CHEMICAL METALLURGY II

HYDROMETALLURGY AND ELECTROMETALLURGY

Assoc. Prof. Dr. M. Seref Sonmez
 Introduction

Extractive metallurgy has three components with

overlapping aspects:
➢hydrometallurgy,
➢pyrometallurgy,
➢electrometallurgy
 Introduction

• Hydrometallurgy as an extractive metallurgy discipline

involves “the recovery of metals by wet methods, i.e.
from aqueous solutions”.
• The third contributor to the extractive metallurgy –
electrometallurgy- can also be regarded as a subset of
hydrometallurgy, if electro-winning and/or electro-
refining of metals is performed from aqueous solutions.
 Introduction
• Hydrometallurgy involves various processing steps, such as:
➢dissolution,
➢separation,
➢concentration,
➢purification,
➢metal winning.
• Except for separation, which may be physical, each of these steps
relies on the chemical principles of oxidation, reduction,
solvation, chelation, hydrolysis, etc.
A Short History Of Hydrometallurgy
 A Short History Of Hydrometallurgy
• Fire to melt
• Aqueous solutions - alchemists - acids and alkalis

• Modern hydrometallurgy (the end of the 19th

century)
• THE CYANIDATION PROCESS FOR GOLD
AND SILVER EXTRACTION AND
• THE BAYER PROCESS FOR BAUXITE
TREATMENT.
 A Short History Of Hydrometallurgy
• Fire to melt
• Aqueous solutions - alchemists - acids and alkalis

• Manhattan Project (1940s) • Modern hydrometallurgy (the end

- uranium extraction. of the 19th century)
➢THE CYANIDATION PROCESS FOR
Replacement of some GOLD AND SILVER EXTRACTION
pyrometallurgical ➢THE BAYER PROCESS FOR
processes. BAUXITE TREATMENT.
A Short History Of
Hydrometallurgy A milestone marking the beginning of hydrometallurgy…

➢ Aqua regia (Latin for "Royal

Water");
➢ 3:1 mixture of hydrochloric acid
and nitric acid
➢ gold, platinum and palladium
from substrates, particularly in
microfabrication and
microelectronics labs.
➢ Glassware may also be washed
with aqua regia to remove
organic compounds only in trace Figure: The Arab alchemist Jabir Ibn Hayyan (720–813 AD),
amounts. discoverer of aqua regia (royal water) for dissolving gold—the
king of metals
 A Short History Of Hydrometallurgy
➢Certain soils containing putrefied organic matter were leached to
extract saltpeter (=salt of stone, potassium nitrate), a necessary
ingredient for the manufacture of gunpowder (Published in
1540).
➢Heap leaching (16th century) - Rı´o Tinto mines in Spain.
➢Pyrite containing some copper sulphide minerals - oxidation and
dissolution of copper
➢Metallic copper «cementation process» - by scrap iron
➢Spanish «cementacio´n» meaning precipitation.
➢Quebec (18th century) - the production of potash for the soap
and glass industries.
➢Na2CO3 production was from ashes and leaching.
 The birth of modern hydrometallurgy dates back to 1887
A Short History Of when two important processes were invented
Hydrometallurgy

➢ The dissolving action of

cyanide solution on
metallic gold was known
as early as 1783 by the
Swedish chemist Carl
Wilhelm Scheele.
➢ L. Elsner in Germany in
1846 studied this
reaction and noted that
atmospheric oxygen
played an important role
during dissolution.
Figure: John Stewart MacArthur (1856–1920), discoverer of the
cyanidation process
 The birth of modern hydrometallurgy dates back to 1887
A Short History Of when two important processes were invented
Hydrometallurgy

➢ The application of this

knowledge to extract gold
from its ores was proposed
and patented much later in
England by John Stewart
MacArthur (1856–1920) in
1887 and became known as
the cyanidation process.
➢ G. Bodlander in 1896 made
the important discovery that
hydrogen peroxide was
formed as an intermediate
product during the
dissolution of gold.
Figure: John Stewart MacArthur (1856–1920), discoverer of the
cyanidation process
A Short History Of
Hydrometallurgy

As a result of introducing
the cyanidation process
worldwide, gold
production increased
greatly during the period
1900–1910

Figure. Increase in world gold and silver production between 1900 and
1910 as a result of introducing the cyanidation process
 The second major hydrometallurgical process of this era…
A Short History Of
Hydrometallurgy

➢ Leaching bauxite,
discovered in 1821
with sodium
hydroxide solution
above its boiling point
in a pressure reactor.

Figure: Karl Josef Bayer (1847–1904), inventor of the process

for the production of alumina from bauxite
A Short History Of Hydrometallurgy

Figure. Bayer process

displaced Le Chatelier
pyrometallurgical route.
 A Short History Of Hydrometallurgy
Further developments…
• 1903 - M. Malzac - ammonia solutions for leaching sulfides of copper,
nickel, and cobalt.
• 1909 - Kingsley - Nitric acid for leaching sulfide ores.
• 20th century, hydrometallurgy of copper received a particular
attention (Oxide ores).
• Electro-winning of copper - in Chile - 1912.
• The First World War (1914–1918) - zinc - for the manufacture
of cartridge brass. The distillation of commercially available
metal from ore. Electrolytic zinc and the leaching of a large
tonnage of ZnO by H2SO4 – 1936 – Cd byproduct.
 A Short History Of Hydrometallurgy
Further developments…
• The First World War (1914–1918) created a demand for the zinc
for the manufacture of cartridge brass. Zinc for this purpose
used to be obtained by the distillation of commercially available
metal in Belgium and Germany from ore supplied by Australia.
This situation inspired industry in North America to supply
additional metal from ores that were not amenable to standard
methods. At Trail in British Columbia and Anaconda in
Montana, the processes for electrolytic zinc and the leaching of
a large tonnage of ZnO by H2SO4 was introduced. The process is
mainly based on a patent by L. Le´trange in France issued in
1881 (Ingallis, 1936). Cadmium gradually emerged as an
important by-product of this process.
A Short History Of
Hydrometallurgy

➢ In the 1950s, pressure

hydrometallurgy
(Sherritt-Gordon
process)
➢ Canadian coins were
produced for over 40
years using
hydrometallurgical
technique.
Figure: Laterite pressure leaching plant in Cuba.
A Short History Of
Hydrometallurgy

1950s - INCO - low-grade

pentlandite–pyrrhotite
concentrate

Figure: Flow sheet of INCO ammonia leaching process that was shut down
because of economic considerations and SO2 emissions..
A Short History Of
Hydrometallurgy

The mechanism of
dissolution of sulphides
was well established and
the formation of
elemental sulphur during
the aqueous oxidation of
sulphides became well
known.
Figure: Regions of stability of elemental sulphur at 100C.
A Short History Of
Hydrometallurgy

CANMET - pyrrhotite–
penthandite concentrate
-autoclaves at 120C
under oxygen pressure.

Figure: Flow sheet showing the formation of elemental sulphur

during the aqueous oxidation of sulphide concentrates.
A Short History Of
Hydrometallurgy

The pyrometallurgical
process for zinc
production was
replaced by the
hydrometallurgical
route.
Figure: Hydrometallurgical extraction of zinc.
 Epilogue
Hydrometallurgy is vigorously competing with old pyrometallurgical
techniques, and in some cases it has displaced such processes. For example:

➢The sodium carbonate sintering process for treating bauxite developed in

1855 was displaced by the pressure leaching process in 1892.
➢The pyrometallurgical route for zinc was displaced in 1970s by pressure
leaching of ZnS followed by electro-winning of zinc from the purified zinc
sulphate solution.
➢There is a good opportunity that nickel sulphides could be treated by
hydrometallurgical route similar to the ZnS process—elemental sulphur being
obtained instead of SO2.
➢The treatment of chalcopyrite concentrate by pressure leaching has been
recently piloted by Phelps Dodge in Arizona as a new method competing
with smelting.
NANOHYDROMETALLURGY
 NANOHYDROMETALLURGY

HYDROMETALLURGY MUST TRANSFORM AND ADAPT

TO THE CURRENT INDUSTRIAL CLIMATE IN ORDER TO
PROTECT ITS OWN VIABILITY…
 NANOHYDROMETALLURGY
Pathway for transformation from Hydrometallurgy to Nanohydrometallurgy:

The physical-chemistry principles governing the

production of bulk materials are the same as the
principles for production of materials on a nanoscale.
 NANOHYDROMETALLURGY
For example:
➢ Wet etching of silicon wafers in the computer industry is in principle no different than the leaching of ore
and minerals in extractive metallurgy.
➢ Controlled adsorption of molecules to form uniform assemblies, as a unit step in the overall
nanoprocessing, is popularly called the self-assembly of monolayers (SAM). But the chemical principles
governing the formation of nanostructures with the SAM approach are no different from the chemical
principles of adsorption of collectors and promoters on minerals in a flotation plant.
➢ Colloidal chemistry principles are often used in hydrometallurgy. Understanding colloidal chemistry is also
critically important for the development of many nanotechnologies based on sol-gel processing.
➢ Extractive metallurgy plants are users of large quantities of water in various unit operations (leaching,
precipitation, washing, purification, etc.), but the computer industry is an even a bigger user of water. The
issue of water quality is essential for this industry, whether water is used for rinsing of wafers or for
preparation of ultra pure solutions for electrochemical deposition of thin films. In parallel, the water quality
and the solution purification issue is also important in many hydrometallurgical operations for production of
large tonnage of metals. Either industry must use identical chemical principles (ion exchange, solvent
extraction) for purification purposes. Ion exchange is a key hydrometallurgical unit operation for
production of many rare earth metals, but also a key water purification approach by the computer industry.
Aqueous Solution Processing
Aqueous Solution Processing

• HYDROMETALLURGY (1st
• HYDROMETALLURGY (2nd
definition): Hydrometallurgy is
definition): The separation of a
concerned with the leaching of
soluble substance from an
ores, concentrates and calcines
insoluble by means of a solvent.
with aqueous solutions to
The solvent is either water or an
dissolve and recover the
aqueous solution.
valuable metals.
Aqueous Solution • They essentially involve the
Processing selective transfer of species in
liquid / solid and liquid / liquid
systems.
• In some circumstances gaseous
reactants or products may also
be present in the systems.
Hydrometallurgical
• Hydrometallurgical processes are
Processing concerned with the production of
Technologies metals or metallic compounds
from ores, concentrates or other
intermediate materials by a
sequence of operations carried
out in aqueous solutions.
 The ultimate objective of any
Aqueous Solution Processing extractive metallurgical process
is to economically extract the
valuable component of an ore
or intermediate product. In
particular, any viable
hydrometallurgical process will
have as its technical objective
Objective of a one or more of the following.
hydrometallurgical • To produce a metal directly
from an ore, concentrate or
process pre-treated concentrate
• To produce a pure metal or
metal compound from a
crude metal or metal
compound
• To minimize the use of reagents,
water and energy in the
production of metals
• To have minimal impact on the
environment in terms of the
disposal of solid and liquid
wastes.

An overall extractive metallurgical process.

Aqueous Solution Processing

General
Characteristics of
Hydrometallurgical
Processes

Basic unit processes in hydrometallurgy

A generic hydrometallurgical process for ores
Typical sequence of processes which
are undertaken in hydrometallurgical
processing of ores.
 Ore is reduced in size to
dimensions suitable for the
subsequent processing.

Typical sequence of processes which are undertaken

in hydrometallurgical processing of ores.
 If physical concentration
needed to increase the ore
grade then the particle sizes
must be reduced to the same
order of magnitude as the
original mineral grain size
before particle selection
process are used.

Typical sequence of processes which are undertaken

in hydrometallurgical processing of ores.
 Size reduction generally results
in faster processing rates

Typical sequence of processes which are undertaken

in hydrometallurgical processing of ores.
 In some cases thermal pre-
treatments may also be carried
out to change the composition
of the compounds present in
the ore to enable selective
dissolution of the species
(leaching) in suitable solvent
solutions.

Typical sequence of processes which are undertaken

in hydrometallurgical processing of ores.
 The pregnant leach solution
then separated from the
residual solids.

Typical sequence of processes which are undertaken

in hydrometallurgical processing of ores.
 Usually further processing is
carried out to remove
unwanted or undesirable
impurities present in the
solution.

Typical sequence of processes which are undertaken

in hydrometallurgical processing of ores.
 Metals or metal compound
products are obtained from
the solution by using variety of
chemical and electrochemical
techniques.

Typical sequence of processes which are undertaken

in hydrometallurgical processing of ores.
Combined mineral processing, pyro- and hydrometallurgical
processes
 Hydrometallurgy
Advantages Disadvantages

• High extraction of the value metal

• Requires very little fuel
• Many materials will not respond to treatment
• Equipment needed is relatively simple and by leaching methods.
inexpensive (Principle expense is the cost of
the necessary chemical reagents. In some • Plant effluents in both liquid and solid states
processes the solvent is regenerated) may have grievous consequences unless
adequately dealt with.
• Suited to the treatment of low-grade ores as
well as concentrates (e.g. gold ores, zinc • Slow reaction kinetics and low recoveries.
concentrates, Al2O3 extraction by the Bayer
process, etc.)
• Less environmental problems.
 • Hydrometallurgical processes
Aqueous Solution are preferred when the
Processing pyrometallurgical route is
impossible or impractical.
• If the metal to be extracted is
more reactive than the
impurities to be removed,
Hydrometallurgical e.g., aluminium, or the grade
Processing of the ore is very low and
Technologies cannot be upgraded by
physical beneficiation, e.g.,
gold and uranium,
hydrometallurgy becomes
important.
• Hydrometallurgical treatments are usually carried out at less than 50C and
the process streams are dilute (less than 1 mol.l-1 of solute).
• Low operation temperatures in hydrometallurgical processes mean, in
general, low reaction rates, whether they are limited by chemical reaction or
by mass transport processes.
• High temperature hydrometallurgical processing is possible but this must be
carried out under pressure to avoid the loss of solvent to the atmosphere.

• For a given throughput of material the size of hydrometallurgical plants are,

in general, larger than those using pyrometallurgical processes.
• On the other hand, the equipments used in hydrometallurgical operations is
more standardized e.g. pumps, piping, etc., and this tends to reduce unit
costs.
• An important feature of hydrometallurgical processes is that the chemical
reactions which are carried out are often far more selective than those
encountered in pyrometallurgical treatments.
• For example, when dissolving a particular mineral from an ore a reagent can
usually be found which attacks the «wanted» minerals but leaves almost
untouched the «unwanted» gangue materials.
Aqueous Solution
Processing Low-grade ores
• Typical gold ore containing
between 1 and 5 g t-1 gold.
• Low grade copper ore containing
0.4% Cu with up to 10% Fe.
Typical feed • Lateritic nickel ore with 1.5% Ni,
materials and 0.2% Co, 70% Fe2O3.
• Low grade uranium ore with 200
products ppm U3O8
• Brines containing 0.5-1.5 g L-1
lithium as chloride.
Low-grade concentrates and
High-grade mattes
calcines
• A matte (synthetic sulphide)
• Vanadium ore after magnetic
produced by the smelting of a
concentration with 3% V2O5, 70%
nickel sulphide concentrate
Fe2O3.
containing 40% Ni, 30% Cu, 20%
S, 1% precious metals.
High-grade concentrates and
calcines
• Calcine from the roasting of a
High-grade metals
zinc concentrate containing 75%
• Anodes for the production of
ZnO, 8% Fe2O3
copper by electrorefining
• Bauxite ore containing 50%
containing 95% Cu, 2% Ni.
Al2O3, 15% Fe2O3
Important minerals treated by hydrometallurgical processes.
The final products of a hydrometallurgical process can be either pure metals
or metal compounds. Some examples are:
• Metals
Gold, copper, zinc, cadmium, nickel, cobalt, platinum, manganese and
cadmium.
• Metal oxides
Alumina (Al2O3), manganese dioxide, vanadium pentoxide, nickel oxide.
• Metal salts
Cobalt or nickel sulphates, manganese sulphate, ammonium vanadate,
ammonium diuranate, lithium carbonate.
Specifications of high grade copper and zinc metals.
 Leaching (or dissolution)
Aqueous Solution
Processing The selective dissolution of the
desired mineral in an ore,
concentrate or intermediate
product can involve one or
more of many different
chemical reactants (leachants)
Unit operations in and can be carried out in many
hydrometallurgy different ways. The degree of
sophistication and complexity
can vary from simple heap
leaching to high
pressure/temperature
autoclave processes.
 Separation, concentration and
purification Precipitation and reduction
After the leaching operation, the
resulting solution or pulp must be The final metal or metal
subjected to one or more compound is produced from the
chemical process steps designed purified solution by a
to remove the impurities and/or precipitation, crystallisation or
concentrate the solution so that reduction step depending on the
the desired metal can be desired product. The reduction
successfully recovered in a pure step can involve electrons as in
form. These processes can involve electrorefining or electrowinning
selective precipitation,
crystallization, cementation, but can also involve chemical
solvent extraction, adsorption or reductants such as hydrogen gas.
ion exchange.
Concentration range of elements in the major streams in the electrolytic zinc process
Analysis of a typical purified leach solution for zinc electrowinning
Aqueous Solution Hydrometallurgical processes
Processing generally involve the
application of chemical
reactions to the dissolution of
solids, purification of the
resulting solutions, recovery of
pure metal products and the
disposal of inert residues. In
Description of a most of these operations,
hydrometallurgical heterogeneous processes are
involved and therefore
process transport of reactants to and
products from interfaces that
may be solid, liquid or gaseous
is an integral part of the overall
reaction.
Schematic procedure for the
quantitative description of
hydrometallurgical processes
 REFERENCES
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• J. J. Moore, Chemical Metallurgy, Butterworths, 1981.
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• M. Nicol, Hydrometallurgy, v. 1 and v. 2, Elsevier, 2022.