Hamilton Mines 0052N 10091

PRODUCTION OF ELEMENTAL SULFUR AND BENTONITE CLAY
GRANULES IN A ROTARY DRUM
By
Ian Wallace Hamilton
A thesis submitted to the Faculty and the Board of Trustees of the Colorado School of
Mines in partial fulfillment of the requirements for the degree of Master of Science
(Materials Science).
Golden, Colorado
Date ______________________
Signed:______________________
Ian Hamilton
Signed:______________________
Dr Reed Ayers
Thesis Advisor
Golden, Colorado
Date ______________________
Signed: _____________________
Dr Michael J. Kaufman
Professor and Head
George S. Ansell Department of
Metallurgical and Materials
Engineering
ii
ABSTRACT
Biological oxidation of sulfur granules is a critical component in elemental sulfur

fertilizers since it converts sulfur to plant available sulfate. The level of biological
oxidation is, in turn, regulated by the size and surface area of the sulfur granules. The aim
of this research was to produce coarse sulfur granules that disintegrate to the correct
particle size for biological oxidation, as well as the correct size for ballistic distribution
from a spreader. Thus the interaction between mineral powders such as serpentine rock
was investigated to get a better understanding of how these types of minerals react at
different size fractions in granulation. Sulfur granules were developed from mixtures of
10% sodium bentonite clay with molten elemental sulfur. This was accomplished by
sprayed a mixture bentonite and elemental sulfur into a falling curtain of fine material
powder within a rotating drum. When comparing the seed materials, the serpentine rock
showed sufficiently lower electrostatic build-up than phosphate rock. Serpentine rock
also appears to help facilitate the disintegration of the granules when they are exposed to
water. The outcome of the research was that it is possible to make a granulated sulfur
fertilizer that had the correct size fraction and disintegration characteristics suitable for
agronomic use.
iii
TABLE OF CONTENTS
ABSTRACT ....................................................................................................................... iii
TABLE OF FIGURES ........................................................................................................ v
Chapter 1 INTRODUCTION .......................................................................................... 1

1.1 Sulfur Source .............................................................................2
1.2 Sulfur fertilizer ..........................................................................7
1.3 Oxidation /Agronomic Availability Sulfur Fertilizers...............9
Chapter 2 METHODOLOGY ....................................................................................... 13

2.1 Raw Materials ..........................................................................13
2.2 Mineral Powder Trials .............................................................15
2.3 Plant Trials ...............................................................................15
2.4 Physical Testing .......................................................................21
2.5 Chemical Testing .....................................................................26
Chapter 3 EXPERIMENTAL LABORATORY TRIALS............................................. 27

3.1 Bentonite Clay Study ...............................................................27
3.2 Mineral Powder Trials .............................................................33
Chapter 4 EXPERIMENTAL PLANT TRIAL ............................................................. 38

4.1 8.6 Meter Long Drum ..............................................................38
4.2 3 Meter Long Drum – One Mixing Tank ................................41
4.3 3 Meter Long Drum – Two Mixing Tanks ..............................49
4.4 Resistivity ................................................................................61
Chapter 5 CONCLUSIONS AND RECOMMENDATIONS ....................................... 62
REFERENCES ................................................................................................................. 64
iv
TABLE OF FIGURES
Figure 1.1 World Production of Sulfur in 2011 Source (Survey 2012) .............................. 3
Figure 1.2 Viscosity of Sulfur (Fanelli 1946) ..................................................................... 5
Figure 1.3 Sulfur Deficient Areas in New Zealand (McLintock, 2009) ........................... 10
Figure 2.1 Layout for Mixing Tank for Sulfur Spray ....................................................... 16
Figure 2.2 8.6 Meter Long Drum ...................................................................................... 17
Figure 2.3 Layout for Sulfur Spray Trial .......................................................................... 18
Figure 2.4 Spray Drum ..................................................................................................... 19
Figure 2.5 Twin Mixing Tanks with Short Drum ............................................................. 20
Figure 2.6 End over End Apparatus .................................................................................. 21
Figure 2.7 Swell Testing ................................................................................................... 22
Figure 2.8 Schematic of the Granule Strength Test Apparatus ........................................ 23
Figure 2.9 Rotary Drum for the Granulation Degradation Test From (Organization and
Center, 1998)............................................................................................................. 24
Figure 2.10 Department of Scientific and Industrial Research Fertilizer Resistivity Meter
................................................................................................................................... 25
Figure 2.11 Hewlett Packard 34401A Multimeter ............................................................ 25
Figure 3.1 Material Retained and Passing a 250 Microns from Bentonite Clays and Sulfur
Mixtures after End over End Testing ........................................................................ 27
Figure 3.2 Samples Greater than 75 Microns and Less than 75 Microns Bentonite Clays
Mixtures after End over End Testing ........................................................................ 28
Figure 3.3 Sulfur in Each Fraction Retained on Sieves after End Over End Testing ....... 29
Figure 3.4 Swelling Index of Benonites ........................................................................... 29
Figure 3.5 Particle Size Distribution for United States of America Bentonite clays ........ 31
Figure 3.6 Particle Size Distribution for Australian Bentonite clays................................ 32
Figure 3.7 Particle Size Distribution for Japanese clays................................................... 32
Figure 3.8 Particle Size Distribution for New Zealand Bentonite clays ........................... 33
Figure 3.9 Mixing using Electric Drill .............................................................................. 34
Figure 3.10 Laboratory Trials using Serpentine Rock, 24 Hour End Over End Test ....... 35
Figure 3.11 Laboratory Trials using Limestone, 24 Hour End Over End Test ................ 36
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Figure 3.12 Laboratory Trials using Gypsum, 24 Hour End Over End Test .................... 37
Figure 4.1 Build up in the Pump ....................................................................................... 39
Figure 4.2 Plant Trial - 8.6 Meter Long Drum - using Serpentine Rock as Seed, 24 Hour
End Over End Test .................................................................................................... 40
Figure 4.3 Laboratory Results “Short Drum– One mixing Tank” 24 Hour End Over End
Test ............................................................................................................................ 42
Figure 4.4 Plant 7 Hour Run - 4 Mixes............................................................................. 44
Figure 4.5 Plant Trial - Short Drum - One Mixing Tank - Phosphate Rock as Seed
Particles Passing the 250 Micron Sieve After 24 Hour End Over End Test............. 45
Figure 4.6 Ammonium Sulfate before Processing ............................................................ 48
Figure 4.7 Ammonium Sulfate after Processing - Second Pass........................................ 48
Figure 4.8 Ammonium Sulfate after Processing - Seventh Pass ...................................... 49
Figure 4.9 Vortex Formed in the Mixing Tanks ............................................................... 50
Figure 4.10 Spray into Granulating Drum ........................................................................ 52
Figure 4.11 Infra Red Measurement Side of Drum .......................................................... 53
Figure 4.12 Temperature of Drum over 100 Minutes ....................................................... 54
Figure 4.13 Twin Tank Sieve Analysis............................................................................. 55
Figure 4.14 Scanning Electron Micrograph of the Surface of a Sulfur Bentonite Granule
................................................................................................................................... 57
Figure 4.15 EDAX on Gray Particles ............................................................................... 58
Figure 4.16 EDAX on the White Particles........................................................................ 59
Figure 4.17 Surface of Sulfur GranulesResistivity ........................................................... 60
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TABLE OF TABLES
Table 1.1 Project Requirements .......................................................................................... 1

Table 1.2 Some Current Sulfur Fertilizers Used ................................................................. 8
Table 2.1 Bentonite Clays ................................................................................................. 13
Table 2.2 Serpentine Rock Chemistry .............................................................................. 14
Table 2.3 Phosphate Rock Chemistry ............................................................................... 14
Table 2.4 Gypsum Chemistry ........................................................................................... 15
Table 3.1 Chemical Analysis of Bentonite Samples ......................................................... 30
Table 4.1 Chemistry and Production 8.6 Meter Long Run ............................................... 39
Table 4.2 Process Data - 3 Meter Long Drum – One Mixing Tank ................................. 41
Table 4.3 Process Data, 3 Meters Long Drum, One mixing Tank, Phosphate Rock Seed
Material ..................................................................................................................... 43
Table 4.4 Chemical Results - Short Drum - 3m long 1.2m ø Drum – One mixing tank
Phosphate Rock Seed Material ................................................................................. 43
Table 4.5 Elemental Sulfur Results on Fractions Retained on Sieves for Plant Trial – 3
Meter Long Drum - One Mixing Tank- Phosphate Rock Seed Material .................. 46
Table 4.6 Fine Ammonium Sulfate Fertilizer ................................................................... 47
Table 4.7 Sulfate of Ammonia Chemistry and Physical Data .......................................... 47
Table 4.8 Sulfur Chemistry of Sieve Retained Material after 24 End Over End Testing. 56
Table 4.9 Molten Sulfur Mixes - Granule Strength & Granular Degradation .................. 56
Table 4.10 Resistivity of Prilled Sulfur Materials ............................................................ 61
vii
ACKNOWLEDGEMENTS
I would like to thank my advisor Dr. Reed Ayers for sticking with me. Really
enjoyed the foundry work I would also like to thank the two on my committee Dr. Ron
Cohen and Dr. David Olson. Thank you for giving me so much encouragement. I could
not have finished without you all. Thanks also to Matthew Karsh who help me out with
the particle sizing and X-ray diffraction
Thanks to Ballace Agri - Nutrients, my current employer for funding the research.
I would like to especially thank the previous Operation Manager, Jeff O'Shea, without
you I would never have got this far. Others at Ballance who have been extremely helpful
were Dr. Terry Smith, Aaron Stafford, Max Thomas (the man behind the engineering of
the plant).
There are several that I would like to thank at Industrial Research Limited’s Bill
Owers who’s worked with me on the resistivity measurements. Also to Dr Neil Milestone
a great encouragement to me in the past and as well as in this journey.
My Wife Wendy for letting me finish my second masters, you Wendy are the love
of my life and there is no way I would have ever got this far without you. Also thanks to
my kids Ruth, Rachel, Paul and John it was wonderful to have you with me in the United
States. But above all I thank God that he opened the door to the trip of a life time and we
as a family were able to experience the beautiful people and country called the United
States of America.
viii
CHAPTER 1 INTRODUCTION
The aim of this research was to produce sulfur granules that have the correct
particle size for biological oxidation, as well as the correct size to allow ballistic
distribution from a spreader. An investigation and design of a suitable process was
carried out. An ideal sulfur fertilizer should have a high concentration of sulfur that is
plant available, be cheap, have a low fire and explosive hazard rating, and be readily
mixed with other fertilizers.
The product’s granule size would be larger than the currently formed sulfur, (See
Table 1.1). Granules of elemental sulfur in the size range of 5 mm to 2 mm would be
suitable to use in an agricultural spreader. These granules need to disintegrate to a
particle size around 150 - 75 microns when exposed to moisture.
This larger size helps improve blending with fertilizers, while at the same time the
elemental sulfur granules have the ability to disintegrate into finely divided particles
when coming into contact with moisture, hence the elemental S is agronomically far more
effective than the current sulfur products available.
Table 1.1 Project Requirements
% Passing the sieve

0.5 250 75
5.0 mm 2.0 mm 1.0 mm mm µm 150 µm µm
Current Formed
Sulfur 100 97 50 17 5
Developed Product 100 0
After Specific
period and contact
with moisture 90 50
The initial development of sulfur fertilizer was accomplished by mixing different

formulations of molten sulfur, bentonite clay and mineral powders such as gypsum,
limestone serpentine rock and bentonite clay.
1
Characteristics of elemental sulfur and its interaction with mineral powders were
researched by:
a) Designing and testing different levels of mineral powders to sulfur.
b) Reviewing the process parameter to identify changes that would enable a
continuous large scale plant to be developed.
c) Reviewing the effect of different bentonite clays on the disintegration of sulfur.
As well as trialing different levels of bentonite to sulfur.
1.1 Sulfur Source
Sulfur occurs abundantly in nature, both in the form of elemental sulfur as well as
in large quantities as sulfates and sulfides. It is estimated that the earth’s crust contains
0.06 % sulfur and Earth’s total mass is 3% sulfur. The reserves of elemental sulfur
worldwide are estimated to be about 5 billion tons (Ober, 2005; Ehlers, Liu et al., 2009).
The international production of sulfur in 2011 was 70 million tons (Apodaca,
2012), with the majority manufactured in the United States, Canada, and Russia, each
producing in excess of 7,000,000 tons (See Figure 1.1). It has been estimated that 90% of
this sulfur is consumed as sulfuric acid and is primarily used in the fertilizer industry,
with sulfuric acid being the world’s largest inorganic chemical.
New Zealand imports most of its sulfur, with minor amounts coming from the
refinery at Marsden Point in Whangarei. Very little is produced from New Zealand’s
natural resources. It is estimated that, on average, about 200,000 tons of sulfur are
imported per annum and primarily used for the manufacture of sulfuric acid (Martin and
Clark, 2000)
In the USA the production of elemental sulfur is 9 million tons with nearly half of
the production coming from Texas and Louisiana alone. This elemental sulfur produced
in the USA is able to supply 75 % of the States’ domestic sulfur requirements. The
remaining 25% came from acid formed as byproduct from other industries such as
nonferrous smelters (Ober, 2010).
1.1.1 Frasch Method Extraction of Elemental Sulfur
Before 1974 seventy five percent of the United States requirement for sulfur was
mined using the Frasch method (McNamara, 1978) developed by the late Dr Herman
2
Frasch from Germany. The Union Sulfur Co commercialized the Frasch process in
Louisiana. This method pumped super heated steam into sulfur rich regions of the
subsurface of the earth. The elemental crystal sulfur then melted and was pumped to the
surface by air.(Ober, 2005)
2005).
Figure 1.1 World Production of Sulfur in 2011 Source (Survey 2012)
The Frasch Method for the extraction of elemental sulfur produced for sulfur.
However, due to the large amount of energy this method required and with increasing
amounts of sulfur becoming available from petroleum refineries, the last processing plant
stopped in 2000 (Mandeville
(Mandeville, 2010).
1.1.2 Petrochemical Extraction of Elemental Sulfur
Currently the major source of sulfur is from the petrochemical industry where it is
produced as a by-product
product from sour crude. (oils and natural gases with high levels of
3
sulfur) in petrochemical refineries Crude oil along with sour natural gas and oil sand
processing were estimated in 2008 to produce 98% of world elemental sulfur. Due to the
availability of sour crudes, the petroleum industry tends to refine higher sulfur crudes.
These crudes have large amounts of hydrogen sulfide which need to be removed.
The main technology used for removing and converting hydrogen sulfide to
elemental sulfur is the Claus process, with 90 to 95% being produced by this method
(Goar, 1986). The Claus process was invented by Carl Friedrich Claus where H2S gas is
fed into a waste heat boiler where it is combusted. The SO2 produced along with excess
H2S, is then cooled and passed over a Al2O3 based catalyst which converts the H2S and
SO2 into elemental sulfur and water according to the following reaction:
2H2S + SO2 3S + 2H2O
The sulfur is removed and the remaining gas is sent to a desulfurization plant
where the sulfur levels are dropped even lower. Any remaining sulfur is burned to sulfur
dioxide (Kohl and Nielsen, 1997; Matar and Hatch, 2001) and fed back into the process.
The sulfur is stored or sold for the manufacture of fertilizer or sulfuric acid.
1.1.3 Sulfur Chemistry.
Sulfur is found in several forms, orthorhombic, monoclinic, amorphous and

plastic sulfur. Rhombic is the most common form and its structure is a S8 molecule where
the sulfur elements are bound together by covalent bonds with a bond angle around 105o
(Mandeville, 2010). The monoclinic form is encountered when molten sulfur crystallizes
above sulfur’s transition temperature of 95.6OC. Amorphous sulfur has no crystalline
form and is produced as the result of a chemical reaction. The “plastic” form is produced
by pouring boiling sulfur into water. This results in random chains of sulfur, but over
time reverts to the rhombic sulfur (Liptrot, 1981). All forms of sulfur will melt into a
yellow liquid. The melting point can be between 113oC to 119oC depending on the forms
of elemental sulfur present.
Figure 1.2 shows the sulfur increase in viscosity at around 160oC. This is because
the sulfur chains disintegrate and tangle with each other. At around 187oC sulfur peaks at
4
93,200 centipoises, and viscosity starts to fall. Around 300oC has it dropped back to 100
centipoises.
Figure 1.2 Viscosity of Sulfur (Fanelli 1946)
1.1.4 Hazards of Sulfur
100% sulfur dust can be ignited by weak frictional sparks, electrostatic electricity
and any other ignition source. Depending on the circumstance, levels as low as 25%
sulfur maybe explosive. Comparing it with other combustible dusts, it has the very low
ignition point of 190oC. Additional risks include numerous materials that have been
found to be explosive when mixed with sulfur, the main ones being chlorates, nitrates and
oxidizing agents.
Thus, governments have developed specific codes for the handling of sulfur. The
New Zealand Government restricts the way that sulfur is handled by requiring industry to
abide by the Code of Practice for the Prevention of Sulfur Fires and Explosions
5
(McKenzie, 1993). This code establishes requirements to eliminate or reduce the hazards
of explosion or fire in the processing and handling of sulfur. In the USA the standards
NFPA654 and NFPA 655 are used with regards to sulfur handling. The NFPA654
standard (Frank, 2006) was developed for all phases of manufacturing where dusty
materials present a fire and dust explosion hazard. The NFPA 655 standard applies where
sulfur is reduced in size and handled in any form (Frank, 2006; Frank, 2012).
1.1.5 Dust Explosions
Dust explosions may occur when using sulfur or any other combustible dust with
a particle size less than 500 microns. At less than 500 microns, combustible dusts are
classified as an explosive, they will burn and explode in the right conditions (NFPA
2008; NFPA 2012). Particles up to 1400 microns will contribute to an explosion after
ignition.
The initial explosion can be defined as the primary explosion and this takes place
in a confined space. The secondary explosion takes place with the dust disturbed from the
first explosion.
Ebadat identified several conditions for dust explosions to occur.
a) The dust must be combustible and airborne as well as have concentrations
within an explosive range.
b) They must also have particle size distribution capable of causing a flame.
c) The atmosphere will be capable of supporting combustion.
d) Have an ignition source with sufficient energy for flame propagation.(Ebadat,
2010)
Conditions will differ for different materials, for example, smaller particles have
more potential for explosions, as these particles are easily suspended in air and require
less energy to ignite.
There are several ways to reduce the likelihood of sulfur explosions:
a) Moisture.
Moisture sticks the particles together, reducing exposed surface area,
increasing the energy required to start an explosion.
6
b) Inerting
This is done by adding an inert gas such as argon or nitrogen. When oxygen is
reduced below 8% the likelihood of explosions reduces. Another method of inerting
is to add an additional material that is not combustible, such as bentonite clay
(McKenzie, 1993).
1.1.6 Elector-Static Electricity
Materials differ in the ease that electricity flows through them. Some materials
conduct electricity, these are called conductors. Some materials resist the flow of
electricity, these are called insulators. Static electricity happens when the flow of
electricity is impeded and the voltage is sufficient enough to cause an electric charge to
jump across an air gap.
Sulfur has an extremely high resistance to the flow of electricity and is a very
good resistor. Static electricity is a very good ignition source (Jones, 1998)and when
sulfur has the right conditions, a dust explosion can occur. One method for measuring
how well sulfur builds up electrostatic electricity is to measure resistivity. Sulfur is one of
the most efficient electrical insulating materials with a resistivity at 2x1023 µΩ-cm
(Mohamed and Gamal, 2010). High resistivity is difficult to measure, however, Boswell
et al., attempted to measure the bulk resistivity of prilled sulfur by using two copper
electrodes clipped to a beaker full of granular sulfur material. They found that they were
able to get reliable readings for granulated materials between 108 and 1012 ohm-cm
(Boswell, Owers et al., 1988a). Boswell also looked at using bentonite clays as an
inerting material and found a ratio of 5% or less of bentonite clay to sulfur could be
hazardous because of electrostatic build up. However, when they changed the ratio of
bentonite clay to sulfur to 10%, the high resistivity was reduced. At 15% or more
bentonite clay to sulfur, the electrostatic build up was not deemed to be problematical
(Boswell, Owers et al., 1988a).
1.2 Sulfur fertilizer
There are many sulfur fertilizers that can be used to improve sulfur deficient soils.
These are classified into two groups, those containing elemental sulfur and those
7
containing sulfates (SO42-). In New Zealand the most widely used sulfur fertilizers are
sulfate based i.e. gypsum, single superphosphate, ammonium, potassium and magnesium
sulfate, see the following Table 1.2.
Table 1.2 Some Current Sulfur Fertilizers Used
Sulfur Formula %S Cost effective Low fire / Plant Readily

fertilizer Note * Fire available mixed
explosive with other
hazard fertilizer
Elemental S 100 Cheapest √
sulfur
Bentonite S 90 Cost effective √ √
clay / Sulfur
mix
Calcium CaSO4.2H2O 18 Cost effective √ √ √
sulfate
Ammonium (NH4)2SO4 23 Expensive √ √ √
Sulfate
Potassium K2SO4 17 Most √ √ √
Sulfate expensive
Super Mixture of 10.5 Expensive √ √ √
phosphate CaSO4 and
3Ca(H2PO4)2
.H2O
Magnesium MgSO4 16 Expensive √ √ √
Sulfate
(Kieserite)
*Based only on sulfur % versus cost of sulfur.
The choice of fertilizer is determined by cost, availability and agronomical

requirements, elemental sulfur fertilizers meet several of these characteristics. They have
a high sulfur concentration (i.e. 100%), are relatively cheap and readily mixed with other
fertilizers, however, they don’t meet two very important requirements i.e. low fire /
explosive hazard and plant availability.
According to McGrath and Zhao (1995) European soils are becoming sulfur
deficient due to:
a) More stringent environmental conditions on industry by regulators. This has
required industry to reduce the discharge of sulfur dioxide. This has reduced the
sulfur being deposited on the soils.
8
b) A shift from sulfur rich fertilizers such as single superphosphate to the sulfur
deficient fertilizers such as urea, di-ammonium phosphate and potash (potassium
chloride). This has reduced the amount of sulfur put on the land.
c) More intensive farming has stripped the nutrients from the soils.
New Zealand soils lack sulfur, nitrogen, potassium and phosphate, key elements
needed for pastoral farming. A fine elemental sulfur can be applied to pastures to reduce
the sulfur deficiency in New Zealand soils (Edmeades, 2005); Christie and Barker, 2007).
New Zealand has predominantly used single superphosphate to compensate for the
phosphate and sulfur deficiency. Superphosphate (a mixture of mainly mono - calcium
phosphate monohydrate and calcium sulfate) is made by reacting phosphate rock
(fluoroapatite) with sulfuric acid (Simpson, Petherick et al., 2006). Single superphosphate
contains significant levels of sulfate sulfur, thus the issues affecting Europe have not
affected New Zealand to the same extent.
However, mid to late last century it was identified (Walker and Gregg, 1975) that
there were several areas in New Zealand (See Figure 1.3), mainly the high country of the
South Island. These areas respond to sulfur fertilizers, preferably elemental sulfur
(Craighead and Metherell, 2006).
1.3 Oxidation /Agronomic Availability Sulfur Fertilizers
Elemental sulfur must be oxidized to sulfate to be biologically available for

plants. For this to happen it must be less than 250 micron diameter. Oxidation takes time
and is controlled by several factors; temperature, and moisture and particle size (Germida
and Janzen, 1993). It has also been identified that different materials that are mixed with
sulfur can change the oxidization levels of sulfur. Bell-Booth et al. found that when
elemental sulfur was mixed with a phosphate rock there was an increase in oxidation
levels (Bell-Booth, Smith et al., 1988). It has been estimated that only half of the mass
elemental sulfur for 1 to 2 mm granules is converted to sulfate after 5 years (Edmeades,
2005). The large particles oxidize slower than the smaller particles, thus the time for the
larger elemental sulfur particles to become bio-available is delayed. Elemental sulfur
applied to the soil is converted to sulfate by Thiobacillis microbial oxidation.
9
Figure 1.3 Sulfur Deficient Areas in New Zealand (McLintock, 2009)
10
The relationships between sulfur particle size and its oxidation rate depend on the
environment. In cooler areas sulfur particles oxidize slowly compared warmer areas
where oxidation of particles takes place more rapidly. (Boswell and Swanney, 1986). To
reduce the size of the elemental sulfur suitable for bacterial oxidation, bentonite clay can
be used which swells and disintegrates the particle when it comes in contact with water.
Research has been done over the years on sulfur / bentonite clay fertilizers (Rothbaum,
Sewell et al., 1980; Charleston, 1983a; Rothbaurn and Evason, 1983a; Boswell and
Swanney, 1986; Nguyen, Wright et al., 1988; Smith and McDougall, 1988; Boswell,
Owers et al., 1988a; Boswell, Swanney et al., 1988b). Where sodium bentonite clay is
mixed intimately with elemental sulfur a solid granule can be formed. Sulfur bentonite
clay granules are normally composed of 90% sulfur and 10% bentonite clay. The amount
of bentonite clay used proportionally to molten sulfur is based on an arbitrary 10% figure
used for several bentonite clay / sulfur mixtures (Gillson, 1960), but bentonite clay
proportions around 15 - 20% appear to suggest the best technique for quick prill
dispersion and finely divided S° particle size (Boswell, Owers et al., 1988a). These
granules are used in the agricultural industry because of their ability to disintegrate and
release elemental sulfur into sulfur deficient soils. As the bentonite clay absorbs moisture
from the soil, the granules swell and break apart, releasing the sulfur particles into
smaller fractions allowing the surface of the sulfur to be exposed to sulfur oxidizing
bacteria, which then convert the elemental sulfur into sulfate.
There are several characteristics that affect the choice of the bentonite clay to be
used in the production of suitable bentonite / sulfur granules. The swelling ability of the
bentonite clays and their chemical composition or impurities are extremely important.
Yuan in 2010 showed that variations in basal spacing, i.e. the distance from one plane in
to the next plane in the corresponding layer, with air relative humidity can be used as an
indicator of the swelling ability of bentonite clays that are not water saturated. Total
saturation is not a condition that is widespread in soils for agricultural use. The basal
spacings can be measured to indicate if there is potential for physical disintegration of
bentonite clay / sulfur fertilizers in dry soils.
Bentonite clays mainly consist of at least 85% montmorillonite and are found in
two types, the swelling sodium form and the non-swelling calcium form. The sodium
11
form has high swell characteristics compared to the non-swelling form in which calcium
is the main exchangeable ion. The physical structure of sodium bentonite clay makes it
unique, in that it has a large swelling chemical surface area. Natural sources of the
sodium bentonite clay are very rare, whereas calcium bentonite clay is quite common
(Odom, 1987 ).
Bentonite clay consists of multiple layers of clay platelets, each about 1 nm thick.
They consist of three layers, an aluminum octahedral layer sandwiched between two
silicon tetrahedral layers. In montmorillonite the alumina (+3 charge) is frequently
substituted by magnesium (+2 charge) that results in an unbalanced negative charge (a
deficiency of +1 charge). This is neutralized by cations such as calcium, sodium,
potassium or magnesium residing in the inter-layers spaces between the platelets
(Murray, 2009; Anderson, Ratcliffe et al., 2010). Different bentonite clays have different
swell characteristics, depending on the cations present. When water is added to bentonite
clay it is drawn between the layers, and osmotic swelling takes place.
Several locations around New Zealand have been identified with wide spread
bentonite clays. There are various locations in the North Island of New Zealand that
contain bentonite clays, including Kaeo, Motatau and Puhipuhi. (Ritchie, 1962).
However, they are not currently mined and the main source in New Zealand is from
Colgate in the South Island. Several other locations are known; there being deposits in
the East Cape, Marlborough and Canterbury, (Christie and Barker, 2007). None of the
New Zealand clays are the swelling sodium bentonite clays. The only location that is
commercially extracting bentonite clay is Colgate, west of Christchurch (Grim and
Guven, 1978). The clay mined in Colgate is the calcium bentonite clay and is modified to
sodium bentonite clay by mixing a solution of NaCO3 with the clay. Significant time is
allowed for the clay to react before drying and crushing.
In the United States of America, 95 % of the market uses swelling bentonite clay
extracted from Wyoming, Montana and South Dakota. The major market for swelling
bentonite clay is for the drilling industry and as a pet waste absorbent material. Very little
bentonite clay is used in the production of swelling bentonite clay sulfur fertilizer (Miles,
2012).
12
CHAPTER 2 METHODOLOGY
2.1 Raw Materials
Several raw materials were used: gypsum, limestone, serpentine rock, phosphate
rock and elemental sulfur.
2.1.1 Bentonite Clay
The bentonite clay used in the plant testing was sodium modified bentonite clay
sourced from Transform Minerals at Colgate, Canterbury, New Zealand. When the
bentonite clay was passed through a 75 µm sieve, only 0.7 % of the original volume of
material was retained on the sieve. Table 2.1 list the other bentonite clays used in the
study
Table 2.1 Bentonite Clays
Code Description Location

2090357 Sodium modified Colgate Canterbury New Zealand
2090797 Calcium Colgate Canterbury New Zealand
2101268 Light gray powder USA
2110005 Flaky material Japan Kunipa G
2110006 Off white fine powder Japan Kunipa F
2110007 White synthetic inorganic polymer Kunimine Industries Sumecton SA
2101278 Off white fine powder Australia
2110019 Off white fine powder Australia Trubond Unimin
2110020 Off white fine powder Australia Active Gel 53
2110029 Light gray powder Australia Amcol 5D
2110040 Off white fine powder Australia Arumpo Ultraben 75
The amount of bentonite clay mixed with sulfur was determined by the level of
molten sulfur used and is based on the arbitrary 10% ratio to sulfur (Gillson 1960).
13
2.1.2 Sulfur
The sulfur was produced by the New Zealand Refining Company and is a bi-
product of their oil refining process; the quality was 99% pure sulfur. It arrived on site
and was passed through a leaf filter to remove any solid material.
2.1.3 Serpentine Rock
The serpentine rock came from the Rorisons Quarry located at Kohua Road in
Aria, New Zealand. Over 40% of the rock dust passes a 500 micron sieve. It had
chemical formula of Mg3Si2O5(OH)4 and has the monoclinic crystal structure.
Predominate elements are Mg, Si, and Fe. (See Table 2.2)
Table 2.2 Serpentine Rock Chemistry
Fe Ca K S P Si Al Mg Na Moisture
% % % % % % % % % %
5.0 0.9 <0.0 <0.0 0.2 16.6 0.2 24.4 <0.0 0.23
2.1.4 Phosphate Rock
The phosphate rock used had phosphate levels of 12% and contained no sulfur. It
was sourced from Gafsa in the Republic of Tunisia. See Table 2.3.
Table 2.3 Phosphate Rock Chemistry
Fe Ca K S P Si Al Mg Na F Moisture
% 5 % % % % % % % % %
0.1 19.6 <0.0 0.8 11.7 1.07 0.2 0.3 0.5 4.4 1.7
2.1.5 Gypsum
The gypsum used was natural material, sourced from Australia through Winstone
Wallboards (Soil Life) and its chemical formula is CaSO4.2H2O (Calcium sulfate di-
hydrate). It is to some extent soluble in water and, therefore, provides some sulfate for
plants. It has a calcium sulfate level of between 93% and 98%. The main elements
present are 23% calcium and 18% sulfur (see Table 2.4)
14
Table 2.4 Gypsum Chemistry
Fe Ca K S P Si Al Mg Na Moisture
% % % % % % % % % %
0.1 23.3 <0.0 18.0 <0.0 0.1 <0.0 0.1 0.1 1.2
2.1.6 Limestone
The limestone was sourced from McDonald’s Lime (AgLime) and has a value of
95% CaCO3.
2.2 Mineral Powder Trials
The sulfur was mixed with the other materials in a stainless steel pot using a
mixer on the end of an electric drill. The bentonite clay used was dried at 100 oC. The
mix was then cooled, crushed to pass a 4 mm sieve and retained on a 2 mm sieve before
analysis.
2.3 Plant Trials
The following sections 2.3.1 to 2.3.3 show the three different pilot processing
plants which were constructed and operated for this thesis.
2.3.1 8.6 Meter Long Drum
Elemental sulfur was mixed (on an as received basis) in a 176 liter tank (see
Figure 2.1). The elemental sulfur was kept heated at above 120oC by steam-heated coils
The mixer’s speed was increased to 750 revolutions per minute to form a vortex that
allowed the steam to escape when the bentonite clay was added. At the addition of
bentonite the temperature of the molten sulfur dropped significantly. After 30 minutes the
temperature rose to 128 - 132 oC. At this point seed material was placed into the rotating
drum. (Figure 2.2). Lifters caused the seed material to form a falling curtain. The pump
sent the liquid sulfur mixture into the 0.17 meter diameter and 8.6 meter long drum. The
sulfur adhered to the falling curtain of seed material forming a sulfur / bentonite clay
granule. The granules proceeded to the end of the drum where they were screened into
over’s (>5 mm), product (<5 mm, >2 mm), and seed (<2 mm) fractions.
15
Figure 2.1 Layout for Mixing Tank for Sulfur Spray
16
The seed material was then returned to the beginning of the drum where it again
formed part of the falling curtain. This process continued until the mixing drum was
emptied of all the sulfur / bentonite clay material.
Figure 2.2 8.6 Meter Long Drum
2.3.2 3 Meter Long Drum – One Mixing Tank
Figure 2.3 is a schematic of the plant used for the elemental sulfur and bentonite
clay trial. The modified plant used the initial mixing tank and pump from the first trials
but the long drum was replaced with a shorter 3 m long 1.2 m diameter drum. The spray
boom was extended to project 3 meters into the drum (see Figure 2.4) and a vibrating
screen was added.
17
Figure 2.3 Layout for Sulfur Spray Trial
18
Figure 2.4 Spray Drum
2.3.3 3 Meter Long Drum – Two Mixing Tanks
Following the successful trials using the 3 m long 1.2 m diameter drum, the plant
was reconfigured to allow continuous running (see Figure 2.5). This was achieved by
adding two tanks capable of holding 1-2 tones of molten sulfur / bentonite clay. These
tanks were capable of being used independently of each other, allowing for bentonite clay
to be added and mixed in one, while the other was sprayed into the falling curtain in the
drum. A bin and conveyor were also added allowing for continuous feeding of seed
material to the entrance of the drum.
19
Figure 2.5 Twin Mixing Tanks with Short Drum
20
2.4 Physical Testing
The physical methods used in this thesis are described in the flowing sections
2.4.1 to 2.4.6.
2.4.1 Temperature Measurements
Temperature measurements were made using a FLIR i5 Thermal imaging camera.

The camera had an accuracy of ±2°C and produced sensitive thermal images which could
detect temperature differences as small as 0.10°C.
2.4.2 24 Hour End Over End
This test gives an indication of the disintegration characteristics of the final

product. The method mixed 40 grams of material with 80 g of water. This was placed in
leak proof containers and placed on the end over end mixer (See Figure 2.6) at 30 rev per
minute for 24 hours at room temperature (20oC). The samples were wet sieved though
2000, 1000, 500, 250, 125 and 75-micron sieves. Each sieve was dried at 105oC then the
fractions were weighed.
Figure 2.6 End over End Apparatus
21
2.4.3 Swelling Index
The swell test was based on the standard method for swelling index of Clay
Mineral Component of Geo-synthetic Clay Liners. (ASTM_D5890-11 2011). A 2 g
sample was poured into a 100 ml measuring cylinder of 90 ml of de-ionized water. 0.1 g
of bentonite clay was added slowly into the measuring cylinder. When the bentonite clay
had absorbed the water it sank to the bottom of the measuring cylinder. This was
repeated until the entire sample was used up. The measuring cylinder was topped up to
100 ml and allowed to stand for at least 16 hrs. The sample absorbed water up to its
maximum absorbing capacity and swelled. The average top height was measured as the
swelling index as can be seen in Figure 2.7.
Figure 2.7 Swell Testing
22
2.4.4 Granule Strength
Samples were poured through a 4.0 mm and 3.35 mm sieve. Twenty granules
were randomly selected from the material retained on the 3.35 mm sieve. Each of these
was placed on a spring balance. A dowel was used to apply pressure to the granule until
the granule broke. The result was the weight in kg force (See Figure 2.8).
Dowell
Granule
Wood Slab
Scale Spring balance
Figure 2.8 Schematic of the Granule Strength Test Apparatus
2.4.5 Abrasion Resistance Testing
A sample was poured through a 5.6 mm sieve and retained on a 1.4 mm sieve.
75g was collected from the material retained on the 1.4 mm sieve. This was placed into
the granular degradation container (Figure 2.9) with 50 x 8 mm steel balls and the lid was
secured. This was then placed on a revolving shaker and rotated for five minutes at 30
rpm. At the end of the time the balls were removed and the contents screened through a 1
mm sieve. The amount retained on the 1 mm sieve gave an indication of the amount the
granules were resistant to abrasion.
23
Figure 2.9 Rotary Drum for the Granulation Degradation Test From (Organization and
Center, 1998)
2.4.6 Particle Size Analysis
Bentonite clay particle size distribution was measured using Microtrac FLEX with
distilled water as the solvent. The Microtrac used a standard circulating system that
transported the sample through a cell where the particles were subjected to laser light
scattering. The machine measured the particle range from 2000 µm down to 0.025 µm.
2.4.7 Bulk Resistivities
Bulk resistivities of the granules were measured between two steel 19.4 cm2
electrodes that were 26 mm apart. Testing was done on an in-house Fertilizer Resistivity
Meter designed by the Department of Scientific and Industrial Research in New Zealand
(see Figure 2.10). Measurements that were higher than 1010 ohm.cm were checked using
a Hewlett Packard 34401A multimeter (see Figure 2.11).
24
Figure 2.10 Department of Scientific and Industrial Research Fertilizer Resistivity Meter
Figure 2.11 Hewlett Packard 34401A Multimeter
25
2.5 Chemical Testing
Section 2.5.1 to 2.5.5 describe the chemical test methods used in this thesis
2.5.1 Elemental Sulfur Analysis
Elemental Sulfur was determined by converting the entire elemental sulfur to

sulfur dioxide by burning at 800°C for 30 minutes.
2.5.2 Magnesium Analysis
Magnesium analysis was carried out by digesting the sample in an HCl / HNO3
solution and measuring on a Varian SpectraAA 220 Atomic Absorption
Spectrophotometer against standard Mg solutions.
2.5.3 Phosphate Analysis
Phosphate analysis was carried out by dissolving the sample in Aqua Rega (20%
HCl / 5% HNO3). This solution was then diluted with distilled water before being reacted
with a solution of ammonium molybdate / ammonium metavanadate and nitric acid
solution. This formed a yellow solution that was then measured on a Helios Gamma
spectrophotometer at 420 nm against standard solutions.
2.5.4 Ammonium Sulfate Analysis
The Kjeldahl method was used for determination of ammonium using a Kjeltec
2006 Digestion System along with the Kjeltec System 1002 Distilling unit. The
ammonium sulfate is reacted with NaOH converting the NH4+ into NH3 using NaOH.
This was then steam distilled into boric acid and back titrated with a standard solution of
H2SO4.
2.5.5 X-ray Fluorescence Analysis
The analyses were carried out after ignition at 1000°C using a wavelength-
dispersive Siemens SRS303 X-ray Fluorescence Spectrometer. Results are expressed on
an oven-dry basis.
26
CHAPTER 3 EXPERIMENTAL LABORATORY TRIALS
3.1 Bentonite Clay Study
The initial study examined the advantage of using clays from different locations.
Fourteen different bentonite clays from New Zealand, the United States of America,
Japan and Australia were investigated with respect to their swelling capacity, chemical
composition and disintegration ability when mixed with elemental sulfur. The results
show that all the bentonite clays have a disintegration effect on the bentonite sulfur
mixes. Figure 3.1 shows that some of the bentonite clay /sulfur mixes were able to meet
the target of 90% passing a 250 micron sieve after breaking down in the end over end
test. All bentonite clays however failed to meet the second target of at least 50 % passing
the 75 micron (see Figure 3.2).
Figure 3.1 Material Retained and Passing a 250 Microns from Bentonite Clays and Sulfur
Mixtures after End over End Testing
A selection of material retained on several sieves was tested for elemental sulfur.
As can be seen from Figure 3.3, all fractions retained on sieves above 75 microns showed
95% or above of elemental sulfur. This was expected as 90% of each mixture was sulfur.
27
The less than 75 microns fraction would be expected to have a high % of bentonite clay
retained in it.
Figure 3.2 Samples Greater than 75 Microns and Less than 75 Microns Bentonite Clays
Mixtures after End over End Testing
Different bentonite clays have different swelling characteristics depending on the

chemical composition. Bentonite clays with sodium as the predominate cation will swell
more than those with calcium as the predominate cation. When comparing the calcium
bentonite clay with the sodium modified bentonite clay, they were found to be similar in
the amount of disintegration of the particles. This was unexpected as the sodium modified
bentonite clays are more likely to swell, and thus disintegrate, than the calcium bentonite.
This may be due to the slight amount of sodium present in the calcium bentonite clay.
As can be seen from Figure 3.4 the material with the highest swelling index of 82
was a purified bentonite clay form Japan. The second highest swell index was the
synthetic magnesium aluminum silicate inorganic polymer giving a swelling index result
28
of 51. This work confirms that done previously by Yuan (2010) who concluded that
Kunimine bentonite clay gave the best swelling levels over all.
Figure 3.3 Sulfur in Each Fraction Retained on Sieves after End Over End Testing
Figure 3.4 Swelling Index of Benonites
29
3.1.1 Chemical Analysis
These fourteen bentonite clays are widely different in composition (see Table
3.1). All the clays have silica levels in the 48 – 70% range plus Al2O3 in the 16 – 22%
range. This is expected for an alumino-silica material. The synthetic magnesium
aluminum silicate material had elevated a magnesium level that was to be expected. All
the bentonite clay from New Zealand had high iron compared to those from Australia and
USA. The calcium bentonite clay had a 0.2% level of sodium that was lower than the
others tested.
Table 3.1 Chemical Analysis of Bentonite Samples

Sample No Origen Si Al Ti Fe Mg Ca K Na
% % % % % % % %
2100044 New Zealand 22.5 8.6 1.4 8.6 1.4 3.0 0.2 2.4
2101267 New Zealand 23.6 9.4 1.6 9.0 1.4 1.5 0.2 1.5
2090797 New Zealand 23.9 9.5 1.6 9.0 1.5 1.4 0.3 0.2
2101268 USA 27.8 10.7 0.1 2.7 1.4 0.9 0.5 2.7
2101269 USA 27.7 10.4 0.1 4.3 1.1 1.4 0.6 1.9
2110030 USA 29.6 10.1 0.4 2.4 1.3 0.9 0.7 1.6
2110005 Japan 28.6 11.6 0.1 1.6 2.3 0.4 0.2 2.4
2110006 Japan 28.4 11.5 0.1 1.5 2.2 0.5 0.1 2.5
2110007 Japan 24.2 2.4 0.0 0.0 17.9 0.0 0.2 2.4
2101278 Australia 30.8 9.8 0.5 2.2 1.1 0.6 0.8 1.5
2110019 Australia 33.1 8.0 0.2 1.9 1.4 0.5 0.5 1.1
2110020 Australia 30.5 8.8 0.2 2.8 2.4 0.6 0.2 1.7
2110029 Australia 29.2 10.7 0.1 2.7 1.4 0.9 0.5 1.7
2110040 Australia 27.4 10.9 0.4 3.4 2.4 0.0 1.0 1.0
3.1.2 Particle size Distribution
The results of the particle size distribution graphs demonstrate the variability of
particle size distributions of bentonite clays from different locations. Figure 3.5 to Figure
3.8 show the bentonite clays from the USA have a broad and similar particle size
distribution, similar to those from Australia. The synthetic Japanese bentonite clay
2110005 has a very distinct peak around 74 microns. As with the other bentonite clays
30
studied, the New Zealand bentonite clays’ particle size distribution was broad but shifted
slightly to a coarser particle size distribution. These differences in particle size
distribution do not seem to have any noticeable effect on the swelling of the clays.
The New Zealand clays gave similar swelling indexes to the USA material and
slightly better than the Australian clays. The results show that there is no advantage using
imported bentonite clays and that the New Zealand clays could be used in subsequent
trials.
The bentonite clays particle size distributions were all within the 124 micron to
0.3 micron range, with the exception of the New Zealand clays, which had wider
distribution range. The New Zealand bentonite clays ranged from 250 microns down to
the 0.1 micron
9.00
2110029 2101269 2110030
8.00
7.00
6.00
Frequency %
5.00
4.00
3.00
2.00
1.00
0.00
00
08
70 5
49 9
35 8
24 0
17 9
12 0
87 4
62 9
44 2
31 0
22 1
15 0
11 5
0
78
50
89
1. 5
1. 4
0. 5
0. 2
0. 7
0. 6
0. 4
0. 3
0. 2
0. 2
0. 6
0. 1
0. 3
0
5.
3.
7.
2.
8.
6.
4.
.9
.2
.0
.1
.0
.5
.0
7
94
37
97
68
48
34
24
17
12
08
06
04
03
7.
5.
3.
2.
20
14
99
microns
Figure 3.5 Particle Size Distribution for United States of America Bentonite clays
31
Frequency % Frequency %
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
20
20
0.00
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
00 00
14
14
08 08
99 99
5.
5.
5 5
70 70
3.
3.
9 9
49 49
7.
7.
8 8
35 35
2.
2.
0 0
24 24
8.
8.
9 9
17 17
6.
6.
0 0
12
2110020
12 4.
4.
4 4
87 87
.9 .9
9 9
62 62
.2 .2
2 2
44 44
.0 .0
0 0
31 31
.1 .1
1 1
22
2110029
22 .0
.0 0
0 15
15 .5
.5 5
5 11
11 .0
2110006
.0 0
0
7. 7.
78 78
5. 5.
50 50
microns
32
microns
3.
2110019
3. 89
89
2. 2.
75 75
1. 1.
94
2110005
94
4 4
1. 1.
37 37
5 5
0. 0.
97 97
2 2
0. 0.
2110040
68 68
7 7
0. 0.
48 48
6 6
0. 0.
34 34
4 4
0. 0.
24 24
3 3
0. 0.
17 17
2 2
0. 0.
12
2101278
12
2 2
Figure 3.7 Particle Size Distribution for Japanese clays

0. 0.
08 08
6 6
0. 0.
06 06
1 1
0. 0.
04 04
Figure 3.6 Particle Size Distribution for Australian Bentonite clays
3 3
0. 0.
03 03
0 0
10.00
2110359 2101267 2090797 2100044
9.00
8.00
Calicium Bentonite Clay

7.00
6.00
Frequency %
5.00
4.00
3.00
2.00
1.00
0.00
70 5
49 9
35 8
24 0
17 9
12 0
87 4
62 9
44 2
31 0
22 1
15 0
11 5
0
1. 4
0. 5
0. 2
0. 7
0. 6
0. 4
0. 3
0. 2
0. 2
0. 6
0. 1
0. 3
0
00
99 8
78
50
89
1. 5
5.
3.
7.
2.
8.
6.
4.
0
.9
.2
.0
.1
.0
.5
.0
7
94
37
97
68
48
34
24
17
12
08
06
04
03
20
14
7.
5.
3.
2.
microns
Figure 3.8 Particle Size Distribution for New Zealand Bentonite clays
3.2 Mineral Powder Trials
Serpentine rock, limestone and gypsum were mixed with sulfur and bentonite
clay. (see Figure 3.9) These trials were divided into two groups, those with bentonite clay
and those without bentonite.
When tested for disintegration, the granules that incorporated serpentine rock
increased the available fine sulfur for oxidation significantly at below 250 microns, not
only in the mixtures containing bentonite clay, but also in those with only sulfur and
serpentine in the mixture.
Figure 3.10 shows that the disintegration is significantly better with the bentonite.
When serpentine rock was replaced with gypsum and limestone, there was a
significant difference in the particle size distribution of the materials retained on the sieve
after 24 hour end over end testing (see Figure 3.11 and Figure 3.12). There was little
disintegration of the solid particles containing gypsum and limestone when no bentonite
33
clay was present. However, when bentonite clay was added to the limestone, there was a
significant increase in material disintegration.
Figure 3.11 shows that when gypsum and sulfur are mixed there is no change in
the breakdown of the samples. The sulfur appeared to bind the gypsum. Serpentine is
advantageous in breaking down the sulfur particles even when no bentonite clay is used.
Following these results it was decided to use serpentine as the seed material in the plant
trials.
Figure 3.9 Mixing using Electric Drill
34
Figure 3.10 Laboratory Trials using Serpentine Rock, 24 Hour End Over End Test
35
Figure 3.11 Laboratory Trials using Limestone, 24 Hour End Over End Test
36
Figure 3.12 Laboratory Trials using Gypsum, 24 Hour End Over End Test
37
CHAPTER 4 EXPERIMENTAL PLANT TRIAL
4.1 8.6 Meter Long Drum
A plant was designed and built capable of producing granules of mixtures of

sulfur, bentonite clay and serpentine rock. The product needed to be hand screened to
produce the required size fraction of minus 5 mm and plus 3 mm samples. The plant used
a screw feeder to feed the serpentine rock, a drum of 8.6 meter long and 0.17 meter in
diameter, a pump and mixing tank. The pump was a Weldon Versamatic that had the
ability to pump viscous materials. To prevent molten sulfur from cooling and solidifying
in the pump structure, the pump was placed into a separate tank containing mineral oil,
which could be heated to 132oC by steam coils.
The first trial used only molten sulfur. The air valve assembly, which was of a
nylon construction swelled allowing air to escape when heated in the oil. The problem
was resolved moving the air valve assembly outside the heated oil. The subsequent trials
were conducted using approximately 10% bentonite clay for the sulfur mixtures. Molten
sulfur was sprayed into a falling curtain of serpentine material in the front of the rotating
drum.
4.1.1 Results
The pilot plant ran successfully in short runs. The moisture content of the
bentonite clay was an issue as water was released, resulting in the molten sulfur and
bentonite mix foaming. This happened because the bentonite clay releases the
interlamellar water from the smectites when heated to 130oC (Charleston, 1983b). One
solution to the foaming problem was to dry the bentonite clay before adding it to the
molten sulfur. However, drying adds complexity to the process. By reducing the volume
of the mixes and speeding up the mixer this foaming issue could be resolved. Several of
the trials resulted in build-ups being found in the pump (see Figure 4.1). It can be seen
that the sulfur and bentonite clay has separated. The grey material sitting on the bottom of
the pipe work had concentrated bentonite clay levels. The target was to prepare a granule
of 90% elemental sulfur / to 10% bentonite and as can be seen from Table 4.1 only 75%
was achieved in the granules.
38
Figure 4.1 Build up in the Pump
Table 4.1 Chemistry and Production 8.6 Meter Long Run
Sample S° in the 2-5 mm 2-5 mm +5 +5 mm - 2mm -2mm Pump

Spray mix fraction fraction mm Run
No (Min)
%S % Mg % So %Mg %S %Mg %S
5.4 70.8 4.2 73.0
20100513 98
3.9 74.9 4.4 75.4 10.2 49.6 15
20100514 98
20100518 88 4.5 69.3 4 68.8 11.5 42.1 9
20100524 90 4.6 70.2 5.1 69.9 8.0 57.8 9

5.5 67.1 4.5 69.9 11.0 45.0 11
20100527 90
The trials ran for 9 to 10 minutes with temperatures maintained at around 130 -
140OC in the mixer. The samples were divided into three segments, plus 5 mm (coarse),
less than 5 mm and greater than 2 mm (product) and finally the dusty material that had
39
less than 2 mm (fines). The chemistry of the 2-5 mm fraction and the plus 5 mm fraction
were similar, ranging from 3.9 to 5.5% for magnesium and 67.1 – 74.9% for elemental
sulfur. When comparing these results to the fine minus 2 mm material, the chemistry
ranged from 8.0 to 11.5 % for magnesium and 42.1 – 57.8% for elemental sulfur
indicating that the fine fractions had a higher percentage of the serpentine rock.
The granule mixtures of over 10% bentonite in the sulfur mixture after the end
over end test disintegrated more when compared to those with no bentonite. The granules
that had serpentine rock present and no bentonite in the sulfur mix did not have the same
disintegration characteristics as the initial laboratory trials when sulfur was mixed purely
with serpentine rock (Figure 4.2).
Figure 4.2 Plant Trial - 8.6 Meter Long Drum - using Serpentine Rock as Seed, 24 Hour
End Over End Test
This maybe because the serpentine rock in the laboratory trials was intimately
mixed with the sulfur, where as in the drum the sulfur was only sprayed on, limiting
40
sulfur contact only to the serpentine rock. An avenue of investigation would be to replace
the bentonite clay with fine serpentine rock to determine if the “swelling “characteristic
of the serpentine rock has a similar effect.
4.1.2 Processing Issues
There was a tendency for the nozzles to block during granulation process. This
inhibited the fan spray pattern and caused dusty granules. This also caused molten sulfur
to dribble out allowing large quantities of molten sulfur build-up on the inside of the
drum.
4.2 3 Meter Long Drum – One Mixing Tank
The 8.6 meter long drum was replaced with a 3 meter long and 1.2 meter diameter
drum, allowing better granulation by:
a) Better control of curtain material (seed material).
b) Better sulfur spray pattern geometry and
c) Better visibility of the process.
It was supposed that the different configuration would enable better contact
between the serpentine rock and sulfur / bentonite mix. Several runs were conducted
using 0, 5 and 10% bentonite clay. The pumps ran at approximately two bar air pressure.
The issue of the small spray nozzles blocking was overcome by increasing the nozzle
size. The larger drum doubled the period the plant could run. See Table 4.2 for the
process data.
Table 4.2 Process Data - 3 Meter Long Drum – One Mixing Tank
Sample Bentonite in Pump Mixing Tank Mixing Tank Stirrer

Sulfur Run Start of Run End of Run RPM
(Min) Temperature Temperature oC
o
C
20100914 0% 11 131 132 610
20100916 5% 8 124 128 706
20100922 10% 19 138 132 706
20101019 10% 11 134 136 460
41
4.2.1 Serpentine Seed Material
The results shown in Figure 4.3 confirmed the trend presented earlier showing an
increase in the disintegration of the granules on the 24 hour end over end disintegration
test as the % of bentonite clay is increased. There is a larger % fraction in the less than
250 micron particles when the 10% was used. The final three runs showed relative
contingency. There was still no indication of the earlier laboratory data showing
breakdown improvements when using serpentine rock.
Figure 4.3 Laboratory Results “Short Drum– One mixing Tank” 24 Hour End Over End
Test
4.2.2 Phosphate Rock Seed Material
Several more tests were conducted using the same plant configuration but using
phosphate rock as the initial curtain material. The production data from the trials showed
that the temperature was kept at around 124 to 134 oC. Trial periods were still restricted
by the volume of sulfur in the tank. The time that the process ran varied from 7 to 24
minutes. The large variation in the periods that the plant was able to run was due to a
variety of issues such as pump failures, seed supply and the volume of liquid in the tank.
Table 4.3 shows the process data collected from the trials.
42
Table 4.3 Process Data, 3 Meters Long Drum, One mixing Tank, Phosphate Rock Seed
Material
Sample Pump Time from Start of End of Stirrer Stirrer

Run addition of Run oC Run oC Speed Speed
(min) Bentonite Mixing Spraying
clay to reach (rev/min) (rev/min)
129oC
20101028a 17 Not recorded 124 128 561 560
20101028b 17 Not recorded 130 130 312 312
20101102a 12 Not recorded 134 126 312 321
20101102b 7 24 132 133 312 312
20101111a 15 Not recorded 131 129 657 363
20101111b 24 50 130 127 657 512
20101111c 14 45 129 132 657 512
20101116a 13 Not recorded 133 134 Not recorded 260
20101116b 24 72 133 126 610 412

20101116c 14 63 130 118 660 412
20101124a 22 57 132 129 650 312
The phosphate rock produced superior granules and produced less dust in the process
than the serpentine rock. The elemental sulfur in the 5 mm to 2 mm granules was around
56.1-78.7% S. The results in Table 4.4 show phosphate levels of 1.6 to- 5.5 % P
indicating a 21 to 54% phosphate rock usage
Table 4.4 Chemical Results - Short Drum - 3m long 1.2m ø Drum – One mixing tank
Phosphate Rock Seed Material
Process Run 2-5 mm 2-5 mm Spray mix
Granules granules
%S %P %S
20101028a 69.2 1.8 81.4
20101028b 68.4 3.2 81.4
20101111a 60.9 4.6 89.4
20101111b 63.0 4.5 91.3
20101111c 56.1 5.5 85.9
20101116a 66.5 3.9 91.8
20101116b 67.2 3.9 92.0
20101116c 64.1 4.5 92.9
20101124a 78.7 1.6 91.6
43
Figure 4.4 shows the process data over a seven hour period. It shows the time to
return the temperature back to 129 - 131oC was approximately 60 minutes from the time
the bentonite clay was added to the molten elemental sulfur. This gave an indication that
more heat needed to be added to the process to get the temperature back to a suitable
level, as well as a need for a two tank system for mixing.
Figure 4.4 Plant 7 Hour Run - 4 Mixes.
The mixing of the bentonite clay was modified by increasing the speed of the
mixer from 400 to 650 revolutions per minute. Increasing the speed of the mixer enabled
the moisture to escape more rapidly, however, the mixer needed to be slowed down when
the pump was running to enable the bentonite clay to be sprayed into the drum. Changing
to phosphate rock as the seed material gave better granules and produced less dust.
44
Being restricted to one mixer made it impossible to run a trial for any longer than
25 minutes. The screen was successful, producing good granules of consistent size. It was
concluded that a twin drum system nneeded
eeded to be developed. This would allow mixing in
one drum while pumping out the other. A conveyer system to feed the back of the drum
was also needed.
Figure 4.5 shows the fractions % of material being retained on a 250 micron sieve
and also those passing the 250 micron sieve. The final 5 production runs showed relative
consistency for the amount of sulfur present in the granules.
Figure 4.5 Plant Trial - Short Drum - One Mixing Tank - Phosphate Rock as Seed
Particles Passing the 250 Micron Sieve After 24 Hour End Over End Test
45
The amount of material retained and passing the 250 micron sieve also showed
consistent results. None of the production runs meet the target of 90% of the particles
passing the 250 micron sieve after the 24 hour end over end test.
The majority of the sulfur was below the 250 microns fraction. Table 4.5 shows
that the sulfur concentrations of the larger particles were very low (around 15%) This is
due to the larger particles of the phosphate rock being predominately present in these
fractions.
Table 4.5 Elemental Sulfur Results on Fractions Retained on Sieves for Plant Trial – 3
Meter Long Drum - One Mixing Tank- Phosphate Rock Seed Material
Elemental Sulfur (%) Retained on Sieves After 24 Hour Disintegration

Mix ID Testing
+ 2.0 + 1.0 + 500 + 250 + 150 + 75 - 75
mm mm µm µm µm µm µm
20101028a 43.5 44.5 46.6 64 77.1 86 57.1
20101102a 46.7 47.2 47.1 50.2 61 81.8 70.4
20101111c 15.2 17.5 53.3 61.2 52.6 63.1 64.3
20101116a 14.7 44.5 62.1 68.3 63.7 77 66.4
20101116b 14.6 19.9 52.3 70 60.6 74.1 67.7
20101116c 15.6 20.5 56.2 68.5 55.6 74.2 64.1
4.2.3 Ammonium Sulfate Seed Material
Ammonium sulfate fertilizer is manufactured by reacting concentrated sulfuric

acid and ammonia (NH4) under pressure. This can produces dusty crystals of ammonium
sulfate. The objective of this section of the research was to review the effect of spraying a
mixture of bentonite clay and molten sulfur onto dusty ammonium sulfate to evaluate the
effect on the “dustiness” of fine materials.
A sulfur bentonite clay molten mix of 96.9% sulfur was sprayed into a mixture of
dusty ammonium sulfate (see Table 4.6) with a chemistry of 20.9% N, 24.3% S The final
product (-5 mm to + 2 mm) were granules of 69.9% sulfur.
46
Table 4.6 Fine Ammonium Sulfate Fertilizer
Fraction Passing Sieve

4 mm 2 mm 1 mm 0.5 mm 0.25 mm 0.15 mm 0.075 mm
100 73.2 23 10 1.4 0.2 0.1
The discharge from the drum was reintroduced to the entrance of the drum and
reprocessed. At each subsequent discharge subsamples were taken and screened though a
4 mm and a 2 mm sieve and the material retained on the 2 mm sieve was used for testing.
Table 4.7 shows the comparison of granular degradation. It can be seen that as we
increase the passes though the plant the granules get stronger while the level of nitrogen
drops.
Table 4.7 Sulfate of Ammonia Chemistry and Physical Data
Mix Type % Ammonium % Granular Degradation Granule Strength

sulfate Abrasion Test mean (kg)
1st pass 70.7 7.1 2.6 kg
2nd pass 62.5 7.1 3.4 kg
3rd pass 48.2 5.9 3.8 kg
4th pass 39.8 4.9 3.9 kg
5th pass 37.3 4.9 4.0 kg
6th pass 34.7 4.7 4.1 kg
7th pass 29.3 3.2 4.7 kg
The samples were passed through a 4 mm sieve and retained on a 2 mm sieve. As

can be seen from the Figure 4.6 to Figure 4.8, when the ammonium sulfate was initially
sent through the drum there were particles of ammonium sulfate still visible. Subsequent
passes through the drum gave particles of increasing density and better shape. The use of
the sulfur bentonite mixes increased the size of the ammonium sulfate by amalgamation,
using sulfur as the bonding material. The results showed that there are definite
advantages coating ammonium sulfate with sulfur. It is beneficial to have sulfate which is
a readily available sulfur combined with a medium release sulfur in the form of elemental
sulfur. By altering the ratio of bentonite clay to sulfur, it is possible to alter the sulfur
release.
47
Figure 4.6 Ammonium Sulfate before Processing
Figure 4.7 Ammonium Sulfate after Processing - Second Pass
48
Figure 4.8 Ammonium Sulfate after Processing - Seventh Pass
4.3 3 Meter Long Drum – Two Mixing Tanks
The information and data collected from the previous section were used to rebuild
and modify the pilot plant, moving from the batch to continuous process. The
modification replaced the single 0.175 m3 mixing tank with two larger 2 m3 mixing tanks.
This allowed the bentonite clay to be mixed with liquid elemental sulfur in the primary
mixing tank while the secondary premixed mixing tank was pumped and sprayed into the
falling curtain of seed material. A conveyor was also added which allowed the seed
material to be returned to the rear of the drum. It was believed that this configuration
would allow for eight hour continuous operation.
49
Over a four month period 20 trials were conducted to determine optimal
production parameters. As the trials progressed, modifications and improvements to the
plant were identified and implemented.
The drum moved anti-clockwise causing the falling curtain of seed material. As
the molten sulfur / bentonite mixture was sprayed into this curtain its temperature
dropped. It was thought that with the correct amount of spray to falling curtain material,
the drum would be protected from build-up.
4.3.1 Mixing
As was identified in previous phases of the project, a vortex was required to allow
the steam to escape from the mixture. Initially, the volumes were too large so the mixing
of bentonite clay was improved by reducing the amount of sulfur. Mixing a lower volume
of sulfur in the mixing drum formed a better mixing vortex as shown in Figure 4.9.
Figure 4.9 Vortex Formed in the Mixing Tanks
50
The time to empty the mixing tank was 30 minutes. It took 15 minutes to mix the
bentonite clay into the molten sulfur. This gave a 15 minute gap between mixing and
pumping. This was adequate time for the process to run continuously.
4.3.2 Seed materials
The initial runs used phosphate rock, followed by three runs using formed sulfur
as the seed. The formed sulfur was damp (the process of manufacturing a fine formed
sulfur uses the principle of spraying liquid sulfur into a bath of water then draining the
water off). This damp material didn’t form a good curtain; however it had an advantage
because the sprayed liquid did not stick to the inside of the drum. This was due to a layer
of damp sulfur that coated the inside of the drum.
On one of the runs the coarse granules and fines were recycled as seed material,
but it was found that due to the coarseness of the seed material, the spray was not
interacting with the seed material in the curtain causing build-up inside the drum.
The main finding was that the seed material needed to be the correct fineness, if
there was too much coarse material present, the sprays would penetrate through the
falling curtain of seed material and build up on the side of the drum.
4.3.3 Sprays
The initial trials found that the number of nozzles in operation needed to be taken
into consideration, or the pump capacity would be exceeded resulting in a lack of
pressure and subsequently poor spray patterns. This meant that sulfur would fall short of
product curtain and form build up on the drum sides. Nozzles tended to clog due to the
sulfur solidifying at the orifice. Clogging was eliminated by covering each nozzle with
rock wool to maintain the desired temperature, enabling a better flow of the molten
sulfur/bentonite clay mixture. Once the trial started, the rock wool was removed. Due to
wear of the bentonite clay against the impeller over several runs, one of the pumps lost
pressure causing a poor spray pattern. During a 30 minute run the pumps were alternated
to assess the possible problems. The only issue noted was the reduced spray pressure.
However there was no noticeable change in the material discharged by either pump 1 or
51
2. As can be seen from Figure 4.10 there is very little build up. It appears that the correct
amount of sulfur to seed material is being processed.
Figure 4.10 Spray into Granulating Drum
4.3.4 Drum
The speed of the drum was increased from 4½ revolutions per minute to 5½
revolutions per minute. The faster speed of the drum moved the product curtain closer to
the spray. However, when the drum speed was increased from 5½ revolutions per minute
to six revolutions per minute no effect was noticed.
After several runs the curtain seed material became more granular, thus less of it
was carried up by each of the lifters in the drum, resulting in a poor curtain. The more
52
granular the seed material became the more the spray penetrated through the curtain and
built up on the internal surface of the drum. A modification was made to the number of
lifters increasing the number of lifters from 8 to 16 as well as also placing a diverter plate
down the center of the drum. This help to facilitate a more consistent seed material
curtain.
4.3.5 Screen
As the trials developed it became apparent the screen was undersized, (initially
had 5 mm and 3 mm holes as the screen size) and several modifications were trialed. In
one modification, the vibration was increased on the screen. However, too much product
passed over the screen too quickly and, therefore, was not screened properly. The angle
of screen was increased but the material continued to move across the screen too rapidly.
4.3.6 Temperature Profile
The side of the drum was measured using an infra read temperature camera (See
Figure 4.11) and was recorded over a 100 minute period (Figure 4.12). After about 30
minutes the temperature stabilized around 50oC, then increased to 60oC. Towards the end
of the drum the temperature dropped to around 40oC due to the introduction of colder
seed material. The temperature of the discharge (6 mm to 3 mm granules) also dropped,
in sympathy
Figure 4.11 Infra Red Measurement Side of Drum
53
Figure 4.12 Temperature of Drum over 100 Minutes
4.3.7 Laboratory Results
From Figure 4.13 it is seen that as the sulfur levels increased so that levels of 90%
sulfur were achieved. However the target of 90 % passing 250 microns was not meet. The
average result was 30% the 250 micron sieve
As can be seen from when the percentage of sulfur in the granules increases, the sulfur
component in the material retained on the sieve, after the 24 hour disintegration test, also
increased in the finer sieves. (Table 4.8)
4.3.8 Molten Sulfur Mixes - Granule Strength & Granular Degradation
Table 4.9 shows that as the sulfur granules that have low particle crushing
strength showed relatively high granular degradation in the abrasion test (up to 26%). The
granules with higher crushing strengths had lower granular degradation in the abrasion
test.
54
Figure 4.13 Twin Tank Sieve Analysis
55
Table 4.8 Sulfur Chemistry of Sieve Retained Material after 24 End Over End Testing
Elemental Sulfur (%) for Sieve Size

% S in + 2.0 + 1.0 + 500 + 250 + 150 + 75 - 75
Mix ID granules mm mm µm µm µm µm µm
20110509a 45.0 25.5 48.2 43.1 59.4 62.5
20110419a 46.0 43.5 44.5 46.6 64 77.1 86 57.1
20110512a 49.0 48.4 42.5 55.6 67.6
20110429a 49.8 87.3 26.7 36.5 58.7 71.2 86.8 60.8
20110511a 51.9
29.5 51.1 46.8 62.3 64.9
20110517a 52.7 55.6 58.7 48.6 55.7 64.4
20110513a 52.8 38.9 54.8 48.8 60.9 62.6
20110511b 54.6 37.3 52.2 47.4 63.1 67.8
20110511c 55.0 51.4 56.9 48 64 67.9
20110720a 80.3 83.1 81.4 83 83.2 79.5 86.4 71.9
20110725b 84.0 87.1 87.9 87 85.3 91.4 68.9
20110804a 88.1 90 92.5 94.2 96.7 61.4
20110809a 88.2 91.3 92.3 93.8 96.5 63.1
20110810a 88.7 92.2 93.2 94.4 96.5 69.2
20110916a 91.7 79.7 92.2 96 96.4 97.3 98 68.9
20110902a 93.4 96.8 97.2 97.2 97.8 98.2 68.3
Table 4.9 Molten Sulfur Mixes - Granule Strength & Granular Degradation
S % Granular Degradation
Code % Abrasion Test Granule Strength mean (kg)
20110509a 45.0 29.6 2.0
20110509b 49.0 20.5 2.2
20110511a 51.9 19.2 2.3
20110511b 54.6 17.2 2.3
20110511c 55.0 17.1 2.1
20110512a 49.0 25.5 1.8
20110517a 52.7 26.0 1.9
20110720a 80.3 11.6 2.3
20110725b 84.0 6.1 2.9
20110802b 87.1 5.6 2.8
20110804a 88.1 4.9 3.5
20110809a 88.2 3.7 4.5
20110810a 88.7 2.4 4.4
56
4.3.9 Scan Electron Microscopy
The samples that were subjected to scanning electron microscopy all show that
the phosphate rock particles were encapsulated by the molten sulfur See Figure 4.14.
Figure 4.15 shows EDAX results that confirm that the gray regions were phosphate rock
as the detectable elements were predominately Ca and P which make up the calcium
fluorapatite (Ca5(PO4)3F). The pale matrix surrounding the particles was confirmed by
EDAX to be sulfur (see Figure 4.16).
Figure 4.14 Scanning Electron Micrograph of the Surface of a Sulfur Bentonite Granule
57
Figure 4.15 EDAX on Gray Particles
58
Figure 4.16 EDAX on the White Particles
59
Figure 4.17 shows the surface of the granules where the sulfur has melted into the
surface giving a pitted effect. This surface is formed in the granulation drum when the
molten sulfur combines with the solid material in the falling curtain. This pitted surface
structure gives greater surface area increasing the area available to interact with the
moisture, escalating the rate of particle disintegration.
Figure 4.17 Surface of Sulfur Granules Resistivity
60
4.4 Resistivity
Table 4.10 shows the resistivity results of several granulated material. It can be
seen that resistivity is low when serpentine rock was used as the seed material compared
to phosphate rock is used as the seed material. The resistivity is greater than 1011ohm cm.
Resistivity is always high in phosphate rock and the solid prilled sulfur as seed material.
Resistivity is higher than 1011 ohm cm whether 11% or 60 % phosphate rock is present in
the granulated material.
Table 4.10 Resistivity of Prilled Sulfur Materials
So Seed Material %P Resistivity (ohm cm) x 108 % Phosphate rock

67 Serpentine Rock 1
69 Serpentine Rock <1
71 Serpentine Rock <1
80 Serpentine Rock 0.5
Serpentine Rock 0.5
45 Phosphate Rock 7.1 1000 plus 61%
92 Solid Prilled sulfur 1000 plus
It is recommended that serpentine rock should be used for seed material due it
reduced explosive risk when producing prilled material using methods described in this
thesis.
61
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS
From the studies to date it, would appear that serpentine rock by itself has some
advantages when mixed with sulfur. The tests indicate serpentine rock reduces resistivity
and assists in the breakdown of elemental sulfur prills. When bentonite clay was added to
the mixture, the resistivity and breakdown characteristics did not change significantly.
Only one source of serpentine rock was trialed and further work should be undertaken to
see if similar effects can be replicated using serpentine rocks from different sources.
Different seed materials showed different characteristics when sprayed and or

mixed with molten elemental sulfur. Research of other materials such as dolomite,
limestone and gypsum, as seed materials should be undertaken, to investigate if a similar
decrease in resistivity and increase of speed of breakdown in the sulfur granules can be
replicated.
Only one bentonite clay was used in the plant phase of the trialing. It is likely that
other bentonite clays will react in differently. Different bentonite clays should be
investigated during future plant trials to determine if other bentonite clays have better
breakdown characteristics.
The final design using two tanks for mixing enabled the process to run for a
longer period of time, giving the ability to batch mix the bentonite and sulfur together.
The size and construction of the tanks allowed for large volumes of mixing materials for
forming a vortex that allowed the steam to escape. The pumps were located in the tanks
restricting the depth and surface area of the vortex thus preventing some of the steam
escaping. An external pump system would improve the mixing of the sulfur and the
bentonite clay by allowing a deeper vortex to be formed.
The bentonite clay mixed with molten elemental sulfur has the tendency to settle
in the bottom of the pipes and tanks causing blockages if not kept in suspension. One of
the ways to overcome the settling of bentonite in the pipes would be to loop the liquid
62
sulfur bentonite spraying system. This would allow the mixture to be returned to the
mixing tanks at the end of a run. It would also provide the ability to pump straight clean
molten sulfur around the system, flushing the bentonite out of the pipe work.
The maximum time that the plant ran was 180 minutes. A longer plant run time is
needed to determine the temperature profile of the plant. For this to happen several
modifications are need. These being; conveyor belt for the return seed material, addition
of a crusher, and automation of plant operations.
One aspect of the process took screened seed material from the front of the drum
and transferred this material to the bin at the rear of the drum. This bin was fed via a time
consuming front end loader operation. This process needed to be modified by feeding the
screened seed material from the exit of the drum directly back to the feed bin via a
conveyer belt.
The key to good granulation is to have the correct amount of seed material falling
as a curtain continually within the drum. Thus the material balance needed to be correct.
Material in equals material out. When the plant produced too many large granules (which
were sent to waste) there was a net decrease of material in the system. This oversized
material needed to be crushed to a suitable size for use as seed material. Therefore a
crusher would enable the material balance to be maintained.
The plant was not very automated and used several operators as well as some
general workers to manually handle the product. Automation of the plant, addition of
bentonite, sulfur and seed materials would help to increase the speed and allow for better
consistency of the final sulfur bentonite prills.
63
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PRODUCTION OF ELEMENTAL SULFUR AND BENTONITE CLAY

GRANULES IN A ROTARY DRUM

Biological oxidation of sulfur granules is a critical component in elemental sulfur

ABSTRACT ....................................................................................................................... iii

TABLE OF FIGURES ........................................................................................................ v

Chapter 1 INTRODUCTION .......................................................................................... 1

Chapter 2 METHODOLOGY ....................................................................................... 13

Chapter 3 EXPERIMENTAL LABORATORY TRIALS............................................. 27

Chapter 4 EXPERIMENTAL PLANT TRIAL ............................................................. 38

Chapter 5 CONCLUSIONS AND RECOMMENDATIONS ....................................... 62

Table 1.1 Project Requirements .......................................................................................... 1

Table 1.1 Project Requirements

% Passing the sieve

The initial development of sulfur fertilizer was accomplished by mixing different

1.1 Sulfur Source

1.1.1 Frasch Method Extraction of Elemental Sulfur

Figure 1.1 World Production of Sulfur in 2011 Source (Survey 2012)

1.1.2 Petrochemical Extraction of Elemental Sulfur

2H2S + SO2 3S + 2H2O

1.1.3 Sulfur Chemistry.

Sulfur is found in several forms, orthorhombic, monoclinic, amorphous and

Figure 1.2 Viscosity of Sulfur (Fanelli 1946)

1.1.4 Hazards of Sulfur

1.1.5 Dust Explosions

1.1.6 Elector-Static Electricity

1.2 Sulfur fertilizer

Table 1.2 Some Current Sulfur Fertilizers Used

Sulfur Formula %S Cost effective Low fire / Plant Readily

The choice of fertilizer is determined by cost, availability and agronomical

1.3 Oxidation /Agronomic Availability Sulfur Fertilizers

Elemental sulfur must be oxidized to sulfate to be biologically available for

2.1 Raw Materials

2.1.1 Bentonite Clay

Table 2.1 Bentonite Clays

Code Description Location

2.1.3 Serpentine Rock

2.1.4 Phosphate Rock

2.2 Mineral Powder Trials

2.3 Plant Trials

2.3.1 8.6 Meter Long Drum

Figure 2.2 8.6 Meter Long Drum

2.3.2 3 Meter Long Drum – One Mixing Tank

2.3.3 3 Meter Long Drum – Two Mixing Tanks

2.4.1 Temperature Measurements

Temperature measurements were made using a FLIR i5 Thermal imaging camera.

2.4.2 24 Hour End Over End

This test gives an indication of the disintegration characteristics of the final

Figure 2.6 End over End Apparatus

Figure 2.7 Swell Testing

Scale Spring balance

Figure 2.8 Schematic of the Granule Strength Test Apparatus

2.4.5 Abrasion Resistance Testing

2.4.6 Particle Size Analysis

2.4.7 Bulk Resistivities

Figure 2.11 Hewlett Packard 34401A Multimeter

2.5.1 Elemental Sulfur Analysis

Elemental Sulfur was determined by converting the entire elemental sulfur to

2.5.2 Magnesium Analysis

2.5.3 Phosphate Analysis

2.5.4 Ammonium Sulfate Analysis