a photoelectron binding energy, measured
relative to the Fermi level, is simply the exciting photon energy (usually 1486.6 eV) minus
the photoelectron kinetic energy minus the spectrometer work function (typically ~4 eV).
A survey electron spectrum excited by 1486.6 eV photons from a chalcocite fracture surface
prepared in air is shown in Figure 1 as a typical example of a wide scan.
In the spectrum shown in Figure 1, photoelectron peaks from the Cu 2s, Cu 2p, Cu 3s,
Cu 3p, S 2s and S 2p core levels and from the valence band are observed. A peak from S 1s
electrons is not observed because their binding energy (~2470 eV) is greater than the photon

Cu 2p

Cu LMM
Cu 3p
S 2p
Cu 3s
C 1s
S 2s
O 1s

1200 1000 800 600 400 200 0

Binding Energy (eV)

FIG 1 – Survey electron spectrum from a chalcocite fracture surface prepared in air.

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energy. There are two well-resolved Cu 2p peaks, Cu 2p1/2 and Cu 2p3/2, because the spin-orbit
splitting (~20 eV) is much greater than the available resolution. The corresponding splitting
of the S 2p1/2,3/2 doublet is not obvious in the wide scan because it is only 1.19 eV, but it is
evident in high resolution narrow scans. By contrast, the Cu 3p splitting (2.47 eV) is of the
same order of magnitude as the experimental linewidth. The expected relative intensity of
the 2p doublet components is [2×(1/2)+1]:[2×(3/2)+1] = 1:2. The Cu 2p peaks are more intense
than the Cu 3p because the photoionisation cross-section at a photon energy of 1487 eV for
the former is significantly greater than for the latter, notwithstanding the fact that there are
six 2p and six 3p electrons in each Cu atom. Peaks from Cu LMM Auger electrons are also
observed, the most intense Cu L3M4,5M4,5 peak appearing at an ‘effective binding energy’ of
569 eV or, more correctly, at a true kinetic energy near 1487 - 569 = 918 eV. Auger electrons
are not ejected directly by photons; rather, they are emitted as part of one of the processes by
which core electron vacancies are filled, the other process being X-ray emission (fluorescence).
Thus, Auger electrons have a kinetic energy that is independent of the energy of the photons
that created the core electron vacancies by photoemission. Auger electron emission is more
probable than X-ray fluorescence for low atomic number elements. Cu L3M4,5M4,5 Auger
electrons are produced when a vacancy in the L3 (2p3/2) level is filled by an electron from the
M4,5 (3d3/2,5/2) levels and another electron from the M4,5 levels is ejected. It will be shown later
that these X-ray excited Auger electrons can be extremely useful for mineral systems; however,
it should be noted that ‘Auger electron spectroscopy’ (AES) usually denotes Auger electron
emission brought about by the creation of core level vacancies by means of an electron beam,
as distinct from the photon beam in XAES. Electron excited AES is practically useless for
surface chemical characterisation of minerals because of the concomitant chemical alteration
brought about by the primary electron beam, although it can be of use for surface elemental
analysis. Finally, in Figure 1 it can be seen that small peaks from C 1s and O 1s electrons are
discernible, the C and O most probably adsorbed from the atmosphere after the mineral had
been fractured. The ubiquitous nature of C and O at the surface of air-exposed surfaces can
prove to be a nuisance when attempts are made to detect collector adsorption by monitoring
photoelectron peaks from those elements. On the other hand, the adventitious C can be useful
as an indicator of any charging of the specimen surface layer. The C 1s binding energy of the
hydrocarbon peak from such contamination should be close to 285.0 eV relative to the Au 4f7/2
binding energy of 84.0 eV for Au metal used in calibration.
A wide scan electron spectrum, then, can reveal which elements are present at the surface,
and their relative concentrations within the depth analysed (typically 1–5 nm), provided
those surface concentrations are greater than the detection limit, which is of the order of one
atomic per cent. The elements present can be identified because the various core electron
binding energies and Auger electron kinetic energies are essentially unique for each element.
Hydrogen has no closed shell electrons, and consequently photoelectrons from H cannot
be identified as arising from that element. However, the great strength of XPS (and XAES)
arises from the fact that the core electron binding energies (and Auger kinetic energies) for a
particular element do vary to a small extent to reflect different chemical environments of that
element. In most cases, this ‘chemical shift’ is large enough to allow adequate discrimination
of different oxidation states, with the binding energy usually increasing with increasing
oxidation state or ‘positive charge’, but not so large that the origin of a photoelectron peak
becomes uncertain. Thus, a survey scan is usually no more than an overview of the chemical
composition of a surface; a detailed surface chemical characterisation necessitates the
determination of a series of narrow, high resolution scans from which the position of each
peak to ±0.05 eV, its intensity (area above background), and its shape (including linewidth)
can be obtained. In many cases, an electron spectrum will consist of a partially resolved

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 ALAN BUCKLEY

superposition of several components, and curve fitting will be required to extract the binding
energy, intensity and shape for each component.
The most important narrow scan for the surface characterisation of sulfide minerals is that
covering the S 2p region. The S 2p spectrum from a fracture surface of the semiconductor
chalcocite is shown in Figure 2 as an example. Although there are 12 S sites (and 24 Cu sites)
in the Cu2S unit cell, the S 2p spectrum is an uncomplicated doublet with no obvious line
broadening arising from the distribution of electronic environments in the lattice. The 2p3/2
binding energy of 161.55 eV is within the range observed for most monosulfide minerals,
which is from 160.6 eV for galena to 161.7 eV for millerite. By contrast, the S 2p spectrum from
a chalcocite surface abraded in air and subsequently washed with water (Figure 2) does not
appear to comprise one uncomplicated doublet. It is certainly different from the spectrum for
the fracture surface, most probably because of the superposition of a second doublet from
an altered, S-rich (Cu-deficient) environment at a binding energy near 162.3 eV arising from
loss of Cu during the abrasion and washing. Similar, atypically high S 2p3/2 binding energies
are observed for unaltered heazlewoodite, Ni3S2 (162.35 eV) and for the five-coordinate S
in pentlandite, (Ni,Fe,Co)9S8 (162.2 eV). The corresponding values for the disulfides such as
pyrite and vaesite (NiS2) are normally in the range 162.4 to 162.7 eV. In between those values
for the disulfides and that for elemental sulfur, S8 (163.6 eV), are the 2p3/2 binding energies for
the oligosulfides (Buckley et al, 1988) and severely metal-deficient sulfide lattice environments
(Buckley and Walker, 1988). The values for S-O species such as sulfite (~166.5 eV) and sulfate
(~169 eV) are significantly higher than those for S with a zero or negative oxidation state.
The S 2p spectrum from essentially unaltered covellite (Figure 3) is much more complicated
than that from chalcocite for at least two reasons. Firstly, there are two quite different
S environments in the unit cell of covellite (CuS but often represented as Cu2S.CuS2), a
monosulfide giving rise to a doublet with a 2p3/2 binding energy of 161.6 eV, and a disulfide
giving rise to a doublet of twice the intensity of the former at 162.4 eV. The monosulfide
2p1/2 component is buried underneath the disulfide 2p3/2 component. Secondly, covellite
has metallic conductivity; consequently, the lineshape of individual components will be
asymmetric, with a ‘tail’ on the high binding energy side arising from the high density of

S 2p

Abraded

Fractured

168 166 164 162 160

Binding Energy (eV)
FIG 2 – S 2p spectrum from chalcocite fracture surface (lower spectrum) and
surface abraded in air and subsequently washed with water (upper spectrum).

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FIG 3 – S 2p spectrum from covellite.

states at the Fermi level (Doniach and Sunjic, 1970). XPS data analysis software packages
usually have at least one asymmetric lineshape that can be used to help fit such spectra. To
further complicate an already complicated situation, there may also be broad contributions to
the spectrum at 2–3 eV higher, binding energy from each principal component arising from
energy loss processes. Fortunately, such energy loss contributions are usually of low intensity
relative to the principal photoelectron peaks, but their possible presence must always be kept
in mind when subtleties are introduced into spectral interpretation. From a practical point
of view, the best way to approach this complexity is to interpret changes in spectra resulting
from a flotation-related treatment.

X-ray excited Auger electron spectra

The Cu 2p and Cu LMM spectra for several sulfide minerals and Cu metal are shown in
Figure 4. It can be seen that there are only subtle differences in the Cu 2p spectra for all
the sulfides, notwithstanding the significant differences in structure. In particular, the
2p3/2 binding energy for each sulfide is in the relatively narrow range 931.95 to 932.4 eV,
compared with the value of 932.6 eV for Cu metal. It is not unusual for metal sulfides of
the same formal oxidation state to have core electron binding energies that are similar and
also close to, or even slightly less than, those for the corresponding metal. For example, the
Ni 2p3/2 binding energies for NiS, (Ni,Fe)9S8, Ni3S2 and Ni metal are 853.15, 852.9, 852.8 and
852.7 eV, respectively. All Cu sulfides are Cu(I), even CuS and CuS2. By contrast to the quite
similar Cu 2p spectra, it is evident from Figure 4 that there is a much greater difference
in the Cu LMM than the Cu 2p spectra for the various sulfides. Such differences in X-ray
excited Auger electron spectra can be extremely useful, especially when investigating
collector adsorption on Cu- and Ag-containing sulfides, and high-resolution narrow scan
Cu LMM and Ag MNN spectra should always be collected at the same time as the Cu 2p
and Ag 3d photoelectron spectra.

Analysis depths
The analysis depths associated with S 2p and Cu 2p electrons are quite different. For excitation
by 1486.6 eV X-rays, S 2p photoelectrons would have a kinetic energy (KE) of about 1487 - 162
= 1325 eV while the corresponding Cu 2p value would be 1487 - 932 = 555 eV. The IMFP for
electrons in solids increases approximately in proportion to √KE beyond a minimum at about
50 eV, so the Cu 2p photoelectrons would be significantly more surface sensitive than the S
2p. While this is of no consequence for a fairly thick surface layer that is uniform throughout
its depth, it can be of crucial importance for non-uniform surface layers, for example in a
comparison of the Cu activation of pyrite and sphalerite. The analysis depth associated with

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 ALAN BUCKLEY

A
A
B
B

C
C

D
D

E E

FIG 4 – Cu 2p and Cu LMM spectra from (A) copper metal; (B) chalcocite; (C) covellite; (D) bornite and (E) chalcopyrite.

Cu 3p photoelectrons, which have a binding energy near 77 eV, is closer to that for S 2p
electrons. Thus, the analysis depth for conventional XPS varies across the binding energy
range, the greatest surface sensitivity being at the highest binding energy (lowest kinetic
energy) end.
An appreciation of the magnitude of the analysis depth and its variation with photoelectron
energy is fundamental to the meaningful application of XPS to flotation-related systems. As
discussed in the introduction, for flotation it is the chemical composition of the outermost
atomic layers that is of most relevance, whereas the analysis depth for XPS varies from
about 1 nm to 5 nm. At best, then, XPS has adequate surface sensitivity, but away from
that maximum sensitivity, the contribution to a spectrum from the outermost atomic layers
becomes a minor one.
It is difficult to provide a precise value for the analysis depth. The intensity of photoelectrons
escaping from a surface through a distance x in a specimen is proportional to (1 - e-x/λ), where
λ is the attenuation length (which takes into account elastic as well as inelastic scattering).
Thus, 63 per cent of the intensity would arise from x = λ, 86 per cent would arise from x =
2λ, and 95 per cent would arise from x = 3λ. In practice, a thickness of 3λ is usually taken as
the thickness analysed, but as explained below, the relationship between that thickness and
the surface layer depth analysed depends on the photoelectron take-off angle (θ). For 1 keV
electrons, λ is of the order of 1–2 nm.

Surface charging and its compensation

Fortuitously, most sulfide minerals have either metallic conductivity (eg pentlandite) or are
low band-gap semiconductors (eg galena, chalcopyrite) with only a few being large band-gap
semiconductors (eg sphalerite). Some of the important oxide minerals also have relatively
high electrical conductivities, including cuprite, magnetite and cassiterite, but most oxides
have high resistivity. Unless purposely isolated electrically from an electron spectrometer
specimen stage, high conductivity minerals do not normally become positively charged as
a result of photoemission. By contrast, the surface layers of minerals with higher resistivity

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can become positively charged, even when a sample is in good electrical contact with the
spectrometer specimen stage, leading not only to photoelectron peak shifting to lower kinetic
energy and hence higher apparent binding energy, but also to peak broadening. However,
when an adsorbate or altered layer is either thicker than a few nm or for some other reason in
poor electrical contact with a highly conducting mineral substrate, even those surface layers
can become sufficiently charged to noticeably affect photoelectron peak energies. With poorly
conducting minerals, and with thick altered or adsorbate layers, a small flux of low energy
(<5 eV) electrons from a flood-gun is used to ‘compensate’ for the positive charge. Although
some spectrometers now have highly effective, in-lens flood-guns, they are operated in a way
that slightly over-compensates, rather than exactly compensates, for the positive charging.
Because the specimen is usually electrically isolated when the flood-gun is in use, the surface
layers become uniformly negatively charged and hence all photoelectron peaks become
narrower and are shifted by up to the flood-gun electron energy to lower apparent binding
energy. The precise energy shift is deduced from the observed position of a peak of known
binding energy (such as the C 1s peak from aliphatic hydro¬carbons), and other binding
energies adjusted assuming that all photoelectron peaks will be shifted by the same energy
(which is a reasonable but not entirely correct approximation).

Collector submonolayer characterisation

Given an analysis depth of 3λ, and values for λ of the order of 1–2 nm for typical photoelectron
kinetic energies, XPS might not always be sufficiently surface sensitive for the characterisation
of adsorbed collector submonolayers. One such case might be when the S in a thiol collector is
the only element other than C, O and H (eg xanthate) and the collector S 2p3/2 binding energy
is close to one of those in the sulfide mineral of interest. This raises the question of whether
the surface sensitivity of XPS can be enhanced. The answer is yes, but not easily. The analysis
depth associated with any particular photoelectrons (eg S 2p) is determined not only by
their kinetic energy (and hence by the exciting photon energy) but also by how the specimen
surface is oriented relative to the electron detector. If the electron detector is aligned with the
normal to the specimen surface (an electron take-off angle of 90°), then the detected electrons
can escape through the surface layer of maximum thickness, and so the analysis depth will
be maximized (Figure 5). On the other hand, if the electron take-off angle is very small, the

h h
e-

e-

63% of
analysis
depth

FIG 5 – Schematic illustration of the effect of electron take-off angle (Θ) on X-ray photoelectron spectroscopy (XPS) analysis depth.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 275

 ALAN BUCKLEY

detected electrons will have passed furthest through the specimen for a given depth below
the surface, and the analysis depth will be minimised. However, only if the specimen surface
is a relatively smooth single particle one will lowering the electron take-off angle lead to a
marked enhancement of surface sensitivity. In practice, the minimum electron take-off angle
is ~15°, but even at that angle, the analysis depth is four times lower than for 90°. For fine
particulate specimens, reducing the take-off angle has a much smaller effect.
The other way to enhance the surface sensitivity of XPS is to lower the photon energy so that
the photoelectron kinetic energy is reduced. If there weren’t a need to also minimise the X-ray
source linewidth and complexity, reducing the photon energy would simply be a matter
of replacing the usual Al or Mg anode in the X-ray source with an anode made of another
suitable metal and utilising an X-ray line other than Kα, such as the 192.3 eV Mζ line from
Mo, but most alternative sources would require the development of a new monochromator
(Krause, 1971). Rather than go down that path, it is preferable to use a synchrotron as a source
of X-rays, as in addition to making SXPS possible, the high flux of photons of tunable energy
and aligned polarisation allows angle-resolved NEXAFS spectroscopy to be carried out. The
application of SXPS to flotation-related mineral systems is covered in a later section.

Collector multilayer characterisation

While surface charging can be considered a nuisance, it is possible to exploit the effect to
obtain valuable information on altered or adsorbed multilayers on low resistivity minerals by
the use of an in-lens flood-gun. Clearly, such an approach is not applicable to high resistivity
minerals, as a flood-gun must always be used for such samples. Given adequate mineral
conductivity, however, with the specimen earthed and the flood-gun off, photoelectron peaks
arising from the multilayer would either broaden or show semi-resolved components on
the high binding energy side because the atomic layers furthest from the mineral substrate
(closest to the solid/vacuum interface) would be in the poorest electrical contact with the
substrate. If the flood-gun was subsequently switched on with the specimen still earthed,
the photoelectron peaks from those outermost atomic layers would now be shifted to lower
apparent binding energy by up to the energy of the flood-gun electrons, depending on the
degree of electrical contact with the substrate. The degree of electrical contact would be
expected to vary with the strength of adsorption as well as the thickness and structure of the
multilayer. Comparison of the spectra obtained with the specimen earthed and flood-gun off,
specimen earthed and flood-gun on, and specimen floating with flood-gun on can often allow
differentiation between chemisorbed and physically adsorbed collector species. For example,
in such an XPS investigation it was established that for chalcocite conditioned for 10 min in
O-isopropyl-N-ethyl thionocarbamate (IPETC) at pH ~6, the adsorbed collector species were
HIPETC, CuIPETC and chemisorbed IPETC (Buckley et al, 2014). The N 1s and Cu L3M4,5M4,5
spectra determined with the flood-gun off (Figures 6a and 6b) and on (Figures 6c and 6d)
while the specimen was earthed showed that for conditioning in a relatively high IPETC
concentration, essentially all of the multilayer species HIPETC and CuIPETC were not in
good electrical contact with the substrate, and hence were almost certainly adsorbed on top
of the chemisorbed IPETC (which was in good electrical contact with the chalcocite surface).
This conclusion was based on the shifting of all the CuIPETC intensity near 915 eV in the
Cu L3M4,5M4,5 spectrum (but none of the spectrum from the underlying chalcocite), all the
HIPETC intensity near 401 eV in the N 1s spectrum, and that part of the 399 eV component
from the deprotonated N in CuIPETC in the N 1s spectrum, to lower apparent binding energy
by up to the ~4 eV energy of the flood-gun electrons.

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

A B

408 404 400 396 392 908 912 916 920 924 928
Binding Energy (eV) Kinetic Energy (eV)

C D

408 404 400 396 392 908 912 916 920 924 928
Binding Energy (eV) Kinetic Energy (eV)
FIG 6 – (A, C) N 1s and (B, D) Cu L3M4,5M4,5 spectra from an abraded chalcocite surface conditioned 10 min in
0.01 M IPETC at pH ~6 obtained with the specimen earthed and: (A, B) flood-gun off; (C, D) flood-gun on.

Surface chemical alteration during characterisation

For any collector/mineral system under investigation, in addition to the possibility of
adsorbed species desorption under UHV stimulated by secondary electrons generated
as a consequence of the X-ray photoemission, it is necessary to establish whether those
secondary electrons and/or the low energy electrons from the flood-gun (if used) might also
cause chemical alteration to some of the remaining adsorbed collector species. This can be
determined by recording spectra at the outset and again towards the end of a spectral suite
and looking for any significant changes. In general, chemisorbed thiol collectors are found
to be quite robust towards chemical alteration during analysis, but it has been observed that
hydroxamate collectors (used mostly for oxide minerals) do undergo not only desorption but
also alteration of some adsorbed species by both secondary and flood-gun electrons. These
changes, illustrated in Figure 7 by the N 1s spectra for cubanite (CuFe2S3) conditioned in
~0.02 M hydroxamate solution at pH ~9.5, must be taken into account when interpreting
the spectroscopic data (Buckley, Hope and Parker, 2014). The alteration has been interpreted
predominantly as deprotonation of the N in bidentate hydroxamate chemisorbed to Fe
atoms in the Cu-Fe sulfide by intramolecular transfer to result in chemisorbed monodentate
hydroxamate (Buckley and Parker, 2013).

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 ALAN BUCKLEY

A B

408 404 400 396 408 404 400 396

Binding Energy (eV) Binding Energy (eV)

C D

404 400 396 392 404 400 396 392

Binding Energy (eV) Binding Energy (eV)

FIG 7 – N 1s spectra from a cubanite fracture surface conditioned 10 min in ~0.02 M hydroxamate at pH 9.5 with specimen: (A–C)
earthed; (D) floating, and with: (A) flood-gun off, at the outset; (B) flood-gun off, at end of initial spectral suite; (C, D) flood-gun on.

Spatial resolution and XPS imaging

Some degree of spatial resolution in XPS can be achieved either by using a small X-ray spot
or by accepting electrons from only a small area of the surface. Areas of less than 150 μm in
diameter can be analysed in high energy resolution spectrometer mode, however, for rough
mineral surfaces, the minimum analysis area would be closer to 500 μm in diameter. Most
modern spectrometers can also be operated in imaging mode, in which spatial resolution of
better than 3 μm is achievable, but that capability is rarely used.

Synchrotron X-ray photoelectron spectroscopy (SXPS)

SXPS for surface characterisation requires an appropriate soft X-ray beam-line and a suitable
end-station. It is preferable for the beam-line to cover as much of the soft X-ray energy range
as possible so that the relevant core levels can be studied both at maximum and at much
lower surface sensitivity to enable surface and subsurface information to be obtained for the
same specimen. The ideal situation is to be able to assemble a non-destructive chemical depth
profile for the S or O and metal(s) in the mineral, and for any other key elements in surface
modifiers such as adsorbed collectors. In this regard it should be reiterated that depth profiles
obtained by ion beam sputtering rarely provide accurate chemical information because of
alteration by the ion beam. An X-ray energy range of 100 to 1500 eV would be considered

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good for mineral studies, and one covering 100 to 2500 eV (which also encompasses the S
K-edge near 2470 eV) would be ideal. In the soft X-ray range, the photon energy is normally
selected by means of a grating monochromator. It is not unusual for more than one grating to
be required to span the full energy range, and for the X-ray linewidth and flux to vary across
the energy range covered by each grating. Thus, photon energy tunability comes at the cost
of resolution varying with energy, but the available flux is usually sufficient to maximise
resolution when necessary. The X-ray ‘spot’ size on the specimen depends on the beam-line,
but it is rarely bigger than 3 × 0.5 mm and is typically 0.5 × 0.1 mm. Because of the high
flux, specimen charging can be a problem with poorly-conducting materials (such as pure
sphalerite), even when a low energy electron flood-gun for charge compensation is employed.
Also, because of the high flux, the possibility for beam damage to the specimen is greater than
in conventional XPS, but in practice, it is more likely that the high flux will be used to improve
resolution (by narrowing slits, for example) than to reduce data acquisition time.
Synchrotron X-ray beams are horizontal, therefore an end-station suitable for SXPS and
NEXAFS spectroscopy is essentially a high-quality XPS instrument with the electron energy
analyser oriented so that its lens is horizontal, with an optimally positioned NEXAFS partial
yield detector, with the specimen mounted on a five-axis manipulator, and with the specimen
handling facilities necessary for investigating mineral fracture surfaces bearing adsorbed
collector species. The end-station on the soft X-ray spectroscopy beam-line at the Australian
Synchrotron is shown in Figure 8. That end-station, which was designed to facilitate minerals
processing research, allows liquid nitrogen cooling in the entry lock, preparation chamber
and analyser chamber to retain any moderately high vapour pressure reaction products on a
specimen surface, has the entry lock within a glove box that can be flushed with an inert gas,
and has a double-blade cleaver for the preparation of mineral fracture surfaces under UHV.
Specimen transfer between the entry lock and various chambers is via a rotary distribution
mechanism. End-stations enabling minerals processing research are available on soft X-ray
beam-lines at most synchrotrons.

FIG 8 – The end-station on the soft X-ray spectroscopy beam-line at the Australian Synchrotron.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 279

 ALAN BUCKLEY

The enhancement of surface sensitivity achieved by ensuring that the photoelectrons of

interest are ejected with a kinetic energy of ~50 eV is illustrated by the S 2p spectra determined
at photon energies ranging from 800 to 210 eV for a Cu-activated fracture surface of relatively
pure sphalerite (Figure 9). It can be seen that at a photon energy of 800 eV, the altered S
environments at the Cu-activated surface are barely evident, whereas at 210 eV, the surface
sensitivity is sufficient to reveal that there are two high binding energy components. The sulfur-
rich composition of the outermost layers, which may arise as a result of limited oxidation after
the Cu-activation, would be expected to impart hydrophobicity to the treated sphalerite.
One of the most convincing demonstrations of the additional information that can be
obtained by progressively increasing the photon energy from the value corresponding to
maximum surface sensitivity to obtain a non-destructive chemical depth profile has been
provided by Szargan et al (1997) for 2-mercaptobenzothiazole (MBT) adsorbed from 10–4
M solution at pH 9.3 on galena fracture surfaces. The S 2p spectrum determined at photon
energies of 210–480 eV revealed (Figure 10) that a chemisorbed monolayer of MBT was
covered by the multilayer species ‘(MBT)2’, or more correctly 2,2’-dithiobis(benzothiazole).
All four S atoms in the dithiolate have a 2p3/2 binding energy near 164 eV, similar to that for
the endocyclic S in chemisorbed MBT, whereas the value for the exocyclic S in chemisorbed
MBT is near 162 eV. Fortuitously, the S 2p doublet for the galena substrate is at a binding
energy sufficiently low to not interfere too badly with the S 2p peaks from the collector.
Another advantage of having the ability to select the photon energy is the possibility to
vary relative photoionisation cross-sections. For example, in XPS at 1487 eV, the S 2p:Pb 4f
photoionisation cross-section ratio is 0.07:1 (Goldberg, Fadley and Kono, 1981), so that the Pb
4f intensity is much greater than the S 2p (Figure 11). This in itself would not be a problem,
but because of the disparate cross-sections, the background under the S 2p spectrum is
complicated by energy loss structure associated with the Pb 4f spectrum situated only 20 eV
to lower binding energy. At a photon energy of 200 eV, near maximum S 2p surface sensitivity,

A B

172 168 164 160 172 168 164 160

Binding Energy (eV) Binding Energy (eV)

C D

170 166 162 158 170 166 162

Binding Energy (eV) Binding Energy (eV)

FIG 9 – S 2p spectra for Cu-activated sphalerite determined at photon energies of (A) 800 eV; (B) 400 eV; (C) 260 eV and (D) 210 eV.

280 FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

IV
S2p
II
III

hv = 480 eV

hv = 350 eV

hv = 240 eV

hv = 210 eV

175 170 165 160

Binding Energy [eV]

FIG 10 – S 2p spectra for 2-mercaptobenzothiazole adsorbed on galena determined at different photon energies (Szargan et al, 1997).

the cross-section ratio is 4.4:1, so that now the S 2p spectrum is much more intense than the
Pb 4f, and it can be difficult to extract chemical information from the Pb 4f peaks. However,
at a photon energy of 250 eV, the cross-section ratio is close to 1:1 while both S 2p and Pb 4f
photoelectrons remain quite surface sensitive.
A major advantage of the ability to tune the photon energy is that X-ray absorption
spectroscopy (XAS) becomes feasible. For surface science and/or for the soft X-ray region, it is
the near-edge structure in the X-ray absorption spectrum that is of interest.

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy

NEXAFS spectroscopy (Stöhr, 1992), also known as X-ray absorption near-edge structure
(XANES) spectroscopy, can be a powerful surface and near-surface characterisation technique
in its own right, but is even more powerful when it complements XPS or SXPS data. The fine
structure that is observed in XAS can extend to several hundred eV above the absorption
edge, but it is the structure in the near-edge region, typically 20 eV above the absorption
edge, rather than the extended structure that is of more interest for flotation-related systems
because in the soft X-ray range there will almost certainly be interference from other
absorption edges in the extended structure region. Notwithstanding the demonstrated value

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 281

 ALAN BUCKLEY

Pb 4f

S 2p

165 160 155 150 145 140 135

Binding Energy (eV)

FIG 11 – S 2p/Pb 4f spectrum from galena determined at a photon energy of 1487 eV.

of NEXAFS spectroscopy in flotation research, the technique has been deemed too specialised
to be included in this Metallurgical Guide, and interested readers are encouraged to refer to
relevant journal reports (eg Goh et al, 2006a, 2008).

Static secondary ion mass spectrometry (static SIMS)

Conventional XPS is the surface chemical characterisation technique most likely to be found in
a surface science laboratory, and if there is another instrument in that laboratory to augment
the XPS equipment, it is likely to be a secondary ion mass spectrometer. In secondary ion
mass spectrometry, a primary beam of positive ions incident on the surface of a specimen
ejects positive ions, negative ions, electrons and neutral species, and the mass-to-charge (m/z)
ratios of those positive and negative secondary ions are determined (Briggs and Seah, 1990b;
Benninghoven, 1994). The primary beam can consist of inert gas ions, or more typically ions
such as 69Ga+ or 197Au+ from a liquid metal ion gun source. Those ions can be quite energetic,
25 keV being not unusual, and SIMS is an inherently destructive technique. SIMS can be static
or dynamic. In dynamic SIMS, the primary ion dose on the specimen is high, and the surface
and subsurface layers of the specimen are progressively sputtered or etched to provide
steady-state elemental composition information as a function of depth below the original
surface. The information is not chemical, as the ion beam can alter the chemical species in the
material underlying the layers removed by selective sputtering. In static SIMS, the total ion
dose on a specimen area analysed is limited to less than 1013 ions.cm-2, so that statistically, no
primary ion hits the same part of the surface twice. Thus, static SIMS is no less destructive
than dynamic SIMS; the fundamental difference is that only the outermost surface layer that
has not been damaged previously by the ion beam is analysed in static SIMS, and hence static
SIMS is highly surface sensitive. Typically, a primary ion beam of diameter ~0.2 μm would be
rastered over a 150 × 150 μm area of a specimen surface. In static SIMS, the secondary ion m/z
is usually determined by means of a time-of-flight mass analyser, in which case the technique

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is called ToF-SIMS. The technique is a UHV-based one, but surprisingly, not all spectrometers
have the facility to cool the specimen before and during analysis. In ToF-SIMS, the primary
ion source is operated in pulsed mode, and a typical repetition rate of 5 kHz gives a mass
spectral range to m/z 1440 with resolution of at least 0.05.
There are several general comments that should be made about static SIMS. The first is that
the primary ion beam usually ejects more neutral species than ions; consequently, there is
no necessary relationship between the abundance of an ion peak at a particular m/z and the
surface concentration of the species giving rise to that peak. Some ions are more stable than
others, and for a given specimen, the intensities of peaks from more stable ions are expected
to be greater than the intensities of peaks from less stable ions. In particular, some species
are more stable as positive ions than negative, or vice versa, therefore it is almost always
better to determine both positive and negative secondary ion mass spectra. For an organic
adsorbate such as a collector, it is possible that only collector fragment ions will be detected
rather than the parent ion (of mass equal to the complete collector radical). In practice, and
with good reason, it is assumed that negligible interaction of ions occurs between ejection and
detection, so that if a substantial ion of a species is detected, then that species is most probably
present at the specimen surface as a discrete entity or as a fragment of a larger entity. The
exception to this assumption is the loss or gain of hydrogen. Hydrogen is often a common
constituent of the vacuum in the vicinity of a material under primary ion bombardment, and
it is not unusual to observe both positive and negative ions that have an m/z one or two atomic
mass units (amu or Da) greater than expected. These observations are not artefacts of an
incorrectly calibrated m/z scale, but it is important that the mass scale is calibrated across as
much of the range as possible with ions of unambiguous m/z. Indeed, mass scale calibration is
a critical aspect of ToF-SIMS when fragment identification is required, and when calibration
difficulties are exacerbated by mineral specimens being rough at the µm level. Most organic
fragment ions of unambiguous identity, such as CH3+, C2H5+, C3H7+, CH⁻ or C2H⁻, have low
mass values, in which case extensive extrapolation is required in order to determine the mass
values of large ions. Elemental ions such as Cl⁻ or K+ would normally be available too, but
it is generally accepted that if molecular ions are of primary interest, atomic ions are best
avoided in the calibration procedure, and it is presumed that the same advice would apply
to organometallic secondary ions. ToF-SIMS mass calibration difficulties have been discussed
by Green, Gilmore and Seah (2006).
As explained below, the unambiguous identification of some ions can require high m/z
resolution, however, for most of the ions encountered in systems related to mineral flotation,
an m/z resolution of 0.05 is usually sufficient. The identification of metal-containing ions is
often facilitated by the diagnostic stable isotopic ratio that is reflected in the cracking pattern.
For example, as can be seen in Figure 12, Cu-containing ions give rise to doublets with
components of intensity ratio approximately 2:1 separated by 2 amu reflecting the 63Cu to 65Cu
ratio of 69:31, and Ag-containing ions produce doublets with components of approximately
equal intensity separated by 2 amu reflecting the 107Ag to 109Ag ratio of 52:48. Ions containing
a single Pb give rise to triplets of intensity ratio ~1:1:2 separated by 1 amu because the 206Pb to
207
Pb to 208Pb ratio is 24:23:52. The natural abundance of the 204Pb isotope is only 1.48 per cent.
Identification of a peak at m/z 28, on the other hand, would require a mass resolution better
than 0.05, as CO would be at m/z 27.995 and C2H4 would be at m/z 28.031.
Secondary ion mass spectra are usually tedious to interpret, but they can contain chemical
bonding information, and some of the findings from static SIMS data for sulfide mineral/
collector systems have been surprising. For example, it is evident from Figure 12 that Cu(DTP)2–

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 ALAN BUCKLEY

S _
A DTP– Cu(DTP)H Cu(DTP)2
3.5 0.08 0.10
3.0 0.06
2.5
2.0 0.04 0.05
1.5
1.0 0.02
0.5
0.0 0.00 0.00
185 190 248 250
Cu2S – DTP

426 428 430 432 434 436 438 440

0.06 0.10
1.2
1.0
0.8 0.04
0.6 0.05
0.4 0.02
0.2
63 79 95 111 0.0 0.00 0.00
185 190 248 250 426 428 430 432 434 435 436 440

B 0.008
Ag(DTP)H– 0.05
Ag(DTP)2–
0.006 0.04
0.004 0.03

DTP– 0.002
0.02
0.01
185 0.000
Ag2S – DTP

0.00
292 294 472 474 476 478 480 482

0.06 0.04
0.04 0.03
0.02
0.02
0.01
0.00 0.00
292 294 472 474 476 478 480 482

0 100 200 300 400 500

m/z

FIG 12 – Negative secondary ion mass spectra for monolayer (upper spectrum) and multilayer
(lower spectrum) diethyl dithiophosphate (DTP) adsorbed on (A) chalcocite and (B) silver sulfide.

ions were detected for multilayer diethyl dithiophosphate (DTP) adsorbed on chalcocite, but
not for monolayer coverage. This observation suggested that the multilayer species might
either be, or contain, Cu(DTP)2, which was not expected as XPS data had indicated that the
multilayer species was (CuDTP)n. The data from both techniques could only be rationalised
if the Cu(DTP)2 ions arose from contiguous CuDTP molecules adsorbed at the surface, or if
the multilayer was predominantly CuDTP but Cu(DTP)2 was a minor component. The Cu L3-
edge NEXAFS spectrum is particularly sensitive to the presence of Cu(II) (Pattrick et al, 1997;
Goh et al, 2006b), and a small Cu(II) peak was discernible in the Cu L3-edge NEXAFS spectrum
for multilayer DTP on chalcocite, an observation consistent with the presence of a small
concentration of Cu(DTP)2 (Goh et al, 2006c). The situation for DTP adsorbed on silver sulfide
was similar, and fortuitously because of the presence of the low concentration of Cu or Ag
dithiolate in the multilayer, it was concluded that differentiation of monolayer and multilayer
coverage by static SIMS alone would be expected for all thiol collector/sulfide systems.

Deduction of chemisorbed collector bonding from static SIMS spectra

The interpretation of the static SIMS spectra from DTP adsorbed on chalcocite was predicated
on the assumption that substantial secondary ions reflect fragments of the chemical species
actually present at a conditioned mineral surface prior to impact by primary ions, rather
than fragments from a scrambled primary ion impact zone. The question is whether such an
assumption is always justified. In static SIMS, the sputtering of material from a surface results
from a collision cascade initiated by the impact of a primary ion. For an organic adsorbate such
as a collector, there is evidence to support the view that mostly atomic and non-characteristic

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small organic fragments are generated in the central impact region, but immediately outside
this impact region, more extensive fragments that might have undergone some structural
rearrangement are produced. Further away from the impact region, the energy available for
rearrangement is lower, so that larger and minimally rearranged fragment ions (and even
parent ions) might be expected. On this basis, it might be anticipated that the larger secondary
ions should better reflect species present at the surface prior to primary ion impact and hence
be diagnostic. However, the larger the secondary ion, the greater the need to extrapolate
the mass range calibration, which means that the more relevant a secondary ion, the more
uncertain would its measured m/z value be. Extended mass range calibration is particularly
difficult for mineral specimens that are rough at the µm level, which is the case for all but
polished single piece specimens. Thus, while static SIMS can complement XPS for determining
the chemical bonding arrangement of a collector adsorbed at a mineral surface, it is unlikely
to be able to establish the bonding independently of XPS. For a multiphase mineral, on the
other hand, static SIMS can provide surface atomic information with high sensitivity that can
reveal to which mineral phase a collector is chemisorbed.

Static SIMS imaging

Because of the relatively small primary ion beam spot size, ToF-SIMS imaging is feasible to
determine the distribution of a particular species across the surface of particles from a flotation
pulp sampled as described near the beginning of this chapter. In a typical application, Hart,
Biesinger and Smart (2006) discuss 256 × 256 pixel secondary ion images (with a secondary
ion mass spectrum at each pixel) covering 100 × 100 μm areas of a slurry sample pressed into
indium foil, and the statistical methods used to identify the different mineral phases present.
Static SIMS imaging has also been used to determine the contact angle of a mineral in
a flotation system. Brito e Abreu, Brien and Skinner (2010) correlated the contact angle of
chalcopyrite conditioned in Na dicresyl DTP ([C7H7O]2PS2Na) solution at pH 10 with 69Ga+
static SIMS analyses. The chalcopyrite was relatively pure apart from an aluminosilicate
phase. Chalcopyrite particles in the size range 20–210 µm, for which contact angles were
measured by the Washburn method, and large polished plates of similar chalcopyrite were
investigated. High spatial resolution, but relatively low m/z resolution, 256 × 256 pixel mass
spectral images were obtained. Multivariate statistical techniques were used to analyse the
abundances of selected positive ions (Na, Al, Si, K, Ca, Fe, Cu, Mg, S2) and negative ions (O,
OH, F, S, SH, Cl, SO2/S2, FeO, FeOH, FeOOH, SO3, CuO, and C7H7O) in order to identify
secondary ions from species that had the greatest influence on the contact angle. Principal
component analysis enabled the identification of three negative secondary ions that correlated
strongly and linearly with the average measured contact angle; S- and C7H7O⁻ with a positive
influence, and O⁻ with a negative influence. Multiple linear regression was applied to derive
an equation for calculating the contact angle using this set of three negative secondary ion
abundances normalised to the total negative ion yield. Using that equation, the distribution
of contact angles within the flotation feed, concentrate and tail fractions could be determined,
enabling the impact of variables such as collector concentration on the hydrophobicity and
floatability of the chalcopyrite particles to be studied.
The correlation between static SIMS data and measured contact angles was extended to
single mineral batch flotation behaviour by Brito e Abreu and Skinner (2011) for chalcopyrite
conditioned for 1 min in 2 and 30 g/t dicresyl DTP, and a real chalcopyrite ore was also
investigated. The SIMS analyses showed that the contact angle distributions were not
necessarily the same for different size fractions, and that the hydrophobicity ranges of

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 ALAN BUCKLEY

concentrate and tail fractions overlapped to some extent for all samples investigated. Although
oxidation products such as FeO and FeOOH contributed to the variation in chalcopyrite
surface chemistry, they were not correlated with the contact angle. To date, a similar approach
to contact angle determination has not been applied to other valuable sulfide minerals or to
pyrite, though fundamental work on the quartz-silane system (Brito e Abreu and Skinner,
2012) suggests the methodology could be extended to different collector-mineral systems.

Scanning tunnelling microscopy (STM) and atomic force microscopy (AFM)

Scanning probe techniques can be useful in a research context, but are not widely applicable
for identifying and solving flotation plant problems. Scanning force microscopy lacks chemical
specificity, but it is useful for monitoring changes in surface morphology following collector
adsorption. It is capable of high spatial resolution provided there is a relatively flat, ~10 µm,
region on the mineral surface, and the specimen can be at atmospheric pressure. Examples of
the application of scanning probe techniques in sulfide mineral flotation research have been
described by Smart et al (2003).

Infrared (IR) reflection spectroscopy

Although the penetration depth of IR radiation is of the order of its wavelength, ie ~1 μm,
effective sub-monolayer sensitivity for IR spectroscopy may be possible for adsorbates such
as collectors on mineral substrates when no more than submonolayers are adsorbed. The two
main IR reflection techniques are the well-known attenuated total reflectance (ATR) and the less
well-known but potentially more powerful external reflection spectroscopy (ERS), also known
as reflection-absorption spectroscopy. Application of ERS for investigating the interaction of
collectors with sulfide mineral surfaces has been described in detail by Mielczarski and co-
workers (Mielczarski, Mielczarski and Cases, 1996; Mielczarski and Mielczarski, 2005) and
the underlying theory for non-metallic substrates has been treated by Buontempo and Rice
(1993). The spectra can be obtained using an FTIR spectrometer equipped with a polariser
before the sample to provide a p- or s-polarised beam, and a mercury cadmium telluride (or
similar) detector. The reflected intensity from the mineral/adsorbate interface as a function of
wavelength is usually normalised by the reflected intensity from the adsorbate-free surface.
There appears to be two disadvantages of ERS for sulfide flotation problem-solving rather
than research-only applications. The first disadvantage is that mineral slab samples (typically
20 × 15 × 10 mm) with one face highly polished appear to be required. Arguably, the surface
of a sulfide mineral that has been highly polished, ultimately with a fine abrasive such as
0.03 μm alumina, would be significantly altered. The second disadvantage, which could be
considered an advantage in a research context, is the complexity of the spectra. An external
reflection spectrum depends on the polarisation and angle of incidence of the IR beam, the
thickness and orientation of the adsorbed layer, and the optical properties of the sulfide
mineral substrate and adsorbate. Of course, in that complexity lies the valuable information,
but correct interpretation of the experimental data requires the calculation of simulated
spectra for comparison. For each specimen, spectra determined at three different incident
angles and two polarisations are typically required for a self-consistent interpretation.

Surface enhanced Raman scattering (SERS) spectroscopy

Like STM and AFM, Raman spectroscopy and SERS spectroscopy are ‘niche’ techniques that
to date have been more useful in a research context than for flotation plant problem-solving.
Raman spectra are complementary to IR spectra, in that transitions between vibrational
energy levels are involved in both, but different selection rules apply. FT-Raman spectra are

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usually determined with a laser source (eg of wavelength 785 or 1064 nm) and a cooled solid-
state detector. The spectroscopy is rendered surface sensitive by suitably ‘roughening’ the
surface of a metal substrate. FT-SERS is now a well-established technique for the examination
of adsorbed layers, including self-assembled monolayers, at electrochemically roughened Ag,
Au and Cu surfaces, and it was used in conjunction with XPS in a flotation-related context
to verify that xanthate chemisorbed on Ag without decomposition (Buckley et al, 1997). By
contrast, the value of SERS spectroscopy for investigating alteration of, and adsorption on,
sulfide mineral surfaces is only starting to be realised. Promising results have been reported
by Hope and co-workers on evaporative ‘decoration’ with gold of an MBT layer adsorbed on
chalcopyrite to induce SERS (Hope et al, 2006), and also on gold decoration of chalcopyrite
prior to interaction with MBT (Buckley et al, 2006). In the latter case, chemisorption of MBT on
the Au decoration was found to be not a problem, as adsorption on the mineral sulfide occurred
at a potential lower than for the Au. However, it cannot always be assumed that collector
adsorption on the Au nanoparticles will not occur for pre-decorated mineral surfaces. While
there is usually sufficient spectral resolution to distinguish scattering peaks from collector
chemisorbed on Au from that chemisorbed on a mineral, for example the C-S stretch in MBT
chemisorbed on Au is at ~710 nm whereas for MBT chemisorbed on the Cu in a Cu sulfide
mineral it is at ~717 nm (Woods, Hope and Watling, 2000), it might not be clear whether a
multilayer species such as (MBT)2 was adsorbed on the Au decoration or on the mineral itself.
Nevertheless, a significant strength of SERS spectroscopy is its spatial resolution, the laser
spot size being typically 5 µm in diameter, and as discussed in a later section, another major
strength is its applicability as an in situ characterisation technique.

Scanning electron microscopy

Scanning electron microscopy (SEM) is not a surface chemical characterisation technique,
but it can provide surface topographic or morphological information, and a near-surface
elemental analysis through electron stimulated X-ray emission (energy dispersive X-ray
spectroscopy, EDS or EDX). The analysis depth for EDS, which is determined by the escape
depth of the X-rays emitted by each element of interest, would be of the order of µm rather
than nm typically, and there would be insufficient energy resolution to provide chemical
bonding information.

Multi-technique ex situ surface chemical characterisation

While some of the ex situ techniques described above are individually quite powerful, in some
cases several techniques need to be applied to obtain sufficient information, especially when
adsorbed flotation collectors are involved. Examples of the complementary information
obtained from the application of XPS, SXPS, NEXAFS spectroscopy, static SIMS and SERS
spectroscopy have been provided by investigations of the adsorption of DTP and MBT on
chalcocite (Goh et al, 2006a, 2008). Nevertheless, as is usually the case, conventional XPS alone
provided a large part of the information sought.

IN SITU SURFACE CHEMICAL CHARACTERISATION TECHNIQUES

In this context, in situ is understood to mean while still wet with the flotation-related aqueous
phase, and not necessarily on-stream, although a few of the in situ techniques could be adapted
for on-stream application. Also in this context, the surface chemical composition must be
inferred from some of the in situ measurements somewhat more indirectly than for most of the
ex situ techniques. The exceptions are the molecular specificity of vibrational spectroscopies for

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 ALAN BUCKLEY

organic adsorbates. In general, the in situ techniques are used less frequently than the ex situ
techniques for flotation plant problem-solving, and hence are described here in less detail.

Electrochemical techniques
The application of electrochemical techniques in flotation research has been described
by numerous authors, including Chander and Gebhardt (1989). The most widely used
electrochemical technique is voltammetry, especially when rotating ring disc electrode and
photoelectrochemical measurements are included, but less common transient response
techniques such as AC impedance spectroscopy and chronoamperometry can be informative
for some systems. The application of linear potential sweep (uni-directional) or cyclic (bi-
directional) voltammetry for investigating the oxidation of sulfide minerals, and the interaction
of sulfide minerals with collectors and other surface modifiers such as hydrosulfide ions,
has been described by Woods in the section on Electrochemical Investigative Techniques in
Chapter 8 and elsewhere in more detail (Woods, 1996). In cyclic voltammetry, the variation of
the current that flows as the potential applied to the mineral electrode is varied in a cyclical
scan reveals the potential at which a reaction (eg chemisorption) occurs at the electrode, and
the extent of that reaction, but it does not unambiguously establish the identity of the reaction
products. The reaction products are deduced from the potential at which the reaction occurs,
the effect of pH on that potential, the inferred reactions of the products on the reverse scan,
and, if a rotating ring disc electrode arrangement is in use, the effect of rotating the electrode
to disperse soluble products. One weakness in this procedure is that inferred reactions are
usually based on bulk rather than surface reaction potentials. Thus, voltammetry is most
powerful when used as an in situ adjunct to an ex situ technique, such as XPS, that does
identify reaction products more directly (Buckley and Woods, 1993, 1995).
It should also be noted that in cyclic voltammetry, electrode reactions are driven at sweep
rates of the order of 10 mV.s⁻1, therefore it is conceivable that a reaction that takes place during
a potential scan may be different from the reaction that takes place spontaneously but slowly
at open circuit. Also, it is possible that a reaction that takes place under the steady-state
conditions of multiple scan cyclic voltammetry might be different from the corresponding
reaction that occurs during the first potential scan. Indeed, when the oxidation behaviour of
pyrite and pyrrhotite fracture surfaces was investigated by means of cyclic voltammetry, it
was found that, commencing at the rest potential, the first and second positive-going scans
for pyrite were similar, whereas they were different for pyrrhotite (Buckley, Hamilton and
Woods, 1988). However, additional information concerning the formation of a metal-deficient
lattice during initial oxidation was obtained from interpretation of those observations.
Voltammetric investigations of the interaction of sulfide minerals with flotation collectors
have revealed a pre-wave on the positive-going scan at a potential below the reversible value
for the formation of the metal thiolate for numerous sulfide/collector systems. In each case,
the charge associated with the prewave corresponds to that expected for the charge-transfer
adsorption of a monolayer of the collector (Buckley, Hope and Woods, 2003).

Infrared spectroscopy
Water is a strong absorber of IR radiation, therefore the in situ application of IR spectroscopy
is not straightforward. Nevertheless, mineral sulfide/collector systems have been investigated
by ERS under potential control in specially designed cells (eg Bozkurt et al, 1996) that enable
the mineral electrode to be positioned close to (within 100 μm of) the cell window during
the recording of single reflection spectra. Calcium fluoride is one cell window material that

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has been used. However, in most of this work, as discussed in the consideration of ex situ
techniques, the requirements of a moderately large area (~10 × 10 mm) and highly polished
mineral specimen surface are disadvantages.
As an alternative to ERS, internal reflection spectroscopy, or ATR, has been used with a
finely ground mineral in carbon paste working-electrode pressed against a Ge ATR crystal
(eg Leppinen, Basilio and Yoon, 1989). These measurements have been extremely informative
in revealing the identity of the adsorbed species for particular Eh/pH conditions, and it is
conceivable that they could be of use in flotation plant problem-solving applications.

Raman/SERS spectroscopy
Raman scattering spectroscopy has some advantages over IR spectroscopy in that water is a
weak (but not negligible) Raman scatterer, and glass cells can be used. In situ SERS spectroscopic
investigations of the interaction of flotation collectors with electrochemically-roughened Au,
Ag and Cu metal surfaces have been carried out under potential control (Hope et al, 2006).
Of more relevance for investigating flotation plant problems, the demonstration that Au
decoration of a chalcopyrite surface to impart a SERS response could be carried out prior
to interaction with MBT solution (Buckley et al, 2006) raised the possibility of determining
in situ SERS spectra of other sulfide mineral/collector systems. More recently, in situ and
ex situ SERS spectroscopy has been used to investigate the interaction at different potentials
of n-octanohydroxamate collector with sulfide minerals (such as pyrite) pre-decorated with
Au (Parker et al, 2012), and the adsorption of thiol collectors on a range of pre-decorated Cu
and Cu-Fe sulfide minerals.

CONCLUDING REMARKS
The purpose of this chapter was to assist a minerals processing practitioner to more fully
appreciate the potential role of surface chemical characterisation in optimising flotation plant
performance, and to better understand any surface analytical data obtained for that reason.
Such data might have been sought to address a particular recovery or grade issue encountered
in a flotation plant. A typical problem might have been a concentrate grade that was lower
than expected, in which case surface chemical information relating to possible explanations
such as whether or not a gangue mineral was inadvertently becoming activated, a target
mineral surface was being altered by physical contact with a non-target mineral, or the
collector used was insufficiently selective, might have been sought. The problem might have
been a recovery that was lower than expected, in which case surface analytical data providing
information on collector coverage, adsorbed collector species, mineral surface oxidation, or
co-adsorption of hydrophilic species might have been pursued. It has been explained in this
chapter that most plant performance concerns can be investigated by surface characterisation
of either pulp samples or mineral pieces appropriately conditioned in a laboratory.
A reader may have gained the impression that insufficient attention was given to some
surface chemical characterisation techniques, and excessive emphasis given to others. In one
sense this is true, but it must be kept in mind that this chapter addressed only those surface
chemical characterisation techniques of most use for optimising flotation plants. It is not
through any bias of the author, who has very little involvement in the day-to-day activities
of a surface analysis facility, that the ex situ techniques of XPS and to a lesser extent ToF-
SIMS have become the almost universal starting point for surface chemical problem-solving.
These spectroscopies have a successful track record, and accordingly, the emphasis in this
chapter has been on them. The synchrotron-based spectroscopies of SXPS and XAS deliver on

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 289

 ALAN BUCKLEY

information needed to complement that from XPS and static SIMS, especially the information
from SXPS, which has the surface sensitivity essential for the identification of some flotation
problems. The application of SXPS and XAS can only increase as more synchrotron soft X-ray
beam-lines become available in countries with vibrant minerals processing industries.

ACKNOWLEDGEMENTS
The author is grateful to Prof Rüdiger Szargan, Leipzig University, for Figure 10, Prof Bill
Skinner, University of South Australia, for the end-station photograph in Figure 8, and Dr Bill
Gong, UNSW Analytical Centre, for assistance in obtaining XPS and 69Ga SIMS data.

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spectroscopy of the integrity of xanthate chemisorbed on silver, International Journal of Mineral
Processing, 51:303–313.
Buckley, A N and Walker, G W, 1988. Sulfur enrichment at sulfide mineral surfaces, in Proceedings XVI
International Mineral Processing Congress (ed: E Forssberg), pp 589–599 (Elsevier: Amsterdam).
Buckley, A N and Woods, R, 1984. An X-ray photoelectron spectroscopic study of the oxidation of
galena, Applied Surface Science, 17:401–414.
Buckley, A N and Woods, R, 1993. Underpotential deposition of dithiophosphate on chalcocite, Journal
of Electroanalytical Chemistry, 357:387–405.
Buckley, A N and Woods, R, 1995. Identifying chemisorption in the interaction of thiol collectors with
sulfide minerals by XPS: adsorption of xanthate on silver and silver sulfide, Colloids and Surfaces A,
104:295–305.
Buckley, A N, Wouterlood, H J, Cartwright, P S and Gillard, R D, 1988. Core electron binding energies
of platinum and rhodium polysulfides, Inorganica Chimica Acta, 143:77–80.
Buckley, F M, Hope, G A, Watling, K M and Woods, R, 2006. Use of an evaporated gold SERS substrate
to detect 2-mercaptobenzothiazole on sulfide mineral surfaces, ECS Transactions, 2:49–60 (The
Electrochemical Society: Pennington, NJ).
Buontempo, J T and Rice, S A, 1993. Infrared external reflection spectroscopy of adsorbates on dielectric
substrates: determining adsorbate orientation in Langmuir monolayers, The Journal of Physical
Chemistry, 98:5825–5834.
Chander, S and Gebhardt, J E, 1989. Application of electrochemical techniques in sulfide mineral
flotation, in Challenges in Mineral Processing (eds: K V S Sastry and M C Fuerstenau), pp 90–108 (Society
of Mining Engineers: Littleton).
Chaney, R L, 1987. Recent developments in spatially resolved ESCA, Surface Interface Analysis, 10:36–47.
Doniach, S and Sunjic, M, 1970. Many-electron singularity in X-ray photoemission and X-ray line
spectra from metals, Journal of Physics C: Solid State Physics, 3:285–291.
Finkelstein, N P, 1997. The activation of sulphide minerals for flotation: a review, International Journal
of Mineral Processing, 52:81–120.
Goh, S W, Buckley, A N, Gong, B, Woods, R, Lamb, R N, Fan, L-J, Wang, Y-w, 2008. Thiolate layers
on metal sulfides characterised by XPS, ToF-SIMS and NEXAFS spectroscopy, Minerals Engineering,
21:1026–1037.
Goh, S W, Buckley, A N, Lamb, R N, Fan, L-J and Yang, Y-w, 2006a. XPS, static SIMS and NEXAFS
spectroscopic investigation of thiol adsorption on metals and metal sulfides, ECS Transactions, 2:107–
119 (The Electrochemical Society: Pennington, NJ).
Goh, S W, Buckley, A N, Lamb, R N, Rosenberg, R A and Moran, D, 2006b. The oxidation states of
copper and iron in mineral sulfides, and the oxides formed on initial exposure of chalcopyrite and
bornite to air, Geochimica et Cosmochimica Acta, 70:2210–2228.
Goh, S W, Buckley, A N, Lamb, R N and Woods, R, 2006c. The ability of static secondary ion mass
spectrometry to discriminate submonolayer from multilayer adsorption of thiol collectors, Minerals
Engineering, 19:571–581.
Goldberg, S M, Fadley, C S and Kono, S, 1981. Photoionization cross-sections for atomic orbitals with
random and fixed spatial orientation, Journal of Electron Spectroscopy, 21:285–363.
Green, F M, Gilmore, I S and Seah, M P, 2006. TOF-SIMS: Accurate mass scale calibration, Journal of the
American Society for Mass Spectrometry, 17:514–523.
Hart, B, Biesinger, M and Smart, R StC, 2006. Improved statistical methods applied to surface chemistry
in minerals flotation, Minerals Engineering, 19:790–798.

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Hope, G A, Buckley, A N, Parker, G K, Numprasanthai, A, Woods, R and McLean, J, 2012. The

interaction of n-octano-hydroxamate with chrysocolla and oxide copper surfaces, Minerals Engineering,
36–38:2–11.
Hope, G A, Woods, R, Parker, G K, Watling, K M and Buckley, F M, 2006. Spectroelectrochemical
investigations of flotation reagent – surface interaction, Minerals Engineering, 19:561–570.
Kartio, I, Laajalehto, K, Suoninen, E, Karthe, S and Szargan, R, 1992. Technique for XPS measurements
of volatile adsorbed layers: application to studies of sulphide flotation, Surface Interface Analysis,
18:807–810.
Krause, M O, 1971. The Mζ X rays of Y to Rh in photoelectron spectrometry, Chemical Physics Letters,
10:65–69.
Leppinen, J O, Basilio, C I and Yoon, R H, 1989. In-situ FTIR study of ethyl xanthate adsorption on
sulfide minerals under conditions of controlled potential, International Journal of Mineral Processing,
26:259–274.
Mielczarski, E and Mielczarski, J A, 2005. Infrared spectroscopic studies of galvanic effect influence
on surface modification of sulfide minerals by surfactant adsorption, Environmental Science and
Technology, 39:6117–6122.
Mielczarski, J A, Mielczarski, E and Cases, J M, 1996. Interaction of amyl xanthate with chalcopyrite,
tetrahedrite, and tennantite at controlled potentials, Simulation and spectroelectrochemical results for
two-component adsorption layers, Langmuir, 12:6521–6529.
Parker, G K, Buckley, A N, Woods, R and Hope, G A, 2012. The interaction of the flotation reagent,
n-octanohydroxamate, with sulfide minerals, Minerals Engineering, 36–38:81–90.
Pattrick, R A D, Mosselmans, J F W, Charnock, J M, England, K E R, Helz, G R, Garner, C D and
Vaughan, D J, 1997. The structure of amorphous copper sulfide precipitates: an X-ray absorption
study, Geochimica et Cosmochimica Acta, 61:2023–2036.
Ruppender, H J, Grunze, M, Kong, C W and Wilmers, M, 1990. In situ X-ray photoelectron spectroscopy
of surfaces at pressures up to 1 mbar, Surface Interface Analysis, 15:245–253.
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particular reference to the effects of particle size, International Journal of Mineral Processing, 42:169–190.
Shchukarev, A, 2006. XPS at solid-solution interface: experimental approaches, Surface Interface Analysis,
38:682–685.
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Smart, R StC, Amarantidis, J, Skinner, W, Prestidge, C A, La Vanier, L and Grano, S, 1998. Surface
analytical studies of oxidation and collector adsorption in sulfide mineral flotation, Scanning
Microscopy, 12:553–583.
Smart, R StC, Amarantidis, J, Skinner, W M, Prestidge, C A, La Vanier, L and Grano, S R, 2003. Surface
analytical studies of oxidation and collector adsorption in sulfide mineral flotation, in solid-liquid
interfaces (eds: K Wandelt and S Thurgate), Topics in Applied Physics, 85:3–60 (Springer: Berlin).
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Szalkowski, F J, 1977. The characterization of surfaces by electron spectroscopy, Journal of Colloid and
Interface Science, 58:199–215.
Szargan, R, Uhlig, I, Wittstock, G and Roßbach, P, 1997. New methods in flotation research – application
of synchrotron radiation to investigation of adsorbates on modified galena surfaces, International
Journal of Mineral Processing, 51:151–161.
Trahar, W J, Senior, G D and Shannon, L K, 1994. Interactions between sulphide minerals – the
collectorless flotation of pyrite, International Journal of Mineral Processing, 40:287–321.
Wang, X, Forssberg, K S E and Bolin, N J, 1989. Adsorption of copper (II) by pyrite in acidic to neutral
pH media, Scandinavian Journal of Metallurgy, 18:262–270.

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Woods, R, 1996. Chemisorption of thiols on metals and metal sulfides, in Modern Aspects of Electrochemistry
(eds: J O M Bockris, B E Conway and R E White), volume 29, pp 401–453 (Plenum: New York).
Woods, R, Hope, G A and Watling, K, 2000. A SERS spectroelectrochemical investigation of the
interaction of 2-mercaptobenzothiazole with copper, silver and gold surfaces, Journal of Applied
Electrochemistry, 30:1209–1222.
Zachwieja, J B, McCarron, J J, Walker, G W and Buckley, A N, 1989. Correlation between the surface
composition and collectorless flotation of chalcopyrite, Journal of Colloid and Interface Science,
132:462–468.

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 CHRISTOPHER J GREET

Appendix – Practical examples of using surface

chemistry to identify problems in flotation plants
Christopher J Greet

ABSTRACT
The application of surface analysis techniques to solving problems in flotation plants can
provide tremendous insights into why things have happened. It is also important to recognise
that surface analysis is not a ‘magic bullet’, but data that complements information collected
from plant metallurgical surveys, recovery-by-size analysis and pulp chemical surveys. This
appendix aims to complement the information provided in Chapter 9 with some practical
examples.

INTRODUCTION
Three examples are provided where surface analysis techniques have been used in tandem
with pulp chemistry and classical metallurgical tests to identify the root cause of the problem.
This has led (potentially) to a more focused solution.

CASE STUDY 1 – INVESTIGATING POOR GALENA FLOTATION AT HELLYER

Pulp chemistry survey
The AMIRA P260 Project – ‘Iron Sulphide Interactions and Their Influence on Sulphide
Mineral Flotation’ found that all minerals within flotation pulps, at Hellyer, were extensively
covered with thick layers of hydroxide oxidation products (AMIRA, 1991). Further work
(Greet, 2002) was conducted to determine where oxidation occurred within the Hellyer circuit.
Both pulp chemical measurements (Eh, pH and dissolved oxygen) and solution analysis data
(ethylene diaminetetraacetic acid (EDTA) extractions), through the grinding and copper/lead
rougher flotation circuits, were collected and analysed.
In general, the Eh profiles (Figure A1) through the grinding and copper/lead rougher
flotation circuits, at Hellyer, were similar to those reported for other lead/zinc concentrators
(Woodcock and Jones, 1970; Grano et al, 1995). The Eh increased from reducing values (-50 mV)
in the grinding circuit to oxidising potentials (+20 mV) in lead rougher flotation. The pulp
potential became more reducing through the grinding chain (semi-autogenous grinding mill
 ball mill  tower mill), as contact with the forged steel grinding media increased (through
anodic oxidation), and also because air ingress into these mills was progressively reduced.
The Eh rose sharply across the first two copper rougher cells then reached a plateau in the last
copper rougher cell and the lead rougher circuit. The slight reduction in Eh in conditioning
tank 04A and the lead high intensity conditioning cell was associated with the addition of
sodium cyanide to the pulp and the exclusion of air from these units.
The pH profile (Figure A1) through the primary grinding circuit showed an increase, which
coincides with the addition of lime to the grinding circuit to pH 9.5. The decrease in pH
between the secondary cyclone overflow and the copper rougher feed was accompanied by
an increase in the Eh and can be explained by simple water equilibria . Both the pH and the
Eh increased across the copper rougher circuit, indicating that some oxidative reactions were

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

120 10.0
100
80

Eh, mV (SHE) and DO, %

60 9.0

40
20

pH
8.0
0
-20
-40 7.0
-60 Grinding Copper rougher Lead rougher circuit
-80 circuit circuit

-100 6.0

er
s

ed
f

il

il

il

il
il

il

il

il
f

o/
o/
u/

ta

ta
ta

ta
ta

ta

ta

ta
ee

at
fe
e
e
en

E
C

G
F
rf

w
on
on

04
D
01

01

04

04
01

04

04
he

s
re

04
cl

es
cl

Circuit position
sc

ug
cy
cy

oc
ro
SM

y
y

Pr
ar
ar

u
D

nd

C
im
Pr

co

Eh Dissolved oxygen pH
Se

FIG A1 – Pulp chemical measurements (Eh, pH and dissolved oxygen) through the grinding and copper/lead rougher flotation circuits.

occurring. Lime was added to conditioning tank 04A, and the pH was gradually reduced
through the lead rougher circuit. This corresponded to an increase in Eh and was explained in
terms of water equilibria1.
The Eh-pH changes through the circuit can be more readily observed in Figure A2. (Note:
The diagonal lines in this graph are parallel to the water-oxygen line.) Changes that are
approximately parallel to the water-oxygen line, for example the grinding circuit (points 1 to 3,
in Figure A2) and the lead rougher circuit (points 8 to 13, in Figure A2), can be ascribed to the
maintenance of water equilibria. However, if the changes are approximately perpendicular to
the water-oxygen line, for example the first two cells of the copper rougher circuit (points 4
to 6, in Figure A2), then oxidative reactions are the cause. Thus, the Eh-pH data suggested that
oxidation was occurring in the copper rougher circuit.

1. It is apparent from the Nernst equation (Equation A1):

a
E = Ec + 0.059 log10 f reactants p (A1)
n a products
that there is a dependence of electrode potential on pH (Moore, 1981). Applying the Nernst equation to water results in a
Pourbaix diagram that describes three domains, separated by lines of equilibria. The upper most of these is the water-oxygen line
(Equation A2), above which water decomposes and oxygen is evolved and below which water is stable:
EO 2 = + 1.23 + 0.015log10 pO 2 - 0.059 pH (A2)
This can be simplified further (Johnson, 1988; Natarajan and Iwasaki, 1973) for an oxygenated aqueous solution with no well-
defined redox couples to (Equation A3):
EO 2 = + 0.9 - 0.059 pH (A3)
What does this mean in terms of chemical reactions that occur in dilute aqueous solutions? In broad terms, if the changes in Eh
and pH result in a line parallel to the water-oxygen line this means that water equilibria is being maintained. That is, any change
in Eh is directly proportional to a change in pH with a similar relationship to that expressed in Equation A3. If the changes in Eh and
pH result in line that is perpendicular to the water-oxygen line then the evidence suggested that oxidative reactions are occurring.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 295

 CHRISTOPHER J GREET

60
11
40 12 10
1
13 6
20 1. DSM screen u/s
7
2. Primary cyclone o/f
5 9
Eh, mV (SHE)

0 3. Secondary cyclone o/f

4. Copper rougher feed 8
5. 01A tail 4
-20 2
6. 01B tail
7. 01C tail
-40 8. 04A tail
9. 04D feed
-60 10. 04D tail 3
11. 04E tail
12. 04F tail
-80
13. 04G tail

-100
7.0 8.0 9.0 10.0
pH
FIG A2 – Eh-pH position of the pulp at each stage within the circuits.
Note: the diagonal lines in this graph are parallel to the water-oxygen line.

The dissolved oxygen profile (Figure A1) indicated that the oxygen levels were low through
the grinding circuit, particularly after tower milling. Once the pulp entered the copper rougher
flotation circuit, the dissolved oxygen levels began to increase, but remained comparatively
low, implying that oxygen was being consumed from the pulp, presumably as oxidation
occurred. The dissolved oxygen concentration reached saturation values in the lead rougher
circuit, and remained relatively constant after cell 04A. Thus, oxygen consumption was low
in the lead circuit and suggests that oxidation may be substantially completed prior to lead
rougher flotation.
EDTA was used in diagnostic leach tests to selectively dissolve the oxidised species from
the surfaces of sulfides to determine the level of oxidation of the various species present in
the system. The EDTA extraction data, collected using the method described by Rumball and
Richmond (1996), are presented in Figure A3.
A small increase in EDTA extractable lead occurred across the primary grinding circuit
(Figure A3) indicating that galena oxidation was reasonably limited in this part of the
circuit. However, the EDTA extractable lead levels increased dramatically across the copper
rougher section, from 2.8 to 5.2 per cent for approximately the same lead head grade. This
implied that significant galena oxidation occurred in the copper rougher circuit. The EDTA
extractable lead profile through the lead rougher showed a substantial increase in oxidised
lead. However, as the lead head grade decreased through lead rougher flotation, these data
suggest that the galena remaining in the lead rougher tailing was in a more oxidised state.
The lead EDTA extraction data therefore indicated that the majority of the galena oxidation
occurs through the copper rougher circuit. Further, the galena that reported to the lead
rougher tailing was significantly more oxidised than the galena in the lead rougher feed (ie
4.9 versus 10.4 per cent). These observations are the same as those made by Rumball and
Richmond (1996).
The EDTA extractable zinc remained comparatively low throughout the circuit (Figure A3).
The EDTA extractable iron (Figure A3) increased across the primary grinding circuit as contact
with the grinding media increased. There was a further small increase in EDTA extractable

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

12.0 1.0

10.0
0.8

% EDTA Zn and Fe
8.0
% EDTA Pb
0.6

6.0

0.4
4.0

0.2
2.0

Grinding circuit Cu rougher circuit Pb rougher circuit

0.0 0.0
s

ed

d
f

il

il

il

il

il

il

il

il
f

o/
o/
u/

ta

ta

ta

ta
ta

ta

ta

ta
e
fe

fe
ne
e
en

E
C

G
on

er

04
D
01

01

04

04
01

04

04
lo
re

04
h
cl

Circuit position
sc

ug
cy
cy

ro
SM

y
y

ar
ar

u
D

nd

C
im
Pr

co
Se

Pb Zn Fe

FIG A3 – The ethylene diaminetetraacetic acid (EDTA) extractable metal

ion analysis data for the grinding and copper/lead rougher flotation circuits.

iron through the copper rougher circuit, which may be associated with the oxidation of pyrite
in this part of the concentrator. The per cent oxidised iron then remained relatively constant
across the lead rougher circuit. It is known that the oxidation products of pyrite, for example,
FeOOH (Hiskey and Schlitt, 1982) and higher iron oxides are less soluble in EDTA (Blesa,
Rueda and Grassi, 1985) than iron hydroxides, and therefore are not as readily extracted with
EDTA. Hence, it can be claimed that the pyrite surfaces on reaching the lead rougher circuit
were coated with FeOOH and higher iron oxide species, which resulted in the passivation of
the pyrite. The lower solubilities of these species in EDTA caused the EDTA extractable iron
concentration to remain approximately the same through this part of the circuit.

Solution chemistry
A major technical issue at the Hellyer concentrator was the low galena recovery (42 per cent)
to final lead concentrate (Richmond, 1993), which is considerably lower than that achieved
by most other lead/zinc operations within Australia. So, a comparison of the lead rougher
concentrate and tailing was made.

Water analysis
The results of the water analysis performed on the lead rougher concentrate and tailing
slurries are presented in Table A1, and the corresponding X-ray fluorescence (XRF) analysis
of the solids contained in the two process streams are provided in Table A2.
The water-soluble lead, zinc, iron and magnesium concentrations were comparatively
low (less than 20 parts per million) in both the concentrate and tailing samples. Calcium
was present at significantly higher concentrations, and was marginally higher in the tailing
sample compared with the concentrate. The high calcium ion content can be attributed to the
addition of lime to the circuit as the pH modifier. These measurements compare favourably
with those made by Woodcock and Jones (1970) and Grano, Ralston and Johnson (1988), who
reported that the levels of soluble lead, zinc and iron in process streams were generally less
than 20 parts per million.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 297

 CHRISTOPHER J GREET

TABLE A1
Cation and anion analysis of water extracted from the lead rougher concentrate and tailing process streams.
Extracted species Pb rougher concentrate Pb rougher tailing
Cations
Pb2+ 8.2 ppm 1.9 ppm
Zn2+ <0.1 ppm <0.1 ppm
Fe2+/Fe3+ <0.1 ppm <0.1 ppm
Mg 2+
13.2 ppm 16.6 ppm
Ca2+ 310 ppm 410 ppm
Anions
OH- <0.1 ppm <0.1 ppm
CO32- <0.1 ppm <0.1 ppm
HCO3 -
<0.1 ppm <0.1 ppm
CN -
32.2 ppm 46.8 ppm
SO4 2-
310 ppm 402 ppm
SxOy2- 10.6 ppm 70.1 ppm

TABLE A2
X-ray fluorescence assays of the lead rougher concentrate and tailing process streams.
Stream Elemental composition (%)
Ag Pb Zn Cu Fe S Ba As Sb
(ppm)
Pb rougher concentrate 551 52.54 6.72 0.24 12.83 25.74 0.20 0.99 0.18
Pb rougher tailing 69 2.90 12.41 0.15 26.01 35.55 0.85 1.99 0.09

The anion analysis showed that hydroxide, carbonate and bicarbonate were below the
detection limit in both streams. Cyanide ions were detected in both process streams, with
marginally higher levels of cyanide detected in the tailing compared with the concentrate. The
sulfate and sulfoxy (possibly thiosulfate) levels observed in the tailing stream were slightly
greater than those recorded for the concentrate (Table A1). Although the cation analysis did
not provide a clear indication of the chemical state of the pulp, the anion data, in particular
the variations in sulfoxy species, did suggest that the tailing sample contained more oxidised
species than the concentrate.

EDTA analysis
It has been recognised by numerous workers (Shannon and Trahar, 1986; Grano, Ralston
and Johnson, 1988; Rumball and Richmond, 1996) that EDTA has the ability to solubilise
the oxidation products of sulfide minerals. However, there is still considerable debate
surrounding the solubility of sulfide minerals in EDTA solutions. Wang and Forssberg (1990)
suggest that in the presence of excess EDTA, after the ‘hydroxides’ have been removed (which
may leave a sulfur-rich surface), the EDTA continues to leach the bulk sulfide (galena, pyrite,
arsenopyrite). However, it was further suggested that the dissolution of sulfide with a sulfur-
rich surface would be slow. Pang and Chander (1992) support this view, for pyrite at least.
Thus, assuming that the dissolution of sulfide minerals with a sulfur-rich surface by EDTA is

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

slow, it is reasonable to assume that the measured concentrations of EDTA extractable ions
relate directly to the oxidation of the constituent minerals present in the pulp provided the
leach time is not excessive.
Greet and Smart (2002) describe experimental work conducted to determine the solubility
of galena and its oxidation products in EDTA. The results can be summarised as:
•• The experiments conducted demonstrated that EDTA readily solubilises lead hydroxide,
lead carbonate, lead sulfate and lead hydroxy-carbonate, all typical galena oxidation
products. Further, a 0.1 molar EDTA solution will solubilise galena oxidation products
rapidly at low concentrations, ie within five minutes. Purging the pulp with argon during
the extraction process significantly reduces the possibility of continuing oxidation during
leaching.
•• EDTA did not extract lead from galena. Continuing lead extraction with time is due to
continuous oxidation of galena.
•• A modified EDTA extraction technique, based on these observations was developed. The
new test employs argon as the purging gas, and a leach time of five minutes. Experiments
were conducted comparing the new method against other commonly used techniques.
The results of these tests suggest that the new method produces significantly lower levels
of EDTA extractable lead than the other techniques. These differences were attributed to
variations in the oxygen content of the pulp during leaching.
The results of EDTA extractions performed on the lead rougher concentrate and tailing
process streams are contained in Table A3.
The concentrations of EDTA extractable lead were similar for both process streams; however,
the significance of this data becomes apparent only when the metal content of the process
stream is considered (Kant, Rao and Finch, 1994; Rumball and Richmond, 1996). In this
example, the lead rougher concentrate assayed 52.5 per cent lead, while the lead rougher
tailing contained 2.9 per cent lead (Table A2). When these grade differences are taken into

TABLE A3
Cation and anion analysis of ethylene diaminetetraacetic acid (EDTA) solutions used in diagnostic
leach tests performed on the lead rougher concentrate and tailing process streams.
Extracted species Pb rougher concentrate Pb rougher tailing
Cations
Pb2+ 2918 ppm 2445 ppm
Zn 2+
106 ppm 184 ppm
Fe2+/Fe3+ 867 ppm 1394 ppm
Mg2+ 42 ppm 116 ppm
Ca 2+
1293 ppm 10 853 ppm
Anions
OH- <0.1 ppm <0.1 ppm
CO3 2-
<0.1 ppm <0.1 ppm
HCO3- <0.1 ppm <0.1 ppm
CN -
26.5 ppm 43.3 ppm
SO4 2-
494 ppm 660 ppm
SxOy2- 24.4 ppm 66 ppm

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 CHRISTOPHER J GREET

TABLE A4
The percentage of ethylene diaminetetraacetic acid (EDTA) extractable lead,
zinc and iron for the lead rougher concentrate and tailing process streams.
Metal ion Pb rougher concentrate (%) Pb rougher tailing (%)
Pb 0.78 15.88
Zn 0.22 0.28
Fe 0.96 1.01

account when calculating the percentage of EDTA extractable lead (or per cent oxidised lead),
significant differences are observed (Table A4):
Mass of Pb in EDTA solution
% EDTA extractable Pb = # 100
Mass of Pb in solids
Using the above equation, the percentage of EDTA extractable lead, zinc and iron for the
lead rougher concentrate and tailing process streams were determined and are presented in
Table A4.
The percentage of EDTA extractable (oxidised) lead in the tailing as a proportion of lead in
the tailing stream was about 20 times greater than that observed in the concentrate (that is,
15.9 per cent versus 0.8 per cent). This suggested that approximately 16 per cent of the lead
in the tailing sample was present as galena oxidation products, and it is proposed that the
galena reporting to the tailing is heavily oxidised compared to the galena in the concentrate.
While differences were observed in the concentrations of zinc and iron, between the lead
rougher concentrate and tailing (Table A3), the percentages of EDTA extractable zinc and
iron were determined to be similar in both process streams, with a small tendency for more
extractable (oxidised) species in the tailing.
Analysis of the anion species contained within the EDTA solutions indicated that the
sulfate content of the tailing was approximately 30 per cent greater than that reported for the
concentrate (Table A3). Again, sulfoxy species (probably thiosulfate) were observed to be in
higher concentrations in the tailing than the concentrate. Gardener and Woods (1979) showed
that in alkaline solutions galena oxidation produced both sulfate and thiosulfate, whereas
pyrite oxidation produced only sulfate (Hamilton and Woods, 1986). Thus, the presence of
higher levels of sulfoxy species in the tailing would suggest that the galena in this stream
was more extensively oxidised than the concentrate. These observations also corroborate the
comments made in relation to the cation analysis presented above.
Both the water and EDTA analysis indicated that the galena in the tailing process stream
was more heavily oxidised than the galena in the concentrate.

Surface analysis
A number of surface analysis techniques were used during this project to examine the surface
composition of particles from various flotation streams. These are listed below.

Sample preparation
In general, the same sample preparation method was used for each of the techniques
detailed below. Slurry from the process stream of interest was collected in plastic phials,
which were purged with nitrogen for two minutes and then sealed. The sealed phial was

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

then ‘snap frozen’ in liquid nitrogen and stored in a freezer until analysis could be arranged
(Smart, 1991).
Samples for examination were introduced into each instrument in much the same way. The
prepared slurry sample2 was carefully spread over the sample stub and placed into the fore-
chamber of the instrument. As this chamber was evacuated, the solution phase of the slurry
sample was evaporated off. Once the pressure in the fore-chamber was approximately the
same as that of the main chamber the sample was introduced and the analysis performed.
Several surface analysis techniques were used during this investigation to determine the
differences in surface composition of galena found in the lead rougher concentrate and
tailing process streams. X-ray photoelectron spectroscopy (XPS) was used initially. The XPS
analysis provided information about the composition of the surface, and the chemical states
of the various species detected. This technique examines an area containing a large number
of particles, and yields the average surface composition. That is, the XPS analysis is not particle
specific. Therefore, the XPS analysis did not give data regarding the surface compositional
differences between individual galena grains from the concentrate and tailing, so other surface
analysis techniques were employed. Scanning Auger microscopy (SAM) and time-of-flight
secondary ion mass spectroscopy (ToF-SIMS) were used to examine individual particles from
the concentrate and tailing process streams.

X-ray photoelectron spectroscopy analysis

In these experiments, samples of lead rougher concentrate and tailing were examined in the
‘as received’ condition. That is, the samples were taken directly from the process stream,
purged with nitrogen, sealed and frozen in liquid nitrogen, prior to transporting them to the
University of South Australia (Smart, 1991). At the University, these samples were thawed and
placed directly into the spectrometer without any pretreatment. A duplicate set of samples
was deslimed (using six cycles of sedimentation, decantation and centrifuging) with nitrogen-
purged, demineralised water in order to remove any fine particles that were suspended in the
pulp. This method also removed any dissolved species from the aqueous phase that may
precipitate out of solution and on to the surfaces of particles during the evacuation of the
fore-chamber of the XPS. The use of nitrogen-purged demineralised water as the replacement
solution was considered valid (Smart et al, 1993), and should minimise further oxidation.
Figure A4a shows a secondary electron image of the ‘as received’ lead rougher concentrate.
It is apparent that the sample contains a considerable quantity of fine (-5 micron) particles,
both free and attached to the larger grains. After desliming (Figure A4b), the surfaces of the
larger grains were observed to be reasonably free of fines. The fines remaining on the surfaces
of the larger particles were considered to be strongly bound to these particles, and therefore
were a legitimate component of the surface texture. A similar result was obtained for the lead
rougher tailing sample.
The atomic concentration data for the lead rougher concentrate and tailing samples
examined appear in Table A5.

2. In some instances, the pulp samples were pre-treated by successive sedimentation/decantation steps, with the solution being
replaced with nitrogen-purged demineralised water. This process was used to remove fine (or slimes) particles, which, as the
solution was evaporated off under vacuum, may deposit on to the surfaces of the minerals of interest and inadvertently interfere
with the surface analysis. This process also removed soluble species (ie sulfates) from solution that may precipitate out of solution
as the solution was evaporated off under vacuum.

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 CHRISTOPHER J GREET

FIG A4 – Secondary electron images of lead rougher concentrate: (A) ‘as received’;
and (B) deslimed (using six cycles of sedimentation/decantation/centrifuged).

TABLE A5
Atomic concentration data for elements detected on the surfaces of particles from the lead rougher concentrate
and tailing in the ‘as received’ and deslimed condition, using X-ray photoelectron spectroscopy (XPS).
Element Lead rougher concentrate Lead rougher tailing
‘As received’ Deslimed 'As received' Deslimed
Original Etched a
Original Etched Original Etched Original Etched
C 28.62 9.56 33.89 10.04 19.78 3.65 16.09 4.12
O 45.71 52.44 37.89 36.24 55.98 62.38 57.48 63.19
S 10.16 12.42 9.16 15.72 7.01 8.14 4.26 5.43
Pb 3.29 5.05 5.73 10.29 0.92 0.83 1.56 1.38
Zn 0.88 1.95 2.00 6.98 1.16 2.57 1.87 3.25
Cu 0.27 5.33 0.07 0.00 0.00 0.00 0.00 0.00
Fe 2.54 0.00 3.67 10.91 1.00 4.97 4.03 6.72
Al 1.69 2.65 2.81 1.99 3.32 4.30 2.99 3.99
Si 2.49 4.83 3.97 6.48 6.54 8.18 9.84 9.68
Ca 4.35 5.77 0.81 1.35 4.29 4.98 1.88 2.24
a. In most instances once data had been acquired from the original surface an etch was applied, using a 3 kV accelerated argon ion beam.
Data was then collected from the ‘fresh’ surface. At the time these experiments were conducted, it was assumed that etching
removed approximately 2.5 nm from the surface (Skinner, personal communication, 1994). The argon ion etch was applied in order to
investigate the subsurface of the minerals.

Comparing the data for the concentrate with the tailing showed that the surface carbon
concentration was significantly greater for the concentrate sample (Table A5). Presumably,
this was because of the presence of xanthate on the surfaces of the galena particles in this
stream.

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The surface oxygen concentration was considerably lower for the concentrate compared with
the tailing (Table A5). This suggested that the tailing contained a higher proportion of oxidised
species. However, if the aluminium and silicon detected on the surface are assumed to be in
the expected forms of alumina (Al2O3) and silica (SiO2), respectively, their contributions to
the surface oxygen concentration can be determined and subtracted from the original oxygen
content. Further, part of the calcium present may be as calcium sulfate. From the sulfur spectra
(Figure A5), it is known that the desliming treatment removed the sulfate from the mineral
surfaces; therefore, it can be surmised that the calcium remaining after desliming was not
present as calcium sulfate. Thus, by subtracting the calcium content of the deslimed sample from
that of the ‘as received’ sample, the concentration of the calcium associated with sulfate can be
estimated, and the associated oxygen content determined. If this value is added to the oxygen
concentrations calculated for the aluminium and silicon surface concentrations, the surface
oxygen concentration attributable to the non-sulfide gangue component can be established.
Subtracting this component from the original surface oxygen content will yield the oxygen
associated with the sulfide component of the surface. Table A6 summarises these calculations.

(1)
(1) Pb rougher concentrate - "as received"
Arbitrary units

(2) Pb rougher concentrate - deslimed

(2)
(3) Pb rougher tailing - "as received"

(4) Pb rougher tailing - deslimed

(3)

M1-xS
FeSO4
(4) PbSO4
PbX2
ZnS

FeS2 PbS

176.0 174.0 172.0 170.0 168.0 166.0 164.0 162.0 160.0 158.0

Binding energy, eV
FIG A5 – Sulfur 2p spectra for lead rougher concentrate and tailing process streams.

TABLE A6
Summary of calculations to determine the oxygen concentration associated with the sulfide mineral
component of the surface for the lead rougher concentrate and tailing process streams.
Lead rougher concentrate Lead rougher tailing
Atomic concentration of O (%) Atomic concentration of O (%)
Original O concentration 45.71 55.98
O associated with Al (as Al2O3) 1.69 × 3/2 = 2.54 3.32 × 3/2 = 4.98
O associated with Si (as SiO2) 2.49 × 2/1 = 4.98 6.54 × 2/1 = 13.08
O associated with Ca (as CaSO4) (4.35 - 0.81) × 4/1 = 14.16 (4.29 - 1.88) × 4/1 = 9.64
Total non-sulfide gangue O 21.68 27.70
Sulfide minerals O 24.03 28.28

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 CHRISTOPHER J GREET

This analysis suggested that the non-sulfide gangue surface oxygen component for the
concentrate sample was dominated by the high calcium sulfate contribution. In the tailing
sample, the alumina and silica were the major components of the non-sulfide gangue
oxygen concentration, and this can be directly attributed to the higher levels of alumina and
silica gangue minerals in this process stream. The oxygen concentration associated with the
surfaces of sulfide minerals was greater in the tailing (28.28 per cent), than that calculated
for the concentrate (24.03 per cent). This suggested that there was more oxygen associated
with the sulfide minerals in the tailing, which implied that the tailing sulfides were more
oxidised than those appearing in the concentrate. It is recognised that this interpretation
relies on uncertain assumptions based on the Si and Al speciation, and can only indicate
relative differences.
The sulfur concentration was significantly greater for the concentrate sample compared with
the tailing (Table A5), suggesting greater exposure of sulfide mineral surfaces (in particular,
galena) in the concentrate. This indicated that the tailing sample was more oxidised (that
is, less sulfur present). This assertion is further supported by an examination of the sulfur
surface to bulk ratio (the bulk solids assays are provided in Table A2), which show that the
concentrate ratio was 0.39, almost double that of the tailing (0.20).
The surface concentrations of lead, zinc and iron were generally higher for the concentrate
sample compared with the tailing (Table A5).
Argon ion etching generally increased the surface content of sulfur, lead, zinc and iron in
both cases. However, the percentage increase in the surface concentration of these elements
was usually greater for the concentrate sample, indicating that the oxidation layers were
comparatively thin on particles contained in the concentrate compared to those in the tailing.
The XPS spectra for sulfur and lead appear in Figures A6 and A7, respectively. These
figures contain the spectra for both the ‘as received’ and deslimed samples of lead rougher
concentrate and tailing. The spectra have been charge corrected to allow better comparison.
The lead rougher concentrates in the original spectra were charge shifted by 0.8 eV for the ‘as
received’ sample, and 0.6 eV for the deslimed sample. The lead rougher tailing samples were
charge shifted by a greater amount, that is 2.2 eV for the ‘as received’ sample, and 3.7 eV for
the deslimed sample. Charge shifting indicates that the surfaces being examined have some
insulating characteristics. In this case, the tailing sample was charge shifted considerably more
than the concentrate, which suggested that the particles in the tailing were more insulating
than those in the concentrate. The insulating characteristics observed in the tailing sample can
be attributed to both the higher proportion of insulating, non-sulfide gangue present, and the
propensity for the sulfide minerals to be more oxidised.
As the system under investigation is a mixture of many minerals, the assignment of specific
binding energies corresponding to known species is difficult. For example, the uncharged S
(2p3/2) signal for galena occurs at 160.4 eV (Buckley and Woods, 1984), 161.6 eV for sphalerite
(Buckley, Wouterlood and Woods, 1989), and at 161.1 eV for pyrite (Buckley and Woods,
1987). Therefore, the surface sulfide peak develops into a relatively broad emission region
accounting for the various sulfide species present (for example, galena, sphalerite, pyrite,
chalcopyrite, arsenopyrite etc).
It is immediately apparent from Figure A6 that there were differences in the spectra between
the ‘as received’ and deslimed samples. The ‘as received’ samples (for both the concentrate

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(1) (1) Pb rougher concentrate - "as received",

original surface

Arbitrary units
(2) Pb rougher concentrate - "as received",
etched surface
(3) Pb rougher tailing - "as received", original
(2) surface
(4) Pb rougher tailing - "as received", etched
surface

(3)

(4)

FeSO4 M1-xS
PbSO4 PbX2 PbS
ZnS FeS2

176.0 174.0 172.0 170.0 168.0 166.0 164.0 162.0 160.0 158.0

Binding energy, eV
FIG A6 – Sulfur 2p spectra for the lead rougher concentrate and tailing process
streams comparing the original and etched surfaces of the ‘as received’ samples.

and tailing) exhibited a sulfate signal at about 168 eV (Buckley and Woods, 1984, 1987)3,
compared with the sulfate-free spectra of the deslimed samples. The variations in the sulfide
peak (nominally 160 to 165 eV) were only slight, with an increase in the intensity of the sulfide
signal and small reductions in the contribution made by the high binding energy shoulders.
Hence, the desliming procedure resulted in the removal of sulfate, but left the remainder of
the surface sulfur species reasonably intact.
A comparison between the lead rougher concentrate and tailing spectra revealed that
significant differences existed between the two process streams. For the ‘as received’ samples,
it is apparent that the sulfate present on the surfaces of particles from the concentrate was
considerably less than that for the tailing. This is illustrated by examining the sulfide:sulfate
peak height ratio. The ratio for the concentrate was 1.6, while the ratio for the tailing was
1.2. When these surfaces were etched, the sulfate present on the concentrate was reduced
considerably, indicating that the sulfate species formed only a thin oxidation layer on the
surface of these particles. Conversely, the sulfate signal remained strong for the tailing sample
after etching, suggesting that the oxidation layers were relatively thick (Figure A6).
Examination of the sulfide region of the S(2p) spectra revealed that the signal for both
concentrate and tailing samples had strong sulfide signals corresponding to galena, at
160.4 eV (Buckley and Woods, 1984), and lead xanthate at 162.1 eV (Laajalehto et al, 1991).
A relatively small high binding energy shoulder, at 163 eV, represented the metal deficient
sulfide species (Fornasiero et al, 1994). The tailing sample also exhibited a very broad sulfide
signal, which contained galena at 160.4 eV (Buckley and Woods, 1984), sphalerite at 161.6 eV
(Buckley, Wouterlood and Woods, 1989), pyrite at 161.1 eV (Buckley and Woods, 1987), and
lead xanthate at 162.1 eV (Laajalehto et al, 1991).

3. The sulfate signal, for both the lead rougher concentrate and tailing samples, appears to occur at a binding energy considerably
greater than that reported by Buckley and Woods (1984, 1987), ie for galena 167.9 eV, and for pyrite 168.5 eV. This is due to the
insulating properties of sulfate species. That is, the sulfate signal is charge shifted to higher binding energies than expected.

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 CHRISTOPHER J GREET

The difference between the ‘as received’ and deslimed lead spectra for the concentrate
sample were only slight (Figure A7). However, the tailing spectra appeared to be very
different. The third peak, at 140.0 eV, between the Pb(4f5/2) and the Pb(4f7/2) signals for
the deslimed sample, corresponded to the Zn(3s) peak. This peak interferes with the Pb(4f)
spectra particularly when the surface concentration of lead is low. It is interesting to note that
desliming the ‘as received’ tailing sample removed sufficient lead species from the pulp to
allow the Zn(3s) peak to interfere with the Pb(4f) spectra. This suggested that some of the lead
oxidation products detected in the ‘as received’ sample were present on the surface of the
minerals as precipitated species formed during the drying process, and were loosely attached
to particles, easily removed by decantation.
There were obvious differences between the concentrate and tailing spectra. The concentrate
sample displayed very sharp, narrow lead spectra, at 137.4 eV, which corresponded to galena
(Buckley and Woods, 1984). A small high binding energy shoulder at 138.4 eV was also
detected, which corresponds to lead hydroxide (Buckley and Woods, 1984). Etching removed
all traces of the lead hydroxide high bonding energy shoulder, implying that these oxidation
layers were comparatively thin. The tailing spectra, however, was broad, with a galena signal
at 137.4 eV (Buckley and Woods, 1984), lead xanthate at 138.1 eV (Laajalehto et al, 1991), lead
hydroxide at 138.4 eV (Buckley and Woods, 1984), and lead sulfate at 139.2 eV (Buckley and
Woods, 1984) detected on the surfaces. Etching did little to sharpen the lead signal; therefore,
it can be assumed that the surface layers produced by the galena oxidation products were
considerably thicker.
Unfortunately, the XPS analysis, while providing information about the surface oxidation
state of particles in the lead rougher concentrate and tailing, does not yield data about the
location of the oxidation products. That is, where do the galena oxidation products occur in
the concentrate sample? Do the lead oxidation products remain on the galena only, or do they
precipitate on to other minerals? To answer some of these questions a number of experiments
were conducted on the lead rougher concentrate and tailing samples using more particle-
specific surface analysis techniques.

(1)
Arbitrary units

(1) Pb rougher concentrate - "as received"

(2)
(2) Pb rougher concentrate - deslimed

(3) (3) Pb rougher tailing - "as received"

(4) Pb rougher tailing - deslimed

PbS
(4) Zn(3s)
PbSO4

Pb(OH)2
PbX2

154.0 152.0 150.0 148.0 146.0 144.0 142.0 140.0 138.0 136.0 134.0

Binding energy, eV
FIG A7 – Lead 4f spectra for lead rougher concentrate and tailing process streams.

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Scanning Auger microscopy analysis

As shown in Figure A4a, the ‘as received’ pulp sample was not suitable for analysis using
SAM due to the high concentration of fine (-5 micron) particles covering the surfaces of
the coarser grains. Therefore, the desliming technique mentioned above was developed to
generate coarse, slime-free particles for analysis.
The intention of this experiment was to examine a statistically meaningful number4 of
individual grains of galena, sphalerite and pyrite from the lead rougher concentrate and
tailing. The surface composition of like minerals was then to be compared to discern if
differences existed between the two sources. Table A7 summarises the SAM data collected.
Unfortunately, no galena particles were found during the examination of the lead rougher
tailing, so a comparison could not be made. This was probably due to two factors: the
low lead assay for this stream (Table A2), and the very fine nature of the liberated galena.
However, it is interesting to note that the galena surface, in the concentrate, comprised mostly
of lead, carbon and sulfur, with small concentrations of oxygen and iron (Table A7). Several
comments are warranted:
•• From the XPS analysis, it is likely that the majority of the carbon was present as both
hydrocarbon contamination (which occurred during sample preparation), and collector.
•• The lead to sulfur ratio was found to be close to that of ‘pure’ galena (that is, for ‘pure’
galena the ratio is 6.4, while the SAM result was 5.8). This suggested that the reactions
occurring at the surface of the concentrate galena (that is, oxidation, collector adsorption
etc) appear to be congruent in nature.
•• The oxygen concentration was low (7 atomic per cent).
•• The iron present was probably due to the adsorption of iron hydroxides generated
through the oxidation of pyrite and the corrosion of the grinding media (high carbon,
low alloy steel).
A comparison of sphalerite from the lead rougher concentrate and tailing process streams
was not possible. Although the surface composition of the sphalerite in the concentrate was

4. Where grains were detected a minimum of 15 particles were analysed.

TABLE A7
Average atomic concentrations of elements detected on the surfaces of galena, sphalerite
and pyrite grains examined from the lead rougher concentrate and tailing process streams.
Mineral/process stream Element, atomic %
C O S Pb Zn Fe
Galena
Lead rougher concentrate 20.1 7.0 10.0 57.6 0.0 5.3
Lead rougher tailing - - - - - -
Sphalerite
Lead rougher concentrate 16.4 10.4 32.6 6.1 34.5 0.0
Lead rougher tailing - - - - - -
Pyrite
Lead rougher concentrate 23.5 5.5 43.2 0.0 0.0 27.8
Lead rougher tailing 21.7 23.6 28.2 3.0 0.0 23.4

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 CHRISTOPHER J GREET

determined, it was not possible to obtain any meaningful data about the surface composition
of the tailing sphalerite due to charging. However, the fact that the tailing sphalerite was charging
and the concentrate sphalerite did not, suggested strongly that the surface composition of sphalerite
from the two sources was significantly different.
The concentrate sphalerite composition was mainly zinc, sulfur and carbon, with minor
quantities of oxygen and lead (Table A7). No iron was detected on the surface of the sphalerite.
Again, several comments are worth noting:
•• Sulfur was close to its stoichiometric value (for zinc sulfide, 32.92 weight per cent), but
the zinc content was considerably below the expected value (67.08 weight per cent). This
suggested that the dissolution of sphalerite, in this case, was through the removal of zinc
ions from the surface, while leaving the sulfur intact. It is assumed, therefore, that the
dissolution process leaves a zinc deficient sulfide surface.
•• The surface carbon was present as both hydrocarbon contamination and residual collector.
•• The presence of lead (6.1 atomic per cent) on the surface was of great interest, and may be
responsible for the inadvertent activation of sphalerite, and subsequent recovery into the
lead rougher concentrate.
•• The oxygen present was most likely the result of lead hydroxide species on the surface.
Particles of pyrite were detected and examined in both the concentrate and tailing samples,
so a comparison was possible. Carbon, oxygen, sulfur and iron were detected on the surface
of both samples; however, lead was found on pyrite particles in the tailing only (Table A7).
There were apparent differences in the surface composition of the pyrite grains:
•• The oxygen content of the pyrite in the concentrate was significantly lower (5.5 atomic per
cent) compared to the tailing (23.6 atomic per cent). This indicated that the pyrite in the
concentrate was considerably less oxidised than that reporting to the tailing.
•• The sulfur concentration of the pyrite in the concentrate (43.2 atomic per cent) was
dramatically greater than that of the tailing pyrite (28.2 atomic per cent). This suggested
that the surfaces of the pyrite in the concentrate were sulfur rich, which was probably the
main contributor to its recovery into the concentrate.
•• Carbon and iron levels were similar for the pyrite from both sources.

Time-of-flight secondary ion mass spectroscopy analysis

Samples of lead rougher concentrate and tailing were examined using the ToF-SIMS at the
University of New South Wales in order to determine the surface composition of galena
particles contained in these process streams. In these experiments, mineral particles (from a
slurry sample) were pressed into freshly cut indium foil, and mounted on a sample stub prior
to introducing the sample into the fore-chamber of the ToF-SIMS. An area of approximately
200 by 200 microns was analysed, in positive mode only. Chemical maps and an average mass
spectrum were collected for each sample.
The data collected in this analysis was qualitative only and as such, the relative intensities
of elements detected on the surfaces of particles were classified as strong, medium or weak.
The elements detected were similar for galena from both samples, and are listed in Table A8.
An examination of Table A8 suggested that there were significant differences in the surface
composition of the galena from the lead rougher concentrate and tailing. The intensities
of copper (Figure A8), potassium, and hydrocarbon fragments were stronger for the lead
rougher concentrate sample (Table A8), than the lead rougher tailing. The iron and calcium

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TABLE A8
Surface species detected on galena from the lead rougher concentrate and tailing process streams using time-of-flight
secondary ion mass spectroscopy (ToF-SIMS). The relative intensity of each element is expressed as strong (s), medium (m)
or weak (w). Note: gallium, from the primary ion beam, and indium, from the sample mount, were also detecteda.
Stream/particle Ion
Pb Zn Cu Fe K Na Ca Si Al C2H3 C3H7
Lead rougher concentrate
1 s w m w s m s m m s s
2 s w w w s w m m w m s
3 s w w w s w w w w m m
4 s w w w w w w w w w w
Lead rougher tailing
1 s w - s s w m s w w m
2 s w - s m w w m w w w
3 s w - m m w m m w w w
4 s m - m s w s m w w w
a. During this analysis, several sphalerite grains from both the lead rougher concentrate and tailing process streams were examined. It was
interesting to note that the sphalerite surfaces in the rougher concentrate had elevated levels of lead, potassium and hydrocarbon
compared to those present in the tailing. These data, although only qualitative, would suggest that sphalerite recovery into the lead rougher
concentrate may be the result of inadvertent lead activation.

A B

Ga Ga

FIG A8 – Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) chemical maps of the lead rougher concentrate:
(A) lead; and (B) copper. The bright areas represent regions of high concentration for each element (Ga – galena).

intensities were weaker for the lead rougher concentrate sample (Table A8), than the lead
rougher tailing.
The intensity data (Table A8) suggested that particles in the lead rougher concentrate
sample had a high concentration of copper associated with their surfaces, while copper was
not detected on the surfaces of particles in the lead rougher tailing sample. An examination of
the ToF-SIMS chemical map of copper for the lead rougher concentrate (Figure A8) indicated
that the copper ions were only weakly associated with the galena grains, and were more
strongly associated with other species within the sample, possibly chalcopyrite or copper
activated sphalerite.
From Table A8 it is suggested that galena particles in the lead rougher concentrate sample
had a higher concentration of collector (potassium amyl xanthate) associated with their
surfaces than particles in the lead rougher tailing sample. An examination of Figure A9,
the ToF-SIMS chemical maps for potassium (Figure A9b) and hydrocarbon (Figure A9c),

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 CHRISTOPHER J GREET

A B

Ga
Ga

C D
Ga

Ga

FIG A9 – Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) chemical maps for the lead
rougher concentrate: (A) lead; (B) potassium; (C) hydrocarbon (C3H7); and (D) iron. The bright areas
represent regions of high concentration for that particular element (Ga – galena).

indicates that the highest intensities for potassium and hydrocarbon correspond to the
highest intensities for lead. This match suggested that the galena particles in the lead rougher
concentrate were strongly associated with collector. The same comparison, when made for
the lead rougher tailing sample (Figure A10), revealed that the intensity of hydrocarbon on
the surfaces of galena particles was lower than that observed for the lead rougher concentrate.
This observation indicates that the galena in the lead rougher tailing may have had insufficient
collector on its surface to produce the required level of hydrophobicity for flotation.
One possible reason for the lower collector coverage of the galena in the lead rougher tailing
is the higher concentrations of iron and calcium on the surfaces of particles in this process
stream compared with the lead rougher concentrate (Table A8). An examination of the ToF-
SIMS chemical maps for iron (Figures A9d and A10d) revealed that the galena particles
contained within the lead rougher tailing sample exhibited higher concentrations of iron on
their surfaces than the galena contained within the lead rougher concentrate sample. While
not shown here, the same observation holds true for calcium. These observations suggest
that galena in the lead rougher tailing process stream is coated with hydrophilic species. For
example, the iron occurs as ‘iron hydroxides’ emanating from the oxidation of pyrite and
the corrosion of the grinding media (high carbon, low alloy steel). It is suspected that the
hydrophilic layers coating the galena in the tailing may have been responsible for blocking the
collector, and preventing adsorption on to these particles, thereby reducing their floatability.

Summary of findings
The chemical characteristics examined showed, for both the solution (that is, free ions in
solution and EDTA analysis) and surface analysis (that is, XPS, SAM and ToF-SIMS), the
abundance of lead oxidation products was significantly greater in the lead rougher tailing
compared to that observed in the concentrate. Further, the XPS analysis indicated that the
oxidation products formed comparatively thick layers on the particles present in the lead
rougher tailing. The ToF-SIMS analysis was more particle specific, and while qualitative in

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

A B
Ga Ga

C D
Ga Ga

FIG A10 – Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) chemical maps for the
lead rougher tailing: (A) lead; (B) potassium; (C) hydrocarbon (C3H7); and (D) iron. The bright areas
represent regions of high concentration for that particular element (Ga – galena).

nature suggested that the galena in the lead rougher concentrate was hydrophobic because of
its strong association with hydrocarbon fragments, derived from the collector. The evidence
also suggests that the galena may have been copper activated. The surface composition of
the galena in the lead rougher tailing was significantly different. The data suggested that this
galena had insufficient collector coverage to render it hydrophobic; and significant coverage
of hydrophilic species, such as ‘iron hydroxide’. Both observations would severely hamper
the galena flotation response.
A secondary observation made from both the SAM and ToF-SIMS analysis indicated
appreciable levels of lead on the surfaces of sphalerite reporting to the lead rougher concentrate.
This suggested strongly that sphalerite recovery into the lead rougher concentrate was due to
inadvertent activation by lead.

CASE STUDY 2 – EFFECT OF GRINDING MEDIA ON ZINC DEPRESSION IN LEAD CLEANING

AT CANNINGTON
Introduction
Laboratory work examining the impact of inert grinding media during primary grinding
on lead and zinc metallurgy was completed in 2004. The results of this study culminated
in a plant trial whereby the cylpebs in the secondary mill (a tower mill) were replaced with
high chrome balls. The results of the plant trial suggested that converting the tower mill to
high chrome grinding media had a positive effect on metallurgy. In fact, the change in pulp
chemistry, brought about by the change to a more inert grinding media, saw an improvement
in the selectivity for galena against sphalerite, which placed more zinc into the zinc rougher
feed process stream. With more sphalerite reporting to the zinc rougher feed consistently
higher zinc recoveries were reported in the plant.

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 CHRISTOPHER J GREET

The positive changes to pulp chemistry and metallurgical response observed with the
change in grinding media in the primary tower mill work provided the impetus to commenced
examining the impact of high chrome grinding media added to the lead regrind circuit on lead
metallurgy. The initial study conducted on lead rougher concentrate, comparing forged steel
media with a variety of high chrome (above 15 per cent chrome) alloys showed forged steel
produced a superior lead grade/recovery curve, with low overall zinc losses when compared
to the high chrome alloys. That is, as the chrome content of the grinding media increased,
and the mill pulp chemical environment became more oxidising, the lead flotation rate,
concentrate grade and recovery noticeably decreased. The deterioration in lead metallurgy
appeared to be related to the increased floatability of sphalerite as the chrome content of the
grinding media increased (Kinal, Greet and Goode, 2009).
A series of laboratory tests were completed to develop an understanding of this behaviour,
and determine which alloy was best to trial in the plant.

Laboratory studies
A sample of fresh lead regrind feed from South 32’s Cannington Mine in north-western
Queensland, Australia was tested in the laboratory. The results showed forged steel produced
a superior lead grade/recovery curve, with low overall losses of zinc compared to the three
high chrome alloys tested. As the chrome content of the grinding media increased, and
the mill pulp chemistry environment became more oxidising (Table A9), the lead flotation
rate, grades and recoveries noticeably reduced. A main reason for the drop in lead flotation
performance was found to be poor selectivity for galena against sphalerite and non-sulfide
gangue minerals.
As the liberation characteristics were nominally the same for both media types, the
conclusion was drawn that it must have been the change in pulp chemistry affecting
selectivity. Surface analysis (ToF-SIMS) of the lead concentrate from a forged and high
chrome test showed that the sphalerite reporting to the lead concentrate in the high chrome
case had more surface coverage of chromium and zinc than the sphalerite particles prepared
using forged steel, which had a higher surface coverage of iron, but also lead and silver
(Figure A11).
The presence of more activating ions (silver and lead) on sphalerite surfaces for the forged
steel case is rather perplexing, as conventional wisdom would suggest that sphalerite
recoveries in this instance should be elevated. However, they are not. Sphalerite recoveries
after grinding with high chrome media were considerably greater than those observed for
forged steel grinding. This suggests that the presence of iron species on the surfaces of
sphalerite tend to control its floatability. That is, when grinding with forged steel the iron
corrosion products tend to react with the sphalerite’s surface more rapidly than the activating
species (for example, silver and lead), and thereby depress its flotation. When these corrosion

TABLE A9
Pulp chemistry data for laboratory lead cleaner tests comparing fresh
lead regrind feed ground with forged steel and high chrome media.
Media Mill discharge Flotation feed
Eh, mV (SHE) pH DO (ppm) Eh (mV) (SHE) pH DO (ppm) EDTA Fe (%)
Forged -62 7.9 0.0 129 7.6 0.0 1.4
Hi Cr 199 8.4 3.9 195 8.4 2.9 1.0

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

0.5
con(326)
+SIMS
0.4 con(327)

0.3

Intensity
0.2

0.1

0.0
Mg Al Si Ca Cr Fe Cu Zn FeOH Ag Ag Pb PbOH
con(326) 0.0455 0.026 0.0556 0.0373 0.0022 0.2917 0.0411 0.1287 0.0058 0.0245 0.0227 0.308 0.011
con(327) 0.0776 0.0485 0.0774 0.0599 0.0068 0.2195 0.055 0.1508 0.0041 0.0106 0.0099 0.2689 0.011

(+) Fragment
0.5
con(326)
-SIMS
0.4 con(327)

0.3
Intensity

0.2

0.1

0.0
CH O OH S SO3 EX IPX IBX AX
con(326) 0.16 0.36 0.25 0.21 0.0057 0.0011 0.0003 0.0004 0.0003
con(327) 0.17 0.38 0.27 0.17 0.0035 0.0009 0.0002 0.0004 0.0002

(+) Fragment

FIG A11 – Statistically evaluated (+) and (-) mass spectra for sphalerite in concentrates during
tests 326 (Forged) and 327 (High Cr). Confidence intervals were calculated for P = 95 per cent.

products are significantly reduced by grinding with high chrome media, the activating species
are now able to react with the surfaces of the sphalerite leading to significantly higher zinc
recoveries to lead concentrate.
Given this surface analysis knowledge, diagnostic tests were conducted on fresh lead
regrind feed ground with high chrome grinding media with different addition of iron sulfate
powder (Fe2(SO4)3) to determine if this would simulate the forged media test (Figure A12).
These data indicated that with increasing iron sulfate addition the lead grade/recovery
improved. That is, the lead concentrate grade at a specific lead recovery increased with
increasing iron sulfate addition due to better electivity for galena against sphalerite. This
suggested a low chrome alloy should restore the lead metallurgy. A low chrome ball was
sourced and tested in the laboratory.
The difference in grinding pulp chemistry between the two media types was noticeably
smaller when the low chrome media was used in place of a high chrome alloy (Table A10).
However, there was still a slight increase in pulp potential that would have an impact on
flotation performance. In fact, Figure A13 shows that the low chrome media had a beneficial
impact on lead cleaner flotation with a small increase in grade and recovery, compared to
forged steel.

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 CHRISTOPHER J GREET

80.0

70.0

60.0
Grade - Pb(%)

50.0

40.0

30.0
Forged Std
20.0
HiCr 1 g Iron Sulfate
10.0 HiCr 5 g Iron Sulfate
HiCr 10 g Iron Sulfate
0.0
0.0 20.0 40.0 60.0 80.0 100.0
Recovery - Pb(% )
FIG A12 – Lead grade/recovery curves showing the effect of increasing
the addition rate of iron sulfate powder to the high chrome grind.

TABLE A10
Pulp chemistry data for laboratory lead cleaner tests comparing fresh
lead regrind feed ground with forged steel and low chrome media.
Media Mill discharge Flotation feed
Eh, mV (SHE) pH DO (ppm) Eh (mV) (SHE) pH DO (ppm) EDTA Fe (%)
Forged -84 8.26 0.11 -110 8.34 0.00 8.26
LoCr -32 7.93 0.12 -69 8.13 0.00 7.30

60.0

55.0

50.0
Grade - Pb(%)

45.0

40.0

35.0 Forged (ave)

Low Cr (ave)
30.0
20.0 30.0 40.0 50.0 60.0 70.0 80.0
Recovery - Pb(%)
FIG A13 – Lead grade/recovery curves for tests completed with forged steel
and low chrome grinding media on lead rougher concentrate samples.

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

Plant trial
Based on these laboratory results a plant trial was arranged. Given that the first cleaner circuit
operates with two parallel grinding/flotation trains, a direct comparative trial was possible.
The pulp chemistry data indicated that the shift from cylpebs to a low chrome ball did result
in a subtle increase in the lead regrind tower mill discharge Eh, but all other pulp chemical
parameters were more or less the same. Metallurgically, the shift to a low chrome ball resulted
in an increase in lead grade through improved selectivity for galena against sphalerite, with
respect to first cleaner feed (Kinal, Greet and Goode, 2009).

Summary
The application of a surface analysis technique, in this case ToF-SIMS, helped identify the
issue of poor selectivity for galena against sphalerite in the laboratory. Knowing this valuable
piece of information led to the identification of a potential solution (ie a low chrome media),
which was tested in the laboratory before successfully transferring this result to the plant.

CASE STUDY 3 – GRINDING CHEMISTRY: THE SURFACE CHEMISTRY OF CHALCOCITE GROUND

IN DIFFERENT GRINDING ENVIRONMENTS
Introduction
Considerable evidence is available in the literature suggesting that grinding media corrosion
products contaminating the surfaces of sulfide minerals have a negative impact on their
flotation behaviour. These studies range from indirect evidence whereby minerals are
prepared in different grinding environments and the resultant flotation behaviours are
compared, to a comparison of pulp chemical parameters such as EDTA extractable metal ion
analysis and correlating this to flotation performance.
However, a better understanding of the surface chemistry of minerals ground with different
grinding media types is required to provide more solid proof that this is in fact the case.
A series of experiments using a sample of naturally occurring chalcocite was designed and
executed where the ‘single’ mineral was ground in the Magotteaux Mill® at pH 10 with
ceramic, high chrome and forged steel grinding media. The pulp chemistry was monitored
throughout the grinding process, and EDTA extractions completed on the mill product.
Subsamples of -38/+20 micron particles from tests performed with each grinding media were
collected for examination using XPS, ToF-SIMS and SAM surface analysis techniques. These
surface analyses were subsequently correlated with the pulp chemistry data.
The case study describes the results of this analysis, clearly demonstrating that as the
grinding media becomes more electrochemically active, the surfaces of the chalcocite become
increasingly contaminated by grinding media corrosion products (ie iron hydroxides).

Pulp chemistry data

The pulp chemistry of the Magotteaux Mill® discharge for the three grinding media types
tested is provided in Table A11. This data shows that the pH for all three media was the
same at 9.9. The pulp potential shifted to more oxidising values as the amount of iron in the
media decreased, with the Eh increasing from 134 mV (SHE) for forged steel to 189 mV (SHE)
for the ceramic media. The dissolved oxygen content in the mill discharge was zero for all
three media types, and the pulp temperature was maintained at around 35.7°C. The EDTA
extractable copper was significantly reduced when grinding with high chrome or ceramic
grinding media. The EDTA extractable iron, which is an excellent indicator of the level of

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 CHRISTOPHER J GREET

TABLE A11
Magotteaux Mill® discharge pulp chemistry.
Media pH Eh, mV (SHE) DO (ppm) Temp (°C) EDTA Cu (%) EDTA Fe (%)
Forged 9.9 134 0.0 35.7 0.77 0.99
HiCr 9.9 179 0.0 36.0 0.35 0.50
Ceramic 9.9 189 0.0 35.5 0.38 0.04

media corrosion, exhibited a marked decrease between the forged steel (0.99 per cent) and
the high chrome alloy (down to 0.50 per cent). The EDTA extractable iron decreased further
to 0.04 per cent when grinding with ceramic media. In essence, as the iron content of the
grinding media was reduced the EDTA extractable iron (or amount of corrosion products
generated) decreased.
The pulp chemistry data showed that moving from the electrochemically reactive forged
steel grinding media to high chrome and then ceramic resulted in the mill discharge pulp
potential becoming more oxidising and the level of corrosion (EDTA extractable iron) to
decrease.

Surface chemistry
The first surface analytical technique applied to the -38/+20 micron sample of chalcocite was
XPS. Generally, XPS is a bulk surface analysis taking an average surface composition of all
particles contained within an area of 400 × 700 microns. This is not an analysis of individual
particles. Fortunately, the sample examined was predominantly chalcocite so the analysis is
a reasonable approximation.
The atomic surface concentration of copper, sulfur, iron and oxygen are provided in
Table A12. The data show that as the iron content of the grinding media decreased the
exposure of copper and sulfur on the surfaces of the chalcocite particles increased. For
example, the atomic concentration of copper increased from 20.5 atomic per cent for forged
steel to 31.0 for ceramic media. This also corresponded to a decrease in the oxygen content
of the surface.
Remarkably, the surface iron concentration increased as the iron content of the grinding
media decreased. This may be related to changes in the surface chemistry of the trace levels
of chalcopyrite, bornite and pyrite contained in this sample of natural chalcocite. That is, as
media corrosion is reduced, moving from forged steel to high chrome to ceramic grinding
media, the mineral surfaces should be cleaner. This means that not only are the surfaces
of chalcocite cleaner (that is, increased exposure of copper and sulfur), the surfaces of

TABLE A12
Surface concentrations of copper, sulfur, iron and oxygen measured using X-ray photoelectron spectroscopy
(XPS) (normalised to remove the effects of carbon, magnesium, silica, sodium and nitrogen).
Media Atomic concentration
Cu S Fe O
Forged 20.5 15.3 4.0 60.2
HiCr 27.1 16.6 5.9 50.4
Ceramic 31.0 19.5 5.3 44.2

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

chalcopyrite, bornite and pyrite particles contained within the sample would also have
less contamination. Therefore, for these minerals (all iron bearing) not only are the surface
concentrations of copper and sulfur increased, so is the iron.
The XPS results only partially answer the question: are particles that are ground with an
electrochemically active grinding media surface contaminated by grinding media corrosion
products? The next level of analysis should examine individual particles to determine their
surface composition. The first such technique used was ToF-SIMS. Unfortunately, ToF-SIMS
while being extremely surface sensitive is not quantitative.
Figure A14 shows the positive SIMS results from the analysis of eight particles in the
-38/+20 micron size fraction prepared by grinding with forged steel, high chrome and ceramic
grinding media. The data does show that the surface iron content does decrease as the iron
content of the grinding media decreased. The data also shows that the particles prepared
using forged steel grinding media had a higher affinity for calcium, magnesium, aluminium
and silicon.
The ToF-SIMS analysis starts to provide evidence that corrosion products for electrochemically
active grinding media do impact the surface chemistry of particles. Unfortunately, as ToF-
SIMS is not quantitative, further work was completed using SAM. The SAM analysis allowed
the examination of individual grains of chalcocite, and obtained the surface concentration of
these particles.
Figure A15 provides an example of the SAM spectra obtained during this experiment. The
atomic concentration data collected are provided in Table A13. These data clearly show that
both the copper and sulfur surface concentration increase as the iron content of the grinding
media decreased. There is a corresponding decrease in the iron and oxygen concentrations.

0.6

0.5
ToF-SIMS counts (normalised)

0.4

0.3

0.2

0.1

0.0
Na Mg Al Si K Ca Fe Cu CuH2SO

FIG A14 – Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) results for positive SIMS.

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 CHRISTOPHER J GREET

Min: -1425 Max: 1668

23609.ACE, Sample 2, Grain 5 Conce ntration (at.%)
Cu1 27.3 %
Fe2 13.6 %
O1 13.6 %
C1 30.8 %
S1 14.7 %

dN(E)

Fe2
O1
C1

Cu1
S1

30 130 230 330 430 530 630 730 830 930 1030
Kinetic Energy (eV)

FIG A15 – Scanning Auger microscopy spectra for chalcocite ground with forged steel.

TABLE A13
Surface concentrations of copper, sulfur, iron and oxygen measured using scanning Auger microscopy (SAM).
Media Atomic concentration
Cu S Fe O
Forged 42.7 29.1 13.5 14.7
HiCr 53.1 37.3 4.6 5.0
Ceramic 59.7 39.1 0.3 0.9

Summary
Changing the grinding media from forged steel to high chrome to ceramic when grinding
chalcocite did alter the pulp chemistry of the laboratory mill discharge to more oxidising Eh
values and lower EDTA extractable iron concentrations (ie lower media corrosion).
The XPS (bulk) surface analysis did show increased exposure of copper and sulfur as the
iron content of the grinding media decreased, which suggests that the chalcocite particles
are cleaner.
The ToF-SIMS surface analysis (individual particles) did show a decrease in the iron
concentration on the surfaces of the chalcocite particles. However, as ToF-SIMS is qualitative
these results are a good indication but further quantitative data is needed.
The SAM (individual particle) surface analysis also showed increased exposure of copper
and sulfur as the iron content of the grinding media decreased. In this analysis, it was
evident that the change in grinding media did result in a reduction in iron species on the
surface of chalcocite.
The pulp chemical data, particularly the EDTA information, is corroborated by the three
surface analysis techniques. That is, more electrochemically active grinding media (ie forged
steel) results in higher percentages of EDTA extractable iron, and reduced exposure of copper
and sulfur, but elevated iron concentration on their surfaces. Shifting to media with lower
iron contents (ie high chrome and ceramic) the EDTA extractable iron decreases as does the
concentration of iron on the particle surfaces.

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 CHAPTER 9 | SURFACE CHEMICAL CHARACTERISATION FOR FLOTATION PLANT OPTIMISATION

REFERENCES
AMIRA, 1991. P260 – Iron sulphide interactions and their influence on sulphide mineral flotation,
Volume 4: Aberfoyle Resources Limited – Hellyer, prepared by the Particle and Surface Technology
Research Group, University of South Australia (Australian Mineral Industries Research Association:
Melbourne).
Blesa, M A, Rueda, E H and Grassi, E B, 1985. Adsorption and dissolution in the system geothite/
aqueous EDTA, Journal of Colloid and Interface Science, 106(1):243–247.
Buckley, A N and Woods, R, 1984. An X-ray photoelectron spectroscopic study of the oxidation of
galena, Applied Surface Science, 17:401–414.
Buckley, A N and Woods, R, 1987. The surface oxidation of pyrite, Applied Surface Science, 27:347–352.
Buckley, A N, Wouterlood, H J and Woods, R, 1989. The surface composition of natural sphalerite
under oxidative leaching conditions, Hydrometallurgy, 22:39–56.
Fornasiero, D, Li, F, Ralston, J and Smart, R StC, 1994. Oxidation of galena surfaces: I. X-ray
photoelectron spectroscopic and dissolution kinetic studies, Journal of Colloid and Interfacial Science,
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Gardner, J R and Woods, R, 1979. A study of the surface oxidation of galena using cyclic voltametry,
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Grano, S R, Ralston, J and Johnson, N W, 1988. Characterisation and treatment of heavy medium plant
slimes in the Mount Isa Mines lead/zinc concentrator, Minerals Engineering, 1:137–150.
Grano, S R, Wong, P L M, Skinner, W, Johnson, N W and Ralston, J, 1995. Detection and control
of calcium sulphate precipitation in the lead circuit of the Hilton Concentrator of Mount Isa Mines
Limited, Australia, in Proceedings XIX International Mineral Processing Congress, volume 3, pp 171–179
(Society for Mining, Metallurgy, and Exploration: Littleton).
Greet, C J, 2002. Galena flotation: Hellyer Mine case study. PhD thesis, University of South Australia.
Greet, C J and Smart, R StC, 2002. Diagnostic leaching of galena and its oxidation products with EDTA,
Minerals Engineering, 15:515–522.
Hamilton, I C and Woods, R, 1986. Investigation of electrochemical properties of lead ethyl xanthate by
linear potential sweep voltammetry, Langmuir, 2:770–773.
Hiskey, J B and Schlitt, W J, 1982. Chapter 7: Aqueous oxidation of pyrite, interfacing technologies
in solution mining, in Proceedings Second SEM-SPE International Solution Mining Symposium (eds:
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Johnson, N W, 1988. Application of electrochemical concepts to four sulphide flotation separations, in
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Kant, C, Rao, S R and Finch, J A, 1994. Distribution of surface metal ions among the products of
chalcopyrite flotation, Minerals Engineering, 7(7):905.
Kinal, J, Greet, C and Goode, I, 2009. The effect of grinding media on zinc depression in a lead cleaner
circuit, Minerals Engineering, 22:759–765.
Laajalehto, K, Nowak, P, Pominowski, A and Suoninen, E, 1991. Xanthate adsorption at PbS/aqueous
interfaces: comparison of XPS, infrared and electrochemical results, Colloids and Surfaces, 57:319–333.
Moore, J J, 1981. Chemical Metallurgy (Butterworths: London).
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circuits, AIME Transactions, 256:323–328.
Pang, J and Chander, S, 1992. The effect of EDTA on collectorless flotation of pyrite, in Proceedings
International Symposium on Electrochemistry in Mineral and Metal Processing III (eds: R Woods and
P E Richardson), p 221.

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Richmond, G D, 1993. Zinc-lead ore concentration by Aberfoyle Limited, Hellyer, Tasmania, in

Australasian Mining and Metallurgy (The Sir Maurice Mawby Memorial Volume), second edition (eds:
J T Woodcock and J K Hamilton), pp 530–535 (The Australasian Institute of Mining and Metallurgy:
Melbourne).
Rumball, J A and Richmond, G D, 1996. Measurement of oxidation in a base metal flotation circuit by
selective leaching with EDTA, International Journal of Minerals Processing, 48:1–20.
Shannon, L K and Trahar, W J, 1986. The role of collector in sulphide flotation, in Advances in Mineral
Processing (ed: P Somasundaran), pp 408–425.
Smart, R StC, 1991. Surface layers in base metal sulphide flotation, Minerals Engineering, 4:891–909.
Smart, R StC, Skinner, B, Netting, A K O, Simpson, D, Bandini, P and Greet, C J, 1993. Protocols for
surface analysis in mineral processing, AMIRA Project P260A.
Wang, X and Forssberg, K S E, 1990. EDTA induced flotation of sulphide minerals, Journal of Colloid and
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Woodcock, J T and Jones, M M, 1970. Chemical environment in Australian lead-zinc flotation plant
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Return to contents

CHAPTER 10
Laboratory flotation testing – an essential
tool for ore characterisation
Kym Runge

ABSTRACT
The properties of the ore have a significant impact on the ultimate grade and recovery
achievable in a flotation circuit. To maximise recovery or yield, the proportion of the
valuable mineral that is floatable should be maximised. To maximise the concentrate quality
or grade, the flotation rate of the valuable mineral should be significantly higher than the
flotation rates of the gangue minerals in the ore. This is often referred to as ‘maximising the
selectivity’.
Laboratory batch flotation, in which a 1–2 kg sample of ore is floated using a standard set
of operating conditions, is the standard technique used to assess ore floatability. These tests
have been performed extensively to determine the ultimate flotation design, screen potential
reagents, determine optimum feed grind size and predict the change in performance of
different ore types. These tests have traditionally been performed using the feed ore sample
to the process, but they are increasingly being used to characterise the floatability of internal
flotation circuit streams and ‘map’ how the floatability is changing around a flotation circuit
and across different processes.
Key ore floatability parameters (flotation rate constants and proportion of mineral in
different floatability classes) can also be derived from the laboratory test flotation response.
The values of these ore floatability parameters can be evaluated and compared to rank
different ore types or reagent suites. These parameters are also suitable for predicting,
through mathematical modelling, the grade–recovery relationship achievable in a multistage
flotation circuit.
There are various graphical and modelling techniques that have been developed to interpret
laboratory batch flotation test results. In this chapter, the recommended procedure for
performing these laboratory flotation tests and the various graphical and modelling analysis
methods used to interpret these test results will be outlined.

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 KYM RUNGE

INTRODUCTION
To achieve separation in the flotation process, those particles containing the valuable mineral
need to float and they need to float more quickly than those containing predominantly gangue
minerals. The particle size, degree of liberation of the minerals and the hydrophobicity of the
mineral surface will in large dictate a mineral’s recovery rate. Grinding and chemical addition
are weapons in the metallurgist’s armoury used to modify particle properties for a particular
ore type in an attempt to achieve maximum separation.
A vast array of techniques can be used to predict the optimum grind size and chemical
suite to use for a particular ore. Ultimately, there is always a need for small-scale testing to
validate the results of these analyses or to explore, screen or prioritise different options. This
is where laboratory batch flotation testing and the various techniques that can be used to
analyse these batch test results are useful. They are relatively easy and inexpensive to perform
in comparison to detailed liberation or chemical speciation analyses and they go some way
to replicating the process conditions that will be present in the full-scale processing plant.
The aim of this chapter is to outline how these ore characterisation tests should be performed
and demonstrate the various graphical and modelling techniques that can be used to
interpret the results produced from these tests.

BATCH LABORATORY TESTING PROCEDURES

The standard procedure
Various designs of laboratory-scale flotation cells can be used to perform the laboratory
batch flotation tests. My preference is to use a bottom driven cell allowing impeller speed
and air rate adjustment, an example of which is shown in Figure 1. This type of cell, used
with a fixed depth scraper to regularly remove the entire froth phase during concentrate
collection, maximises the likelihood of producing reproducible test results even between

FIG 1 – A bottom driven laboratory flotation cell supplied by Runge Engineering.

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

different operators. When using a cell where the impeller is top mounted, reproducibility can
be improved by using two fixed-depth scrapers with rubber glued to the end of each scraper.
This rubber moves around the impeller shaft as the scraper is brought forward from the
back of the cell to the cell lip, thus enabling the entire froth phase to be removed during each
scrape. Whatever cell is used to perform the test work, it is important that a great deal of care
is taken to keep the procedure as consistent as possible.
A typical test involves washing an ore pulp sample into the laboratory cell. Make-up water
is added to achieve the desired volume. The impeller is started and set to the desired speed.
Frother, collector and depressant (if required) are then added and appropriate conditioning
time is allowed to elapse. The order by which these reagents are added is important and
should be tailored to achieve the desired surface chemistry. Depressant, for example, often
needs to be added prior to the collector to stop collector attaching to gangue mineral surfaces.
The appropriate reagent addition rates are best determined from reagent optimisation testing.
At the instant the air flowmeter is set to the appropriate air rate, the timing of the test
commences. The concentrate produced from the cell flows and/or is scraped into trays and
at designated time intervals the trays are removed and replaced. Water is continually added
to the cell to maintain the desired froth level. The test continues until the froth is barren
and no more particles are reporting to the froth in significant quantities. It is recommended
that one more concentrate be collected after this point to ensure the end point of the test can
be established.
All concentrate samples and the final tailing sample are weighed wet and dry and assayed
for the elements of interest. These results are used to calculate the rate of mineral recovery as
a function of time, usually on a cumulative basis. A typical cumulative mineral recovery curve
is depicted in Figure 2.
As an aside, the water in the concentrate versus the water in the flotation cell will be used
to estimate recovery by the entrainment mechanism. Thus, known quantities (or no) water
should be used to wash concentrate into the tray.
Samples to be tested can be collected directly from an operating flotation circuit, referred to as
‘hot samples’, or prepared in the laboratory – grinding to produce the appropriate particle size
or adding reagent to achieve the required pulp chemistry. The time between sample collection/
preparation and flotation should be minimised to prevent ageing or oxidation of particle
surfaces prior to testing.

100
Mineral Recovery (%)

80

60

40

20

0
0 2 4 6 8 10 12 14

Time (min)
FIG 2 – Typical mineral versus recovery time curve obtained from a laboratory batch test.

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 KYM RUNGE

The weight or size of sample added to the laboratory flotation test should be chosen to
achieve the required pulp density. Pulp density is a variable that often affects batch flotation
test results and therefore comparative tests should be performed at the same pulp density.
When attempting to replicate plant performance it is recommended that one use the same
per cent solids as in the plant. When performing tests to assess or model ore floatability,
however, it is recommended that all samples be floated at a low per cent solids (that is, less than
ten per cent solids). The use of a low per cent solid minimises the risk of bubble saturation
or overloading. In tests where there is a high proportion of floatable solids performed using
a low air rate and at a high pulp density, bubble surfaces can become saturated, resulting in
low recovery rates. This condition should be avoided as the result is no longer a function of
just the ore, but the air rate used in the test as well.
The water used to dilute the samples and added during a test to maintain froth depth
should be as similar to that used (or to be used) in the plant as possible. Water properties (that
is, pH, Eh, temperature, dissolved oxygen and dissolved ions) will affect the composition of
reagent and deposition products on particle surfaces, which ultimately affects ore floatability.
Whenever possible, plant water should be used. When plant water is not available, synthetic
plant water created after an analysis of the cationic and anionic chemistry should be added.
Reagent additions may also need to be increased when using synthetic plant water because
of the lack of residual collector, which is often present in the recycled water used in a plant.
Frother (so long as it has no collecting properties) should also be added to all make-up water
in sufficient quantities to maintain a constant bubble size in the pulp and minimise bubble
breakage within the froth phase. For most frothers, a concentration of 20 ppm within the
make-up water will be sufficient for this purpose. Distinct additions of frother in the middle
of a test should be avoided as they can result in a spike in flotation recovery.
It is important that all tests are performed using the same air rate, impeller speed, froth
depth and froth scraping rate so that any change in a batch test result is a consequence of a
change in the ore characteristics rather than to any change in the environment in which it is
floated. The air rate chosen should be high to prevent bubble saturation and maintain a fluid
non-collapsing froth. Air rates of 10–18 L/min are usually appropriate for tests performed
using a 5 L cell. Impeller speed should be sufficient to keep all solids in suspension but not so
high that molecules loosely deposited on surfaces are stripped off. An impeller speed between
750 and 1000 rev/min is recommended for standard flotation tests, although higher speeds
may be required when processing very coarse material.
Ideally the froth should be removed the instant it is formed so that differences in results can
be attributed to changes in pulp flotation kinetics rather than to any change in the flotation
froth characteristics. As a practical compromise, it is recommended that 2 – 3 cm of froth
be maintained throughout the test and a scraper of sufficient depth be used to remove all
but 0.5 cm of this froth at regular time intervals. Make-up water should be added regularly to
maintain a constant froth depth as solids and water report to concentrate. A fast froth scraping
rate is desirable but one stroke every ten seconds is usually a speed that allows the execution
of other tasks (addition of water and changing of trays).
The time intervals over which each concentrate is collected should be chosen such that the
shape of the mineral recovery time curves can be well established for the particular operating
conditions chosen to do the tests. A test of a slow floating platinum ore, for instance, may require
45 minutes to an hour to reach completion and thus the first concentrate can be collected after
two minutes of flotation. A faster-floating copper porphyry flotation test, however, may finish
in five minutes and a first concentrate may need to be collected after 20 seconds.

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

Depending on one’s circumstances, some deviation may be required from the recommended
test conditions (for example, use of high per cent solids to obtain sufficient concentrate
samples for assay or samples left to sit for long periods). Tests should be performed to
establish whether any adverse effect arises from the proposed change.

Refloatation and locked cycle tests

The grade versus recovery relationship derived from a standard batch laboratory flotation test
will not be that achievable in a multiple stage flotation circuit. Multiple stage flotation results
in a more efficient separation between particles of different floatability. Figure 3 demonstrates
this point by showing the flotation separation curves for a batch flotation test (calculated
using flotation modelling techniques) performed over different time periods and for tests in
which the concentrate has been refloated. The flotation separation curve is a plot of recovery
versus the flotation rate of a particle in a particular flotation process. If a flotation process
was a perfect separator, the separation curve would be a vertical line – complete recovery
of particles to the right of the line and no recovery of particles to the left. The probabilistic
nature of the flotation process, however, results in non-ideal separation.
It is clear from these graphs that a change in flotation time (Figure 3a) simply increases
or decreases flotation recovery but does not result in changes in separation efficiency.
A steepening of the separation curve, however, results from refloating the concentrate

A 100
90
80
16
70
Recovery (%)

60
8
50
40
4
30
20
10
0
0.001 0.01 0.1 1 10

Flotation Rate (min-1)

100
B
90
80
70
Recovery (%)

60
50
Reflotation
40
30
20
10
0
0.001 0.01 0.1 1 10
-1
Flotation Rate (min )
FIG 3 – Recovery of particles with different flotation rates: (A) after four, eight and 16 minutes
of flotation, and (B) after one, two and three refloatation stages of eight minutes in duration.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 325

 KYM RUNGE

(Figure 3b). This occurs because of the increase in the fast to slow ratio of particles in the
feed to subsequent stages. The net result of this improvement in separation efficiency is an
improvement in the concentrate grade or purity achievable at a particular mineral recovery.
Locked cycle batch flotation experiments provide a better insight into the expected grade
and recovery achievable from multistage processing of an ore. These tests are performed such
that they replicate, on a small scale, the full-scale flow sheet. To incorporate the effect of
recycle streams, they are often performed multiple times with the recycled streams from a
previous test added at the appropriate place in the subsequent test. Tests are performed until
the mass flow in all samples converges to a constant value. Figure 4 shows a schematic of
a locked cycle test performed to replicate a rougher/cleaner flotation circuit in which the
cleaner tail is recirculated back to the feed.
The disadvantage of these types of tests is that they are time consuming to perform and they
pertain to a single flow sheet arrangement. To investigate an alternative flow sheet or a change
in the residence time of a stage, another experiment needs to be performed.
A more time-effective option for estimating multistage circuit grade and recovery is to
model the data from a single-stage experiment (or a locked cycle test). This model can be
used to predict circuit grade and recovery achievable from different circuits mathematically.
The procedures to perform this type of analysis will be outlined later in the chapter.

TECHNIQUES AVAILABLE FOR INTERPRETING BATCH LABORATORY FLOTATION TEST RESULTS

Mineral recovery, grade versus recovery and selectivity curves
Mineral recovery, grade/recovery and selectivity curves are all graphs that can be constructed
from the information collected during a single batch flotation experiment. These curves are
ideal for comparing the results of different tests.
The mineral recovery curve displays the cumulative mass of mineral (on a percentage basis)
recovered as a function of time during a test. The slope of this curve is an indicator of the rate
of flotation recovery and the recovery value at which the curve asymptotes is an indicator of
the proportion of floatable mineral in the tested sample (Figure 5).

New Feed
Recycled Tail

New Feed
Recycled Tail

New Feed Circuit Tailing

Circuit Concentrate

FIG 4 – Locked cycle test schematic.

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

Cumulative Mineral Recovery Versus Time

100

Mineral Recovery (%)

80 Increasing Proportion of
Floatable Mineral
60
Increasing Flotation Rate

40

20

0
0 2 4 6 8 10 12 14
Time (min)

FIG 5 – Cumulative mineral recovery curve with the important features denoted.

It is desirable that the valuable mineral in a sample exhibit fast flotation kinetics (steep
slope) and the proportion of non-floating mineral in the sample be minimised. The
proportion of non-floating valuable mineral is an indicator of the amount of mineral that
is either in particles too large or small for flotation, locked with non-floating particles or
with a hydrophilic surface due to insufficient collector coverage or depressant coatings.
Regardless of the reason, non-floating mineral is not recoverable in a flotation circuit and
should be minimised if circuit recovery is to be maximised.
Flotation is a separation process and thus it’s important that the valuable mineral is not only
recoverable but that it’s recoverable to a greater extent than the gangue mineral. Selectivity
curves are ideal for this type of evaluation. On these curves, the recovery of the valuable
mineral is plotted against the recovery of a gangue mineral of interest (Figure 6).
The 45 degree line on this plot represents the points at which no selectivity occurs – the
recovery of the valuable mineral is equal to the gangue mineral recovery and no separation
is achievable. The further to the right of this line the selectivity curve lies, the better. Different
selectivity curves should be created for each of the gangue minerals of interest as different
minerals often exhibit different degrees of selectivity with the valuable mineral.
The overall measure of selectivity in the batch flotation test is the grade (or purity) of the
concentrate produced. The cumulative concentrate grade versus cumulative recovery curves
(Figure 7) produced from different tests can be compared to determine those conditions that
result in the best selectivity with respect to all minerals.
These curves do not, however, give an estimate of the grade and recovery achievable in a
multiple stage flotation circuit. Locked cycle tests or modelling are better suited to this task.
These curves do give a good relative measure of selectivity. An improvement in selectivity in
these tests should result in a better grade at a particular recovery at full scale.

Entrainment assessment techniques

Gangue can report to the concentrate either attached to bubbles (due to its own
hydrophobicity or because of an association with a hydrophobic mineral) or entrained
with the water phase. It is important to be able to differentiate between these two recovery
mechanisms as ultimately this distinction may affect the strategy that is adopted to reduce

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 KYM RUNGE

100

Gangue Mineral Recovery (%)

80

60

40

Increasing Selectivity
20

0
0 20 40 60 80 100
Valuable Mineral Recovery (% )
FIG 6 – Mineral selectivity curves with the important features denoted.

100
Improving Overall Selectivity
Cumulative Recovery to

80
Concentrate (%)

60

40

20

0
0 5 10 15 20
Cumulative Concentrate Grade (% )

FIG 7 – Cumulative recovery versus cumulative concentrate grade produced during a batch flotation experiment.

gangue recovery. This section outlines techniques that can be used to estimate the degree of
entrainment in a laboratory batch flotation test.
Entrainment is a consequence of particles suspended in the pulp phase following the
water into the froth and ultimately into the concentrate. The mass of a mineral entrained into
the concentrate is proportional to the water flow to concentrate and can be estimated using
Equation 1 (Johnson, 2005). Equation 2 is an alternative equation used to estimate entrainment.
It is a simplification of Equation 1 but is only valid at low water recovery values.

Fi = C f, i ~ i, pulp Fw (1)

where:
Fi is the flow of component i into the concentrate due to entrainment
Cf,i is the classification function for component i
ωi,pulp is the mass of component i to the mass of water in the pulp phase
Fw is the flow of water to the concentrate

Rent,i = Cf,i Rw (2)

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

The classification function (Cf,i) is a factor to account for the degree of drainage with respect
to the water flow and must be estimated to perform the calculation. It is known to fall between
zero and one; zero representing the condition of total drainage where there is no entrained
recovery of particles regardless of the water recovered, and one representing the condition
where there is no drainage and the concentration of particles in the water in the concentrate
(due to entrainment) is the same as in the pulp phase. Cf,i is known to be strongly dependent
on size with the coarser particles exhibiting a high degree of drainage (Cf,i = 0) and the fine
particles usually following the water phase (Cf,i = 1).
Thus, to calculate the recovery by entrainment in a batch test, the water to solids ratio
in the pulp, water flow to concentrate and an estimate of Cf,i is required. The water flow
to concentrate can be measured and the average water to solids ratio in each stage can be
estimated based on knowledge of the cell volume and the particle mass balance. The challenge
is to estimate the degree of drainage in the system.
If one of the minerals is known to be non-floating, an inversion of Equation 1 can be used to
calculate a Cf,i estimate for the other minerals in the ore. This, unfortunately, is not usually
the case with even the non-floating minerals locked to some extent with the valuable and
exhibiting floatability. Johnson (2005) published typical values of Cf,i for siliceous non-sulfide
gangue (Table 1). These values coupled with knowledge of the particle size distribution of a
particular sample can enable a reasonable estimate of Cf,i to be calculated.
Alternatively, Cf,i can be estimated using results from the batch test by recognising
that towards the end of an experiment, the predominant particle recovery mechanism is
entrainment. If one calculates the ratio of mineral to water in both the concentrate and
pulp and plots this value for each stage of a batch experiment (Figure 8), it usually decreases,
asymptoting at a particular value towards the end of the test. This value is an estimate of the
Cf,i value. The larger values at the beginning are because recovery is due to entrainment and
flotation in these earlier stages.

TABLE 1
Typical values of Cf,i (after Johnson, 2005).
Size fractions (μm)
-11 -16 +11 -23 +16 -33 +23 -44 +33
0.77 0.46 0.30 0.24 0.13

2.5
Gangue to Water Ratio in Concentrate
Ratio =
2.0 Gangue to Water Ratio in Pulp

1.5
Ratio

Maximum Cfi Limit

1.0

0.5
Cfi Estimate
0.0
0 5 10 15
Time (min)

FIG 8 – Cf,i calculated using Equation 1 versus time in a batch flotation test.

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 KYM RUNGE

Once a Cf,i estimate has been obtained and the gangue entrainment flow has been calculated
(Equation 1), a cumulative entrainment recovery curve can be constructed that can be compared
to the overall recovery curve for that mineral (Figure 9). The difference in these two curves is
the proportion of the mineral recovered due to true flotation (attachment to bubbles).

Ore floatability mapping in a flotation circuit

Traditionally, batch flotation tests have only been performed using samples representative of
a flotation circuit feed. Much can be learnt, however, by floating the samples collected from
different streams of an operating flotation circuit.
During flotation the faster floating particles will report to the concentrate streams, whereas
the slower floating particles will report predominantly to the tailing streams. This results in
different streams possessing very different ore floatability properties. As an example, Figure 10
shows the copper recovery achieved in batch flotation tests performed using different streams
from Rio Tinto’s Northparkes flotation circuit (Runge et al, 2003).
This information can then be assessed in terms of mineral recovery and selectivity.
A traditional rule of thumb is to recirculate streams to a point of similar assay. A better
philosophy is to recirculate streams to a point of similar floatability.

70
Gangue Recovery (%)

60

50
Overall
40
Entrainment
30 Estimate
20

10

0
0 5 10 15
Time (min)

FIG 9 – Curves used to assess the predominant gangue recovery mechanism in a batch flotation test.

100 Rougher Feed

Rougher Concentrate
Copper Recovery (%)

80 Rougher Tail
Scavenger Concentrate

60 Scavenger Tail
Cleaner Feed
Cleaner Concentrate
40
Cleaner Tail
Recleaner Feed
20
Recleaner Concentrate
Recleaner Tail
0 Cleaner Scavenger Tail
0 2 4 6 8
Time (min)

FIG 10 – Copper recoveries achieved in the batch tests performed on

different streams in the Northparkes flotation circuit (Runge et al, 2003).

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

The final tailing is of special importance as it is discarded and any valuable mineral
contained in this stream is a lost opportunity. High valuable mineral recovery rates coupled
with good selectivity in a tailing stream batch test is an indication of insufficient residence
time in the circuit. Slow floating material in the final tailing, however, is often unrecoverable
in a circuit without producing an unacceptable concentrate grade. Increasing circuit residence
time to recover slow-floating material will often only result in large recirculating loads and
no improvement in overall recovery. Large quantities of slow-floating material in the tailings
is an indication that particle modification (either in terms of particle size or chemistry) is
required in the circuit to increase recovery.
Internal streams with poor valuable mineral to gangue mineral selectivity are appropriate
targets for regrinding or depressant or collector addition. Batch flotation of different streams
in a flotation circuit, combined with liberation analysis, enables the appropriate streams for
this type of modification to be delineated from those that would not benefit from this type
of processing.
Regular batch laboratory flotation test mapping during circuit surveys will provide a record
of ore floatability properties and enable the comparison of this property between different
surveys.

Nodal analysis comparisons

The nodal analysis technique was developed to compare the floatability of particles before
and after processes (nodes) within a flotation circuit (Runge et al, 1997). It involves comparing
the mineral recovery rate and selectivity achieved in batch laboratory flotation tests of the
feed and product streams of a node. A node is defined as a point in a circuit where streams
are either combined, separated or altered in some way (Figure 11). A node can be a single unit
such as a flotation cell, a regrind mill or a pump sump, a combination of units (for example, a
bank of cells) or even an entire circuit with the feed being split into the final concentrate and
final tailing stream.
The experimental feed and product mineral recovery rates or mineral selectivity curves
derived from laboratory batch flotation tests can be compared directly when there is only one
feed stream and one product stream from a node.
This direct comparison is difficult, however, when there are multiple feed or product streams.
In many cases, it is also impossible to obtain ‘the desired’ samples from the flotation process.
In these cases, the mineral recovery rate of a ‘combined feed’ or ‘combined product’ stream
can be estimated by mathematically combining the experimental results of the standard
laboratory batch flotation tests on two or more streams (Equation 3) based on their relative
flows in the circuit.
n
/F Stream s
Mineral j
# R Stream s, t minutes
Mineral j
R Combined Stream, t minutes
Mineral j
= s=1
n
(3)
/F Stream s
Mineral j
s=1

where:
F Mineral
Stream s
j
is the flow rate of mineral j in stream s

R Stream s, t minutes
Mineral j
is the cumulative recovery of mineral j in stream s after t minutes of flotation
in the standard laboratory batch flotation test

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 KYM RUNGE

A B

C D

FIG 11 – Examples of nodes in a flotation circuit. (A) Flotation cell; (B) tower mill; (C) pump sump; (D) flotation circuit.

Take for example a flotation column. A column has a single feed but two product streams.
Equation 3 can be used to recombine the concentrate and tailing stream to produce a single
‘combined’ product stream result. The combined stream floatability can then be compared
to the feed stream floatability to assess whether there has been any change across
the unit. Figure 12 shows the galena recovery rate measured in a batch flotation test of the
feed, concentrate and tailing streams of an industrial column. It also shows the calculated
‘combined product’ stream which, in this case, is very similar to the column feed. It can,
therefore, be concluded that floatability does not change significantly across this unit. The
difference in galena recovery rates in the concentrate and tailing stream is attributed to the
faster-floating galena-containing particles concentrating in the concentrate streams and the
slower-floating galena-containing particles concentrating in the tailing streams. Using this
technique in a number of different flotation circuit operations, it has been shown that ore
floatability is not often affected in a full-scale flotation cell (Runge et al, 2006).
Regrinding and reagent addition are employed in a flotation circuit specifically to alter
particle floatability. The effectiveness of these processes can be assessed by a statistically
planned and analysed on-off plant trial. Alternatively, comparison of ore floatability using
nodal analysis techniques can enable a direct assessment of the effectiveness of these
particle modification operations. In Figure 13a for example, it is obvious that staged reagent
addition has resulted in a significant increase in the proportion of floatable copper in the
circuit. In Figure 13b it is obvious that regrinding has not resulted in an improvement in
the chalcopyrite/pyrite selectivity. These types of observations provide the metallurgist with
invaluable information regarding the effect of an ore modification process.
These techniques will be demonstrated in a worked example included at the end of this
chapter. For a more detailed example, the reader is referred to Runge, Franzidis and Manlapig
(2004) in which these techniques are used to assess the effect of staged reagent addition,
regrinding and lime addition on ore floatability in an industrial circuit.

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

100
90

Galena Recovery (%)

80 Column Feed
70
60 Column Concentrate
50 Column Tail
40
30 Column Concentrate
20 + Column Tail
10
0
0 10 20 30 40
Time (min)

FIG 12 – Galena recovery versus time for the feed, concentrate, tailing and combined
product of an industrial-scale flotation column (after Runge et al, 1997).

A
Chalcopyrite Recovery (%)

100

80

60

40
Feed to Reagent Node
20
Product of Reagent Node
0
0 2 4 6 8 10
Time (min)

B 100
Combined Feed
Pyrite Recovery (%)

80 Product

60

40

20

0
0 20 40 60 80 100
Chalcopyrite Recovery (%)
FIG 13 – Nodal analysis comparative graphs: (A) mineral recovery before and after
collector addition, (B) chalcopyrite/pyrite selectivity before and after regrinding.

Ore parameter estimation techniques

The mineral recovery response measured in a laboratory batch flotation experiment can
be used to calculate ore floatability parameters. These are numbers that represent the rate
and extent to which a mineral will float. These parameters can be used as a means of
comparison of different batch test experiments or within a flotation model for performance
prediction.

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 KYM RUNGE

Flotation is considered a first-order kinetic process, recovery being a function of the time in
the process (t) and a flotation rate constant (k). In a batch laboratory flotation environment,
recovery can be calculated using Equation 4.
R = 1 − exp(−kt) (4)

The flotation rate constant is a function of the operating conditions in the cell and also the size,
mineralogy and surface chemical speciation of the particles being floated. There are a number
of different types of particles in an ore sample and each will float with a different flotation rate
– thus an ore sample exhibits a distribution of floatabilities. There are no methods currently
available for measuring each particle’s individual rate. Instead, the problem is simplified by
assuming the form of the floatability distribution. The two methods most commonly used
involve assuming a continuous shape for the distribution (for example, rectangular distribution
(Klimpel, 1980)) or splitting a mineral into different floatability components. In this chapter,
derivation and use of multiple component parameters will be discussed. For those wanting
more information regarding shaped distributions, the reader is referred to a paper written by
Chander and Polat (1994).
Mineral recovery in a batch flotation test using multiple components can be calculated using
Equation 5.
n
R= / m (1 - exp (- k t))
i i
(5)
i=1

The rate of each component (ki) and the proportion of the mineral in that class (mi) are the
ore floatability parameters of the system that can be derived from batch laboratory flotation
test data. This involves calculating the ‘best’ set of these parameters that minimise the sum
of squares difference between the recoveries calculated using Equation 5 and that measured
in the laboratory batch flotation experiments. This difference can, optionally, be weighted by
the standard deviation of the experimental data (Equation 6). These problems are easily set
up on an Excel spreadsheet using the Solver add-in to perform the minimisation.
(R j,calculated - R j,experimental) 2
SSE = / SD j,experimental 2
(6)
j

The number of components that can be derived to describe a mineral’s floatability is

dependent on the amount of data available to do the parameter estimation. Unfortunately,
the data from a single batch laboratory flotation test is only sufficient to determine, with
statistical confidence, the parameters associated with a simple representation of the system.
Thus, it is common to describe the data from a single batch flotation test with a floating and
a non-floating fraction (Equation 7). In this model, Rmax is the proportion of material that
is floatable while (1-Rmax) is the proportion of material that is non-floating with a rate of
zero. Alternatively, the Kelsall fast- and slow-floating rate model (Equation 8) can be used
(Kelsall, 1961).

R = R max (1 - exp (- k t)) (7)

R = m f (1 - exp (- k f t)) + ms (1 - exp (- ks t)) where mf+ms = 1 (8)

More complex representation of the floatability distribution requires an increase in the

experimental data set size. Harris (1998) recognised that the data set size could be increased

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

by using information collected from laboratory batch flotation tests performed using different
streams of a circuit. A circuit by its very nature results in a redistribution of the floatability
components – fast floatability components predominantly reporting to the concentrate streams
and the slower and non-floating components predominantly reporting to the tailing streams.
If we assume that the feed consists of a number of floatability components, the other streams
are also made up of these same floatability components, just in a different ratio. Analysis
involves assuming the rate of each floatability component in the different batch tests is the
same and that the mass of each floatability component is conserved across different nodes in
the process. These constraints enable the data to parameter ratio to be significantly increased
and enable parameters of multicomponent systems to be derived with statistical confidence.
It is the author’s experience that a two floating and one non-floating model (Equation 9) is
usually sufficient to describe or model the behavior of minerals in a flotation circuit. The
measured distribution of this type of model around a circuit derived using the Northparkes
batch flotation test data depicted in Figure 10 is shown in Figure 14.

R = m f (1 - exp (- kf t)) + ms (1 - exp (- ks t)) where mnon floating = 1 – mf - ms (9)

In a similar vein, laboratory batch flotation tests can be performed with multiple stages or
with recycle streams to increase the number of data points available for parameter estimation.
Thus, multiple ore floatability parameter estimation can be performed without the need to
collect samples from an operating flotation circuit.
A step-by-step worked example of ore parameter derivation from a multiple stage batch
flotation test will be provided at the end of this chapter. The reader is also referred to

88.9 3.8 3.8 1.3

5.8 3.7 4.2 3.7
5.3 5.3 5.3 5.3

85.1
2.5
2.1
0.5
0.0
0.0 0.0
11.7 0.5
2.7 0.0
80.7
0.0
1.8 11.7
0.0 2.2
0.0
4.8
Legend
1.9 6.9 Fast Floating
0.0 0.3 Slow Floating
0.0 Non Floating

FIG 14 – Mass in different copper floatability components around the Northparkes industrial
flotation circuit (based on 100 units of copper in the feed) (Runge et al, 2003).

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 335

 KYM RUNGE

Varadi, Runge and Franzidis (2010), who provides additional examples of model parameter
derivation from multi-stage batch laboratory flotation data.

Comparison of ore floatability parameters

Ore floatability parameters provide the metallurgist with numbers that can be used to
quantitatively assess and compare the floatability of ore in different laboratory batch
flotation tests.
For optimal separability in a flotation circuit, the valuable mineral flotation rate should
be high and the proportion of slow or non-floating valuable mineral should be minimised.
Gangue flotation rates should ideally be low, and a large proportion of the gangue mineral
should be non-floatable. It will not be possible to separate mineral components of similar
flotation rate, so the ratio of the slow floating gangue to slow floating valuable mineral
flotation rate is also an important parameter.
Hay and Rule (2003) characterised the ore floatability of the ore feeding a number of
different platinum concentrators using a two floating component model. They found that
the concentrate recovery and grade were strongly correlated with the fraction of fast-floating
valuable mineral with a proportion of the slow-floating fraction being recoverable when the
ratio of the slow valuable mineral to gangue flotation rate ratio was above a threshold value.
Ore floatability component mapping, as illustrated in Figure 14, can be used in conjunction
with the mineral recovery and selectivity graphical information to assess the appropriate
destination of recycle streams and the target streams for regrinding, collector or depressant
addition.

Simulation using ore floatability parameters

The advantage of ore floatability parameters over the traditional graphical techniques, is that
they can be used for prediction. Once determined, they can be used to rapidly investigate
many circuit scenarios. They can replace the need for complex locked cycle tests, giving
estimates of the ultimate grade and recovery achievable in multistage flotation.
The aim of simulation is to calculate the distribution of floatability components across a
proposed circuit. Beginning with the feed and the first unit in the circuit, recovery in the
product streams is calculated. This calculation sequence is continued for each unit process,
the product of earlier processes forming the feed to subsequent processes. Recycle streams
during the first iteration are set to zero and multiple iterations of circuit calculations are
performed until the mass in these recycle streams converges to a constant value. Once
convergence has been achieved, the mass of the different floatability components of each
mineral in each stream can be added together. These mineral masses can be used to calculate
stream mineral grade (mineral mass divided by total mass in stream) and recovery (mass
with respect to feed).
At each process in the circuit, recovery equations are used to calculate product component
flows. Wherever streams are mixed, for instance, the mass of each floatability component in
the product stream is equal to the addition of the mass of this same floatability component in
the feed streams.
The recovery equation used for a flotation process is dependent on its particle residence time
distribution. For a semi-batch process (like that performed in the laboratory batch flotation
test) recovery of each component is calculated using Equation 4. Conventional mechanical
cells behave as perfect mixers and thus have a different recovery equation (Equation 10).

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

R= kx (10)
1+kx
The flotation recovery equation can be extended to include parameters associated with
entrainment and the cell operating variables (for example, air rate, froth depth). Flotation
cell water recovery equations are also required to calculate the circuit water flow information
required for cell residence time calculations. For more information on these types of simulations
and the methods required to determine the parameters of these relationships, the reader is
referred to Harris et al, 2002.
A simplification of these more complex models can be used to assess the separability of a
particular ore in a particular flow sheet. The effect of the cell operating variables and residence
time can be lumped into a single parameter, the cell operating constant, θ (Loveday, 1966),
which typically varies between zero and 100. Flotation recovery of a component is a function
of only this parameter and its particular batch flotation test rate constant (Equation 11).
k batch i
R= (11)
1 + k batch i
Multiple simulations are performed for a particular flow sheet, with the cell operating
constants, θ, randomised in each stage. This randomisation is a representation of the range
of different cell volumes/cell operating conditions that could be used to achieve flotation
separation. It is equivalent to the flotation operator slowing or speeding up the process to
achieve the desired concentrate grade and recovery at each stage.
The resulting final concentrate grade/recovery numbers from these simulations can be
plotted. Figure 15 shows examples of the type of curves generated using this type of analysis.
These curves were generated using ore floatability constants derived from batch laboratory
experiments applied to a three-stage flotation circuit. The result is not a single grade versus
recovery relationship, as changes in the cell operating constant in one stage results in both a
change in recovery but also a change in the separation efficiency of the circuit.
These curves can be generated to compare the floatability of different ore types (Figure 15b)
or to compare the ability of different flow sheets to separate the minerals in a particular ore
sample (Figure 16).
Simulations required to create these curves can be performed on an Excel spreadsheet.
Alternatively, packages such as JKSimFloat, HSC Chemistry©, and Limn© have been designed
to enable these types of simulations to be performed rapidly in a user-friendly environment.

Estimation of full-scale recovery based on batch test results

The time it takes for a mineral to be recovered in a batch laboratory flotation test can be used
to estimate its recovery in the full-scale flotation circuit. Recovery rates in the batch cell
environment are usually significantly higher than those measured at full scale due to either
higher amounts of turbulence or higher froth recoveries achievable at small scale. A scale-up
factor (C) can be introduced to the full-scale recovery equation to account for these differences
and relate full-scale recovery to the rates measured in a batch laboratory flotation test (kbatch)
(Equation 121).
n Cki,batch x
R = mi/ 1 + Cki,batch x
(12)
i=1

1. Note that this perfect mixing equation can only be used to predict flotation recovery from a single flotation cell. If multiple cells are
present in a bank, then recovery should be calculated for each cell individually and then combined to predict the overall recovery.

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 KYM RUNGE

56
A

Final Concentrate Grade (%)

54
52
50
48
46
44
42
40
40 50 60 70 80 90 100
Circuit Recovery (%)

B 56
Final Concentrate Grade (%)

54
52
50
48
46
44
42
40
40 50 60 70 80 90 100
Circuit Recovery (%)
FIG 15 – Circuit grade and recovery simulated in a three-stage flotation circuit. (A) For a particular
ore type, (B) for the same ore subject to different reagent/regrinding schemes.

60
Final Concentrate Grade (%)

58
56
54
52
50
48 Three Stage
46 Four Stage
44
42
40
40 60 80 100
Circuit Recovery (%)

FIG 16 – Circuit grade and recovery simulated for the same ore processed in a three- and four-stage flotation circuit.

The cell scale-up factor is a complex function of the operating conditions at full scale
and those used in the batch laboratory flotation test. It will also be strongly dependent on
the ore, its particle size distribution and its effect on the full-scale froth characteristics. It is
often assumed that the batch test rate is about twice the rate at full scale (that is, C = 0.5).
In reality, the scale-up factor can change significantly with the cell operating conditions used

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

in both the batch test and full-scale cells and typically is between 0.05 and 1. It is the author’s
recommendation that this scale-up factor be determined by comparing batch and full-scale
kinetics in an existing concentrator or assumed to be equal to that measured in another
operation treating a similar type of ore. Scale-up numbers will usually be higher in a rougher
and cleaner bank than a scavenger bank (Runge et al, 2001, 2003). Scale up is also sensitive to
particle size with coarser particles having a lower scale-up number than fines because of low
coarse particle froth recoveries in the full-scale cells. A worked example is provided at the
end of this chapter demonstrating an example of how the scale-up factor can be determined.
The other complication when scaling the kinetics from a batch test is that the multiple
component parameters required to fully describe the floatability of an ore (that is, fast, slow
and non-floating rates and mass fractions) cannot be determined confidently from a single
test. To overcome this problem, simplified model structures such as the one floating and
one non-floating model can be used. These simplified models can be used to predict the
recovery achievable off an industrial bank of flotation cells based on a batch test of its feed.
However, prediction of the performance of an entire circuit where streams are recycled
based on results from a single batch test of a feed sample will be poor with this simplified
type of model structure.
Full-scale multiple stage circuit prediction requires the model to better incorporate the
distribution of floatabilities in the feed. There are a number of options. Parameter estimation
can be performed using locked cycle batch test data (rather than a single batch flotation
test) to enable the data to be modelled using fast, slow and non-floating components.
Alternatively, the products from a single batch test can be sized and the rate and proportion
of floatable mineral can be determined for each size class. In this approach, each size class
will need to be assigned a different scale-up constant due to the scale-up constant being
sensitive to particle size.
Once the batch test ore floatability parameters and estimates of cell scale-up numbers have
been established, simulations can be performed. For a new operation, one can estimate the
number of flotation cells of a particular volume required to achieve a particular recovery from
a flotation bank. Additional capacity is usually factored into this analysis to account for any
error and the usual increase in capacity (over design) often demanded from a flotation circuit
over time. Alternatively, for an existing plant, the response of different ore types or the effect
of changing variables such as reagent conditioning, grinding environment or particle size on
the grade and recovery achievable in the plant can be predicted.

AREAS OF APPLICATION
Laboratory batch flotation testing can be used as a diagnostic tool throughout the development
and life of a flotation circuit.
Even before a project has commenced, batch laboratory flotation of drill core samples provides
the information required to make decisions regarding a project’s viability. Throughout the
development of a flotation circuit flow sheet, batch tests are used to screen and determine the
appropriate reagent suite and dosage rates, the target grind size and an estimate of the circuit
residence time requirements.
From the day a flotation circuit is commissioned, the metallurgist strives to better understand
the process and implement changes that will improve or optimise operation. Batch laboratory
flotation testing is one of a suite of tools used in this process. New reagents are almost always
screened first in these small tests before implementation at full scale.

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 KYM RUNGE

After implementation of a change in grind size, reagent or circuit change at industrial scale,
batch flotation tests can be used to assess the effect of the change on mineral recovery rates and
selectivity.
The ore feeding a flotation circuit is continually changing as rock is extracted from different
areas of the mine. Batch testing is a valuable tool for comparing the floatability of different
ores or predicting the metallurgical performance that will be achieved when a particular ore
is processed. Geometallurgical programs are often conducted, involving hundreds of batch
flotation tests to achieve this objective.
Flotation modelling techniques published in the literature (Harris et al, 2002; Runge et al,
2001; Coleman, Urtubia and Alexander, 2006) are using batch testing to determine ore
characterisation properties. These models can be used for flotation circuit design, flotation
circuit diagnosis and simulation of alternative operating strategies. They enable an estimation
of the overall change in grade and recovery achievable in a particular process fed an ore with
a particular mineral selectivity.
In summary, laboratory batch flotation testing is an essential tool that, when used
appropriately, helps a metallurgist design new flotation processes, develop strategies for
improving a flotation circuit and ultimately assess the effectiveness of these strategies.

ADVANTAGES AND LIMITATIONS OF USING BATCH FLOTATION TESTING FOR CIRCUIT DIAGNOSIS
Small-scale batch laboratory tests are relatively cheap and easy to perform. Almost all
concentrator laboratories are equipped with laboratory flotation cells and the associated
equipment required to prepare and process the samples produced from a test. They also
have the advantage that, to a significant degree, they replicate the flotation process that occurs
at full scale.
Batch tests also have the advantage that they enable the ore floatability to be analysed in
isolation to those effects related to circuit operation. Poor flotation recovery measured in a
circuit survey can be due to a number of different effects: poor ore floatability, insufficient
residence time, use of overly deep froth depths, to name a few. Batch laboratory tests are usually
performed using the same operating conditions and thus any change between tests can be
attributed solely to a difference in ore floatability. Batch tests performed in conjunction with
circuit surveys can help decouple ore floatability and circuit operation effects and highlight
the cause of flotation recovery loss.
What is often forgotten when analysing batch flotation test results, however, is that they are
a good measure of pulp floatability but sometimes a poor indicator of full-scale froth phase
performance. The froth in a small-scale laboratory test is only a couple of centimetres in
depth and is continually removed. In a full-scale cell the froth can be 5 cm to 50 cm in depth
and there are usually significant transportation distances between a point on the surface of the
froth and the nearest launder. The froth produced in a small-scale cell is often very different
in bubble size, texture and viscosity to that observed when the same ore is processed at full
scale. This can result in a particular reagent suite, producing a superior pulp floatability
(and thus batch test result) but poor recovery in a full-scale cell because of its effect on
movement of the froth phase.
The primary assumption associated with batch laboratory test analysis is that pulp
selectivity in the small scale is similar to what would be achieved in the full-scale flotation
machine. It’s likely this is a valid assumption in mechanical cells but less likely in
alternative flotation technologies. The low degree of turbulence in a column, for instance,

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

can result in the poor recovery of coarse particles, which are recovered quickly in a batch
flotation test.
Another risk during batch laboratory flotation testing is the removal of loosely deposited
surface coatings. The higher agitation energies that exist in a small-scale cell can sometimes
remove molecules that would remain in situ in the full-scale flotation environment.
These limitations, as with most diagnostic techniques, mean that those conclusions drawn
from batch laboratory testing should be verified through full-scale trials.
Much can be gained by performing batch laboratory flotation tests in conjunction with other
measurements. Batch laboratory flotation tests indicate the overall result of a change. Sizing,
mineralogical and chemical analysis tools can be used to determine the reason for a particular
result, often suggesting alternative batch laboratory experiments to trial.

CONCLUDING REMARKS
In this chapter, batch laboratory testing procedures and the modelling and graphical
techniques that can be used to analyse the results of these tests have been reviewed.
It has been demonstrated that batch laboratory flotation tests have a role to play throughout
the lifetime of a particular flotation circuit operation. They can be used during the design of
new flotation processes, to develop strategies for improving a flotation circuit and, ultimately,
to assess the effectiveness of these strategies.
They have the advantage that they are relatively cheap and easy to perform and to an extent,
replicate the full-scale flotation process. They enable an assessment of ore floatability without
the complication of changing cell operating variable effects. Effects, due to differences between
the small-scale and full-scale cell, should be kept in mind when interpreting results.
The value of laboratory batch flotation testing is greatly enhanced when performed in
parallel with other techniques that can assist with data interpretation.

REFERENCES
Chander, S and Polat, M, 1994. In quest of a more realistic flotation kinetics model, in Proceedings
IV Meeting of the Southern Hemisphere on Mineral Technology and III Latin American Congress on Froth
Flotation (eds: S Castro and J Alvarez), pp 481–500.
Coleman, R G, Urtubia, H E and Alexander, D J, 2006. A comparison of BHP Billiton’s Minera Escondida
flotation concentrators, in Proceedings 38th Annual Meeting of the Canadian Mineral Processors, pp 349–
370 (Canadian Institute of Mining, Metallurgy and Petroleum: Montreal).
Harris, M C, 1998. The use of flotation plant data to simulate flotation circuits, in Proceedings SAIMM
Mineral Processing Design School (Southern African Institute of Mining and Metallurgy: Johannesburg).
Harris, M C, Runge, K C, Whiten, W J and Morrison, R D, 2002. JKSimFloat as a practical tool for
flotation process design and optimization, in Mineral Processing Plant Design, Practice and Control,
vol 1, pp 461–478 (Society for Mining, Metallurgy, and Exploration: Littleton).
Hay, M P and Rule, C M, 2003. Supasim: a flotation plant design and analysis methodology, Minerals
Engineering, 16(11):1103–1109.
Johnson, N W, 2005. A review of the entrainment mechanism and its modelling in industrial flotation
processes, in Proceedings Centenary of Flotation Symposium (ed: G J Jameson), pp 487–496 (The
Australasian Institute of Mining and Metallurgy: Melbourne).
Kelsall, D F, 1961. Application of probability in the assessment of flotation systems, Transactions of the
Institute of Mining and Metallurgy, 70:91–204.

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 KYM RUNGE

Klimpel, R, 1980. Selection of chemical reagents for flotation, in Mineral Processing Plant Design, pp 907–
934 (The American Institute of Mining, Metallurgical, and Petroleum Engineers: Littleton).
Loveday, B K, 1966. Analysis of froth flotation kinetics, Trans IMM, 75:C219–C225.
Runge, K C, Dunglison, M E, Manlapig, E V and Franzidis, J-P, 2001. Floatability component modelling
– a powerful tool for flotation circuit diagnosis, in Proceedings Fourth International Symposium on
Fundamentals of Minerals Processing, pp 93–107 (Canadian Institute of Mining, Metallurgy and
Petroleum: Montreal).
Runge, K C, Franzidis, J P and Manlapig, E V, 2004. Optimisation of flotation pulp selectivity utilising
nodal analysis, in Proceedings 36th Annual Meeting of the Canadian Mineral Processors, pp 575–597
(Canadian Institute of Mining, Metallurgy and Petroleum: Montreal).
Runge, K C, Franzidis, J P, Manlapig, E V and Harris, M C, 2003. Structuring a flotation model for
robust prediction of flotation circuit performance, in Proceedings 22nd IMPC Conference, Cape Town,
September.
Runge, K C, Harris, M C, Franzidis, J P and Manlapig, E V, 2006. Conservation of floatability across
processes in industrial flotation circuits, in Proceedings XXIII International Mineral Processing Congress
(eds: G Onal, N Acarkan, et al), vol 3, pp 1909–1914 (Promed Advertising Agency).
Runge, K C, Harris, M C, Frew, J A and Manlapig, E V, 1997. Floatability of streams around the Comino
Red Dog lead cleaning circuit, in Proceedings Sixth Annual Mill Operators’ Conference, pp 157–163 (The
Australasian Institute of Mining and Metallurgy: Melbourne).
Varadi, R, Runge, K C and Franzidis, J P, 2010. The rate variable batch test (RVBT): a research method
of characterising ore floatability, in Proceedings XXV IMPC, pp 2471–2480 (The Australasian Institute
of Mining and Metallurgy: Melbourne).

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

Appendix – Worked examples

EXAMPLE 1 – REGRIND EVALUATION
A tower mill has been incorporated into the Eureka lead circuit to regrind lead rougher
concentrate in an effort to improve liberation and thus the grade achievable in the lead flotation
circuit concentrate. Batch laboratory flotation tests were performed on the rougher concentrate
and the reground rougher concentrate (after reagent addition) to assess whether this unit is
having the desired effect. Six timed concentrates and a tailing sample were produced from
each test. Table A1 outlines the mineral grade measured in each of these samples. This data
was then used to calculate the cumulative grade and recovery achieved as a function of time in
these tests. Figure A1 shows the grade versus recovery curve and Figure A2 shows the galena
gangue selectivity curves.
In contrary to what was expected, regrinding has not resulted in an improvement in the
floatability of the ore. At low galena recoveries, the grade recovery relationship is significantly
poorer in the ‘after regrinding’ batch test. At high galena recoveries, the relationship in the
two tests is very similar.

TABLE A1
Mineral grade of samples produced from batch flotation testing of a lead concentrate before and after grinding.
Sample Time Before After regrinding
(min) Galena Sphalerite Pyrite NSG Galena Sphalerite Pyrite NSG
Concentrate 1 0–0.5 76.71 14.08 4.02 5.20 72.80 14.86 6.77 5.58
Concentrate 2 0.5–1.5 68.66 20.80 5.73 4.81 68.54 17.67 7.66 6.13
Concentrate 3 1.5–4 48.42 31.44 9.12 11.03 57.27 25.34 9.52 7.87
Concentrate 4 4–8 25.88 45.83 16.35 11.95 28.29 44.10 15.60 12.00
Concentrate 5 8–12 18.17 50.83 21.40 9.60 15.99 50.99 19.02 14.01
Concentrate 6 12–20 12.54 51.77 23.49 12.21 12.19 50.05 20.80 16.96
Tailing 4.72 53.02 21.25 21.01 5.75 45.20 22.84 26.21
NSG – non-sulfide gangue.

100
Galena Recovery (%)

80

Rougher Concentrate
60

40 Reground Rougher
Concentrate
20

0
40 50 60 70 80
Galena Grade (%)

FIG A1 – Galena recovery versus grade achieved in batch flotation tests of the lead rougher concentrate before and after regrinding.

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 KYM RUNGE

A 70

Sphalerite Recovery (%)

60
Rougher Concentrate
50
Reground Rougher
40
Concentrate
30
20
10
0
0 20 40 60 80 100
Galena Recovery (%)

70
B
Rougher Concentrate
60
Pyrite Recovery (%)

50 Reground Rougher
Concentrate
40
30
20
10
0
0 20 40 60 80 100
Galena Recovery (%)

60
C
Rougher Concentrate
50
NSG Recovery (%)

Reground Rougher
40 Concentrate
30

20

10

0
0 20 40 60 80 100
Galena Recovery (%)

FIG A2 – Galena versus gangue mineral selectivity before and after regrinding of the lead rougher concentrate.

This result is primarily due to deterioration in the pyrite-galena selectivity. Galena recovery
rate has changed very little by the regrinding process, whereas there has been a significant
increase in pyrite recovery (Figure A3). There is very little difference in the galena-sphalerite
selectivity and a marginal improvement in galena-gangue selectivity.
The grinding environment often results in changes in the condition of particle surfaces – iron
hydroxide coatings, for instance, can deposit on all surfaces during grinding with mild steel
balls. Some change is occurring to the pyrite particles in this grinding system, resulting in
an increased recovery rate. Surface chemical speciation of particle surfaces before and after
grinding would almost certainly explain the reason for this observed result and maybe suggest
strategies to reverse the effect.

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60
A

Pyrite Recovery (%)

40

Rougher Concentrate

20 Reground Rougher
Concentrate

0
0 5 10 15 20 25
Time (min)

100
B
Galena Recovery (%)

80
Rougher Concentrate
60
Reground Rougher
40 Concentrate

20

0
0 5 10 15 20 25
Time (min)

FIG A3 – Mineral recovery versus time before and after regrinding of the lead rougher concentrate.

Under the current chemical conditions, however, regrinding of lead concentrate should be
discontinued.

EXAMPLE 2 – CIRCUIT SURVEY COMPARISON USING NODAL ANALYSIS

Lime is used periodically in the zinc cleaner scavenger flow sheet (Figure A4) of the Eureka
concentrate to depress pyrite. Debate reigns as to whether this lime results in an improvement
in performance. To try and resolve the dispute between those advocating lime addition and
those against it, two circuit surveys of the zinc cleaner scavenger flow sheet were performed
– one with lime on and one with lime off. Batch laboratory tests were performed to measure
the floatability of the feed, concentrate and final tailing of the circuit. Regrinding and staged
reagent addition is also used within this section to optimise the zinc gangue selectivity in
the circuit.
Results from the survey indicate that, although similar grade is achieved, zinc recovery is
significantly lower in the survey performed when lime is added to the circuit (Table A2). This
survey information alone fails to resolve the dispute. Those advocating lime addition suggest
that the feed floatability and the operation of the circuit were probably very different during
the two surveys.
Table A3 shows the cumulative mineral recovery data generated from the feed, concentrate
and tailing sample batch laboratory flotation tests.
The feed mineral recovery rate curves of the various minerals can be compared to assess
whether feed floatability is different between the two surveys. A review of Table A3 shows

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 KYM RUNGE

Activator Collector
To Final Tail
Stage 1 Sump

Lime Activator
Regrind

Collector
Stage 2

To Final Concentrate
Sump

Cleaning Columns

FIG A4 – Eureka zinc cleaner scavenging circuit.

TABLE A2
Metallurgical performance achieved during each survey.
Details of survey Concentrate grade (%) Recovery to concentrate (%)
Galena Sphalerite Pyrite NSG Galena Sphalerite Pyrite NSG
No lime added 6.2 79.7 7.0 7.2 57.8 86.2 11.4 5.5
Lime added 5.0 79.0 8.0 8.0 33.0 61.5 8.4 4.2
NSG – non-sulfide gangue.

that the sphalerite, galena and non-sulfide gangue mineral recovery rates are very similar
in the feed batch flotation tests. The pyrite recovery rate is low and thus sphalerite/pyrite
selectivity of the feed is superior in the lime survey (Figure A5). It can therefore be concluded
that the low recoveries in the lime survey are not due to poorer feed ore floatability.
Lime is supposed to improve sphalerite/pyrite selectivity by depressing pyrite in preference
to sphalerite. The change in sphalerite/pyrite selectivity in the two circuit surveys can be
assessed using nodal analysis techniques. The circuit is a node with a single feed and two
product streams. The two product stream results can be combined using Equation A1 to create
an estimate of the combined product floatability.
R Concentrate
Mineral j
# R Concentrate,
Mineral j
t
+ R Tail
Mineral j
# R Tail, t
Mineral j
R Combined Product, t
= (A1)
Mineral j 100
where:
R Concentrate
Mineral j
is the recovery of mineral j to concentrate

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

TABLE A3
Cumulative mineral recovery achieved in the feed, concentrate and tailing batch tests performed during the two circuit surveys.
Cumulative time Mineral cumulative recovery in feed batch test
(min) No lime addition Lime addition
Galena Sphalerite Pyrite NSG Galena Sphalerite Pyrite NSG
0.33 22.5 33.3 10.8 7.5 23.2 36.4 9.7 10.3
1 49.9 63.4 28.2 19.8 49.0 66.6 22.2 21.8
2 66.8 79.1 43.3 29.9 65.7 80.7 33.5 31.8
4 82.4 89.2 58.0 40.9 79.3 90.4 48.3 42.0
8 89.5 94.3 69.6 51.1 87.7 94.8 62.1 52.2
12 92.4 96.1 75.5 57.6 91.2 96.5 69.7 58.9

Cumulative time Mineral cumulative recovery in concentrate batch test

(min) No lime addition Lime addition
Galena Sphalerite Pyrite NSG Galena Sphalerite Pyrite NSG
0.33 32.2 37.5 18.9 16.6 19.3 22.9 15.0 16.6
1 68.6 74.9 42.1 38.2 46.8 53.8 37.7 36.9
2 86.0 90.4 59.3 52.7 65.2 73.2 52.5 52.3
4 94.7 97.3 76.2 68.7 80.4 87.8 67.6 67.7
8 98.0 99.1 89.0 81.1 91.1 96.0 81.5 83.0
12 98.7 99.5 91.8 83.8 94.6 98.0 87.4 88.5

Cumulative time Mineral cumulative recovery in tailing batch test

(min) No lime addition Lime addition
Galena Sphalerite Pyrite NSG Galena Sphalerite Pyrite NSG
0.33 13.5 24.2 8.4 6.2 13.8 18.7 7.6 5.9
1 31.7 53.0 23.0 11.6 33.9 41.2 19.0 13.8
2 46.8 68.4 35.9 17.5 49.5 56.0 29.9 20.0
4 61.0 77.1 48.1 25.7 62.9 67.0 40.7 25.7
8 73.0 84.1 62.6 35.0 75.2 75.9 53.8 34.2
12 77.4 86.0 67.2 40.1 80.2 79.3 60.6 39.7
NSG – non-sulfide gangue.

R Tailing
Mineral j
is the recovery to tailing of mineral j

R Stream s, t
Mineral j
is the cumulative recovery of mineral j in the batch test of stream s after t minutes
of flotation
The results of this calculation are shown in Table A4.
Once the combined product floatability has been calculated, feed and product mineral
recoveries can be compared. Figure A6 shows the sphalerite/pyrite selectivity in the feed
and product streams of this particular circuit. Sphalerite/pyrite selectivity in the survey when
lime is not added, improves dramatically across the circuit. It can therefore be concluded that

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 347

 KYM RUNGE

100
Survey - No Lime Added

Pyrite Recovery (%)

80
Survey - Lime Added
60

40

20

0
40 50 60 70 80 90 100
Sphalerite Recovery (%)

FIG A5 – Sphalerite/pyrite selectivity measured in the feed batch tests performed during the two circuit surveys.

TABLE A4
Cumulative mineral recovery of the combined product streams from the two circuit surveys.
Cumulative time Mineral cumulative recovery in combined product
(min) No lime addition Lime addition
Galena Sphalerite Pyrite NSG Galena Sphalerite Pyrite NSG
0.33 24.3 35.7 9.6 6.8 15.6 21.2 8.2 6.3
1 53.0 71.9 25.2 13.1 38.2 49.0 20.6 14.7
2 69.5 87.4 38.6 19.4 54.7 66.6 31.8 21.4
4 80.5 94.5 51.3 28.1 68.7 79.8 43.0 27.5
8 87.4 97.0 65.6 37.5 80.4 88.2 56.2 36.3
12 89.7 97.6 70.0 42.5 85.0 90.8 62.9 41.8
NSG – non-sulfide gangue.

regrinding and the reagent addition during this survey have had a positive effect on the ability
to separate sphalerite and pyrite. In contrast, sphalerite/pyrite selectivity deteriorates in the
survey in which lime is added.
This deterioration in sphalerite/pyrite selectivity is due to a decrease in the sphalerite
recovery rate (in contrast to an increase when lime is not added to the circuit) and a small but
similar decrease in the recovery of pyrite (Figure A7).
Use of nodal analysis in this example has shown that lime addition in the circuit does not
result in appreciable improvements in sphalerite/pyrite selectivity. The deterioration in
valuable to gangue mineral selectivity will have had a significant impact on the ability to
separate minerals in this circuit. Adjustments in circuit operation would have occurred to
maintain grade but at a cost of losing zinc recovery.
As a confirmation of this conclusion, nodal analysis was also performed before and after
lime addition in this circuit (Runge, Franzidis and Manlapig, 2004). These tests show that lime
addition dramatically decreases the floatability of all minerals, but sphalerite in particular.
It thus can be concluded that lime addition is clearly not the solution to improving sphalerite/
pyrite selectivity in this circuit. Batch laboratory testing performed in conjunction with survey
work enabled a more definitive analysis of circuit operation.

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

A Survey - No Lime Added

100

Pyrite Recovery (%)

80
Feed
60 Combined Product

40

20

0
40 50 60 70 80 90 100
Sphalerite Recovery (%)

B Survey - Lime Added

100
Pyrite Recovery (%)

80
Feed
60 Combined Product

40

20

0
40 50 60 70 80 90 100
Sphalerite Recovery (%)

FIG A6 – Sphalerite/pyrite selectivity measured in the feed and product of the two circuit surveys.

EXAMPLE 3 – ORE FLOATABILITY PARAMETER MODELLING OF LABORATORY BATCH TEST DATA

There is a concern that a future ore to be fed to the Eureka concentrator will be more difficult
to treat in the lead circuit than the current ore. Liberation analysis has indicated it has a more
complex lead mineralogy.
A multiple-stage batch laboratory flotation test was performed using the future ore to enable
its ore floatability parameters to be determined and compared to those of the current ore.
Grind size and reagent dosage rates were similar to those used in the plant. The test involved
floating a sample of the future ore for eight minutes with two samples of concentrate collected
– one from the first two minutes (denoted rougher concentrate) and one from the two to
eight minute time period (denoted scavenger concentrate). The rougher concentrate was then
refloated in a cleaner stage where concentrates were collected from zero to 20 seconds, 20 to
40 seconds, 40 to 60 seconds and from one to two minutes. The scavenger concentrate was
then combined with the tailing from the cleaner stage and refloated in a cleaner scavenger
stage for six minutes. Concentrates were collected from zero to 0.5 minutes, 0.5 to one minute,
one to two minutes and two to six minutes. A diagram depicting the stages of the test and
samples produced is shown in Figure A8.
The samples produced from the test were dried and weighed and analysed for lead
content – the results of which are shown in Table A5.

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 KYM RUNGE

A 100

Sphalerite Recovery (%)

80

Feed No Lime
60
Feed Lime
40 Product No Lime
Product Lime
20

0
0 5 10 15
Time (min)

100
B
Pyrite Recovery (%)

80

60
Feed No Lime
40
Feed Lime
20 Product No Lime
Product Lime
0
0 5 10 15
Time (min)

FIG A7 – Sphalerite and pyrite recovery rates measured in the feed and product of the two circuit surveys.

Rougher Scavenger
(2 minutes) (6 minutes)
New Feed Tailing

Cleaner Clner Scav

(2 minutes) (6 minutes)
Cleaner
Tailing

Concentrates
FIG A8 – Representation of multiple stage batch laboratory flotation test – samples produced denoted by a red circle.

It is decided to represent the ore floatability of the system by three lead components (fast,
slow and non-floating lead) and three gangue components (fast, slow and non-floating
gangue). Three components are the maximum number that could be derived with confidence
from the experimental data available. Gangue is a term to refer to the weight in each
sample that is ‘not lead’. To determine the flotation rate and proportion of lead and gangue
in each of the floatability components, an Excel spreadsheet was set up to calculate the weight
and assay of the experimental samples based on a flotation model. Solver, an add-in tool to
Excel, was then used to determine the ore floatability parameters that minimise the difference
between the measured and calculated sample information.

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

TABLE A5
Multiple-stage batch test results.
Sample Solids (g) % Lead % Gangue
Cleaner concentrate 1 13.4 75.9 24.1
Cleaner concentrate 2 10.0 74.0 26.0
Cleaner concentrate 3 7.5 71.9 28.1
Cleaner concentrate 4 13.5 67.3 32.7
Cleaner scavenger concentrate 1 9.2 55.8 44.2
Cleaner scavenger concentrate 2 6.7 50.5 49.5
Cleaner scavenger concentrate 3 8.9 42.8 57.2
Cleaner scavenger concentrate 4 14.5 25.7 74.3
Cleaner scavenger tailing 19.6 7.2 92.8
Tailing 2096.7 0.9 99.1
Recalculated feed 2200.0 3.1 96.9

Tables A6, A7 and A8 show the calculation tables that were set up in Excel to perform the
computations.
The calculations are performed separately for each component. The first table for the lead
calculation contains the parameters to be derived from the fitting exercise. The values first input
into the table are an estimate. Note that the rate and mass fraction of the non-floating component
are not fitted parameters. The rate of the non-floating component is zero and the proportion of
material in the non-floating component is one minus the fraction in the other components.
The second table calculates the recovery of each component in each stage of the batch test
(Rs). Recovery is a function of the flotation rate of the component (ki) and the time of flotation
(t) (Equation A2).

Rs = 1 − exp ( −ki t) (A2)

In the final table, the weight of each component in each batch test sample throughout the
duration of the test is calculated. The weight in each component in the test feed is established
by multiplying the total weight of lead in the feed (an input) by the proportion of lead in
each component as specified in the first table. The weight in the concentrate of each stage is
determined by multiplying the weight in the feed to the stage by the stage recovery (Rs). The
weight in the tail of each stage is the feed minus the concentrate weight. These calculations
are performed in sequence, with either the concentrate or tailing (or both in the case of the
cleaner scavenger feed) of previous stages becoming the feed to subsequent stages.
The total weight of lead reporting to each concentrate or tailing stream in the batch test is
then calculated by summing the weights of its floatability components.
The identical calculation sequence is performed to determine the mass of gangue in each of
the batch test samples according to a set of gangue specific floatability components (Table A7).
The weight of lead and gangue calculated in each stream can be used to calculate the total
weight of solids and the lead and gangue assay of each batch test sample. This calculated
assay is then compared to the actual assay measured during the test (Table A8).

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 KYM RUNGE

TABLE A6
Lead flotation model Excel spreadsheet.
Parameter table Fast Slow Non
Lead flotation rates (min )-1
0.932 0.201 0.000
Proportion of lead in feed in each component 0.642 0.099 0.258

Stage recovery matrix Time (min) Calculated recovery in stage

Fast Slow Non
Rougher 2 84.5% 33.1% 0.0%
Scavenger 6 99.6% 70.1% 0.0%
Cleaner 1 0.333 26.7% 6.5% 0.0%
Cleaner 2 0.333 26.7% 6.5% 0.0%
Cleaner 3 0.333 26.7% 6.5% 0.0%
Cleaner 4 1 60.6% 18.2% 0.0%
Cleaner scavenger 1 0.5 37.3% 9.6% 0.0%
Cleaner scavenger 2 0.5 37.3% 9.6% 0.0%
Cleaner scavenger 3 1 60.6% 18.2% 0.0%
Cleaner scavenger 4 4 97.6% 55.3% 0.0%

Component distribution matrix Weight of component in sample (g)

Batch test sample Fast Slow Non Total
Feed 43.84 6.78 17.64 68.26
Rougher concentrate 37.05 2.25 0.00 39.29
Scavenger concentrate 6.77 3.18 0.00 9.95
Tailing 0.03 1.35 17.64 19.02
Cleaner feed (rougher concentrate) 37.05 2.25 0.00 39.29
Cleaner concentrate 1 9.89 0.15 0.00 10.03
Cleaner concentrate 2 7.25 0.14 0.00 7.39
Cleaner concentrate 3 5.31 0.13 0.00 5.44
Cleaner concentrate 4 8.85 0.34 0.00 9.19
Cleaner tail 5.75 1.50 0.00 7.25
Cleaner scavenger feed (SC + CT) 12.51 4.68 0.00 17.19
Cleaner scavenger concentrate 1 4.66 0.45 0.00 5.11
Cleaner scavenger concentrate 2 2.93 0.41 0.00 3.33
Cleaner scavenger concentrate 3 2.99 0.70 0.00 3.68
Cleaner scavenger concentrate 4 1.89 1.73 0.00 3.62
Cleaner scavenger tailing 0.05 1.40 0.00 1.44
Combined cleaner concentrate 31.30 0.74 0.00 32.05
Combined cleaner scavenger conc 12.47 3.28 0.00 15.75
Total concentrate 43.77 4.03 0.00 47.79
Total tailings 0.07 2.75 17.64 20.47

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

TABLE A7
Gangue flotation model Excel spreadsheet.
Parameter table Fast Slow Non
Gangue flotation rates 0.654 0.099 0.000
Proportion of gangue in feed in each component 0.009 0.030 0.961

Stage recovery matrix Time (min) Calculated recovery in stage

Fast Slow Non
Rougher 2 73.0% 17.9% 0.0%
Scavenger 6 98.0% 44.7% 0.0%
Cleaner 1 0.333 19.6% 3.2% 0.0%
Cleaner 2 0.333 19.6% 3.2% 0.0%
Cleaner 3 0.333 19.6% 3.2% 0.0%
Cleaner 4 1 48.0% 9.4% 0.0%
Cleaner scavenger 1 0.5 27.9% 4.8% 0.0%
Cleaner scavenger 2 0.5 27.9% 4.8% 0.0%
Cleaner scavenger 3 1 48.0% 9.4% 0.0%
Cleaner scavenger 4 4 92.7% 32.6% 0.0%

Component distribution matrix Weight of component in sample (g)

Batch test sample Fast Slow Non Total
Feed 19.70 63.15 2050.89 2133.74
Rougher concentrate 14.37 11.32 0.00 25.70
Scavenger concentrate 5.22 23.18 0.00 28.40
Tailing 0.11 28.65 2050.89 2079.65
Cleaner feed (rougher concentrate) 14.37 11.32 0.00 25.70
Cleaner concentrate 1 2.81 0.37 0.00 3.18
Cleaner concentrate 2 2.26 0.35 0.00 2.62
Cleaner concentrate 3 1.82 0.34 0.00 2.16
Cleaner concentrate 4 3.59 0.96 0.00 4.55
Cleaner tail 3.89 9.29 0.00 13.18
Cleaner scavenger feed (SC + CT) 9.11 32.47 0.00 41.58
Cleaner scavenger concentrate 1 2.54 1.56 0.00 4.11
Cleaner scavenger concentrate 2 1.83 1.49 0.00 3.32
Cleaner scavenger concentrate 3 2.27 2.77 0.00 5.04
Cleaner scavenger concentrate 4 2.28 8.70 0.00 10.98
Cleaner scavenger tailing 0.18 17.95 0.00 18.13
Combined cleaner concentrate 10.49 2.03 0.00 12.51
Combined cleaner scavenger concentrate 8.93 14.52 0.00 23.45
Total concentrate 19.42 16.55 0.00 35.96
Total tailings 0.29 46.60 2050.89 2097.78

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 TABLE A8
354

Calculation of the sum of squares error associated with the model fit.
Calculated data Experimental data Standard deviation Squared error
Batch test sample Assay Solids (g) Assay Solids (g) Assay Solids (g) Assay Solids (g)
Lead Gangue Lead Gangue Lead Gangue Lead Gangue
Feed 3.10 96.90 2202.00
Rougher concentrate 60.46 39.54 64.99
Scavenger concentrate 25.94 74.06 38.34
Tailing 0.91 99.09 2098.67 0.85 99.13 2096.7 0.19 1.00 52.4 0.09 0.00 0.00
Cleaner feed (rougher concentrate) 60.46 39.54 64.99
Cleaner concentrate 1 75.94 24.06 13.21 76.7 24.09 13.4 1.00 1.00 0.3 0.58 0.00 0.22
Cleaner concentrate 2 73.84 26.16 10.00 73.1 25.97 10.0 1.00 1.00 0.3 0.54 0.04 0.00
Cleaner concentrate 3 71.56 28.44 7.60 71.0 28.09 7.5 1.00 1.00 0.2 0.31 0.13 0.10

KYM RUNGE
Cleaner concentrate 4 66.85 33.15 13.74 65.0 32.67 13.5 1.00 1.00 0.3 3.43 0.23 0.36
Cleaner tail 35.48 64.52 20.43
Cleaner scavenger feed (SC + CT) 29.25 70.75 58.77
Cleaner scavenger concentrate 1 55.45 44.55 9.22 58.3 44.16 9.2 1.00 1.00 0.2 8.10 0.15 0.03
Cleaner scavenger concentrate 2 50.07 49.93 6.65 48.2 49.51 6.7 1.00 1.00 0.2 3.49 0.18 0.02
FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

Cleaner scavenger concentrate 3 42.23 57.77 8.72 41.1 57.17 8.9 1.00 1.00 0.2 1.28 0.36 0.39
Cleaner scavenger concentrate 4 24.81 75.19 14.60 24.0 74.35 14.5 1.00 1.00 0.4 0.65 0.71 0.06
Cleaner scavenger tailing 7.38 92.62 19.57 7.5 92.79 19.6 0.82 1.00 0.5 0.02 0.03 0.00
Combined cleaner concentrate 71.92 28.08 44.56
Combined cleaner scavenger concentrate 40.18 59.82 39.20
Total concentrate 57.06 42.94 83.76
Total tailings 0.97 99.03 2118.24
Sum of squares error 21.52
 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

To calculate the total sum of squares error associated with the system, the error of each
experimental data point must be estimated. For this exercise, the Whiten function is used to
estimate the standard deviation of the assays (Equation A3) and a relative error of 2.5 per cent
is used as the error of the solid weights.

SD = 1 if assay > 9%
SD = assay / 10 + 0.1 if assay < 9% (A3)

The squared error associated with each experimental data point is calculated using
Equation A4. The total sum of squares error is the sum of the squared errors.
(dcalculated - d experimental) 2
SE = (A4)
SD experimental 2

Once the spreadsheet has been set up in the way described above, Solver (an add-in tool in
Excel) can be used to determine the lead and gangue parameters that minimise the total sum
of squares error. For this example, Solver is able to find a set of parameters that result in a
good fit to the experimental data.
In Table A9, the parameters derived from the analysis above are compared to those
derived from a similar test performed using the ore currently processed by the plant.
The flotation rates of the different components in the two different ores are similar. The ore
does have poorer floating characteristics than the current ore. The proportion of floatable
lead is significantly lower and the proportion of floatable gangue has increased. This is an
indication that the future ore is less liberated at the grind size tested.
The flotation model that was developed to determine the ore parameters can also be used
to simulate various different batch test configurations – predicting the change in grade and
recovery that would be produced if the test was run in a different way.
To use the model, the parameters of the ore are input into the parameter table and the time
of each stage is input into the stage recovery matrix. The lead grade and lead recovery of the
combined concentrate (cleaner and cleaner scavenger concentrate) is calculated by the model.
Using the parameters derived for the current ore and the future ore, the model was used to
predict the combined concentrate lead grade and recoveries that would be achieved if
different times were used in the various stages of the batch test. Table A10 shows the different
simulations that were performed and the results. Figure A9 shows a graphical comparison of
the results derived for the two ores.
The ore floatability of the future ore, as measured in the batch flotation test, is clearly
poorer than that currently treated. The lead recovery achievable at a particular grade is

TABLE A9
Stage batch test ore floatability results.
Parameter Future ore Current ore
Fast Slow Non Fast Slow Non
Lead flotation rates 0.93 0.20 0.0 0.99 0.16 0.0
Proportion of lead in each component in feed 0.64 0.10 0.26 0.71 0.08 0.21
Gangue flotation rates 0.65 0.10 0.0 0.62 0.07 0.0
Proportion of gangue in each component in feed 0.009 0.03 0.96 0.007 0.02 0.97

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 KYM RUNGE

TABLE A10
Multiple stage batch test simulation results.
Model Batch test stage time (min) Future ore Current ore
simulation Rougher Scavenger Cleaner Cleaner Lead Lead Lead Lead
scavenger grade (%) recovery (%) grade (%) recovery (%)
Base case 2.00 6.00 2.00 6.00 57.06 70.02 70.44 74.72
Simulation 1 2.00 6.00 0.50 1.50 66.69 55.63 77.69 61.67
Simulation 2 4.00 12.00 2.00 6.00 52.54 71.41 66.97 75.92
Simulation 3 6.00 18.00 2.00 6.00 50.52 71.78 65.05 76.32
Simulation 4 12.00 24.00 2.00 6.00 48.91 72.04 63.26 76.61
Simulation 5 12.00 24.00 4.00 12.00 43.01 73.71 57.32 78.28
Simulation 6 12.00 24.00 1.00 3.00 55.64 68.08 69.04 73.31
Simulation 7 6.00 18.00 1.00 3.00 57.03 67.83 70.34 73.08
Simulation 8 2.00 6.00 1.00 3.00 62.21 66.21 74.16 71.71
Simulation 9 2.00 6.00 0.50 1.50 66.69 55.63 77.69 61.67
Simulation 10 1.00 3.00 0.50 1.50 69.76 52.34 79.80 58.69
Simulation 11 1.00 3.00 1.00 3.00 66.11 62.97 76.87 69.06
Simulation 12 1.00 3.00 2.00 6.00 62.02 66.60 73.98 72.02

90
80
Lead Recovery (%)

70
60
50 Future Ore
40 Current Ore
30
20
10
0
0 20 40 60 80 100
Lead Grade (%)

FIG A9 – Simulated batch test lead grade and recovery of the future and current ore.

ten per cent lower in the future ore simulations than in the current ore simulations. Increased
recoveries may be possible at a finer grind. Additional test work would be required to
substantiate this hypothesis.

EXAMPLE 4 – DETERMINATION OF BATCH TO INDUSTRIAL CELL SCALE-UP FACTORS

Metallurgists at the Eureka concentrator have performed a number of rougher batch flotation
tests to test the kinetics of ores to be processed through the plant in the future. They need
estimates of the batch to industrial cell scale-up factors to predict the recovery that will be
achieved when processing each ore through the plant based on these test results.
To determine the scale-up factor, a sample of the plant rougher feed was collected and
floated in a batch flotation test using the same procedure as used for the future ore kinetic

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

tests. In parallel, feed tonnage was recorded and samples were collected from the plant
(designated in Figure A10) to determine the kinetics in the rougher and scavenger bank when
processing this ore.
It was decided to use one floating and one non-floating component to describe the
floatability distribution of the ore (a simplification that is possible because it was only the
rougher and scavenger bank recoveries that were to be predicted). Solver in Excel was used
to determine the batch test flotation rate (kbatch) and the proportion of floatable lead in the feed
to the circuit (Rmax), which minimised the difference between the recoveries calculated using
Equation A5 and that measured experimentally in the batch flotation test. The rate calculated
was 1.04 min-1. Rmax or the proportion of lead in the feed that was floatable was determined to
be 92.3 per cent.
R = R max (1 - exp (- k t)) (A5)

The survey data was mass balanced to determine the solids, water and lead flow in the
sampled streams. A circuit model was then set up to predict the flow of lead to every stream
of the circuit. The circuit consists of four banks of cells, with each bank consisting of two or
three cells. All cells in a particular bank were assumed to behave in a similar manner and have
the same scale-up factor (as individual factors could not be derived as individual cells were
not sampled). Recovery, however, was calculated for each cell individually down each bank
using Equation A6.
C j kbatch x
R = mf (A6)
1 + C j kbatch x

The proportion of floatable lead feeding the circuit was defined as that fitted and
determined using the batch flotation test data. The proportion of floatable lead feeding each
individual cell was a function of the amount recovered in the preceding cells. Residence
time was estimated by dividing the total cell volume of a bank by the volumetric flow
rate measured in its feed and then dividing by the number of cells in the bank. This is

Rougher
Scavenger 1A Scavenger 1B
Scavenger 2

Grinding
Circuit
To
Tailings

To
Cleaning

FIG A10 – Eureka rougher scavenger flotation circuit denoting points at which samples were collected during a survey.

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 357

 KYM RUNGE

a reasonable approximation for rougher and scavengers where the flow in the feed and
tailing of each cell is similar.
A unit matrix and a stream matrix were set up in Excel to calculate the unit recoveries
and stream flows for the model (shown as Tables A11 and A12). Solver in Excel was used
to calculate the scale-up factors for each bank, which minimised the difference between the
calculated lead bank recoveries produced by the model and that measured experimentally in
the circuit survey. As the problem has zero degrees of freedom, the model is able to exactly
match the experimental data and the total sum of squares error associated with the problem
is zero.
The derived bank scale-up factors are higher for the cells in the rougher and lower for the
scavenger cells at the end of the circuit. This is usual and is a consequence of froth recoveries
in the scavengers, where there is little mass being recovered, being significantly less than
in the roughers. Thus, if additional capacity were to be added to this bank, the cells would
behave in a similar manner to scavenger 2 and have significantly lower recovery rates than
achieved in the rougher cells.
Future ore flotation recoveries can now be calculated using the developed model, assuming
that the bank scale-up numbers remain the same. This should be a reasonable assumption so
long as the ores do not have a property that would significantly affect full-scale froth recoveries.
The batch flotation tests performed using these future ores can be used to determine the batch
flotation rate and proportion of floatable lead in the feed required as input to enable these
simulations to be performed.

TABLE A11
Spreadsheet table used to calculate lead recovery based on model parameters.
Bank of circuit Model parameters Lead
Cj Res time kbatch mf recovery
(min-1/min-1) (min) (min-1) (%) (%)
Cell 1 0.63 3.3 1.04 92.3 63.25
Rougher Cell 2 0.63 3.3 1.04 81.5 55.85
Cell 3 0.63 3.3 1.04 66.0 45.26
Cell 1 0.50 3.1 1.04 51.6 31.89
Scavenger 1
Cell 2 0.50 3.1 1.04 42.0 26.00
Cell 1 0.23 3 1.04 34.9 14.65
Scavenger 1B
Cell 2 0.23 3 1.04 31.4 13.18
Cell 1 0.04 2.9 1.04 28.5 2.77
Scavenger 2
Cell 2 0.04 2.9 1.04 27.9 2.71

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 CHAPTER 10 | LABORATORY FLOTATION TESTING – AN ESSENTIAL TOOL FOR ORE CHARACTERISATION

TABLE A12
Calculated flow of floating and non-floating lead in the streams of the rougher
and scavenger bank based on the calculated unit recoveries in Table A11.
Stream Lead flow (based on 100 units in feed) Bank recovery (%)
Floating Non-floating Total Modelled Exp SSE
Rougher feed 92.30 7.70 100.00
Rougher Cell 1 concentrate 58.38 0 58.38
Rougher Cell 1 tailing 33.92 7.70 41.62
Rougher Cell 2 concentrate 18.95 0 18.95
Rougher Cell 2 tailing 14.98 7.70 22.68
Rougher Cell 3 concentrate 6.78 0 6.78
Rougher Cell 3 tailing 8.20 7.70 15.90
Combined rougher concentrate 84.10 0 84.10 84.1 84.1 0.00
Scavenger 1A Cell 1 concentrate 2.62 0 2.62
Scavenger 1A Cell 1 tailing 5.58 7.70 13.28
Scavenger 1A Cell 2 concentrate 1.45 0 1.45
Scavenger 1A Cell 2 tailing 4.13 7.70 11.83
Scavenger 1A combined concentrate 4.07 0 4.07 49.6 49.6 0.00
Scavenger 1B Cell 1 concentrate 0.61 0 0.61
Scavenger 1B Cell 1 tailing 3.53 7.70 11.23
Scavenger 1B Cell 2 concentrate 0.46 0 0.46
Scavenger 1B Cell 2 tailing 3.06 7.70 10.76
Scavenger 1B combined concentrate 1.07 0 1.07 25.9 25.9 0.00
Scavenger 2 Cell 1 concentrate 0.08 0 0.08
Scavenger 2 Cell 1 tailing 2.98 7.70 10.68
Scavenger 2 Cell 2 concentrate 0.08 0 0.08
Scavenger 2 Cell 2 tailing 2.90 7.70 10.60
Scavenger 2 combined concentrate 0.17 0 0.17 5.4 5.4 0.00
Combined concentrates 89.40 0 89.40
Final tailing 2.90 7.70 10.60 Total SSE 0.00

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 Return to contents

CHAPTER 11
Designing and analysing plant trials
Tim Napier-Munn

ABSTRACT
This chapter deals with the principles of running plant trials. The purpose of a plant trial
is (usually) to determine whether a change in some process condition will lead to an
improvement in performance. Detecting the presence and magnitude of any change in
process performance is difficult against the inevitable background of process noise (error) if
the correct procedures are not followed. The source and management of error is discussed,
and then several desirable experimental methods are described, including the paired t-test,
the analysis of variance (ANOVA) and the randomised block design. Other designs discussed
briefly include the factorial experiment and evolutionary operation (EVOP). A formula is
given for the number of trials required for a t-test, and a procedure for eliminating outliers.
If a formal design cannot be implemented or is desired to analyse historical data, modelling
is the appropriate method, and several approaches are described. CUSUM (cumulative sum)
control charts are recommended as a powerful way of examining data collected in a time
sequence. The chapter finishes with a consideration of some of the practical aspects of doing
a plant trial.
There really is no alternative to the adoption of a formal experimental design or, if all
else fails, a rigorous analysis of the data from some other experimental activity. Experience
repeatedly shows that a systematic approach to conducting plant trials will produce the
correct answer in the minimum time at minimum cost. Any other approach is very likely
to take much longer and cost more to produce the wrong answer, or at best to produce no
answer at all.

INTRODUCTION
The great statistician R A Fisher (1938), whose work and philosophy underpin many of the
methods described in this chapter, once said:
To call in the statistician after the experiment is done may be no more than asking him to
perform a post-mortem examination. He may be able to say what the experiment died of.

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 TIM NAPIER-MUNN

Fisher was a brilliant mathematician who worked for 20 years at the famed Rothamsted
Agricultural Research Station in England, and the experimental methods that he developed
for Rothamsted’s scientists have been practical and effective, and have stood the test of
time. The problems that agricultural scientists face are very similar to those encountered by
metallurgists charged with a policy of ‘continuous improvement’ and the consequent testing
of new reagents, equipment or process circuits. The data are very noisy and the experiments
often difficult to do.
This chapter is a plea to follow Fisher’s implicit advice. You don’t necessarily have to call in a
statistician, but you do have to plan the experiments properly. Many laboratory experiments
and plant trials are conducted with the naïve view that hard work and enthusiasm are
adequate substitutes for planning, rigour and thought. The protagonists throw themselves
into an experiment in which hope triumphs over method, and the answer is optimistically
expected to emerge from the fog, like advice from the oracle. As a consequence this often
leads to no clear result or, worse still, the wrong result. The irony is that the right way to
do things is often cheaper than the wrong way, and leads to the correct result more quickly.
There is therefore no real excuse for doing a poor experiment.
In the past the Eureka concentrator was no exception. Figure 1 shows the daily recovery
from a plant trial conducted some years ago to test the efficacy of an expensive new reagent.
The average zinc recovery with the new reagent was found to be seven per cent more than
with the old. This is an astonishing improvement and duly excited the metallurgical staff
no end.
Would you, looking at this simple graph of the recovery time series, support the view that
Eureka should invest in the new reagent? I hope not. There is good visual evidence that the
recovery was climbing steadily even before the new reagent was introduced, and in fact one
could take the view that the improvement was actually impeded by the new reagent, even
though the average recovery under the new condition was much higher than that under
the old.
The key point to take from this all too familiar scenario is that, in the absence of other
information, there is no way in which any change in metallurgical performance can be unequivocally

90
85
80
75
Zn Recovery (%)

70
65
60
Reagent 1 Reagent 2
55 R = 70% R = 77%
50
45
40
0 20 40 Day 60 80

FIG 1 – A plant trial to test a new reagent.

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attributed to the new experimental condition. This is the fundamental flaw in such ‘before and
after’ experiments, and it cannot be avoided, except by doing some special analysis, which
is discussed further on. A much better option is to adopt a simple experimental protocol to
deal with the problem illustrated in Figure 1 and use the corresponding methods of data
analysis, rather than suffer the indignity of Fisher’s wrath and, more importantly, the waste
of time and money (and sometimes credibility) that failure brings. The good news is that
appropriate protocols and analysis methods exist that are relatively easy to implement and
so maximise the chance of a successful outcome. And once the design is chosen, the data
analysis is straightforward.
This chapter describes the most accessible experimental designs and data analysis
procedures. In most cases the analysis can be carried out using Microsoft Excel’s excellent
statistical toolbox, and reference is made to the appropriate routines. The methods can
be applied to laboratory experiments, pilot plant tests and full-scale plant trials, and no
distinction is made between these other than some discussion at the end of the chapter about
the particular practical problems of conducting plant trials. The quality system Six Sigma has
much in common with the techniques described.
This chapter is not a textbook on statistics. It is intended to introduce metallurgists to
the use of good practice in experimental design and analysis to assist process optimisation.
Discussion is confined to principles, and demonstration of the use of Excel in some of the
more widely used methods. For a more comprehensive discussion and the underlying
mathematics, the interested reader is referred to the references and further reading list,
including Napier-Munn (2014a).

THE PROBLEM STATEMENT

Mineral processing experiments are usually carried out to determine whether there is a benefit
in introducing some change in process operating conditions, or to identify and quantify the
effect of key process variables on metallurgical performance. Examples are testing a new
reagent in a flotation plant; an alternative piece of equipment or equipment setting; or a new
circuit configuration. It could also involve answering the questions:
•• Does feed rate affect recovery?
•• Are two parallel circuits performing the same way?
Other examples of the need for appropriate experimentation and data analysis include
the assessment of sampling or assay methods, and the calibration of instruments including
on‑stream/in-stream analysis (OSA/ISA) systems.
As one of the greatest experimenters of all, Robert Hooke, famously said in 1683:
The object of experiment is improvement, and an experiment should lead to something beyond
itself.
In the metallurgist’s world, this process often starts in the laboratory with experiments to
test a new idea, a new reagent or piece of equipment recommended by a vendor. If these
experiments are promising, the next step is often a full plant trial to test whether the benefit
can be realised in practice.
A plant trial is usually the only way of determining with confidence whether a process
benefit really exists; improvements seen at the laboratory or pilot scales often evaporate when
implemented at the full production scale. However, plant trials are expensive to conduct, and
can interfere with normal plant operation. They may even reduce plant performance for a while.

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It is therefore very important to conduct the trial in such a way that a firm conclusion is
reached (one way or the other) in the minimum time. The problem, as in all experiments, is
to understand and deal with the basic experimental error. In plant trials, as often as not, this
is apparent mainly as a variation of performance with time. Figure 2 shows the actual daily
variation in recovery from historical plant data. A one per cent recovery improvement may
be worth several million dollars a year in a large operation, but how is one to detect it in data
that varies over a 25 per cent range? The answer is: easily, if you do the right experiment.

ERROR AND HOW TO MANAGE IT

Accuracy and precision
Every data point has uncertainty associated with it. This is true whether it is an assay, a
feed rate, or a value calculated from other data using a formula such as estimating recovery
or yield from a two-product formula. This uncertainty is given the term error (electronics
engineers call it noise). We hope that the error is random, but systematic error due to mistakes,
incorrect sampling, miscalibration of instruments etc can cause bias in any result. Random
and systematic errors are reflected in the terms precision and accuracy respectively, which
mean different things. Precision implies the natural variation in the measurements we make,
which we hope to minimise by being careful but will always be there. Accuracy implies
getting the right answer. Precision is measured by the standard deviation (or its square,
the variance), and its management in various forms is the basis of the statistical methods
discussed in this chapter.
In experiments of the kind to be discussed, error can generally only be estimated by
replicating1 the measurement or experiment, ie by doing it more than once under the same
conditions. The formula for the standard deviation is:

1. Strictly speaking one should make a distinction between repeats, which are repeats of a particular measurement, and
replications, which are repetitions of experiments or parts of experiments. Similarly there is a distinction between repeatability,
which for example measures the variability of a particular assay method within a particular laboratory, and reproducibility, which
measures the variability between laboratories.

85

80
Metal Recovery (%)

75 70% ?

70

65 69%

60

55
0 10 20 30 40 50 60
Day Number

FIG 2 – Daily variation in recovery.

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s=
/ (x - x)
i
2
(1)
n-1
where:
xi = data point i
x = the mean or average
n = number of data points
(n - 1) is called the degrees of freedom
(The units of s are the same as those of the original data.)
For n = 1, s is indeterminate. A single result therefore carries no information about precision,
and, one might argue, in those cases where little if anything is known about the experimental
system being studied, no information of any kind. So it is important to get into the habit of
performing replicates. A plant trial run over many days or weeks (or even months) produces
many replicates. Laboratory tests can also be done with many replicates. In assessing the
value of a particular quantity (recovery in a laboratory float test for example) replication
directly reduces variance, thus making real differences between conditions (eg reagents)
easier to detect against the background noise of experimental error.

Where does error come from?

Sampling
Every sample taken, whether of ore, slurry, solution, concentrate or any other product, has
inherent uncertainty associated with it. Samples should be taken according to the proper
sampling protocols. Gy’s theory and the associated methodologies are an important guide.

Laboratory practice
Variations in operator, machines, batch of reagent, method, ambient conditions and many
other sources will contribute to error.

Assay
The baseline of error is nearly always an assay: chemical, mineralogical or particle size.
The repeatability of assay methods should be well characterised by the assay chemist or
metallurgist.

Metallurgical accounting and mass balancing

Metallurgical accounting and the associated mass or material balancing should be carried out
according to correct and rigorous protocols. This includes the use of redundant data (more
data than the minimum needed to close the balance) to get the best estimate in a least squares
sense of all important quantities, including assays, mass flows and computed quantities such
as grades and recoveries. Rigorous mass balancing will require the entry of estimates of the
standard deviation of all measured quantities to ensure the optimum weighted balance.
Chapter 3 discusses these issues in more detail. See also Morrison (2008).

The plant
The plant is home to the biggest variabilities of all, usually driven by feed changes over
time, but also by poor feed distribution, shift variations, parallel circuit differences, ambient
conditions, reagent and many other factors. Figure 2 is a good example of the trends, cycles

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and random noise evident in concentrator recovery over a two-month period. Figure 3 shows
a consistent bias in recovery between two parallel flotation circuits, Line 1 operating at about
1.3 per cent higher recovery than Line 2, and Figure 4 shows a statistically significant negative
impact of feed rate on recovery.
All these effects conspire to increase the variability of plant data, making it essential to adopt
the correct experimental design procedures to be able to detect differences (improvements)
that are often small compared to the background noise.

Hypothesis testing and risk

Of course we work to limit the variability of our data, by good experimental practice and
careful measurement. But there will always be a residual error that gets in the way of
comparing one condition against another. We therefore need a rigorous way of comparing
values that takes into account the magnitude of the uncertainty in those values. Hypothesis
testing or significance testing is the approach used for this purpose.
The hypothesis test is rather like a court case in which the accused is always presumed
innocent until proven guilty by the evidence. This is a very important distinction, and one
which is followed in the hypothesis test. We generally assume the null hypothesis (denoted
by the symbol H0) to be true unless the data ‘prove’ otherwise. The null hypothesis can
be any quantitative relation you wish to test, but by far the most common is that there is
no difference between the quantities being compared. Thus, for two mean values X 1 and
X 2, the null hypothesis H0 is that X 1 - X 2 = 0. The alternative hypothesis, H1, is that the

95
90
Cu Recovery (%)

85
80

75
70 Line 1
65 Line 2
60
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31
Day

FIG 3 – Differences in parallel flotation circuit performance.

100
Cu recovery (%)

95

90
R = -0.31
85

80
200 250 300 350 400 450
Feed rate (t/h)

FIG 4 – A negative impact of feed rate on recovery.

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difference is not zero, ie there is a real difference between the two means: X 1 - X 2 ≠ 0.2 We
will only accept H1 if there is a sufficiently low risk in doing so, and it is the great power
and ingenuity of these statistical methods that allows the risk to be quantified and rational
decisions made on that basis.
Statistical tests of significance generate a probability, P, which is interpreted as the risk of
being wrong in rejecting the null hypothesis, ie concluding that there is a difference when in
fact there isn’t, which statisticians call a Type I error. 100(1 - P) is the confidence level of the
test. So, if the test returns a P-value of 0.05, we infer that there is a five per cent chance of being
wrong in concluding there is a difference, or, conversely, we are 95 per cent confident that
there is a difference. P will always exceed zero so there is always a risk of being wrong – the
only certain things in life are death and taxes!
A question which always arises is: what level of risk (or conversely, confidence) should we
choose as a hurdle rate for making decisions? This will depend on the consequences of the
decision. The lower the value of P we choose the less chance we have of making a mistake
but also the less positive decisions we will make. If we were doing a reagent trial in the plant
and the new reagent was much more expensive than the old, we would need to be more
certain of a difference before recommending the change than if there were no real downside
to the decision.
If you have nothing else to go on, the most common hurdle rate for P used by most
experimenters is 0.05, following recommendations originally given by Fisher in 1926.
However, there is no magic bullet. It would probably be unwise to choose P to be any more
than 0.1 as this gives a one in ten chance of being wrong. If you were in a casino with a
90 per cent chance of success in each game, you would never leave! But here we are dealing
with a different situation: you want to minimise the chance of failure; in fact you would prefer
never to fail, but as we know that P > 0, we want to limit the chance of failure as much as
possible, especially if the decision turns out to be career-limiting.
Now we will consider a number of different methods of making decisions about differences
in quantities of interest. All are based on the principle of the hypothesis test.

COMPARING MEANS
The two-sample t-test
This tests the difference between the averages (means) of two samples of data, which need
not be of the same size. An example is the testing of two different ore sources or two different
reagents using a standard laboratory float test. Example 1 shows a test of a new zinc collector
at Eureka, in which a single sample of ore was ground, split ten ways, and four float tests done
with the old collector (A) and six with the new (B). The null hypothesis is that the difference
in means is zero. Excel’s two-sample t-test is invoked as follows: Data > Data Analysis3 >t-test:
Two-Sample Assuming Equal Variances4 and complete the dialogue box. The result is as
shown in Example 1 (data on the left, Excel output on the right).

2. Strictly speaking, we distinguish between H1: X1 - X2 ! 0 , and H1: X1 - X2 > 0 , the first being a ‘two-sided’ test and the second
a ‘one-sided’ test. More of this later.
3. If the Data Analysis option is not visible, find Add-Ins and check the Analysis ToolPak box.
4. Excel also provides a routine for unequal variances. ‘Unequal’ means statistically different (usually determined using an F-test).
In most cases variances can be considered ‘equal’ even though they may look different. Using the ‘unequal’ routine reduces the
confidence in any observed difference.

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EXAMPLE 1
Two-sample t-test for laboratory flotation test.
A B
Mean 86.5 87.65
Variance 0.366667 0.971
Observations 4 6
Pooled variance 0.744375
A B Hypothesised mean difference 0
85.8 86.5 df 8
87.1 89.0 t stat -2.06494
86.2 87.2 P(T< = t) one-tail 0.0364
86.9 86.8 t critical one-tail 1.859548
88.5 P(T< = t) two-tail 0.072799
87.9 t critical two-tail 2.306004

The important numbers to interpret are means and variances, hypothesised mean difference
and P(T<= t).

Means and variances

Excel does not compute the difference in means, which is the key piece of information (it is this
value that is being tested using the t-test), but this is easily done. The individual sample means
and variances and the pooled (weighted average) variance are given in the Excel output.

Hypothesized mean difference

The default value in the dialogue box is zero (ie H0 is that there is no difference between the
collectors), but it could be any value the experimenter wishes to enter in the dialogue box.
In most cases zero is appropriate:

P(T<= t)
P(T<= t) is the chance (risk) of a Type I error, ie saying there is a difference when in fact there
isn’t one. A low P means that the calculated value of t is unlikely to have arisen by chance
and that the difference is therefore statistically significant. Whether it is one- or two-sided
(‘tail’) will depend on how the objective of the experiment has been defined. In general, if
we are seeking a change in a particular direction (eg an improvement) it is one-sided. If the
question is ‘are the means different?’ (in either direction) it is two-sided. As can be seen from
the Excel output, a two-sided problem has a higher risk and lower confidence than a one-
sided problem.
In this experiment the comparison is one-sided as we are seeking an improvement. P =
0.036, ie there is a 3.6 per cent chance of being wrong in rejecting H0, or alternatively, we are
96.4 per cent confident that the difference is not zero (and our best estimate of the difference
is 87.65 - 86.50 = 1.15 per cent). Is this enough? This is up to the experimenter and will depend
upon the consequences of the decision, but in most cases if P <0.05 we would conclude that the
difference is real.

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A useful statistic to calculate is the confidence interval, CI, for the difference in means,
given by:

CI = ta s 1 + 1 (2)
n1 n 2
where:
tα = t-value for a two-sided P-value of α
s = square root of pooled variance (from the Excel output)
n1 = number of results in sample 1
n2 = number of results in sample 2
tα can be obtained from tables of the t-distribution, or from the Excel function TINV(α, df)
where df = degrees of freedom = n1 + n2 - 2, and α is the two-sided P-value for the chosen
confidence level. For example, if a 90 per cent two-sided confidence interval is required, α
is 0.10.
In Example 1, CI95% = ±1.28 per cent, ie the difference in mean recoveries is 1.15 ± 1.28
with 95 per cent confidence. There is no contradiction in the fact that this interval includes
zero, even though our t-test has told us that we are more than 95 per cent confident that
the difference is not zero. The t-test was a one-sided test and the confidence limits here are
two-sided.
In fact, it can often be useful to form a one-sided confidence limit. This is done by using
½ α in Equation 2 and the Excel function T.INV in place of TINV. T.INV produces a one-
sided value for the α level of confidence, preceded by a minus sign. For Example 1, the
one-sided 90 per cent confidence interval is -0.78, and we could interpret this as saying: we
are 90 per cent certain that the recovery improvement is at least 1.15 - 0.78 = 0.37 per cent
(the worst-case scenario). If a cost-benefit analysis requires the difference to be at least
one per cent to get a return on the increased cost, then one might be justified in not
proceeding with the new collector even though it was shown to be better than the old by
more than one per cent, because the risk of failure is too high.
The two-sample t-test is not always appropriate for plant trials because it implies that the
data have not been collected under one of the protocols suggested below. For example, they
may have been collected in the ‘before and after’ fashion illustrated in Figure 1. If so, even
though the t-test may show a real difference, there is no guarantee that the difference is due
to the variable being investigated rather than some other factor that was not controlled by the
experimental design.

The paired t-test

Pairing is a form of blocking to deal with common variability, and is always to be preferred if
the experiment can be set up to achieve it. The main advantage of the paired t-test is that the
standard deviation due to error is greatly reduced because much of it is essentially removed
by taking the difference of two performance values in which common variation is subtracted
out. The test is therefore more sensitive and smaller differences can be detected. It is also
easier to attribute any observed difference unequivocally to the factor being investigated.
Paired values must be alike in all senses other than the factor being studied. In the assay
laboratory, an example would be a comparison of two assay instruments in which a number
of samples, which could be of different origin, are each divided in two and one aliquot tested
in each instrument. In plant trials pairing can be achieved in two ways:

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1. using parallel circuits or machines

2. sequential pairs in time, ie on-off (more of this later).
Where parallel circuits are available, each circuit can be run on one condition. The difference
in daily performance (eg recovery) is then calculated and the paired t-test applied daily until
a conclusion is reached. The problem is that parallel circuits are rarely identical; a common
problem is biased feed. Any difference between the circuits will bias the difference it is desired
to detect. The best way to deal with this is to switch the treatment on a random basis (Excel
has a random number generator, but tossing a coin would do just as well) (see Table 1).
The t-test is then applied to the differences. The test can be done each day and the experiment
terminated when a conclusion is reached or when the prescribed number of pairs has been
completed (see below). The significance of t can then be determined from the Excel routine by
inspecting P, exactly as for the two-sample t-test.
The confidence limits on the mean difference d are given by:

d ! ta sd n (3)

where:
sd = standard deviation of the paired differences
n = number of pairs
tα has the same meaning as in Equation 2

Example 2
Two flotation circuits are operated in parallel. Each day, one circuit is run with the usual
collector (A) and the other with a new collector (B). The order is switched randomly between
the circuits each day to avoid any systematic differences between the circuits. The experiment
is run for 12 days, and the daily recovery is monitored. It is required to determine whether the
new collector gives a significantly improved recovery. The results are as shown in Example 2.
The mean difference is 0.88 per cent. The question (as always) is: is that difference real, or
has it arisen by chance due to experimental error? Excel provides a routine to do the analysis:
Data > Data Analysis > t-Test: Paired Two Sample for Means. Again, this is a one-tailed test as
we are seeking an improvement. P(T< = t) = 0.075. Thus, we are 92.5 per cent confident that the
difference is not zero. Is this sufficient confidence? If the new collector were more expensive,
we may wish to improve our confidence by doing more trials (see below for a formula for the
number of trials needed).

TABLE 1
Typical arrangement for paired trial in parallel circuits.
Day Circuit A Circuit B Difference
1 T N T-N
2 N T T-N
3 T N T-N
4 N T T-N
5 T N T-N
6 etc etc etc

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EXAMPLE 2
Paired t-test for plant flotation trial.
Day Collector A Collector B t-test: paired two sample for means
1 84.2 85.8 A B
2 71.9 75.0 Mean 79.03333 78.15
3 77.8 76.6 Variance 22.06788 16.88818
4 80.1 82.5 Observations 12 12
5 75.6 77.7 Pearson correlation 0.90725
6 70.8 70.0 Hypothesised mean difference 0
7 81.3 85.0 df 11
8 82.6 80.6 t stat 1.544139
9 78.5 77.1 P(T< = t) one-tail 0.07541
10 79.2 81.5 t critical one-tail 1.795885
11 80.6 82.2 P(T< = t) two-tail 0.15082
12 75.2 74.4 t critical two-tail 2.200985

The power of the paired test is illustrated by using Excel’s two-sample t-test to analyse the
same data. P(T< = t) = 0.31 (not significant) and we would have to accept the null hypothesis
and thus erroneously conclude that Collector B was no better than A.

Number of trials needed

It is very important to have some idea of how long an experiment is likely to take, ie how
many data points must be collected to achieve the purpose. The number of trials can be
calculated, given the difference it is required to detect and the risks that the experimenter
wishes to take.
However, the risks are of two kinds. We have already encountered the Type I error, which
is the risk of saying that there has been a change in mean when in fact no such change has
occurred, ie rejecting the null hypothesis incorrectly. This is controlled by choosing an
appropriately small value of P, which for the Type I error we will now call α.
It is easy to see that there exists another potential trap into which the unwary experimenter
could fall: the error of asserting that no change has occurred when in fact there is a real
difference; this is called a Type II error. In trials to achieve process improvement, the Type II
error is an opportunity lost.
Simply doing a t-test considers only Type I errors. When the chosen significance level is
exceeded, the experimenter is justified in concluding that a change has occurred, ie that the
null hypothesis is false. However, when no significant difference is found he is not equally
justified in asserting that the null hypothesis is true. This can only be done by conducting
sufficient experiments to control Type II errors at some chosen confidence level, β.
The decision options and their respective errors are illustrated in the ‘truth table’ (Table 2).
The test (ie decision) is made at a probability level of α (one- or two-sided).
The total number of experiments required in a t-test to detect a difference as large as D
with the Types I and II errors controlled at confidence levels of α and β respectively is (for
large samples):

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TABLE 2
Truth table for decision-making.
Decision Truth about the population
H0 true H0 false
(no difference) (true difference)
Reject null hypothesis H0 Type I error Correct decision
P=α P=1-β
Accept null hypothesis H0 Correct decision Type II error
P=1-α P=β

2 (z a + z b) 2 s 2
n= (round n up to a whole number) (4)
D2
where:
zα = normal deviate at a confidence level of α (one or two-sided)
zβ = normal deviate at a confidence level of β (always one-sided)
s = expected standard deviation
n is the size of each sample for the two-sample t-test, and the number of pairs for the paired
t-test. For small samples n should be multiplied by the ratio (f + 3)/(f + 1), where f is the
degrees of freedom: f = 2n - 2 for the two-sample t-test and n - 1 for the paired t-test. zα and zβ
are the standard normal deviates for probability levels α and β. These can be obtained from
tables of the normal distribution, or from the Excel function NORMSINV(1-P) where P is α or
β one-sided (use (1 - P)/2 for two-sided α), or from Table 3. Note that for the paired t-test, the
leading two in Equation 4 is omitted, and n = number of pairs.
After carrying out n experiments, the t-test is then conducted at a confidence level of
α (taking the usual account of whether the test is one or two-sided). If P(t) ≤ α, then the
alternative hypothesis is accepted (there is a real difference) with a probability α of being
wrong (Type I error). If P(t) >α, then the null hypothesis is accepted (no real difference of
size D) with a probability β of being wrong (Type II error). 1 - β, the probability of correctly
concluding that there is a difference, is called the power of the test.
Some textbooks provide power curves (Mason, Gunst and Hess, 1989; Montgomery and
Runger, 1999) or tables (Davies, 1967), allowing the experimenter to read off the number of
trials required from an assumption of α, β and the expected signal-to-noise ratio D/s.
The balance of α and β is important. Because the number of experiments needed to control
both types of error can be large, and increases as α and β decrease, β is sometimes chosen to
be somewhat larger than α to limit the number of tests. Thus if we choose α = 0.05 (95 per cent
confidence level) then we might choose β = 0.2 (80 per cent confidence level), since it is usually
more important to avoid concluding that there is a real difference when there really is not

TABLE 3
Values of z.
Tail α or β
0.3 0.2 0.1 0.05 0.025 0.01
One-sided 0.524 0.842 1.282 1.645 1.960 2.326
Two-sided 0.842 1.282 1.645 1.960 2.326 2.576

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(Type I error, controlled by α) than to assert no difference when one really exists (Type II
error, controlled by β). In trials of new operating conditions, for example, this gives more
weight to retaining the status quo.

Example 3
Equation 4 can be used to determine the number of paired trials to be conducted in the
flotation trial of Example 2. Here, s is the standard deviation of the paired differences, sd.5 It is
desired to control the risk of incorrectly concluding that there is a process improvement
when there is not at five per cent (α = 0.05) and to have a 90 per cent chance of detecting a
recovery improvement as large as one per cent – the power of the test (β = 0.1). From previous
experiments it is believed that sd ≈ 2. How many pairs of tests should be conducted? From
Table 3, one-sided z0.05 = 1.645, one-sided z0.10 = 1.282. Substituting directly in Equation 4 with
D = 1 and s = 2, and with the correction for degrees of freedom gives n = 37 pairs.
It is easy to use Equation 4 to construct general curves relating the number of trials required
to the signal-to-noise ratio D/s for a range of confidence levels for one-sided and two-sided
tests. Figure 5 shows such curves, from which it is clear that as the signal-to-noise ratio
declines (either the error increases or the difference required to detect it decreases, or both)
the number of trials required increases rapidly.

The reference distribution

One of the problems with using parametric tests such as the t-test or regression analysis (see
below) is that these methods make assumptions about the independence of the data and the
normality of residuals that are not always fulfilled in mineral processing. The non-parametric
reference distribution method overcomes this problem as it makes no assumptions as to
random sampling or data independence (Box, Hunter and Hunter, 1978; Cavender, 1993;
Bruey and Briggs, 1997; Napier-Munn, 2008, 2014a).
The method is based on the assumption that a body of consistent data is available
representing the condition of the process before the trial starts (the ‘reference distribution’).
The characteristics of the trial data are then compared with those of the reference distribution
to determine the probability with which they are likely to have arisen, assuming there has

5. The sd of the paired differences can be estimated from historical plant data by calculating the sd of 30 or more sequential pairs
of differences.

FIG 5 – Number of trials required as a function of expected signal-to-noise ratio.

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been no change in the process. If that probability is small (eg ≤ 0.05), then it is concluded that
a real change has occurred. So essentially it is another significance test. However, in this case
the probabilities are measured directly from the historical data.
Suppose that the trial period gives us ten results, with a mean recovery three per cent more
than the mean of the last ten results immediately before the change. The question, as ever,
is: ‘is this difference significant (real) or has it arisen by chance?’. This can be re-stated rather
more formally as: ‘what is the probability with which such a difference would arise, if no
change had occurred?’. This is answered directly by interrogating the reference distribution.
Suppose that the reference distribution (RD) comprises 100 sequential data points. We can
then look at the 100 - 10 + 1 = 91 sequential sets of ten results (1–10, 2–11, 3–12 etc) and see how
many times one set of ten (eg 1–10 or 2–11) is followed by another set of ten (eg 11–20 or 12–21)
with a mean recovery higher by three per cent. If this occurs rarely in the RD (eg ≤5 per cent
of times), then the trial result must be regarded as significant.
The problem with this method is the key assumption that the reference distribution is
stable and represents the constant condition of the process before the change. This is an
assumption which is often not met – the process mean moves around and it is difficult to
define the appropriate RD. The cusum chart (see below) can help to determine whether the
RD is homogenous. Also, it cannot help with the nuisance influence of covariates such as feed
grade, and it is a less efficient test than the t-test, generally requiring many more data points.
But it is free of the statistical assumptions required by many of the other methods.

Outliers
Outliers may be cynically regarded as inconvenient points, ‘wild’ results that do not appear to
belong to the rest of the data set or perhaps conflict with our prejudices. They are best identified
by plotting the data. They can often have a significant effect on hypothesis tests, mainly due
to the substantial increase in standard deviation that they cause. As a general rule, however,
outliers should not be rejected without some formal justification. For example, if it is found
that a mistake was made in collecting the data, such as a biased sample, or a miscalibrated
instrument, then the relevant point(s) can be rejected. If, however, no such reason can be
found but suspicion persists that they do not belong, a formal test can be invoked.
Several such tests have been devised, but there is no consensus amongst the statistical
community and certainly no magic bullet. Mason, Gunst and Hess (1989) recommend the
Grubbs test for a normally distributed sample whose mean is of interest. This test is more
powerful than some others and can reject more than one outlier at a time. The test statistic
is a ratio of sums of squares, (xi - x ) 2 , the SS of the data without the outlier(s) being divided
by the SS of all the data with the outlier(s), giving a ratio less than one. The column of data
should first be sorted using the Excel Data >Sort option. The outlier(s) will be at the top
or bottom of the column depending on whether they are the highest or lowest values and
how the sort has been done. The Excel function DEVSQ (array) is then used to calculate the
two sums of squares, with and without the outliers. The ratio of these is then compared
with Table A26 in Mason, Gunst and Hess (1989) (also given as Table A1.3 in Napier-Munn
(2014a)) with n = total number of data points and k = number of outliers. (The values in the
table have been multiplied by 103 to avoid the confusion of decimal points.) If the calculated
ratio is less than the tabulated value at the desired α-value then the outlier(s) should be
considered for rejection.

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COMPARING SEVERAL CONDITIONS

The one-way analysis of variance
The analysis of variance (ANOVA) is a powerful procedure for partitioning the sources of
variance in an experiment, and judging their significance by comparing them against an
estimate of error variance. There are several versions, used in many different applications.
The one-way ANOVA is in a sense a multiple t-test; in fact it is identical to the two-sample
t-test for two means. Its strength, however, lies in its capacity to consider several sources of
variation (several means) simultaneously. It is useful in comparing multiple ore sources in
future ores testing, or perhaps a number of different collectors on a single ore. The ‘one-way’
implies that there is only one source of variation other than experimental error. Several repeat
tests are conducted on each condition being investigated (eg each ore source or collector).

Example 4
In a large feasibility study, several operators in different laboratories are involved in laboratory
float tests. It is important to ensure that the operators do not produce statistically different
results. To establish whether they all give similar results, a single ore sample is divided and
each of four operators conducts a number of repeat tests on the sample. The results are shown
on the left side of Example 4. On the right is the Excel output invoked by Data > Data Analysis
> ANOVA: Single Factor. The full block of data is selected, including the labels in the first row,
and the ‘Labels’ box in the dialogue box is checked.
The summary gives the number of tests for each operator, and the corresponding mean
recoveries and variances. The ANOVA table provides the key information to judge whether
there are differences between the operators (see Example 4). This is done by comparing
the mean squares (MS) of the ‘Between Groups’ and ‘Within Groups’ variation, which
have units of variance. The ‘Between Groups’ variance is due to real differences between
the operators, and the ‘Within Groups’ variance is experimental error, measured from the
repeats done by each operator. The comparison is made by forming the ratio of the two MS
values, which is called the F-ratio (after Fisher, who invented it); the P-value then gives the

EXAMPLE 4
The one-way analysis of variance (ANOVA) in comparing operators.
ANOVA: Single factor
Op 1 Op 2 Op 3 Op 4 Summary
67.3 60.5 63.5 60.7 Groups Count Sum Average Variance
66.2 58.9 64.9 64.7 Op 1 4 261.42 65.35393 3.222062
63.3 54.1 66.4 67.3 Op 2 3 173.45 57.81624 10.82865
64.6 64.3 Op 3 3 194.78 64.92636 1.993553
Op 4 4 256.97 64.24125 7.376275
ANOVA
Source of variation SS df MS F P-value F crit
Between groups 118.557 3 39.51887 6.880095 0.00855 3.7083
Within groups 57.4394 10 5.743942
Total 175.996 13

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Type I error risk. In this case P = 0.009, ie there is less than one per cent risk in saying that
the operators do indeed give different results, or conversely, we are more than 99 per cent
sure that they are different.
A glance at the summary shows that Operator 2 produced a lower mean recovery than the
other three, and therefore some mentoring or re-training might be in order.
A useful piece of additional information is the MS for ‘Within Groups’, which is the
experimental error variance based on the repeats. The square root of this value (2.4 per cent)
is the error standard deviation, which can be used in planning future experiments, eg in
Equation 4. In this case it should be calculated after Operator 2’s data have been removed.

Randomised block design – the two-way analysis of variance

The purpose of this experimental design is to eliminate (or rather separately identify) the
effect of an uncontrolled nuisance variable, such as feed condition or parallel circuit, by
blocking this variable. For a simple unreplicated two-condition experiment this is the same
design as the paired t-test, and analysis by an ANOVA will give the same answer. However,
it is more appropriate where three or more conditions are being compared.
Time can be thought of as a proxy for feed condition, and the variable blocked in a
concentrator trial is therefore often time, though it can also be ‘circuit’ in plants that have
parallel circuits. In the time case, the trial is divided up into time blocks of appropriate
duration and each condition tested at least once in each block, the order being randomised within the
block. Replication within a block is desirable to improve the estimate of experimental error,
though it is not essential. If the conditions to be tested are A, B and C, the experiment might
look like this:

ABC BAC CBA BCA ACB

Time
Each block might be three days, so each condition is tested for a day, in random order.
Analysis is by a two-way ANOVA, either unreplicated or replicated, both of which are
available in Excel. Note the important design criteria that each treatment is tested at least
once in each block in random order. If these criteria are not followed, the ANOVA analysis is
invalid. Randomisation, which is essential, can be done using Excel’s Data Analysis routine
‘Random Number Generation’.

Example 5
A trial is conducted on a concentrator with three parallel closed grinding circuits. The purpose
is to increase the fineness of grind by using an alternative cyclone geometry (a combination
of vortex finder and apex). After doing simulations and consulting the manufacturer, three
likely geometries are selected for test, plus the current arrangement. It is thought likely that
the circuits do not operate exactly the same but it is important that the conclusions apply
to all the circuits. A randomised block design is therefore run, with ‘circuit’ the blocked
variable and each of the four geometries being tested in random order once in each circuit.
A composite sample of cyclone overflow is collected for each circuit/geometry combination
and the per cent -75 μm determined.
The results are shown on the left side of Example 5. On the right is the Excel output invoked
by Data > Data Analysis > ANOVA: Two Factor Without Replication. The full block of data is

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selected, including the labels in the first row and column, and the ‘Labels’ box in the dialogue
box is checked.
Now there are three sources of variation: the geometries (rows), the circuits (columns) and
error. The null hypotheses are that the four geometries give the same product size, and the
three circuits also give the same product size. The P-values for the F-tests show that both
hypotheses can be rejected: the geometries and the circuits are significantly different. The
geometry effect is significant at >95 per cent confidence (P = 0.043). We can therefore choose
the best cyclone with the finest product (from the summary – Cyclone C).
The circuit effect is significant at 93.6 per cent (P = 0.064), which is probably sufficient in a
trial of this kind to conclude that the difference is real, as suspected. Inspecting the summary
shows that Circuit 3 produces a coarser product than the other two. This bonus information
can be used to explore why this is so and perhaps correct Circuit 3 so that an additional
process improvement can be achieved.
The square root of the error MS (2.5 per cent -75 μm) is the experimental standard deviation
for the trial.
Note that if the experiment had not been blocked, ie not arranged as a formal randomised
block design, the block variation (columns) would not have been distinguishable from the
error. The consequence of this can be simulated by analysing the data as a one-way ANOVA,
as in Example 4. In this case the circuit labels are not selected as ‘data’, so the analysis simply
compares the four cyclone geometries against an inflated error variance (now including
the circuit differences). P = 0.11, which would suggest that there is insufficient evidence to
conclude that the geometries gave different product sizes.

EXAMPLE 5
The two-way analysis of variance (ANOVA) in comparing cyclone geometries.
ANOVA: Two-factor without replication
Cyclone Circuit 1 Circuit 2 Circuit 3 Summary Count Sum Average Variance
A 73.8 74.2 69.0 A 3 217 72.33333 8.373333
B 68.9 75.5 65.2 B 3 209.6 69.86667 27.22333
C 79.2 78.5 73.8 C 3 231.5 77.16667 8.623333
D 72.5 69.6 70.0 D 3 212.1 70.7 2.47

Circuit 1 4 294.4 73.6 18.23333

Circuit 2 4 297.8 74.45 13.69667
Circuit 3 4 278 69.5 12.49333
ANOVA
Source of SS df MS F P-value F crit
variation
Rows 95.9367 3 31.97889 5.139464 0.042715 4.75706
Columns 56.0467 2 28.02333 4.50375 0.063904 5.14325
Error 37.3333 6 6.222222
Total 189.317 11

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FACTORIAL DESIGNS
The factorial is a widely used and powerful experimental design, and is comprehensively
covered in the literature (eg Davies, 1967; Box, Hunter and Hunter, 1978; Mason, Gunst
and Hess, 1989; Napier-Munn, 2014a). It is the basis of the Evolutionary Operation (EVOP)
process optimisation method discussed briefly below, but is most widely used in the
laboratory environment. It will therefore not be dealt with in detail here; the reader is
referred to the literature.
The key feature of a full factorial is that each factor (variable) is investigated at every level
of every other factor, ie a measurement is made at every factor combination. The number of
experiments needed is cxn, where x is the number of levels, n is the number of factors and c
is the number of replicates of the whole experiment. If three factors are investigated at two
levels each without replication, the number of tests required is 23 = 8. A 23 factorial can be
thought of as a cube in space, with each of the three dimensions representing one of the three
factors, A, B and C. A test is run at each of the eight corners of the cube (see Figure 6).
The analysis falls into two parts: the calculation of the actual effects (how each factor affects
the response), and testing of the significance of each effect using an ANOVA. Some estimate
of error is required for the ANOVA – either a full replication of the experiment, or a number
of centre point runs at the centre of the experimental space (as shown in Figure 6), or some
other source. No specific routines are available in Excel for the analysis of factorials, though a
two-level factorial can be analysed by a simple method suitable for spreadsheets, called Yates’
analysis (Box, Hunter and Hunter, 1978; Mason, Gunst and Hess, 1989; Napier-Munn, 2014a).
The two-level factorial only detects linear relationships between factors. This is satisfactory
in many cases. However, three or more levels are required to detect non-linear effects. A
specialist statistics package is best used both for the design and analysis of the factorial and
its many variants.
The design is not limited to the same number of levels for each factor. However, a
disadvantage is that many tests are required if the situation calls for several levels and/or
several factors, the number of tests increasing exponentially with the number of factors. In
such cases subsets of the full design can be used, called fractional factorials. Special designs
such as the central composite rotatable design (CCRD) are also available. The CCRD is able to
investigate quadratic effects for the development of response surface models in fewer tests
than would be required for a full three-level factorial; the models can be used for process
optimisation (Napier-Munn, 2014a, 2014b). CCRDs are particularly useful for laboratory and

FIG 6 – A 23 factorial experiment: three factors each at two levels.

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pilot plant experiments, but in recent years some have also been successfully conducted in
sections of production flotation plants (eg Venkatesan, Harris and Greyling, 2014).
The factorial has important advantages over other less formal approaches to experimentation,
including:
•• It is mathematically the most efficient way of estimating the factor effects. This is
particularly useful in collecting data for modelling (see below).
•• It is necessary to detect interaction, in which the effect of one factor depends systematically
upon the level of one or more other factors.
•• It can incorporate blocking and randomisation, which are important weapons in dealing
with error to improve the ability of the experiment to detect important effects.
•• The conclusions hold over a wide range of conditions.

MODELLING YOUR WAY OUT

A formal design such as the paired trial or randomised block design is always to be preferred
as it will generally provide a robust conclusion in the shortest time. If, however, for whatever
reason, it is not possible to do a formal trial, then it is possible to use modelling to assess the
significance of any new condition that is being investigated. Modelling is also helpful for
historical data not collected from a planned trial (Napier-Munn, 2008).

Dealing with the effect of an uncontrolled variable – intervention analysis

It often happens that there is one particular variable that is known to influence the performance
criterion of interest, but over which the experimenter has no control. A good example is the
way feed grade generally drives recovery. One way to deal with such a variable is to use its
influence to develop a simple model of the performance variable of interest (eg recovery) in
terms of the nuisance variable (eg feed grade) and to add the presence or absence of the trial
condition (eg a new reagent) as a second variable. This is called intervention analysis when
used by economists to analyse time series data (Box, Hunter and Hunter, 1978). (The method
is essentially equivalent to the comparison of two regression lines (trendlines in Excel-speak)
described by Napier-Munn, 1998, 2014a.)
The model looks like this:

Y = a0 + a1X + a2T + ε (5)

where:
Y = performance variable of interest, or dependent variable (eg recovery)
X = uncontrolled variable (eg feed grade)
T = a dummy variable representing the trial condition: T = 0 for the old condition
and T = 1 for the new condition6
a0, a1, a2 are coefficients to be estimated from the data
ε represents the residual error (noise)
X and T are independent variables. The null hypothesis here is that the trial condition does
not influence recovery, ie that a2 = 0.

6. If the trial variable has several quantifiable levels (eg collector concentration) then of course it can be represented as a normal
quantitative variable.

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Example 6
A plant trial was conducted to test a new flotation reagent. An appropriate protocol (eg a
paired trial) could not be conducted, so data using the new reagent were compared with a
historically equivalent period when using the plant’s usual reagent. Equation 5 is fitted to
the data by invoking the Excel regression tool: Data > Data Analysis > Regression, which
estimates the linear parameters (coefficients) in the model using the least squares method.
The Y-range in this case is the column of Recovery, and the X-range the contiguous block
of feed grade and trial condition, including the labels. Example 6 shows part of the data set
on the left, and the Excel output on the right (excluding the 95 per cent confidence limits
for clarity).
The key parts of the output can be interpreted as follows. The significance in the ANOVA
(refer Example 6) (1) is the P-value for a test of whether the whole regression is significant.
A value much less than 0.01 is desirable, and certainly less than 0.05. The trial coefficient (2)
is an estimate of the magnitude of the effect that the trial condition has had on recovery: in
this case an increase of 1.48 per cent. (Note that this will not be equal to the difference in the
mean values, which is 1.8 per cent, because it is essentially a mean weighted towards the
centre of gravity of the data.) It is essential as always to test whether this is significant, using
the corresponding standard error (3) and t-value. This is done as usual with the P-value (4),
in this case 0.046, which is significant at the 95 per cent level of confidence. (Similar P-values
are available for the grade coefficient (5) and intercept, both of which are highly significant.)

EXAMPLE 6
Regression model of a plant trial with intervention analysis.
Feed grade Trial Recovery Summary output
0.364 0 66.9 Regression statistics
0.320 0 63.7 Multiple R 0.59745195
0.453 0 66.7 R square 0.35694883
0.413 0 75.0 Adjusted R square 0.34514973
0.617 0 76.8 Standard error 3.86107058
0.503 0 82.9 Observations 112
0.500 0 73.4
0.518 0 72.6
… … … ANOVA
0.560 1 68.8 df SS MS F Significance F
0.493 1 68.1 Regression 2 901.9914438 450.996 30.2522 3.54308E-11
0.590 1 75.8 Residual 109 6 1624.957399 14.9079 1
0.697 1 73.3 Total 111 2526.948843
0.560 1 73.6
0.570 1 74.6 Coefficient Standard error t stat P-value
0.520 1 66.0 Intercept 53.4035743 2.180237461 24.4944 4E-46
0.537 1 71.0 Grade 32.4636222 4.40265655 7.37364 3.4E-11 5
0.580 1 74.7 Trial 2 1.47612985 0.731053365 3 2.01918 0.04592 4

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Note that Excel returns a two-sided P-value for the coefficients. If a one-sided value is
required, as in this case (we are looking for an improvement), then use the Excel function ‘=
TDIST(t, df, 1)’. t is the value of t for the trial coefficient (2.02 in this case), df is the degrees
of freedom for the residual (6) (109 in this case), and ‘1’ implies a one-sided test (use ‘2’
for a two-sided test). In this case TDIST returns the value P(t) = 0.023; so we are more than
97 per cent confident that the new reagent gives a higher recovery than the old.
The standard error for the trial coefficient (3) can also be used to calculate one- or two-sided
confidence limits, as before. The 95 per cent two-sided confidence interval is approximately
1.96 × standard error = ±1.4 per cent. So we are 95 per cent confident that the trial conditions
produces an increase in recovery, and our best estimate of that increase is 1.5 per cent
± 1.4 per cent. (These limits are given in the Excel output but not shown in Example 6).

Models with many variables

The intervention analysis approach described above can be extended to many process
variables.

Example 7
Historical data for 114 values of daily feed rate and feed grade were available from two
periods running with a different flotation reagent. Trial = 0 indicates the period running with
the old reagent and Trial = 1 the period with the new (see Table 4).
Recovery is the dependent variable (Y) and feed rate, feed grade and ‘trial’ (the dummy
variable) are the independent variables (X1, X2, T). Choosing Excel’s Data > Data Analysis >
Regression will produce the basic output as shown in Example 7 (leaving out the ANOVA
for clarity).
The P-value (two-sided) for the trial coefficient (1) is 0.310, and the one-sided P-value
calculated from the function TDIST is 0.155. Neither is statistically significant, and the main
conclusion of the trial is that the new reagent has no significant effect on recovery.

TABLE 4
Data from plant trial for Example 7.
Day Feed rate (t/h) Feed grade (%) Trial Recovery (%)
1 354 1.63 1.00 90.1
2 364 1.71 1.00 90.3
3 343 1.62 1.00 90.5
4 324 1.75 1.00 91.8
5 365 1.70 1.00 89.9
6 373 1.39 1.00 87.6
… … … … …
109 352 2.06 0.00 92.8
110 353 1.87 0.00 91.4
111 337 1.95 0.00 93.1
112 343 2.05 0.00 93.3
113 328 1.93 0.00 93.0
114 334 1.86 0.00 92.1

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EXAMPLE 7
Multi-variable regression model of a plant trial with intervention analysis.
Summary output
Regression statistics
Multiple R 0.81970252
R square 0.67191222
Adjusted R square 0.66296437 2
Standard error 1.06188161 3
Observations 114

Coefficient Standard error t stat P-value

Intercept 88.5948393 1.478259002 59.932 8E-86
t/h -0.0193845 0.003091221 -6.271 7.2E-09
Feed grade 5.49063873 0.439740137 12.486 8.1E-23
Trial -0.216325 0.212147581 -1.02 0.31011 1

However, the model is quite interesting in its own right. The model itself is:
Recovery (per cent) = 88.59 - 0.019 (feed rate) + 5.49 (feed grade) (6)
This simple process description gives us additional useful information from the trial.
An increase of 0.5 per cent in feed grade increases recovery by about 2.7 per cent, and an
increase of 50 t/h decreases recovery by about one per cent.
Excel provides statistics to judge the quality of the model. The adjusted R2 (2) is the coefficient
of multiple determination (adjusted for the degrees of freedom), which is a goodness-of-fit
criterion describing the proportion of the total data variation accounted for by the model (the
balance would be due to missing terms, model inadequacies and error). R2adj = 66 per cent is
high for plant data of this kind in which values of less than 50 per cent are not uncommon,
and suggests that the model gives reasonable predictions. This is confirmed by the standard
error (3), which is the standard deviation of the residuals, the difference between the observed
and predicted values of recovery. 1.96 × standard error gives approximately the 95 per cent
confidence interval of the predictions of the model, in this case ±2.1 per cent.
Regression models of this kind are helpful but users should be aware of their limitations
and dangers:
•• They are simplistic models and should not be over-interpreted. In particular they will not
apply to different process conditions and so should not be extrapolated.
•• The model may be biased if terms (eg other significant process variables) have been omitted.
•• Outliers should be removed where appropriate, and the regression re-run. These can
be identified by plotting observed Y (on the y-axis) versus predicted Y (on the x-axis) –
this is a useful plot anyway, giving a visual indication of the goodness-of-fit. The points
should be scattered around the 45° line, the closeness of the points to the line indicating
the quality of fit. Outliers will lie outside the general cluster of points. A more rigorous
way of rejecting them is to select Standardised Residuals from the regression dialogue box.
These are residuals divided by a standard error and form a kind of t-test. Any absolute
value greater than about 2.5 can be considered for rejection with 99 per cent (two-sided)

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confidence; though don’t forget that a large data set would be expected to have one per
cent of its residuals of this value or greater by chance alone.
•• The least squares method is based on a number of assumptions. One of the most important
is that the residuals (predicted – actual values) are normally distributed; this can be visually
checked using a histogram (the Excel regression dialogue box permits you to produce a
column of residuals and predicted values). Another is that the errors are independent; this
assumption is violated when the data are serially correlated, and the time relationship
would need to be accommodated in the model (see below).
Regression analysis is a big subject and interested readers should consult appropriate
texts for further details (eg Box and Draper, 1987; Box, Hunter and Hunter, 1978; Chatfield,
1983; Draper and Smith, 1998; Montgomery and Runger, 1999; Snedecor and Cochran, 1968;
Napier-Munn, 2014a).

Time series models and intervention analysis

Data plotted in time such as those shown in Figures 1 and 2 can be modelled as a time series.
These models exploit the fact that such data are often ‘serially correlated’ – that is, each
result is to some extent dependent on the previous results (like the weather!). The degree of
dependence is measured by ‘autocorrelation’, defined similarly to the correlation coefficient,
R (the square root of R2 which is given by Excel’s ‘Add Trendline’). There is a family of time
series models known as Box-Jenkins models that take this approach (Napier-Munn, 2014a).
A simple TS model that is useful in mineral processing time series is the autoregressive
model of order 1 (AR(1)), which simply says that the current result is dependent to some
extent on the previous result (Napier-Munn and Meyer, 1999):

yt = μ + φ(yt-1 – μ) + et (7)

where:
yt = performance (eg recovery) in current time period (eg today)
yt-1 = performance in previous time period (eg yesterday)
φ = autocorrelation coefficient (0 ≤ φ ≤ 1), which measures how strongly yt depends on yt-1
μ = process mean: the value about which the process is randomly oscillating
et = error for time t: a measure of the residual error after the model is fitted
Equation 7 can be rearranged in the form of a linear expression, which can be easily fitted
by Excel’s regression tool or ‘Add Trendline’ in Chart.

yt = μ(1 − φ) + φ(yt − 1) (8)

Here yt is the column of daily data and yt-1 is this column displaced down by one cell. (The
first yt value and the last yt-1 value must be eliminated to produce two columns with the same
number of data points.) a0 (the intercept of the fitted line) = μ(1 – φ), and a1 (the gradient) = φ,
and so μ = a0/(1 – a1).
Now we invoke Equation 5 to perform intervention analysis on the time series model:
yt = a0 + a1(yt-1) + a2T (9)

where again:
T is the presence or absence of the trial condition
The process shown in Example 6 is then followed.

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Example 8
One type of experiment that is difficult to do on a plant scale is the testing of grinding media,
which cannot be switched easily to conform to a particular experimental protocol such as a
paired t-test. In this example a study was made of the effect of two types of grinding media
on final concentrate grade from the flotation plant. A homogeneous period using the first
type of media was taken as representing that condition (T = 0). The new media was then
progressively added to the mill and a second period of data collected once the mill was fully
charged with the new media (T = 1). Three hundred and ten days of data were available in all.
The data and Excel Regression output were as shown in Example 8.
The media coefficient is -1.31 per cent and its two-sided P-value 1.8E - 06, which is highly
significant. We may therefore conclude that moving from Media 0 to Media 1 reduced the
concentrate grade by 1.3 per cent.
Note that the concentrate grade (t - 1) coefficient is 0.45. This is a measure of the dependency
of each day’s concentrate grade (t) on the previous day’s figure (t - 1), and is also highly
significant. This confirms the validity of using the AR(1) time series model.

CHANGES IN PROCESS MEAN – THE CUSUM CHART

In analysing plant trials, it is always worth plotting the performance data (eg recovery)
as a simple time series, as shown in Figure 1. This will often show trends, cycles or other
features that are not apparent in statistical tests. These features are helpful in guiding
the subsequent analysis of the data. Figure 7 shows the performance of a precious metal
concentrator over five months in which an improvement in recovery and a reduction in
variability in the last month are clearly apparent; this was the result of introducing a new
control system.
However, process changes are generally more subtle and less apparent than this. In such
cases a cumulative sum chart can often identify changes in process mean more clearly.

EXAMPLE 8
Modelling a plant trial as a time series.
Media Conc grade (t-1) Conc grade (t) Summary output
0 34.34 33.27 Regression statistics
0 33.27 32.86 Multiple R 0.6092497
0 32.86 33.11 R square 0.3711852
0 33.11 30.44 Adjusted R square 0.3670887
0 30.44 29.99 Standard error 2.0754444
… … … Observations 310
1 28.50 28.39
1 28.39 28.79
1 28.79 28.50 Coefficient Standard error t stat P-value
1 28.50 27.23 Intercept 16.531569 1.535578721 10.766 3.83E-23
1 27.23 29.85 Media -1.312924 0.26970263 -4.868 1.81E-06
1 29.85 29.55 Conc grade (t-1) 0.4530328 0.050493461 8.9721 2.95E-17

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 CHAPTER 11 | DESIGNING AND ANALYSING PLANT TRIALS

FIG 7 – Time series of plant performance.

A ‘cusum’ chart is a time sequence plot of the cumulative sum of the current value minus
some mean value plus the previous cusum. In symbols:

Ct = Ct-1 + Rt – µ (10)

where:
Ct = cusum at time t
Ct-1 = cusum at time t – 1
Rt = value (eg recovery) at time t
μ = some mean or target value (often the process mean over the period)
Figure 8 (top) shows a normal time series of mill P80 over an 18-month period from a gold
plant. Apart from the usual noise, there appear to be three distinct periods of prevailing
P80, a low leading to a high and then back to a low again. The bottom image in Figure 8 is
the cusum series of the data, using a mean value μ = 174 μm (the mean of the whole series).
The points of change are now very clear, and careful inspection of the chart shows that the
changes occurred on days 130 and 404. This information can now be used forensically to
explore the reason(s) for the change.
In cusum charts, the absolute value of the cusum at any point is not important. It is the
gradient of the line over a characteristic period that indicates the prevailing process mean
over that period, and changes in gradient indicate changes in process mean. A change in gradient
can be from positive to more or less positive, negative to more or less negative, or more
dramatically (as in Figure 8) from negative to positive or vice versa. If the gradient over a
given period is negative then the prevailing mean is less than μ, if positive then the prevailing
mean is more than μ, and if flat then the prevailing mean is equal to μ.
In constructing a cusum chart, therefore, the choice of μ is important, and it is usually
worth trying several to see which gives the most obvious changes in gradient. This is easy if
Equation 10 is implemented in a spreadsheet. Typical choices are the total mean of the data
(as in Figure 8, for which the cusum of the final point will always be zero), some target value
for the process being sought, or the mean for the period before a known change is made to a
process variable.
In many cases, changes in gradient can be assessed by eye. However, rigorous methods are
available for determining if the change in gradient at any given point is statistically significant
(Himmelblau, 1970; Montgomery and Runger, 1999; Napier-Munn, 2014a).

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 TIM NAPIER-MUNN

300
250

P80 (micron)
200
150
100
50
0
0 100 200 300 400 500
Day

3000

2000
Cusum of P80

1000

-1000

-2000
0 100 200 300 400 500
Day

FIG 8 – Time series and cusum chart of daily mill P80.

EVOLUTIONARY OPERATION
Evolutionary Operation, or EVOP, has been widely used in some process industries and has
been advocated for mineral processing (Mular, 1971; Mular and Bull, 1973; Napier-Munn,
2014a, 2014b) but never seems to have caught on. It is not clear why this should be, as its
features suit the characteristics of concentrators rather well. EVOP is a process optimisation
procedure in which simple factorial designs are used to explore and approach the optimum
performance in a noisy process. The range of each factorial is small to prevent damaging
interference to the process. The basic experiment is replicated until effects become statistically
significant, and the design follows the contours or response surface of the process until it detects
a maximum. It is one of a broad class of optimisation methods called hill climbing techniques,
and has a number of variants including SSDEVOP: simplex self-directed EVOP. It is easy to
implement and to calculate, and is promoted as a method in which plant operators can play
an important role. It does, however, require a commitment to the process over long operating
periods. The method is covered in detail in Mular and Bull (1973) and Napier-Munn (2014a)
and is also discussed in Box, Hunter and Hunter (1978) and Himmelblau (1970).

RUNNING PLANT TRIALS

There are three main ways to conduct an effective full plant trial:
1. in pairs of some kind, so that the paired t-test can be used to eliminate the effect of any
uncontrollable variable such as feed conditions or parallel circuit
2. if more than two conditions are to be compared, then use a randomised block design,
in which the effect of the unwanted variable (eg time as a proxy for feed condition) is
removed by blocking
3. without a formal design, using models to assess any differences.

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 CHAPTER 11 | DESIGNING AND ANALYSING PLANT TRIALS

Of these, the paired t-test is probably the most efficient if only two conditions are being
tested. The randomised block design is appropriate where more than two conditions are
being trialled. Modelling using intervention analysis will generally require more data than
the other two, and is normally used only where practicalities prevent the use of a formal
design, or in the analysis of historical data. Some comments on each follow.
Clearly it is no good running for a time (a day, week or month) with one condition, then
switching to the other condition for the same period, and then comparing mean performance
over the two periods, as was done in the experiment illustrated in Figure 1. Other factors
may have changed with time which would interfere with the comparison, most notably ore
type or grade. The error would also be high and uncontrolled. The paired trial or randomised
block design are intended to deal with this situation. In both cases, it is necessary to choose a
duration for each replicate of the experiment, eg for each member of the pair. Selection of an
appropriate time period will depend on:
1. How the plant does its metallurgical accounting and reconciliation.
2. Material residence time in the process (the period must be selected to be long compared
to mean residence time; at least three residence times are required, and preferably much
more – five to ten).
3. The period of large-scale changes and trends in process performance, such as those evident
in Figure 2. The replicate times should be short compared to this period.
Common durations for a replicate are a shift or a day. A day is preferred, as shift performance
often varies systematically over the 24-hour cycle, and a day is usually long compared with
mean residence time but short compared with long-term trends. However, the longer the
period, the longer (and more expensive) is the total duration of the experiment.
The switching order in the trial must be randomised. A problem arises if it is difficult
to switch condition, eg when a major item of equipment is to be included and excluded,
although this is often easier than it seems if a little thought is given to the problem. In such
cases the switch can be made less frequently but the trial will have to proceed for longer to
ensure a time bias does not accumulate.
In some cases identical parallel circuits are not available. Here the pairs are generated
sequentially in time. It is often considered that after switching a condition the plant requires
a full period (eg a day) to settle down, and the performance of the day following any change
should therefore be ignored. The order of each pair must also be randomised. This produces a
sequence of groups of three or four days: four days when the first day of the group is different
to the last day of the previous group, and three days when the first day is the same as the last
day of the previous group and no day is required for stabilisation. A typical sequence is as
shown below (groups numbered in sequence; N = normal and T = trial condition). The pairs
used in the analysis are underlined:

1. NNTT 2. NNTT 3. TNN 4. NTT

5. NNTT 6. TNN 7. NTT 8. NNTT
9. TNN 10. NTT 11. TNN 12. NTT
13. TNN 14. TTNN 15. NTT 16. NNTT etc

If 16 ‘pairs’ were required to detect a difference in this case, then the experiment would run
for 55 days, assuming no breaks.

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 TIM NAPIER-MUNN

A checklist
In planning a plant trial (or any experiment), work through the following checklist:
1. Define the objective(s) of the trial; write them down and be specific. Why are you doing it?
What will be your actions depending on the outcome?
2. Formulate the objectives in experimental terms. What experiments need to be conducted
to achieve the objectives?
3. What response(s) and factors are to be selected for investigation? What do we know about
the random variation of the response(s) – ie experimental error? Conduct pilot-scale tests
if necessary.
4. Over what range do we need to alter the factors? Are we interested in knowing factor inter­
action? Is there any unwanted or uncontrollable variable whose effect must be eliminated?
5. Taking into account all of these considerations, plus the time, money and labour available,
and the possible effect on current operating processes, select an appropriate experimental
design.

WHICH IS THE BEST METHOD?

The most powerful designs for plant trials are the parametric methods such as the paired
t-test or randomised block design.
‘Powerful’ means that they are more sensitive and will detect smaller differences faster than
other methods. The only restrictions on their use are:
1. practical – the process cannot accommodate the design
2. statistical – the assumptions of randomness and independence are violated.
Problem 1 can often be managed with a little lateral thinking. Problem 2 can also be managed,
as the t-test in particular is very robust to departures from these assumptions, and experience
shows that the data pairs (as distinct from the original data) very often exhibit properties
indistinguishable from those required; in particular they are not serially correlated. Also, a
modified version of the paired t-test has been developed (Napier-Munn and Meyer, 1999),
which uses the AR(1) model to deal with the problem of serially correlated data.
If there is any doubt, raise the confidence level (reduce the P-value) at which you are
prepared to make a decision, thus reducing the risk of making a Type I error.
If the parametric methods cannot be used, then you have to model your way out, or use the
reference distribution (Napier-Munn, 2008). The latter is advocated by some, but as noted
above it is susceptible to the assumption that the chosen RD is characteristic of the (constant)
process before the trial. Models have the advantage that they accommodate other variables that
are known to affect the response, such as feed grade or time, so improving the precision of the
comparison. They also don’t need a formal design and can sometimes throw up other useful
information. However, again they depend on the validity of the assumptions underlying the
method of least squares, such as normally distributed and independent residuals. And again,
experience in mineral processing suggests that these assumptions are not as wildly infringed
as some suggest. A disadvantage of modelling is that the effect of a trial condition can only
be unequivocally established if all other material effects are included in the model. This is not
always possible.
Here is the preferred order:
1. paired t-test, or randomised block if there are more than two conditions
2. regression model with important process variable(s) and trial as a dummy variable

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 CHAPTER 11 | DESIGNING AND ANALYSING PLANT TRIALS

3. time series model with trial as a dummy variable (intervention analysis)

4. reference distribution.
The cusum chart can be a useful way of spotting or illustrating process changes visually.
Process optimisation procedures such as EVOP may be worth a try.

Some final thoughts

1. Plan the trial, stick to the plan, analyse the data rigorously, and then make a decision. The
decision might be that there is no decision, or to continue the trial, but there must be an
outcome to every experiment.
2. Always plot the data, particularly time series data. Potential outliers should show up
clearly, as should trends and cycles in the data, which may have important implications.
3. Replicate, replicate, replicate. You cannot make a comparison between conditions unless you
have some idea of error.
4. It is usually all too easy to follow local tradition or to cut corners, particularly in plant
trials. Traditions often grew up in an age of ignorance, and cutting corners, especially in
regard to replication, is almost always wrong. Doing the right experiment will always
produce the right answer in the minimum time (and at the minimum cost). A little lateral
thinking will usually solve the apparently intractable practical problems of getting the
plant environment to conform to the required experimental design. Cutting corners, such
as not replicating, is a seductive alternative to rigour in experimental design. History tells
us that this always leads to a non-optimal outcome, sometimes to the wrong outcome, and
often to no outcome at all. And those who forget history are condemned to repeat it.
5. Most of the data analysis methods described in this chapter can be handled in Excel.
For the more complex experimental designs, such as large factorials or the CCRD, it is
recommended that you invest in one of the specialist statistics software packages both
for designing the experiment and analysing the data. However, be aware that there is a
substantial overhead involved in coming to grips with such packages, and retaining the
skill of using it over time.
6. And finally, ponder the well-known quotation: An unsophisticated forecaster uses statistics as
a drunken man uses lamp-posts – for support rather than for illumination, attributed to the Scottish
man of letters Andrew Lang (1910). In conducting and interpreting our experiments, let us
seek the illumination of wisdom and eschew the lamp-post of prejudice.

REFERENCES
Box, G E P and Draper, N R, 1987. Empirical Model-Building and Response Surfaces (John Wiley and Sons:
New York).
Box, G E P, Hunter, W G and Hunter, J S, 1978. Statistics for Experimenters (John Wiley and Sons: New
York).
Bruey, F and Briggs, D, 1997. The REFDIST method for design and analysis of plant trials, in Proceedings
Sixth Mill Operators’ Conference, pp 205–207 (The Australasian Institute of Mining and Metallurgy:
Melbourne).
Cavender, B W, 1993. Review of statistical methods for the analysis of comparative experiments, SME
Annual Meeting, Reno, February, Preprint 93–182 (Society for Mining, Metallurgy, and Exploration:
Littleton).
Chatfield, C, 1983. Statistics for Technology, third edition (Penguin).
Davies, O L (ed), 1967. Design and Analysis of Industrial Experiments (Oliver and Boyd: London).

FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25 389

 TIM NAPIER-MUNN

Draper, N R and Smith, H, 1998. Applied Regression Analysis, third edition (John Wiley and Sons: New
York).
Fisher, R A, 1926. Statistical Methods for Research Workers (Oliver and Boyd).
Fisher, R A, 1938. Presidential Address to the First Indian Statistical Congress, Sankhya, 4:14–17.
Himmelblau, D M, 1970. Process Analysis by Statistical Methods (John Wiley and Sons: New York).
Lang, A, 1910. Speech quoted in Alan L Mackay The Harvest of a Quiet Eye (1977), as reported in Chambers
Dictionary of Quotations (2005), p 488.
Mason, R L, Gunst, R F and Hess, J L, 1989. Statistical Design and Analysis of Experiments (John Wiley
and Sons: New York).
Montgomery, D C and Runger, G C, 1999. Applied Statistics and Probability for Engineers (John Wiley and
Sons: New York).
Morrison, R D (ed), 2008. An Introduction to Metal Balancing and Reconciliation (JKMRC, The University
of Queensland: Brisbane).
Mular, A L, 1971. The selection of optimization methods for mineral processes, in Proceedings Decision-
Making in the Mineral Industry, special volume 12, pp 442–450 (Canadian Institute of Mining,
Metallurgy and Petroleum: Montreal).
Mular, A L and Bull, W R, 1973. Mineral Processes: Their Analysis, Optimization and Control, course
manual, 1969–1973.
Napier-Munn, T J, 1998. Analysing plant trials by comparing recovery-grade regression lines, Minerals
Engineering, 11(10):949–958.
Napier-Munn, T J, 2008. Some practical problems in running statistically valid plant trials, and their
solution, in Proceedings Metallurgical Plant Design and Operating Strategies (MetPlant) 2008, pp 249–258
(The Australasian Institute of Mining and Metallurgy: Melbourne).
Napier-Munn, T J, 2014a. Statistical Methods for Mineral Engineers: How to Design Experiments and Analyse
Data (JKMRC, The University of Queensland: Brisbane).
Napier-Munn, T J, 2014b. Cunning solutions to process improvement, in Proceedings 12th AusIMM Mill
Operators’ Conference, pp 5–10 (The Australasian Institute of Mining and Metallurgy: Melbourne).
Napier-Munn, T J and Meyer, D H, 1999. A modified paired t-test for the analysis of plant trials with
data autocorrelated in time, Minerals Engineering, 12(9):1093–1100.
Snedecor, G W and Cochran, W G, 1968. Statistical Methods, sixth edition (Iowa State University Press:
Oxford).
Venkatesan, L, Harris, A and Greyling, M, 2014. Optimisation of air and froth depth in PGM flotation
using a CCRD design, Minerals Eng, 23:621–626.

FURTHER READING
Cochran, W G and Cox, G M, 1966. Experimental Designs, second edition (John Wiley and Sons).
Davies, O L and Goldsmith, P L (eds), 1972. Statistical Methods in Research and Production, fourth edition
(Oliver and Boyd).
Napier-Munn, T J, 1995. Detecting performance improvement in trials with time-varying mineral
processes – three case studies, Minerals Eng, 8(8):843–858.

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 Return to contents

CHAPTER 12
Project evaluation and communication
Joe Pease

ABSTRACT
This chapter is about the final stage of project approval – economic evaluation and
communication to ‘sell’ the project. It is an exciting stage and easy compared to the work you
have done to reach this point. But be careful not to underestimate it; many poor projects are
approved and many good projects rejected because of mistakes made at this stage. Economic
calculations are easy but depend entirely on the quality of data and assumptions. Meanwhile,
the approach to ‘selling’ a project is quite different from the rigorous engineering process you
needed to get to this point.
The chapter starts with a discussion on some of the simple evaluation techniques used to
assess projects. More importantly, it highlights the dangers in such techniques; that is, their
simplicity can conceal the unavoidable uncertainty in your data. The really hard work in the
project evaluation is retrieving the right data and knowing its limitations.
We then look at how to increase the chances of project approval. This is where engineering
meets marketing and psychology. The directors might be clever, hard-working people, but
they may not be metallurgists so you cannot assume they grasp the details; they need to ration
capital between an extensive list of competing projects. Because you are trained in the scientific
method you avoid quoting anything that is not backed up by hard data. Some of the groups
competing for funds are not so rigorous, but they do fantastic PowerPoint presentations.
So how do you ensure that the company considers your project fairly and makes the right
decision? Importantly, communication is an ongoing process that starts in the earliest stages
of the project. Indeed, it starts with selecting the right project to work on in the first place.

EVALUATION TECHNIQUES
This section is deliberately brief. There are many well-qualified texts that demonstrate the
theory and mechanics of project evaluation methods and risk analysis. Calculators have
built in net present value (NPV) and internal rate of return (IRR) functions and spreadsheets
are ideal for laying out an economic evaluation. These techniques can be easily researched

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 JOE PEASE

elsewhere. The crucial task is to use the right numbers in the evaluation. This can take years,
whereas the economic model will take just hours. Spend your time making sure you look at
the right project in the right way and collect accurate numbers. Your company will want a
financial analyst to review your project against the company standards and you’ll need to
help. Understand what is important to their analysis and make sure they understand the
basic metallurgy and limiting mineralogy behind the project. Encourage them to ask you
tough questions – better to deal with them now than at the Board Meeting. If you establish
mutual professional respect with the financial analyst you’ll have an influential ally.

THREE COMMON EVALUATION TECHNIQUES

Texts often summarise these as the three most common techniques used for evaluation.
Rather than being a choice of which one to use, they all look at the same numbers with a
slightly different perspective. Table 1 shows a simple example analysed by all three methods.
The sensitivity analysis in Figure 1 shows the effect of the various assumptions. This indicates
whether the project is robust and which numbers are really important for success.

Net present value (NPV)

NPV is considered the most correct project evaluation method. Yet NPV is always trumped
by GIGO (garbage in, garbage out) – if your assumptions or data are wrong nothing can stop
the answer from being garbage.
NPV represents the value of future cash flows associated with the project in today’s money.
Future cash is discounted back to today’s value using a ‘discount rate’ that will be set by your
company. It may include:
•• the cost of borrowing
•• the inflation rate
•• an additional factor to cover risk and margin.
The cost of borrowing is effectively the interest rate your company pays – if you borrow $100
and the interest rate is eight per cent, you owe $108 next year. Or put the other way, $108 next
year is worth $100 today.

NPV, $ M
15

Change in revenue
12 – eg production,
recovery, prices
Change in capital or
operating cost (lines 9
overlap)

3
1 year commissioning delay

0
-30% -20% -10% 0% 10% 20% 30%

-3 % change in assumption

FIG 1 – Sensitivity of net present value (15 per cent) to key assumptions.

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 CHAPTER 12 | PROJECT EVALUATION AND COMMUNICATION

Further, if the inflation rate is four per cent, you’ll need $104 next year to buy what $100 would
buy you today. In this case $104 is called ‘nominal’ dollars and $100 is ‘real’ dollars (today’s
value of the future amount). You need to account for both interest and inflation. Usually
inflation is handled by doing evaluations in ‘real’ (today’s) dollars. Your company will have its
own procedures for forecasting inflation, costs and metals prices. Just make sure all numbers
are compatible. If you are using today’s dollars, the discount factor, metal price forecasts and
operating cost forecasts all need to be compatible and expressed in today’s dollars.
As well as allowing for interest and inflation, discount rates usually add a risk factor. Projects
and future assumptions are risky. The company needs a margin on projects to allow for risk
and still leave room for profit. The risk factor will vary with the perception of risk, the need
for profit and the company’s financial situation. Often a high risk factor is used to ‘ration’
capital and resources to select only the highest performing projects.

The base case

Your project is analysed against the base case. Often the base case is ‘do nothing’, which
compares the project with current performance. But think carefully – is the base case really
‘do nothing’? Maybe there is a better alternative. For example, assume you are considering
installing extra grinding power to improve liberation and recovery. The capital cost is $20 M
for a five per cent recovery increase. Before you do the analysis you must check whether there
are any other alternatives. Is the current grinding circuit performing as well as it can? Can
you improve grind size by reducing media size, replacing cyclone components, better use of
grinding control and improving operating practices? What if spending $1 M on these items
can achieve three per cent recovery? In that case, you must first fix grinding and classification,
then analyse the remaining benefits.
This sounds obvious, but a depressing amount of projects are proposed (and approved)
without rigorously analysing the base case. Yes, that is hard work, but it is your job to first
achieve the best out of your existing equipment: ‘no new toys until you are using all your old
toys properly!’ Ultimately this will pay you back – you want a reputation for spending money
wisely, that you would not ask for capital unless you really need it. That is the credibility
required when you have the right project.

Checklist and conventions for NPV spreadsheets

•• Make sure you include all relevant cash flows; for example, capital spares, deferred capital,
extra operating and maintenance costs, depreciation of capital equipment, scrap value at
the end of the project.
•• Use compatible numbers; for example, ‘real’ numbers for cash flow, discount rate, metal
prices.
•• Include tax. This is a complex area best left to company professionals; however, you
should ensure your project does not rely on tax benefits to be viable (for example, tax-free
status from carried over losses, or tax incentives such as research and development [R&D]
schemes). Tax laws change, so if the project isn’t viable, don’t do it.
•• Never quote an NPV without three qualifiers – the discount rate, real or nominal dollars,
before or after tax. To say the project has an NPV of $10 M is meaningless; NPV is
determined by the discount rate. The same project can have an NPV of $100 M at
five per cent discount, but negative $100 M at 30 per cent discount rate.

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394

TABLE 1
Simple financial analysis spreadsheet.
No Item Year 0 Year 1 Year 2 Year 3 Year 4 Year 5 Years 6–13 Year 14 Year 15 Note
1 Capital cost -10 000 000 1
2 Additional commisioning -500 000 2
3 Additional operating -1 800 000 -2 000 000 -2 000 000 -2 000 000 -2 000 000 etc -2 000 000 0 3
4 Ramp-up profile 81.3% 100% 100% 100% etc 100% 0% 4
5 Increased concentrate tonnes produced 12 188 15 000 15 000 15 000 etc 15 000 0 5
6 Net value of one tonne of extra concentrate 500 500 450 400 etc 400 6
7 Net sales revenue of extra concentrate 6 093 750 7 500 000 6 750 000 6 000 000 etc 6 000 000 7
8 Net salvage value (after decommissioning costs) 750 000 8

JOE PEASE
9 Net operating cash flow before tax -10 000 000 -2 300 000 -4 093 750 5 500 000 4 750 000 4 000 000 etc 4 000 000 750 000 9
10 Allowable depreciation on new equipment -1 500 000 -1 500 000 -1 500 000 -1 500 000 -1 500 000 Stops in year 7 10
11 Extra operating profit before tax -3 800 000 2 593 750 4 000 000 3 250 000 2 500 000 etc 4 000 000 750 000 11
12 Extra tax paid 1 140 000 -778 125 -1 200 000 -975 000 -750 000 etc -1 200 000 -225 000 12
13 Cash flow after tax (real dollars, undiscounted) -10 000 000 -1 160 000 3 315 625 4 300 000 3 775 000 3 250 000 etc 2 800 000 525 000 13
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14 Cumulative cash flow (after tax, undiscounted) -10 000 000 -11 160 000 -7 844 375 -3 554 375 230 625 3 480 625 etc 46 302 813 46 827 813 -
15 Payback period 4 years 14
16 At 15 per cent discount rate: discounted cash flow -10 000 000 -1 008 696 2 507 089 2 158 369 2 158 369 1 615 824 etc 395 720 64 520 15
17 NVP (15 per cent) 11 543 000 16
18 At 30 per cent discount rate discounted cash flow -10 000 000 -892 308 1 961 908 1 957 214 1 321 732 875 319 etc 71 113 10 257 17
19 NVP (30 per cent) 986 100 -
20 Internal rate of return (IRR) 33% 18
FLOTATION PLANT OPTIMISATION | SPECTRUM SERIES 25

All dollar values estimated in real dollars (ie in today’s dollar values). This example uses single years. You may have to break early years into months to capture cash flow details.
Notes:
1. Capital cost includes all items from your analysis in the Sample Financial Analysis section, including capital spares. State the accuracy of the estimate, eg ±10 per cent, ±30 per cent.
2. Budget to use extra resource and for contingencies during commissioning.
3. Includes concentrator, filtering and drying, transport, etc.
4. This example assumes 50 per cent of benefit in first three months, 75 per cent for next three months, then 100 per cent. The ramp up profile will relate to project complexity, quality of engineering, and quality
of commissioning.

CHAPTER 12 | PROJECT EVALUATION AND COMMUNICATION

5. Ultimate increased annual tonnes, 5000 × ramp up profile (Row 4).
6. Calculated from your estimate of concentrate quality, and company assumptions of metal prices, exchange rates, treatment charges, penalties, transport costs, etc. In this example the company forecasts prices
to fall in year 4.
7. Row 5 × Row 6.
8. Estimate. After discounting, it has little effect on project value.
9. Rows 1 + 2 + 3 + 7 + 8. This is the net operating cash flow before tax. Rows 10 to 12 now calculate the effect on tax paid.
10. Depreciation rate will vary for different equipment – get accounting advice. This example assumes 15 per cent. Don’t forget to stop depreciation when full value has been written off – in this case after 6.7 years.
11. Row 10 + Row 11, ie operating cash flow less allowable depreciation. It is this amount that tax is paid on
12. Assuming company tax rate of 30 per cent. The positive tax in Year 1 assumes the company is profitable, so the the loss will reduce tax paid on other profit.
13. Row 9 + 12.
14. The project has paid back its invested cash about four years after the money is spent.
15. For example in year 3, divide Row 13 by 1.153.
16. Sum across Row 16. You could also use the NPV function on Row 13. However, writing down values in Row 16 shows the impact of variables, and helps you see anomolies or errors.
17. For example in year 5 divide Row 13 by 1.35.
18. Use IRR function on Row 13.
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 JOE PEASE

Important considerations when working with NPV

•• Compare the right options – the right project against the right base case using the right
numbers.
•• NPV doesn’t capture everything. You can’t quantify some things; for example, environmental
impact or effect on your company’s public perception. You may be able to ameliorate the
impact by spending additional capital on improved design to minimise the impact, or for
subsequent restoration. Either way, the Board need to understand any possible adverse
consequence (or benefit) compared with the base case.
•• NPV may fail to capture the relative risk of projects. Sensitivity analysis can quantify the risk
of error in the assumptions (Figure 1). You can demonstrate the effect of uncertainty in all
inputs by preparing a probability distribution of final outcomes. This can be powerful,
but is still only as good as the assumptions used. Whether we use a single value or a
probability distribution, too often our assumptions are optimistic. We are born optimists
and habitually underestimate capital cost, impact on existing operations, commissioning
time etc and we often overestimate the benefits. Rather than doing a more complex financial
analysis, spend your time making sure your estimates are supported by the mineralogy,
that your project is robust, and that you have contingency plans to deal with surprises.
•• NPV favours short-term projects over long-term company-building projects. This is especially
true if a high discount rate is used to ration capital. At a discount rate of 15 per cent (real,
after tax) one dollar in 15 years’ time is valued at 12 cents today. At a 30 per cent discount
rate it is worth only two cents, and there is little value to any return beyond ten years.
The high discount rate favours projects with low upfront capital, short duration and early
cash flows, and penalises long-term or complex projects with slower returns – even if they
are company-building projects with long-term value. You can’t change your company’s
policy, and don’t even think about ‘fiddling’ the numbers to improve the NPV. But if you
think your project is low risk and fundamental to build future strength, you can argue that
a lower discount rate may be appropriate. You may be unsuccessful, but you should give
the Board the opportunity to assess this.
•• NPV says nothing about your relative competitiveness. The NPV calculation uses your
company’s assumed metal prices and calculates profit, but any project that increases
production looks good at high prices. What about when prices drop? As business magnate
and philanthropist Warren Buffett (2002) says – and the mining industry demonstrates
every cycle – ‘it is only when the tide goes out that you see who was swimming naked’. So
always calculate the effect of your project on the unit cost of producing the final product;
for example, c/lb of metal). If it increases unit cost, then beware. Do you really want to
spend capital to become less competitive? Redesign the project to seek both increased
revenue and lower unit cost.

Internal rate of return (IRR)

After you complete an NPV calculation, calculating IRR is simple: it is the discount rate that
makes the NPV zero. A project may have an NPV (real, after tax) of $15 M at 15 per cent,
and an IRR of 31 per cent. Even if the company discount rate (or hurdle rate) for projects
was 30 per cent, the project would still have a (slightly) positive NPV and would be
considered viable.
Though it is closely related to NPV, IRR adds a different dimension. You can compare the
relative risk/reward of projects. For example, consider the two projects in Figure 2:

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 CHAPTER 12 | PROJECT EVALUATION AND COMMUNICATION

$119 M
Project NPV
$39 M

$80 M

$43 M
Project
NPV
$23 M
$20 M

NPV of Net
Capital NPV of Net Capital
Revenue
Revenue

Internal Rate of Return : 28%

Internal Rate of Return : 43%

Project A Project B
FIG 2 – Which is the better project?

•• Project A costs $80 M, and has an NPV (real, after tax at 15 per cent discount rate) of $39 M,
for an IRR of 28 per cent
•• Project B costs $20 M, and has an NPV (real, after tax at 15 per cent discount rate) of $23 M,
and an IRR of 43 per cent.
Assume both proposals have been prepared professionally. Which is the better project?
NPV comparison says Project A. But consider two other factors:
•• What is the risk/return and the unavoidable uncertainty in the analysis?
•• Many projects will be competing for limited capital.
While Project B has a lower NPV, it risks less capital and achieves a higher return (IRR) on
it. Even the most professional work can’t eliminate risk – metal prices may fall, treatment
charges and exchange rates will change, the mine may not achieve its schedule. Project B may
be more robust against this uncertainty than Project A.
Further, the Board will be considering lots of projects and capital is limited. They need to
choose the highest returning projects. If they only have $80 M to spend, doing four projects
such as Project B will have a higher NPV than just doing Project A. This also spreads their risk.

Payback period
Payback period simply ranks projects by how many years it takes to pay back the investment.
Like IRR, it can be easily obtained from the NPV spreadsheet. Though it is simplistic and
favours simple short-term projects over ‘company builders’ it is nevertheless useful to
consider. A project that is paid back in three years is inherently less risky than one that takes
ten years to pay back, especially if there is metal price risk or sovereign risk.

Sample financial analysis – Table 1

The project
You propose to install additional grinding power to improve liberation and improve recovery
of lead, copper and zinc by two per cent each. The capital cost is $10 M, and the project will

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 JOE PEASE

take 18 months to execute. You estimate it will take three months after start-up to deliver full
recovery gains.

Work done prior to the financial evaluation

•• Circuit surveys backed up with sizing and mineralogical work to determine the theoretical
benefits of extra grinding. You have quantified the reasons minerals are misplaced in your
circuit (that is, of the diluents in concentrate and values in tails) due to:
•• inadequate liberation
•• entrainment with water
•• poor flotation selectivity (after accounting for entrainment).
•• Laboratory and/or pilot-scale work to demonstrate the gains from extra grinding. This
work has been backed up with quantitative mineralogy.
•• Evaluated different grind sizes and determined the cost and benefit of each to ascertain
the optimum grind size.
•• Evaluated different places to apply the grinding power (do you need to grind the whole
stream, or can you achieve 90 per cent of the gain by grinding 50 per cent of the stream?).
You may need to compare different options to choose the best capital versus return, or best
‘bang for your buck’.
•• Evaluated all test results in terms of the effect on grade/recovery curve and determined
what the project will achieve: increased grade at the same recovery, increased recovery at
the same grade or a combination of both.
•• Considered the impact on impurities in concentrate; for example, silica, MgO, halides,
mercury and so on – anything that may be relevant to your smelter, refinery or customer.
•• Worked with geologists and mine planners to ensure that the ore you did your test work on
was representative, and that you understand future ore supplies (grade and mineralogy)
and how this might influence the project returns (and base case).
•• Having chosen your target grind size, you have then done test work and simulation to
choose what grinding and classification equipment is needed.
•• Determined whether the additional grinding will require extra flotation equipment.
•• Designed for all downstream impacts – froth handling (launders and sprays), froth
pumping, thickening, filtering, concentrate drying and transportable moisture.
•• Checked for all infrastructure impacts and allowed for additional costs if necessary –
power supply, power distribution, control system capacity, supply and reticulation of
water, compressed air, instrument air, gland water, blower air and so on.
•• Checked with customers whether the finer concentrate will have any influence on their
volumes or treatment charges.
•• Checked that you are comparing against the right ‘base case’. Is your current grinding/
classification circuit running as well as it can, or does it need to run better before you can
evaluate the benefit of extra grinding?
•• Done adequate engineering evaluation for your cost estimate. Your engineers will advise
the accuracy of this estimate; for example, ±30 per cent, ±20 per cent and so on.
•• Included recommended initial spares holding as part of the capital cost.
•• Spoken with the operating and maintenance personnel to make sure they understand
the implications of what is being proposed and what additional support it will need in
construction, commissioning and operation.

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•• Estimated maintenance and operating costs such as power, water, air, reagents,
maintenance consumables, operating and maintenance labour and instrument labour.
•• Estimated a start-up profile for your project for cost increase and revenue increase. What
resources are necessary to achieve the start-up profile? These will be significant if you are
to start up quickly.
•• Considered any impacts on safety and environment. You will have done a ‘hazop’ or risk
analysis study to meet company procedures, and allowed for any mitigating actions that
resulted from this study.
So, that was the hard bit. The financial analysis is a breeze!

COMMUNICATION
There is nothing worse than a good project not gaining approved because of poor
communication and presentation. As they say, presentation isn’t everything, it is the only thing.
Actually, there is something worse – bad projects that do gain approval because of great
communication and presentation. Here, style has replaced substance and it is the Board’s
job to recognise this. Of course, it will get it wrong sometimes, and there is nothing you
can do about that. Your focus is to ensure that your numbers are right and that you will
deliver if your project is approved. Then you can add some style to your substance. Sure, the
Board likes style, but most of all it likes to back a proven winner. Develop a track record of
delivering on your promises.

Communication or presentation?
What we’ve just discussed refers to the Board presentation, but this is misleading – the
real communication work should be done long before you present to the Board. The final
presentation should be a formality; they should be convinced before you even walk into the
room. Let’s consider the different stages of communication.

Step 1 – choose the right project

This might sound trite, but it is the most important step. You are going to spend a considerable
part of your life on this project – research, test work, analysis of alternatives, designs, costings
and ‘marketing’. If you succeed, you will be involved in detailed design, scheduling, training
and implementation. Meanwhile, there’s your day job of keeping production going while
juggling the installation and cut-ins. Then you have to commission it and nurse it until it
delivers and your reputation remains intact. You will spend more time with this project than
with your family and friends for the next three years. Are you really sure it is worth it?
To answer this, ask yourself some questions:
•• Is this project addressing a symptom or a root cause? For example, our project of installing
extra grinding addresses the root cause of poor mineral liberation. An alternative project
that tries to improve flotation by changing impellors or reagents may alleviate some of the
symptoms but fails to address the root cause. If you only treat symptoms you will end up
with a more complicated plant. You want to simplify plant operation not complicate it, so
look for the root cause. If flotation performance is poor, quantify it in mineralogical terms.
How much is due to poor liberation, flotation selectivity and entrainment. What mineral
classes do you need to affect to change this?
•• Have I really considered all the alternatives? Am I getting the best out of my current equipment?
Are there other projects that can deliver some of the gains more simply and cheaply?

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•• Am I prepared to stake my reputation on the project? If not, find another project. Otherwise be
happy – your plant is running well and you can save the company’s money for important
projects elsewhere.
By answering these questions honestly you know how to justify the project. If you still
believe in the project, you will have the passion and commitment to convince others.

Step 2 – do your homework

Be rigorous. The financial analyst and the Board can’t check your metallurgy. They have
no idea how well your tests were designed, how accurate your samples were, whether you
drilled down to the root cause. That is your job and they expect you to do it. Maybe others
propose less rigorous projects that are less obvious to the Board. Too bad. You just have to
ensure your numbers are right so that you can stake your reputation on the project.
Ask a colleague you respect to check all your assumptions and analysis. None of us are
perfect and peer review is an important part of being a professional.

Step 3 – develop champions and momentum

You can’t do a big project by yourself. You need a ‘critical mass’ – research, engineering,
maintenance and operations people. A wrong word from any one of these can kill the
project. Talk to maintenance staff early – what is needed to maintain the extra equipment?
Can you make their job easier rather than harder? What spares are needed? What about the
operators and operating superintendent – are you making their job easier or harder, more
interesting or just overwhelming? How can you involve them in the design and are they
happy with the access, sample points, training and clean-up points? Can the project solve
some of their existing problems? Consider the senior metallurgist who has been pushing an
alternative project for years without success. How do you make them an ally so as to avoid
them undermining your project? Can you include some of their ideas and share in the credit?
Remember the important rule in any organisation: you can achieve anything you like so long as
you don’t mind who receives the credit.
If it is a good project and you involve these people early enough, they will have ownership.
With enough people wanting it to happen, a project builds momentum and eventually
appears inevitable.

Step 4 – cover all the angles

Remember that senior management and the Board have to paint on a much broader canvas
than you. They will be concerned with corporate governance, public image, share market
perceptions, safety performance, environmental issues, carbon footprint, strategic direction,
debt levels, employee relations, competitors, unit cost reduction, external regulations and
audits and so on. Put yourself in their shoes: what might they need to know about your
project besides the recovery improvement? Can you design it to improve performance in
several areas and not just recovery and profit? It is easier to approve a project that increases
profit, reduces unit cost, simplifies the plant, improves housekeeping and safety and improves
environmental performance.
Maybe it just takes broader thinking. On first appearance the Board might assume extra
grinding power will increase the carbon footprint. But if you increase recovery on ore that has
already been mined, crushed and ground, this may reduce energy per unit metal. Increasing
concentrate grade will reduce transport energy and energy used in smelting. It might seem
obvious but you may need to calculate and communicate it.

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Step 5 – disarm the torpedoes

Despite your best efforts in Steps 3 and 4 there will be some negative people. Some will
have the power to derail your proposal with a single comment – a project-killing torpedo.
Seek these people out, spend time with them and try to make them positive. If they are still
negative, avoid wasting energy trying to change them but make sure you understand their
concern and deal with it proactively. Disarm the torpedo before they fire it rather than go into
damage control after it has hit your project. Some examples of torpedoes that could be aimed
at our grinding project are:
•• Why would we want to grind finer when most of our losses are in the fines fraction; won’t
we just make it worse?
•• We’ll be unable to filter the finer concentrate.
•• Our customers already complain about our concentrate being too fine. We won’t be able
to sell it.
•• Finer tailings will affect tailings disposal or generate more acid in the dam.
•• If you ran your plant properly you wouldn’t need ‘new toys’ to increase recovery.
•• This is a ‘gold-plated’ design. I did a similar project for half the cost.
•• The ore is going to change next year so your test work is meaningless.
•• We would make more money by spending this capital on the mine/smelter/IT system.
•• If all the metallurgists’ projects had worked, we would be at 150 per cent recovery by now.
These criticisms may or may not be fair. But they exist and are dangerous, so you need to
prepare for them.

Step 6 – obtain high-level champions

Perhaps this is covered in Step 3, but it is important enough to discuss separately. You need
high-level support – the earlier the better. Explain the project to senior management, getting
them interested and involved early. What do they need to sell it to their bosses? They have
experience with company politics and procedures. Don’t worry if it seems that the boss will
receive all the credit – if the project makes them successful you will be successful too. Ask the
high-level contacts to work on the parts of the organisation that you cannot influence – maybe
the mine manager, the general manager and Board members. Find out what concerns they
have and the angles they take and what torpedoes are out there?

Step 7 – timing and patience

Steps 1 to 6 are a continuous process that weave through the entire project development. You
probably have to justify time and research money on this project from the very start, so use
that time to build momentum in case the research turns into a viable project.
Persevere: projects are rarely approved first time. People require ‘soak time’ to grow
comfortable with an idea; they may even hope that a cheaper alternative emerges, or that the
problem will go away. As in sport, timing and persistence is as important as skill. It might be
a great project but a bad time to propose it – there may be a lot of other demands on capital,
or a lot of good competing projects right now. Don’t despair – if it’s a good project its time
will come. Use the delay to continue to build understanding and momentum, so that when
the opportunity arises you are ready to strike.

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 JOE PEASE

Step 8 – be passionate and committed, and be prepared to walk away

If you don’t really believe in the project how can you sell it to the Board? If you are not
prepared to stake your reputation on it then walk away from it. Sure you have spent a lot of
time on it already, but refrain from wasting more time and reputation by proceeding with
an inferior project. We should award medals to the cool heads who walk away from poor
projects and redirect their focus to find a good one.
If, however, you have faced this question honestly and still believe in the project, your
passion will show and you should have all the answers for the Board.
There is another time when you should also walk away. You have done a thorough job
planning the project and are sure of your costings, scheduling and plant design. You ask for
$50 M and 18 months to execute the project, and the IRR is 30 per cent. But the Board says
they will approve it if you do it for $30 M in 12 months. What do you do? First, find out what
can be done to the costs and schedule. Are the risks acceptable? Maybe you aren’t prepared to
live with the risks – perhaps the new design will be a maintenance and operating nightmare.
In that case, tell them you would rather walk away from the project than do it badly as you
can no longer guarantee the returns. You have to be serious about this – it cannot be a bluff.
They may see your passion and decide to accept your 30 per cent return. Or they may not.
But you live to fight another day, and you have saved them from a badly executed project that
would have wasted $30 M, several years of your life and your reputation.

THE PRESENTATION
By now the presentation should be easy. You have done all the hard work answering
the questions and disarming the torpedoes. You have built champions at all levels of the
organisation. People have had a long time for the ideas to ‘soak in’. Momentum has been
built, and there is a sense that the project is inevitable. You have put yourselves in the shoes
of your boss, the senior management and the Board, and have considered what they are
interested in and what they need to know.
There are plenty of books and courses on presentation skills so I’ll avoid repeating them here.
If your project has rigour and substance and you have passion, you will get the presentation
right. Just follow some simple rules:
•• Keep it brief. These are very busy people with a lot on their mind. They do not need to know
the details of your job – they just need to do their job. Distil to the essence. Less is more.
•• Structure – tell ’em what you’re gonna tell ’em, tell ’em, then tell ’em what you just told ’em.
•• Tell a story. Try to link your data with a meaningful narrative. That is how people learnt
and remembered long before writing.
•• Less words, more pictures. Use pictures and graphs wherever possible. Look for the picture
that ‘tells a thousand words’. Dwell on it, give it time to talk. Powerful presentations can
be based on a single slide.
•• Keep each slide simple. Use the bare minimum of words. Limit them to a few brief dot points
per slide.
•• Avoid fancy effects. Choose simple colours with good contrast (keeping in mind that many
people are red–green colour blind).
•• Keep graphs simple. Eliminate all unnecessary grids, legends, titles and so on. Use the
minimum amount of ink to quickly convey the message in the data, and the minimum
number of graphs – try to seek the single graph that captures the story of your data. Tufte

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(1983) has produced an excellent text on this topic, with Figures 3 and 4 demonstrating the
principle of removing unnecessary ink that he refers to as ‘chart junk’.
•• Put yourself in their shoes. They are smart people, but they are not metallurgists. You are so
familiar with mineral ‘liberation’ that you don’t even consider it jargon. Are you sure they
know what you mean?

A CASE STUDY … OR, TWO PICTURES THAT SAID A THOUSAND WORDS

This example comes from the Mount Isa lead zinc concentrator in the 1980s. The ore had
become progressively finer grained, and recoveries dropped accordingly. Our project team
tried everything to arrest the decline – circuit and reagent changes. Because recovery and
revenue were down, we did what all good operators do – increased tonnage to make grind
size coarser. We made more concentrate but metallurgy was on a downhill spiral.
The team did an enormous amount of work to define the problem – laboratory work,
future ores testing, pilot plant work and reduced tonnage trials in the plant. There were huge
amounts of quantitative optical mineralogy, then automated mineralogy via QEM*SEM. The
evidence was absolutely overwhelming: grind finer.
From the time of gaining irrefutable evidence, it took about five years to get the project
approved. There were two barriers, one of which was us. Money was tight and there were
many competing projects, so the Board imposed a very high hurdle rate of return to ration

90
80
70
60
50 East
40 West
30 North
20
10
0
1st Qtr 2nd Qtr 3rd Qtr 4th Qtr
FIG 3 – Too much ink hides the message in the data.

100

80 East

60

North
40
West
20

0
1 2 3 4
Quarter
FIG 4 – A simple graph lets the data speak clearly.

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 JOE PEASE

available capital, up to 100 per cent RR. The team could guarantee a 30 per cent return but
the project was too big and complex to achieve 100 per cent. This might have been overcome
except for the real barrier – the Board failing to understand what we were talking about!

The communication gap

Time after time the project team would present its progress to the Board and would then be
told to do more work on it. Can’t you just change the circuit? We hear that columns have improved
recovery by five per cent at ACME mining – why don’t you put in some columns? A supplier told me
they have a new collector that improved recovery by five per cent at XYZ; have you tried that? We were
stunned – we had put enormous resources into quantitative mineralogy and test work and
had just given them a comprehensive presentation on a mineralogical circuit balance showing
what was happening to different composites in every part of the circuit. There was an ocean
of mineralogical data proving beyond any doubt that the problem was composite particles.
We had shown countless graphs and tables to demonstrate this – the distribution of sphalerite
binaries with galena, pyrite and gangue for each size fraction in the lead concentrate, zinc
concentrate and tailings. But the Board sent us back to look at columns and reagents! Did they
think that reagents ground composites? Don’t they know that columns deal with entrainment,
not composites? And so we tried harder, producing even more detailed work. Next time we
would wow them with irrefutable scientific evidence.
The team had done so much work and were so close to the data that the Board was
overwhelmed with it. It never occurred to us metallurgists that they were unable to grasp a
mental image of what we were talking about. Finally, we realised that we were the problem,
not the Board. We tore up all the old presentations and developed a stunningly simple one
using two slides like in Figures 5 and 6. In ten minutes these two simple slides communicated
what five years of presentations could not. They look dated now, being from the days of
overhead projectors, but it shows the power of a simple presentation that reveals the forest,
not a million trees.
Figure 5 is a simplification, it imparts no quantitative information about the mineralogy but
it powerfully conveys the key concept. We left this picture on the screen for a few minutes
and discussed our options:
•• if we recover these particles we lose money
•• if we don’t, we lose recovery.
So the Board said: ‘You need to grind it’. No one mentioned collectors or columns or
organisational change.
We followed Figure 5 with Figure 6, adding quantitative rigour to the mental picture they
now had of poor liberation. While we had an ocean of quantitative mineralogical data – as
you always do – we wanted to distil it into a single picture to show the forest for the trees. The
detail was our job; the Board just needed to know that the ten-year decline in recovery was
caused by the decline in liberation.
Suddenly, approval was a formality. The project was a great success.

REFERENCES
Buffet, W E, 2002. Chairman’s 2001 Letter to Shareholders, Berkshire Hathaway Inc. annual report,
28 February. Available from: http://www.berkshirehathaway.com/2001ar/2001letter.html [Accessed:
15 January 2016].
Tufte, E R, 1983. The Visual Display of Quantitative Data, 197 p (Graphics Press: Connecticut).

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Zinc losses in final tailing

Period 10 1989/90

Particle size
300 microns

Key:
1. ZnS = sphalerite (grey)
2. Gangue = non-sulfide gangue
3. PbS = galena (white)

Particle size
300 microns

Key:
1. ZnS - easily liberated piece of sphalerite
2. ZnS - more difficult to liberate
3. Gangue (dark)
4. Pyrite (spherulitic)

These particles are coarse, but we do not have the grinding capacity to grind them finer.
These particles assay less that 30 per cent zinc, so we would lose money if we put them
in a concentrate.

More than ten per cent of the zinc in plant feed

reports to final tailings in particles like these.

FIG 5 – The picture that says a thousand words.

Zinc Recovery is Determined by Liberation

75

70

Recovery to Zinc concentrate

65
Per cent

60

55
Sphalerite Liberation

50
1982 1983 1984 1985 1986 1987 1988 1989 1990 1991

Month/Year
FIG 6 – The graph that distils a thousand graphs.

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Return to contents

CHAPTER 13
Operational geometallurgy
Dean David

ABSTRACT
The orebody is the only asset that a mine has at its disposal to generate revenue. Nature rarely
provides neat and consistent orebodies, so it is essential that process engineers understand
orebody variability and how this interacts with the proposed mine plans. A fundamental
difficulty in understanding the orebody is that most of the available information is geological
in nature and not readily accessed by process engineers. To make matters worse, the
metallurgical information is typically sparse and disconnected from the geology. This chapter
is an attempt to unlock some geological mysteries and provide tools for the process engineer
to link the geological and metallurgical data sets to their maximum advantage, especially
when attempting to optimise base metal flotation plants.

INTRODUCTION
Geometallurgy can be defined as the marriage of geological and metallurgical concepts in
order to provide useful inputs to process design and operational planning. The focus of
geometallurgy is entirely on process outcomes but its basis should be firmly in the geology.
Orebodies are naturally occurring phenomena with little consistency from location to
location. Orebodies situated within a few hundred metres of each other can be as geologically
different as orebodies on opposite sides of the earth. Within a single orebody it is possible
to have primary igneous rock sources, igneous intrusions, faulted zones, metamorphosed
alterations, oxidised zones, alluvial accumulations and much more. From a geological
viewpoint, the various aspects of each orebody can be defined with scientific definitions and
statistical accuracy using well-established conventions. As with any science, the terminology
used in geology is specific to the discipline and meets its own requirements.
The consequent problem for the process engineer is interpreting the science with the aim of
finding a place for the geological information within the metallurgical world. It must always
be remembered that geological data is primarily aimed at satisfying geological needs and
not process ones. Therefore, much of the available geological information may not be of any

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 DEAN DAVID

practical use to the process engineer. The process engineer must carefully and selectively
examine the relationship between geological data and process response before committing to
a geometallurgical strategy.

DEFINITIVE ISSUES
Geometallurgy, like any study topic, requires a problem definition before embarking upon an
analysis. The process engineer must define problems and issues that, if solved, generate value
for the organisation. Geometallurgy becomes important when it is identified that the key to
understanding or solving a process problem lies in an improved understanding of the source
and nature of the ore being fed to the plant.
Examples of geologically based issues that regularly arise for process engineers in base
metal sulfide operations include:
•• inability to predict and manage semi-autogenous grinding (SAG) mill feed rate variability
•• inability to predict and manage concentrate grades
•• inability to predict and manage minor elements in concentrates
•• simultaneous control of plant feed grade and throughput rate
•• planning for throughput expansions
•• planning for new ore types or orebodies to be treated in an existing plant.
The economic importance of an issue is determined by estimating the value that could
be realised if it was eliminated or addressed successfully. The potentially redeemable
value becomes the basis for justifying the resources that need to be invested to solve the
problem. For example, stabilising an erratic SAG mill feed rate typically results in an average
throughput benefit of five per cent. A five per cent throughput benefit achieved through
operational stabilisation typically translates to a five per cent revenue improvement with
little or no real capital or operating cost penalty. Additional revenue at little or no cost equals
profit. Assuming a two-year payback is acceptable to management, it should be justifiable to
invest seven to ten per cent of annual revenue in a single solution that provides a five per cent
throughput benefit by stabilising the SAG mill feed rate. However, this is unrealistic and all
investment decisions are tempered by risk assessment. More importantly, there are always
other projects competing for attention, claiming the same slice of the profit cake and enabled
by the same source of funding. For example, on a plant having an annual revenue of A$100 M,
it may be realistic to expect management to commit A$1 M to a project with good potential to
increase SAG mill throughput by five per cent. In difficult times it may be a problem getting
A$100 000 approved to target a five per cent throughput increase.
Establishing an economic case is relatively easy compared to providing the practical
pathway to solving the problem. Often, the opportunity to apply a large sum of resources to
a problem leads to the implementation of an expensive and generic off-the-shelf solution. On
occasions, this is appropriate and successful, but in many instances it is not, and could even
have an overall negative economic impact. A greater degree of success is often achievable by
understanding the problem, both in detail and breadth, and then applying a solution fit for
the purpose at hand.
The first step to understanding the problem in detail is defining the goal. In this example
the goal is stabilised SAG mill feed rate. What are the definitions of instability and stability
in this context?

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Instability, at its worst, involves stop-start operation where it should be continuous.

Commonly, instability is observed as a boom-bust operational cycle where the plant
is pushed to its throughput limits and then beyond, resulting in the need to significantly
reduce throughput to bring the circuit back under control. Often the ‘boom-bust’ throughput
variations exceed 15 per cent of average feed rate and can be as large as 30 per cent. The average
throughput that results is usually more than ten per cent below the maximum achievable in
the circuit. As well as a loss of feed tonnes, the other major effects of this instability are erratic
flotation feed stream properties including F80 values, per cent solids and volumetric flow.
The economic effects are a loss of feed tonnage coupled with a loss of flotation performance
resulting in less than optimal recoveries and grades. A general rule for troubleshooting any
process is that any upstream instability that has the definite potential to cause problems
should be addressed before attempting to solve apparent in-stream or downstream problems.
Stability is then defined as smooth operation of the plant. However, when is a process
operating smoothly? Smooth operation of a ball mill circuit may be seen as continuous
operation with the feed rate varying by one to two per cent on an hourly basis. However,
operation of a SAG mill is usually accepted as being smooth if hourly throughput variations
are within four to eight per cent. The reason for the difference is that the SAG mill throughput
rate has a greater dependence on ore properties than does the ball mill.
The next step is to determine what is causing the problem. There are a number of possible
causes for an unstable SAG mill feed rate, including:
•• inappropriate manual control actions
•• inappropriate automatic control actions
•• poor feed rate control capability
•• poor or no control of multiple stockpile reclaim feeders
•• inadequate blending capability for the level of ore variability
•• lack of variable mill speed capability
•• poor grinding circuit equipment design.
Apart from the blending issue, these examples are independent of the orebody geology and
each should be dealt with using proven process operation, process design, process control
and engineering practice. If any of these issues is a problem, then elimination may achieve
the target throughput improvement without entering the realm of geometallurgy. These are
relatively easy problems to solve as the technical solutions are readily available from vendors,
engineering companies and experienced process engineers.
If, however, the engineering problems are addressed but the feed stability problem
persists, then the primary cause of variability is probably related to either the hardness or the
competence of the ore. Achieving feed rate stability will then only be possible if a method is
available to predict and manage the hardness and competence of the ore that is delivered to
the plant for processing. A prerequisite for understanding what is being delivered to the plant
is an understanding of what makes an ore competent or incompetent with respect to SAG
milling, and what makes it hard or soft with respect to fine grinding.
The operating process engineer will have several historically developed devices or models
available to understand the comminution properties of the ore, ranging from simple to
complex. The earliest of these methods would have been developed by process engineers
during the design phase of the project. Subsequently, operating process engineers would have
arrived at their own conclusions about the main drivers of plant throughput and developed

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new or modified models. The first job of the process engineer is to determine which of the
available predictive methods provides real information about the ore properties (and the
associated plant responses) and which methods are ineffective.
The ultimate proof of the method is in its use. In this example the definitive question is ‘Is
it possible, using the chosen method, to successfully predict the SAG mill feed rate ahead of time for
a range of plant feed situations?’ If not, then the method is either wrong or incomplete. If the
method can successfully predict feed properties then there is probably a management issue
that is causing the feed variability, such as poor implementation of the predictive method or
poor control over ore sources and feed blending.
On the (often true) assumption that the prediction of ore properties is ineffective in practice,
it is then necessary to determine if a predictive method can be developed at all. It is here that
the process engineer enters the realm of geometallurgy.

AVAILABLE DATA
The starting point for any geometallurgical investigation is the geological model for the
orebody and especially its relationship to the mine model. The geological model contains
drill data while the mine model contains ore and waste blocks derived from the drill data.
Together, this is the biggest geometallurgical asset for the process engineer but, for some, it
can be the biggest liability in such an investigation. Two characteristics of drill data libraries
and block models make them difficult for process engineers to work with: their size and their
complexity.
Geological data libraries (drill libraries) are much larger than the databases process
engineers usually work with, such as tables of metallurgical test results. Geological databases
can contain data derived from 20 000 m of drilling during the early exploration phase of a
project and during the operational phases the database can grow to more than 200 000 m for
a modest sized operation. At the simplest level the database usually contains multi-element
assays for every metre or two metres of drill intersection. However, the database is also likely
to contain information related to lithology (rock type), alteration characteristics, colour,
mineralisation, veining, competence (rock quality designation – RQD), point load index (PLI,
a measure of rock strength), specific gravity (SG), positional survey and any number of other
measures depending on the ore type involved.
The size of such a database makes it difficult to manage and presents challenges when it
comes to isolating useful information. The software tools used to manage drill databases
are geologically based and rarely suit the requirements or experience of process engineers.
Another complicating factor in the operational stage of a project is that a large portion of
the database may be irrelevant to future operations as it represents ore that has already
been mined.
The complexity of the database is the second negative factor for process engineers. The
complexity in terms of the multiplicity of data sets has been mentioned previously. More
problematic than the number of data sets is the variety of bases on which those data sets are
arranged. For example, the assays will be determined on a regular one or two metre interval
basis but the lithology is likely to be provided as irregular intervals, the lengths of which
relate to the extent of each lithological unit. Within the geological database there may be five
or more different data set tables, each with their own individual length interval set. Further
complication can happen if the geological model has been built up by a number of successive

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companies or geologists, each with their own ideas about what data is important and what is
not, or even which assay method should be used for a particular element.
To make the drill library database accessible to process engineers, it is best to use
geological software to generate a single suitable database. Packages such as GenSys can
de-survey geological data sets so that all properties can be reported on a common spatial
coordinate (ie X, Y and Z) basis rather than on a multiplicity of hole and depth bases.
The ideal outcome is for each individual record of the geometallurgical database to have
a unique spatial address and include every measured data type that has any chance of
being useful. The process engineer can then analyse, and add to, the single database using
appropriate tools such as spreadsheets.
An accessible geological data set is only useful to the process engineer when coupled with
additional information about the orebody and how it is to be delivered to the process plant
over time. In an operating mine, the economic limits of the orebody will be well understood
by the geologists, and the plant ore delivery schedule is defined by the short-term, medium-
term and long-term mine plans.
A spectrum of mine-related data will exist with relevance ranging from the imminent to
the distant future, the available mine planning data can be thought of as falling into the time-
based categories as described below:
•• Imminent – ore that is ready to be processed within the next week (and often within the
next month) and is likely to be either already blasted, ready for blasting or in stockpiles
ahead of the primary crusher. This ore is the subject of the daily production planning
processes on site. It can be well defined in terms of actual grade through assay of blasthole
drill cuttings or grade control drilling ahead of blasting. Likely comminution or flotation
performance is either based on the test result for the closest available metallurgical sample
or based on assumptions about the properties of ore types.
Factors that impede or blur the process engineer’s understanding of imminent ores include
medium-term and long-term run-of-mine (ROM) stockpiles, blending stockpiles for plant
feed, inadequate grade control drilling and analysis, lack of a blasthole sample program,
lack of blasting (ie free dig ore), multiple or numerous ore sources (typically a problem
for complicated underground mines) and a high degree of short distance variability in the
orebody (as may be seen in vein type deposits).
•• Short term – each mining operation has a short-term planning process to make decisions
about the upcoming waste and ore allocations. The basis for short-term decision-making
is usually in-fill drilling conducted during the construction and operational phases of the
project. In-fill drilling is designed to fill the gaps between the exploration drillhole data
and allow final ore/waste decisions to be made about each block in the mine model. It is
likely that mine block sizes (the volume of ore considered to have similar properties and
is assumed to be mined as a unit) will be reduced in size, compared to blocks used for
exploration or long-term planning, to better match the upcoming production schedule.
The in-fill drilling data set will certainly provide ore grade, problematic elements and, in
some cases, it may provide comminution data. The mine block properties are recalculated
using all available drill information and blocks are then designated as ore or waste based
on economic parameters.
The most significant complicating factor influencing the process engineer’s understanding
of short-term planning data is the mathematics used to derive the block properties. It is
essential that the process engineer understands the source of the data underpinning short-

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term planning and understand how it has been manipulated on its way to becoming block
data. Manipulations can include truncation of high-grade spikes, data smoothing, data
kriging and erroneous data exclusions. To understand how data has been manipulated
during block modelling it is necessary to do some before and after comparisons. With the
assistance of miners and geologists, compare the short-term planning block predictions
with the raw drill data that has been used to define the block. The full extent of smoothing
is then evident and the ore variability expectations can be assessed by the process engineer.
•• Long term – the long-term mine plan is essentially an extension of the final operational
plan arising from the exploration phase. The ore included in the long-term plan is usually
based more on geological orebody models than high density drill data. The presence or
absence of ore in a particular location, its associated grade and recovery, its lithology and
alteration characteristics are all much less certain than the data available for ore that is
to be processed within the week or mined within the month. Much of the ore will not
even classify as Proved under JORC 2012 (or similar geological reporting regulations). The
long-term plan is typically updated annually, firstly to reflect new drilling that is designed
to convert Probable ore into Proved ore and secondly to reflect ore depletion as a result of
actual mining progress.
The long-term plan is most useful for gaining an understanding of the overall orebody
and mine shapes, documenting the proportions of the major ore types that are expected in
future years and understanding trends with time and location for critical measures such
as grade, impurities, hardness and competence.
When using block model data it is important to note a number of mathematical facts:
1. The properties assigned to an ore block are dependent upon the measured properties of a
few drill intersections. It is possible, and valid, that there are no drill intersections within
a particular mining block.
2. Geostatistical techniques, especially kriging, are used to estimate the distribution of
geological properties between drill holes.
3. Some ore block properties may have been calculated using complex equations that could
have an unintended outcome.
4. Some ore block properties will be dependent upon the location of the block relative to
a geological model boundary (eg above or below water table, oxidised versus fresh ore
zone, etc).
5. Some of the block properties, or even the underlying data, may have been filtered or
truncated to avoid illogical or extreme outcomes.
A good check when first encountering a block model is to look at both the model and the
underlying geological data in the same orebody location and ensure that there is a reasonable
relationship between the two. In general, the predictive methods are reliable but it is always
advisable to verify information, especially where important decisions are being made.
The weakest link in the available data for geometallurgical analysis is invariably the
metallurgical data set. It is rarely, if ever, practical to analyse the orebody metallurgically
to anywhere near the data density that is available geologically. For example, an orebody
of 100 Mt with 10 000 m of intersections identified within ore has a geological data density
of 100 samples per million tonnes of ore. Assuming there are three major lithologies that
have been tested metallurgically and each lithology has had 50 variability samples tested
for flotation properties and grindability, the metallurgical data density is only 1.5 samples
per million tonnes of ore. At 5 Mt/a plant throughput (for example) each year’s production is

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effectively based on the results from 7.5 metallurgical test samples compared to reliance on
500 m of drill intersections. In some operations, each year’s production is defined by less than
one metallurgical test sample.
One ore block typically represents hours or minutes of ore and this means block data
can be useful for short-term metallurgical planning. Usually a subset of the long-term
plan block model is populated with infill drill data and then smaller mining blocks are
chosen for medium-term planning purposes. A subset of the medium-term plan can then be
populated with blasthole assay data for production grade control purposes for the imminent
production horizon. In a few instances the metallurgical database is continually updated
with preproduction testing and may find its way into the medium and imminent planning
outputs. Generally, however, the testing gap between geology and process continues to
widen as the project advances. Fortunately, the amount of available process data begins to
catch up once production begins. It is at this point that the adequacy, or otherwise, of the
metallurgical predictions is revealed.
It is important for the process engineer to become familiar with the planning processes and
the available data sources on site. Perhaps more importantly, the process engineer should
become acquainted with the owners of the various databases, the individual geologists and
mine planners. Apart from forming essential professional networks on the site there is also
the issue that databases always have quirks and skeletons, so it is best to have an expert assist
you to navigate to the data sources essential for your own problem solving.
It is not necessary, or desirable, for process engineers to become users of mining or
geological software. Usually specific data is required to solve a problem and it is preferable
to have the experts extract the necessary data from the sources so it can be analysed offline
using familiar tools such as spreadsheets. Although it may be useful to learn how to use the
specialised software, it is not normally efficient. All modern geological and mining software
packages have excellent data export and interchange capabilities that should be exploited.

MAKING PROCESS SENSE OF THE DATABASES

The disparity between the geological and process databases presents a problem and an
opportunity. The problem is that the metallurgical database is comparatively small and it is
not going to get larger very quickly. The opportunity that exists is the potential to link the
databases together and make some metallurgical use of the geology.
Linking the metallurgical and geological databases cannot progress without a critical mass
of metallurgical data. There is no real point proceeding if all that is available is a few tests
on each of the major ore types. It is especially problematic if these few tests do not reveal
unique characteristics about the ore types. In many operations there is a library of process test
data that is available for interpretation but it may not be gathered together in one place. The
starting point should be the available data and making the most of it rather than embarking
on a new test program.
One criticism of existing metallurgical data that is often heard is that because the test was
done many years ago, the results may not be reliable. In a few isolated instances, and only
because of specific circumstances, this may be a valid criticism. However, in general this is
a foolish first position to have, as you may be ignoring the most valuable data resource you
have. Saying that test data is unusable because of age implies that one of the following is true:
•• the test procedure used was at fault or is irrelevant to the existing flow sheet
•• the operator that conducted the test was at fault

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•• the ore tested had no relevance to current or future operations

•• the way the ore was tested (ie inappropriate blending) devalues the results
•• there is no information about what the sample represents geologically.
In the absence of a clear problem it is advisable to assume all past test results are valid until
proven otherwise. Collect all past test data and bring it into the geometallurgical analysis.
Historical metallurgical data is often characterised by its diversity of form. Each process
engineer or laboratory superintendent is likely to have had their own ideas about the test
methodology, test products generated, assays conducted and calculations performed. It is
essential to get back to raw data, especially test conditions, product masses, process times and
original assay data. It is also worth noting that there may be comments by operators that are
relevant and that even identification of the operator can be a valuable piece of data.
Once the body of test data is identified, the metallurgical database can be built. Although
time consuming, it is usually better to be comprehensive rather than selective when
compiling the database. Critical factors for interpreting the test work often emerge during
the analysis process, so it is better to include all available raw data. It is not necessary to
incorporate calculated data as this can be derived as required. The metallurgical database
should also include reference data such as test numbers, dates, sample numbers and ore
types. As the aim is to link back to the geological database it is also essential to incorporate
all relevant geological information such as drill hole numbers and downhole depths. Try
to standardise the data so that it is possible to analyse the metallurgical database using
spreadsheet or database tools. It is recognised that this can be a daunting task where an
extensive library of tests exists. However, the usefulness of the metallurgical database
alone is enough to justify the investment, regardless of the multiplied benefits once the
geometallurgical linkages are established.
Establishing linkages to the geological database is entirely a case-by-case process. Both the
metallurgical database structure and the geological database structure are likely to be unique
so it is not possible to list the methods by which they can be linked. However, several aspects
of each database are standard and provide a starting point.
Geological databases typically contain:
•• drill hole numbers
•• references to properties (assays, lithology, etc) by depth
•• hole locations (collar positions)
•• hole directional information (dip, downhole survey, etc)
•• ore properties – possibly including:
•• assays
•• lithology
•• alteration
•• density
•• magnetic properties
•• radiometric properties
•• mineralisation (ore and gangue minerals)
•• rock quality designation (RQD)
•• fracture frequency (FF)
•• point load index (PLI).

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In order of priority, the most important information after the positional data is the set of
chemical assays, followed by the lithology. Where there is limited comminution data from
metallurgical testing, drill core structural information (RQD, FF) and the strength data (PLI)
then become more important.
Note that the above description is typical of a database that has not been subject to
metallurgical influence. If detailed metallurgical testing has been conducted on the orebody
for geometallurgical purposes some of the following may appear either in the drill database
or in the mining block model:
•• drop weight index (DWI)
•• SAG power index (SPI)
•• Bond (or equivalent) work indices
•• liner and milling media abrasion indices (eg Ai)
•• ore abrasion index (ta)
•• mill feed F80 predictions
•• recovery predictions for products
•• concentrate grade predictions
•• SAG throughput rate (in an existing operation)
•• achievable grind P80 (with existing mills).
If such information does exist then a few checks need to be made to ensure the data is useful
in an operational sense. For example, in an existing operation it should be relatively simple to
check if the geometallurgical predictions are useful to the operators and planners. If the data
is ignored by the operators then it is either a poor predictor of performance or systems have
not been put in place to ensure that the metallurgical information is made available to those
that need it. The latter is often the case when the data has been collected during the design
period for the purpose of selecting major equipment, but no operationally useful systems
were implemented at plant start-up.
If it is found that the geometallurgical predictions do not match operational reality then
there is something wrong with either the data that is being used, the interpretation method or
the method of distributing the data across the geological databases.
Examples of inappropriate use of metallurgical data include:
•• the use of Bond ball mill work indices to predict SAG or AG mill throughput rates
•• the adoption of unverified relationships between ore measurements and operational
outcomes
•• inappropriate assignment of metallurgical ore properties to geological categories, such as
lithologies, where there is no proven linkage between the two
•• the use of predictive methods that ignore key factors, for example prediction of copper
concentrate grade based on head grade without reference to copper mineralogy.
In a modern operational environment there is usually enough data available to verify
or discredit these predictive systems. If not, then systems should be implemented and
instruments installed to allow, at a minimum, the verification of the predictive information
that is meant to drive decision-making in both the mine and the plant. The saying ‘if you
can’t measure it, you can’t manage it’ is especially true when it comes to geometallurgy.
Unfortunately, in many instances, it appears that measurement is being done but because
the measurements or the interpretation are inappropriate the consequential management
is misdirected.

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Where there is no metallurgical data in the geological information systems, the

geometallurgist must endeavour to insert some in a useful manner. The success of establishing
geometallurgical links will depend on the type, quantity and quality of the metallurgical data,
the spatial distribution of the metallurgical samples and the ability to link the metallurgical
data to geological properties and locations.
Here is a theoretical example of establishing a set of useful geometallurgical linkages for a
copper mine, having mixed copper sulfide mineralogy and using a SAG/ball mill comminution
circuit, which experiences significant swings in throughput rate. Note that many things are
‘known’ in this example that may not hold true for other operating sites:
1. Decide what metallurgical predictions are necessary for effective management of the
process. In this example the following predictions are required:
•• plant feed rate based on both SAG and ball mill limitations
•• copper concentrate grade
•• copper recovery
•• gold recovery.
Note that fundamental metallurgical inputs such as feed grade and ore type are assumed
to be already available because they are geological and mining model outputs rather than
based on specific metallurgical test work or interpretation.
2. Decide what measurements are useful for predicting plant performance.
•• JK A×b has been proven to be an effective predictor of SAG throughput at the site
so a related inexpensive test, such as SMC, can be used to economically establish a
metallurgical database.
•• BWI has been shown to be useful for predicting ball mill performance so either a full
BWI test or an inexpensive modified BWI will be used.
•• Copper concentrate grade is strongly related to the copper mineralogy so either
directly measuring mineralogical mix or inferring mineralogical mix from Cu:S ratio
are to be used. As the geologists have included copper sulfide mineralogical proportion
estimates in the database and sulfur assays are available, both methods of predicting
concentrate grades will be used and the most appropriate will be chosen after a period
of verification.
•• Copper recovery is also strongly related to mineralogy and it is known that recoveries
are lower when chalcocite and covellite are present. It is also related to oxidation, which
is a function of depth, alteration and ore type. Copper recovery is also well predicted
by simple laboratory flotation tests on samples. As copper recovery has been highly
variable and prediction has been only moderately successful from the geology a simple
rougher flotation test will be carried out to estimate recovery.
•• Gold recovery is variable and difficult to predict. No current methods are reliable. The
rougher flotation test will also be used to attempt to predict gold recovery.
3. Choose calculation methods for the predictions.
•• The plant feed rate prediction will be based on a calculation that determines if the
SAG or ball mill is going to limit production based on DWI (from the SMC test) and
BWI; and applying operating constraints such as available milling power, maximum
acceptable flotation feed F80 values and maximum acceptable flotation circuit
volumetric feed rate.

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•• An established relationship between plant feed Cu:S ratio and final concentrate grade
will be applied to the geologically based block model Cu and S assays. A second
prediction will be based on the mineralogical information logged by the geologists.
Inconsistencies will be flagged for potential investigation.
•• The flotation plant feed will be sampled hourly to provide shift composites for 30 days.
Shift composites will be subjected to a standard grind and flotation test. The flotation
test Cu and Au recoveries will be compared to the shift recoveries in an attempt to
develop copper and gold flotation recovery predictors. In addition, the ore source for
the shift or period will be noted. Additional flotation tests will be conducted using
freshly drilled diamond core samples to firm up the relationship with ore from known
locations and geological characteristics.
4. Implement the predictive framework.
•• The predictions can be implemented in one of two locations. The first, and most
comprehensive is in the geological database. The second, and most convenient, is in the
mining block model.
•• Adding the predictive framework to the geological model invokes considerable
complexity because the useful process outcomes of the predictive calculations will not
be needed in the geological model but in the form of short-term planning outputs from
the mine block model.
•• The geological data set is also problematic because the inherent variability is high
and the range of ore properties encountered will always be much broader than those
encountered shift by shift in plant feed and broader than the conditions represented
in the metallurgical test sample set.
•• Adding the predictions into the geological model requires that one or more of
the many data tables be expanded to include the predictive calculations. The data
table to be expanded depends upon the inputs to the calculations. For example,
if the calculations are assay based then the assay table should be expanded. If the
calculations are ore type based then it may be necessary to expand the lithology table.
•• Adding the predictive framework to the block model is simpler because the block
model is numerically simpler than the geological model (it is a single database) and
has already been manipulated to eliminate problematic data. The block model is also
mathematically driven in its construction compared to the geological model, which is
data entry driven. Virtually all information in a block model is mathematically derived
so it is a relatively simple matter to add or generate new data sets using mathematical
equations and rule sets.
•• The prediction of SAG mill feed rate will be made in the block model using modelled DWI
and BWI values.
•• It has been found that DWI is related to lithology and to depth, so each lithology will be
assigned a base DWI value that will be increased in direct proportion to depth.
•• Similarly, the BWI value has been found to be related to lithology and depth with the
exception that one lithology is considerably harder in the north than the south. This
lithology will be divided in north and south types and each have its own base BWI and
depth relationship.
•• As a first estimate the SAG feed rate for a block will be the minimum throughput rate
based on DWI versus available SAG power and BWI versus available ball mill power.

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The estimate will be capped to allowable plant maximum and minimum throughput
rates.
•• Copper concentrate grade predictions will be made in two independent calculations, an
assay-based calculation and a mineralogy-based calculation.
•• The first step is to ensure both assay (Cu and S) and copper mineralogy information
has been carried through into the block model output.
•• An equation will be inserted into the block model that is a calibrated theoretical
relationship between the Cu:S ratio and final concentrate grade. A Cu concentrate
grade will be predicted for the ore block.
•• A second equation will be added that uses the stoichiometric copper proportion of each
mineral present in the block to calculate a second estimate of the Cu concentrate grade.
•• Both grade predictions will be reported separately and compared with actual outcomes.
•• Copper recovery predictions will initially be made in the block model on the basis of
constant tails grade. This relationship will be updated following the results of the planned
flotation test program.
•• Gold recovery predictions will also be made in the block model on the basis of constant
tails grade and will be subsequently updated when actual test results are available.
•• The data that needs to be carried through from the geological model to the block model
output for all these calculations to be possible includes:
•• for SAG mill feed rate prediction it is necessary to carry the lithology through and it is
also necessary to know the block location in three dimensions
•• for copper concentrate grade prediction it is necessary to carry per cent Cu, per cent S
and copper mineralogy
•• for copper and gold recovery prediction it is necessary to carry the per cent Cu and g/t
Au values.
Assuming the outcomes are mathematically valid and there is enough data to make the
predictions statistically useful, it is now possible to add the desired predictions of SAG
throughput, copper concentrate grade, copper and gold recovery to the short-term planning
outputs. Equally important is setting up a comparison to see how accurately the predictions
matched the actual production outcomes.
This is only one example of how geometallurgical predictions can be implemented. Each
site will have different prediction needs, different data sources and different planning needs.

PLANNING
The most obvious use of the predictive data is for short-, medium- and long-term metallurgical
planning. Applying the predictions to the long-term planning process should reveal future
constraints on throughput or production that will need to be accommodated. Predictions of
this nature feed into the capital planning process and also provide early warning of systemic
problems such as hardening ore or changing mineralogical mixes.
Using such tools, the process engineer can participate more fully in the long-term
planning of the overall project. For example, hardening ore without a compensating grade
change or throughput increase will lead to a revenue reduction that must be counteracted.
Counteraction measures range from plant optimisation to plant expansions or even to new
plant construction. Marketability of the concentrate is also influenced by its grade, another of
the possible predictions. A trend to lower grade concentrates may lead to early discussions
with customers, a reduction in revenue expectation, planning for increased throughput or

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sourcing of new customers for the concentrate. Note that a site with a smelter as well as a
concentrator will have an even more pressing need for a concentrate grade prediction than a
site that sells its concentrate to multiple customers.
Equally important can be the educational aspect that arises from geometallurgical planning.
Provided the predictions are shown to be reliable, the mining engineers and geologists learn
what is important to the process plant and are able to contribute more effectively to the overall
site optimisation. For example, the geologists may change the way they look at the orebody
and report more ore characteristics. Alternatively, the mining engineers may introduce, or
modify, blending practices to smooth the process plant operation by avoiding the delivery of
undesirable ore packages.
Without an integrated predictive geometallurgical system it is difficult for the process
engineer to participate in an effective manner in the site planning process, beyond stating the
fundamental requirements of recovery and quality targets.

TROUBLESHOOTING
Troubleshooting is an ongoing responsibility of production process engineers. Any system
that assists in the troubleshooting process not only makes life easier but also improves the
company bottom line by solving problems faster. An integrated predictive geometallurgical
system would facilitate rapid troubleshooting by providing a consistent basis for sourcing
and analysing data. In addition, a reliable integrated system would have a significant benefit
of having established trust with the mining and geological departments and also with the site
management. Not only would it be possible to generate the necessary data to build a case for
change, but it should also be possible to get rapid agreement on implementation.
Typically, on operating sites there is no available system where data can be instantly
sourced to back-up metallurgical arguments. In these situations it is necessary to carry out
ad-hoc geometallurgical investigations to complement a particular investigation. Examples
may include tracking down periodic recovery drops, reducing concentrate grade variability
or tracking down the source of an impurity such as arsenic or fluorine.
An ad-hoc geometallurgical investigation would typically follow a similar pattern to that
used to set up an integrated system. Even though each particular investigation is unique and
could be dealt with in a rapid and possibly superficial way, it is advisable to take a little more
time to set up generic geometallurgical tools that can be used in future investigations. Begin
by tracking back as reliably as possible from the symptom of the problem to the source. For
example, high arsenic in concentrate is related to high arsenic in feed and arsenic in feed may
be the result of any one of a number of geological features, such as particular ore types or
alteration zones. Tracing back from the problem to the source allows the issue to be managed
by flagging the current geological source of the problem, identifying possible future geological
sources, checking if past instances have a similar cause and implementing a suitable solution
such as avoidance of the ore, blending to dilute the problem, or implementing a processing
solution such as depressing the arsenic minerals during flotation by the use of cyanide.
An ad-hoc investigation still requires a good level of understanding of the geological
information and a good working relationship with the geologists and mining engineers.
It also requires a full understanding of the factors that influence the ability to establish a
link between the symptom and the source. Common complications arise from the delays
and mixing caused by storage systems such as stockpiles, fine ore bins, ROM storage and
concentrate storage. These necessary devices can make it virtually impossible to isolate the

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source of a problem in the mine. It may even be necessary to arrange for extended runs on a
single ore type to ensure the ore source is unequivocal during an investigation.
Other complications can arise from generic property assignment to ore types. In these
instances it is necessary to test the assumptions by real ore testing. For example, if a particular
ore type is assumed by others in the organisation to have a constant BWI value then take five
samples of that ore (as defined by the geologists) from different locations in the mine and test
them. Repeat the exercise on other important ore types. If the results support the assumption
then continue to use it. If they disprove the assumption then it is likely to be necessary to
modify site systems and re-educate people. Where the assumption is found to be invalid, and
it is necessary to rely on the BWI value in reaching a solution to the problem at hand, then the
situation must be corrected. Additional BWI tests on ore samples specific to the investigation
are easily justified.
Statements such as ‘all this ore type is the same’, or ‘there is not much variability in the
orebody’ must be tested by examination of available data or by collecting more. In most cases
these statements prove to be false and can derail investigations at the start.

EXPANSIONS
Plant expansions are special cases where geometallurgy is essential if the intended outcome is
to be achieved. Many expansions have been less than successful because the ore to be treated
did not meet the expectations of the designers. This is a direct result of a poor understanding
of the future orebody and its properties.
The first rule with expansions is to check all assumptions that drive the process design.
If the expansion is throughput driven it is essential to check that tests have been carried out
on samples representative of the ore that is to be treated by the expanded plant. In the absence
of supporting data it is not adequate to assume that because the ore blend will be 30 per cent
X and 70 per cent Y that the properties can be predicted from past experience. Take multiple
samples of X and Y from the ore zones to be treated by the expanded plant and subject them
to all the necessary tests to prove the design assumptions.
To check if this additional geometallurgical expense is necessary, it is relatively simple
to repeat the financial calculations with ten per cent lower throughput than predicted, or a
five per cent lower recovery.
An expansion decision must be based on a reasonable guarantee of a return from the
ensuing revenue stream. The same principles that are applied to exploration companies, ie
proving the presence of the ore and establishing its grade, are the first steps in justifying an
expansion. In most cases this is well established. However, in some cases the mineralisation
in question may lie in the inferred category and will need to be elevated to a higher status
before proceeding. Note that if the mineralisation is inferred, then it follows that all available
‘ore’ properties are inferred, including the status of the mineralisation as ore.
If the expansion is based on treating future ores according to established lithological
categories then check that lithology has been a useful indicator of process properties in the
past. If this has not been the case then the future will be no different to the past and it will be
essential that metallurgical tests are conducted on samples of the future ores.
When carrying out a metallurgical test program on the future ore there will be a set of
obvious tests to perform and there will be some less obvious tests. Perform the obvious tests
(comminution, flotation, abrasiveness, etc) and then carry out some speculative tests, such
as full elemental analysis or mineralogical analysis of concentrates. For reference it is best to

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carry out the same tests on current production samples. These types of tests are simple and
inexpensive checks designed to identify if there are any new problems that may arise from
the future ore. If problems are confirmed or indicated by the tests then a more comprehensive
test program may be required to identify mitigation strategies. It is far less expensive to solve
these problems in design than to rectify after installation of any new capital.
Another possibility in preparing for an expansion is to conduct a plant trial on the future
ore. This is highly desirable if it is known that the future ore differs from the past ore. The
existing plant is the ideal ‘pilot plant’ facility. The ability to conduct a meaningful plant
trial is contingent upon ore access and ore volume availability. A plant trial has additional
benefits such as providing concentrate samples for customer evaluation and providing a
clearer evaluation of plant areas that are dependent upon concentrate availability, such as
regrinding, thickening and filtration. Another less obvious benefit is that the plant operators
are exposed to the future ore. It is usually the operators that notice operational effects first
and the crew should be well prepared before, and debriefed after, the trial.
At the implementation stage of an expansion project the major risk areas must be mitigated
to the satisfaction of the disciplines on site and to the satisfaction of the management team.
If the factors listed below have been established definitively, then the expansion has been
underpinned geometallurgically:
•• future ore tonnage and grade established
•• future ore metallurgical response is known
•• acceptable concentrates can be sourced from future ore
•• future ore throughput properties are known and have been used in comminution design
•• the variability of the future ore is understood.

DATA ANALYSIS
Effective and efficient analysis of geometallurgical data is essential to any geometallurgical
exercise. It is often necessary to manipulate very large databases and spreadsheets and
summarise them into meaningful sources of information. It is also necessary to correlate
properties from the geological and metallurgical realms so that trends and indicators can be
established. It is in the data sets that the important information resides, the difficult part is
extracting it. Even more difficult can be communicating this information to others.
The breadth of available geological data has been described previously. Also described has
been the necessity to develop analysis tools useful to process engineers. Unfortunately, it is
not possible to provide a one-size-fits-all solution to geometallurgical data analysis as the
geological and mining data formats are as diverse as the orebodies they describe.
The first step is to organise the data into a form that can be manipulated meaningfully. One
method (that is preferred by the author and described earlier) is to arrange all the available
geological data into a single spreadsheet table against a common set of depth intervals. In
addition, the data is de-surveyed to convert drill hole numbers and depths into 3D, spatial
coordinates (ie X, Y and Z). This is best done with the assistance of a geologist that is expert
in using the geological software and, with direction as to which data is required, the task can
be completed in hours or minutes. Once the database is available it is then possible to begin
detailed analysis.
Spreadsheet packages, such as Microsoft Excel, contain many useful statistical and data
manipulation tools. Probably the most useful tools for manipulating large and unwieldy
geometallurgical databases are the ‘Pivot Table’ tool and the ‘AutoFilter’ tool. Excel tutorials

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will not be provided here, but all readers that deal with large data sets of any kind are strongly
encouraged to become familiar with these tools; they have the ability to extract data and
trends from multi-million-cell databases with a few keystrokes.
Before making use of the data it is essential that each column of data be checked for unusual
features or errors. For example, sometimes numerical data is actually present as text in the
spreadsheet rather than as numbers. Often text information has a minimum length and what
appears to be a three-letter code is three letters followed by ten spaces. Such data anomalies
confuse the analysis and the analyser. Check for data artefacts inserted by the geologists,
for example sometimes missing data might be represented by an impossible value for the
particular parameter, say 9999 or -1. Check for entry errors such as a mix of ppm values
in a per cent column or per cent values greater than 100. There are infinite possibilities
for problematic data in databases. The general rule is if unexpected results appear during
analysis then go back and check if the data that you thought you were incorporating is in
the appropriate form. If erroneous or misleading data is found, then prepare a report and
feed the information back to the custodian of the geological data so that problems can be
addressed across the site. Errors will typically influence geological interpretation to an equal
or greater extent than they will the geometallurgical interpretations.
It is usually necessary to add additional data columns to the geological databases. For
example, ore and waste are rarely defined in the geological data because these are mining
terms. A data column that classifies the intervals into simple ore and waste sets according to a
reasonable grade cut-off level is easily added. A consequent sort on ‘ore’ then removes all the
material that process engineers are not interested in. Note that in orebodies with a relatively
simple geological structure, this assignment does not have to be strictly in accordance with
mine planning discriminations as there are many factors, such as run length, that are difficult
to incorporate into a simplified geometallurgical model. It must be remembered that planning
is not done in a geometallurgical database, it is a tool for finding data relationships.
However, in banded or vein orebodies, it may be necessary to re-interpret the ore and
waste definitions to match the reality of mining limitations. For example, ensure that 1 m
waste intervals within an ore band are considered as ore because they will not be selectively
excluded. Similarly, if the minimum mining cut width is 4 m in a vein deposit then include
some waste on either side of significant ore intersections. These limitations are best discussed
with the miners before being implemented in the database. Once implemented it is essential
that a reality check is carried out to ensure that the effect of the data manipulation is consistent
whenever it is invoked. Check between ten and 20 instances through the database of any new
data manipulations.
In databases compiled by different geological teams over time there are likely to be duplicate
assay columns or lithology columns. Decisions must be made as to how this is reduced to a
single consistent column describing that property.
Another common manipulation is to round the X, Y, Z data into useful intervals. For
example, it is much more useful to know that ore is within the depth range RL 100 to RL 150
m than it is to know that the ore RL is precisely 123.27 m. This then allows the database to be
analysed by depth slices or slices in the north or easterly directions. It also allows the ore to
be examined as blocks. Blocks defined by this rounding method are usually much larger than
the mining model blocks and are best distinguished by the term ‘Metblock’.
Another useful addition to the database is to indicate those drill intersection samples that
have been utilised in metallurgical test programs. If full core has been taken for testing then

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these samples are not available for any future test work. Even if only half the core has been
taken for testing it may be desirable to retain the remaining material for future geological
reference. Again, this can be tedious, but it provides an excellent basis for evaluating the
representative nature of past sampling and is a guide to selection, or non-selection of samples
for future test programs.
If bad data exists and it is not possible to correct it to something meaningful, then several
alternatives exist. One is to eliminate the offending data record or column by deletion (or shift
it to another place in the spreadsheet so it is known to have been removed). Another option
is to ‘fix’ the data, such as by averaging the corresponding values for the records above and
below. Another is to move a decimal point if it is unequivocal that the reported value is not
real but is the result of a typographical slip. Any manipulations should be noted and the
information returned to the geologists. This is usually valuable information that can lead to
improvements in the integrity of the geological database.
Once verified, the database is ready to use. Several guidelines are useful here:
1. Identify the ore that is important to the metallurgical issue being addressed.
Analysing ore that will never be mined or will be mined 15 years from now is rarely useful.
Identify, with the assistance of mining engineers, the ore that impacts on the decision or
problem at hand and then concentrate on it. One method may be to add an additional
column to the database and flag the important ore with a ’1’ or a TRUE. The data can
then be sorted on this basis. Another alternative is to assign a future year number to ore
intervals, but this is much more complicated. This sort of assignment is best done in the
block model.
2. Identify the properties that are of most importance to the metallurgical issue.
These properties then become the subject of data analysis and guide the analysis to the
important aspects of the data set. For example, in a copper flotation plant the copper grade
is obviously important but so is the sulfur grade, the arsenic grade and probably the gold
grade. Using the data tools mentioned above, it is then simple to make these measurements
the subject of the analysis.
3. Use the data tools to focus on the important ore and the important properties.
Using pivot tables, it is possible to quickly construct a table constrained to ore in the
relevant time frame and examine average Cu, Au, S and As grades, and to then identify
the number of core intervals in each category. It is also possible to view this data in plan
on the orebody by arranging it within the rounded X and Y data axes categories. The user
can then step down through the orebody by selecting an individual RL value or a set of
RL values.
Once the data is in this form, the orebody can be examined from a process perspective.
For example:
•• trends of arsenic with location, depth or ore type can be quickly extracted
•• trends in Cu:S with time can be examined
•• specific locations for extracting new metallurgical test samples can be identified and a
click will instantly drill down into the database and show the relevant drill intersections
in that particular Metblock.
It is also possible to use graphical and statistical techniques to search for correlations
between factors, for example plot %As against g/t Au on an X/Y plot to see if gold and arsenic
are related. If a relationship is suspected within a particular ore type then use the pivot table

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drill down facility to extract the relevant records then plot the specific data comparison again
on the selected data.
Tools such as correlation tables can be used to search large data sets for significant linear
correlations between large numbers of pairs of data columns. Multiple linear regression can
be applied to see if a particular property is a function of a number of other properties.
Regression tools are particularly useful when investigating the relationship between the
limited metallurgical data set and the extensive geological data set. Assuming the drill
samples that were tested metallurgically have been correctly identified, it is possible to extract
the geological data for those intervals from the database, calculate the averages of the interval
properties and correlate them to the measured metallurgical properties. It may be possible to
identify geological predictors of metallurgical properties in this manner.
Ideally the metallurgical test samples will have been made up of contiguous intervals
of single lithologies; this is much more useful than single test samples being formed as
composites from across the orebody. It is especially problematic when the only available
data relates to composites formed from across the orebody and a mix of lithologies. Both
these situations make it almost impossible to establish any linkages between geological and
metallurgical properties.
One of the most rewarding outcomes for the process engineer from such an analysis is the
deeper understanding that is gained about the orebody. With this, the process engineer is
well equipped to contribute to discussions on the future of the operation and to converse
meaningfully and factually with the geologists and mining engineers on site. If nothing else
is gained, then the improved communication across the various disciplines on site is usually
worth the effort.

REFERENCES
JORC, 2012. Australasian Code for Reporting of Exploration Results, Mineral Resources and Ore Reserves
(The JORC Code) [online]. Available from: <http://www.jorc.org> (The Joint Ore Reserves Committee
of The Australasian Institute of Mining and Metallurgy, Australian Institute of Geoscientists and
Minerals Council of Australia).

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