Hydrometallurgia A Presion

PRESSURE HYDROMETALLURGY 2012
42nd Annual Hydrometallurgy Meeting
Editors
M.J. Collins, D. Filippou, J.R. Harlamovs, E. Peek
Organized by
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PROCEEDINGS OF THE 51ST CONFERENCE OF METALLURGISTS,

HELD WITH PRESSURE HYDROMETALLURGY 2012,
42ND ANNUAL HYDROMETALLURGY MEETING,
SEPTEMBER 30 TO OCTOBER 3, 2012, NIAGARA FALLS, ONTARIO, CANADA

Editors
M.J. Collins
Sherritt International
Fort Saskatchewan,
Canada
D. Filippou
Rio Tinto Iron & Titanium
Sorel-Tracy, Canada
J.R. Harlamovs
Teck Resources
Trail, Canada
E. Peek
Molycorp
Peterborough, Canada
Symposium Organized by the Hydrometallurgy Section of the Metallurgy and Materials Society of the
Canadian Institute of Mining, Metallurgy and Petroleum
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Foreword
The Second International Symposium on Pressure Hydrometallurgy is organized by the
Hydrometallurgy Section of the Metallurgy and Materials Society of the Canadian Institute of Mining,
Metallurgy and Petroleum (CIM) and constitutes its 42nd Annual Hydrometallurgy Meeting. A primary goal
of these meetings is to bring together scientists and engineers representing metal producers, equipment
suppliers, engineering firms, test laboratories and academia from around the world to share knowledge and
exchange ideas. Pressure Hydrometallurgy 2012 builds on the foundations established by the first Pressure
Hydrometallurgy conference, held in Banff in 2004.
Although pressure hydrometallurgy is becoming an increasingly mature and conventional
technology, it remains an exciting area of both study and application. Processes operating at high
temperature and under pressure enjoy fast kinetics, enhanced solubilities of reagent gases, and improved
liquid-solid separation characteristics, purity of product streams and stability of residues. Pressure vessels
have been commercially used for the extraction of aluminum, nickel, cobalt, zinc, uranium and copper, for
the oxidation of refractory gold feeds, and for the purification and recovery of various metals and metal byproducts. New construction materials and autoclave design improvements continue to extend the
application of these vessels, in an effort to keep up with innovative new processes being developed at the
laboratory and pilot plant stage. The scope of the present symposium embraces all of these aspects. The
manuscripts provided in these proceedings describe a wide range of commercial applications covering the
above topics, as well as test programs and scoping studies in areas that have yet to be realized on a
commercial scale. The future of this field remains bright.
M.J. Collins
D. Filippou
J.R. Harlamovs
E. Peek
Editors
Niagara Falls, Ontario, Canada

October 2012
Editors Biographies
Mike Collins received a B.Sc. degree in Chemistry from the University of Victoria in 1977. After
employment with the Defense Research Establishment Pacific and Royal Roads Military College in
Victoria, B.C., he attended McMaster University in Hamilton, Ontario, where he studied the polyatomic
cations of sulphur, selenium and tellurium in super-acid systems and received a Ph.D. in Chemistry in 1984.
A visiting fellowship at the National Research Council in Ottawa followed, for studies in solid-state NMR
spectroscopy of main group elements. In 1985, Mike joined Sherritt Gordon Mines Ltd. in Fort
Saskatchewan, Alberta, becoming manager of the Sherritt Research group in 1997. Shortly thereafter, he
became Manager, Research for the newly formed Metallurgical Technologies Division of Dynatec
Corporation. Additional roles with Dynatec included Senior Consultant, and Manager, Research and
Analytical Services, prior to the acquisition of Dynatec by Sherritt International Corp. in 2007. Mike is
currently Director, Process Development within the Sherritt Technologies Division. Work at Sherritt and
Dynatec has primarily involved laboratory and pilot plant testing in the field of pressure hydrometallurgy.
Author of more than 75 technical publications and holder of eight patents, Mike is a former chair of the
Hydrometallurgy Section of the Metallurgy and Materials Society of CIM and was co-chair of Pressure
Hydrometallurgy 2004. He received the Sherritt Hydrometallurgy Award in 2005.
Dimitrios Filippou obtained a Dipl.Eng. degree in Mining and Metallurgical Engineering from the
National Technical University of Athens (Greece) in 1988, and a Ph.D. degree in Metallurgical Engineering
from McGill University (Canada) in 1994. He has extensive experience in zinc, iron, arsenic and titanium
hydrometallurgy in sulphate and chloride media. Since 2003, he works for Rio Tinto Iron and Titanium at
the companys Technology Centre in Sorel-Tracy, Quebec, where he currently holds the position of
Metallurgist, TiO2 Products. His fields of interest include R&D project management, process scale-up and
costing, and Life Cycle Assessment. He has authored several papers and in 2010, he was awarded a TMS
Best Paper Award for a publication in the JOM journal. Since 2008, he is the Secretary of the
Hydrometallurgy Section of the Metallurgy and Materials Society of CIM. He is also a licensed engineer.
Juris Harlamovs was brought up and educated in England, obtaining a B.Sc. in chemistry and
going on to do a Ph.D. in zinc solvent extraction at the University of Birmingham. In 1980, he joined Anglo
American Research Laboratories as a Research Metallurgist. Juris then joined Cominco Research, (now
Applied Research and Technology, Teck Metals Ltd.) as a Senior Research Metallurgist and has been a
Group Leader, Chemistry and Environment and a Principal Hydrometallurgist. Juris has broad interests in
hydrometallurgy especially in copper, zinc, nickel, specialty metals and their associated impurities; but his
first love still is solvent extraction. He is currently Section Leader, Copper and Zinc. This section provides
technical metallurgical back-up for the various Teck Metals mines and smelter.
Edgar Peek received a M.Sc. (1991) and Ph.D. (1996) degree in Raw Materials Technology from
the Department of Mining and Petroleum Engineering of the Delft University of Technology in The
Netherlands. Raw Materials Technology is the treatment of primary and secondary raw materials using a
combination of Extractive Metallurgy, Mineral Processing and Recycling skills. In 1995 he joined the
Research and Development group of Falconbridge Limited in Sudbury, Ontario to work on the laboratory
and pilot plant aspects of nickel laterite flow sheet development. Key areas of focus were high pressure
pumping, solid-liquid separation, heat exchange and autoclave operation. In 1999 Edgar joined the Projects
& Engineering group located at the Kvaerner/Hatch offices in Toronto to work on the joint
hydrometallurgical and pyrometallurgical scoping study for the Koniambo laterite ore deposit. Areas of
responsibility were the overall site water balance and operating cost model. From 2002 to 2006 he was
seconded to the Technical Services group of the Falconbridge Nikkelverk AS refinery in Kristiansand,
Norway. He worked on medium-term plant support or Six Sigma stage gate projects in the areas of tailings
disposal, solvent extraction, cementation, filtration and precious metal processing. In 2006 Xstrata Plc.
acquired Falconbridge Ltd. and Edgar moved back to Sudbury, Ontario to become the Manager of
Extractive Metallurgy at the newly created Xstrata Process Support (XPS). XPS provides commercial
consulting and metallurgical test work services to the mining and minerals industry. While Edgar focused
his time on topics such as nickel pig iron, process engineering support (Aker Solutions/Jacobs Engineering)
and business development, the Extractive Metallurgy team centred on primarily pyrometallurgical services.
vii
Since 2011 Edgar is Manager of Process Development, Rare Metals Division, Neo Performance Materials
(recently merged into Molycorp Inc.) based in Peterborough, Ontario. Author of more than 20 technical
publications and holder of one patent, Edgar is the former Treasurer and current Chair of the
Hydrometallurgy Section of the Metallurgy and Materials Society of CIM and was the co-chair of Chloride
Metallurgy 2002.
viii
Table of Contents
Foreword ......................................................................................................................................................... v
Editors Biographies ..................................................................................................................................... vii
REFRACTORY GOLD
Design of the AGA Brasil Refractory Gold Pressure Oxidation Plant ............................................................3
M. Collins, K. Buban, M. Faris, I. Masters and M. Antonio
The Mobilization and Potential In-autoclave Recovery of Gold During Pressure Oxidation
and Leaching of Auriferous Sulfide Materials............................................................................................... 15
G.P. Demopoulos, J.-C. Parisien-La Salle and D. Blais
Kinetics of the CESL Gold Process ............................................................................................................... 31
E. Asselin, P. Sauve and H. Salomon-de-Friedberg
Enhancing CIL Gold Extraction by Hard Paraffin Wax Blanking of Double Refractory Ore
Pre- Or Post-pressure Oxidation (POX) ........................................................................................................ 41
G. Van Weert, J. Jiang, O. Wang and Y. Choi
Alkaline Pressure Oxidation of Pyrite in the Presence of Silica: A Surface Study ........................................ 53
A. Dani and V.G. Papangelakis
Gold Extraction from Pyritic Ores Through Simultaneous Pressure Leaching/Oxidation ............................. 63
J.L. Valenzuela G., L.S. Quiroz C., J.R. Parga T., P.J. Valenzuela G. and P. Guerrero G.
MODELING
Simulating the Iron(III) Precipitation Rate During Medium Temperature Chalcopyrite Oxidation in
Batch and Continuous Autoclaves ................................................................................................................. 75
J.D.T. Steyl
Use of Numerical Methods, Scale-up and Lab Tests in the Design of HPAL Autoclaves ............................ 91
J. Jung, W. Keller and A. Zucht
Chemical Modeling in Pressure Hydrometallurgy Using OLI ..................................................................... 105
V.G. Papangelakis, A. Anderko, G. Moldoveanu, M. Carlos and G. Azimi
PROCESS DEVELOPMENT
Influence of Iron on the Complexation and Oxidation of Quebracho: An Investigation on
the Stability of Sulfur Dispersing Agent ...................................................................................................... 121
L. Tong, D. Dreisinger, B. Klein and J. Li
Advances in the Use of Polytetrafluoroethylene During Medium Temperature Pressure Oxidation
of Chalcopyrite ............................................................................................................................................ 137
E. Guerra
ix
Hydrothermal Production of Gallium Oxide ............................................................................................... 143

L. Becze, E. Peek, C.J. Ferron, G. Evans and K. Reading
Synthesisof Li2TiO3 Powders by a Hydrothermal Process .......................................................................... 153
Y.J. Li, L. Li, C. Xu, V.G. Papangelakis and L. Kong
Effects of Hydrothermal Processing on the Crystallinity and Morphology of the Precursor
of In2O3 ....................................................................................................................................................... 163
Y. Li, Z. Liu, Q. Li, C. Wu and Z. Liu
Pressure Leaching of Alkali-pretreated Limonitic Laterite Ore in Nitric Acid ............................................ 175
C. Wang, Y. Zhang and Z. Xu
Low-temperature Pressure Leaching Kinetics of Zinc Sulphide Concentrate ............................................. 187
Z. Xu, F. Guo and C. Wang
Treatment of Thompson Copper/Arsenic Residue ....................................................................................... 199
T. Xue, A. Singhal, I. Mihaylov and D. Wrana
The Co-processing of Nickel Sulphide and Laterite Materials Using Low Oxygen Pressures .................... 211
R. McDonald, M. Rodriguez, J. Li, D. Robinson, M. Jackson and T. Hosken
COPPER
The Mechanism of Chalcopyrite Leaching in Acidic Ferric/Ferrous Sulfate Media in the Presence
of Silver-enhanced Pyrite ............................................................................................................................ 229
G. Nazari, D.G. Dixon and D.B. Dreisinger
Reduction Kinetics of Fe(III) on Chalcopyrite Up to 110 C ...................................................................... 241
G.K. Yue and E. Asselin
Hydrothermal Purification and Enrichment of Chilean Copper Concentrates. The Behavior of
Bornite, Covellite, Pyrite and Enargite ........................................................................................................ 257
G. Fuentes and J. Vials
Uniform Corrosion of Titanium Under Medium Temperature Chalcopyrite Concentrate
Leaching Conditions .................................................................................................................................... 269
J. Liu, E. Asselin and A. Alfantazi
Arsenic Stability and Characterization of CESL Process Residues ............................................................. 281
R. Bruce, K. Mayhew, G.P. Demopoulos and A. Heidel
Chalcopyrite: Bioleaching Versus Pressure Hydrometallurgy..................................................................... 295
F. Habashi
ZINC
Leach Residue Filtration at the Hudbay Zinc Pressure Leach Plant ............................................................ 305
S. Shairp
Copper and Cadmium Removal from Zinc Sulphate Solution ..................................................................... 313
S.M. Rebelo and R.G. Helberg
EQUIPMENT DESIGN
Stress Analysis of Brick Lined Autoclaves ................................................................................................. 327
K. Brooks
Effect of Pressure in Leaching of Low Grade Sulphide Ore at Ambient Temperature Development
of Hydrostatic Pressure Reactor .................................................................................................................. 335
M.J. Latva-Kokko and T.J. Riihimki
Direct Contact Heat Transfer Between Steam and Aqueous Slurries .......................................................... 343
D.T. White
Refractory Lining Design for Pressure Oxidation Autoclaves..................................................................... 367
I. Donohue, E. Barrette and M. Pearson
Advanced Control of Pressure Hydrometallurgical Plants .......................................................................... 379
R.K. Jonas
The Flash Recycle System for the Cooling of Autoclaves Process Design and Operation .......................... 391
F. Crundwell and N. Steenekamp
Special Design Considerations for Pressure Hydrometallurgy Pilot Plants ................................................. 401
P. Martin
Application of Tube Digestion Technology to the Non Ferrous Metals Industry ........................................ 413
J.A. Gorst, B. Haneman and W. Slabbert
PLATINUM GROUP METALS
Development of the Twin Metals Minnesota Flowsheet Incorporating the Platsol Process .................... 427
J.A. Brown, C.A. Fleming and G. Barr
The Chemistry and Mineralogy of a Nickel Copper Matte Leach ............................................................... 443
G.C. Summerton, D.C. Craig, P. Dinham, N. McCulloch and S. Dowling
The Lonmin Platinum Base Metal Refinery Operations and Continual Improvements
1985 to 2012 ................................................................................................................................................ 457
N. Steenekamp and M. Turner-Jones
Author Index................................................................................................................................................ 469
xi
Refractory Gold
DESIGN OF THE AGA BRASIL REFRACTORY GOLD PRESSURE OXIDATION PLANT

*
M. Collins1, K. Buban1, M. Faris1, I. Masters1, M. Antonio2

1
Sherritt Technologies
8301 113 Street
Fort Saskatchewan, AB, Canada T8L 4K7
(*Corresponding author: mcollins@sherritt-tech.com)
2
AngloGold Ashanti Brasil

Fazenda Cristina s/n, Zona Rural, Brumal, Santa Brbara
Minas Gerais, Brazil
ABSTRACT
AngloGold Ashanti Brasil, with assistance from Sherritt International Corporation, has recently
commissioned a new autoclave for the pressure oxidation of refractory gold feeds at their Corrego do Stio
operation in Brazil. Design of the new plant, including feed acidulation, pressure oxidation, oxidized
solids washing and solution neutralization circuits, was based on the results of test work conducted by
Sherritt at their pilot plant in Fort Saskatchewan, Alberta. This paper describes the results of the pilot plant
study as well as highlights of the design exercise.

Proceedings of the 42nd Annual Hydrometallurgy Meeting
held in conjunction with the 51st Annual Conference of Metallurgists of CIM (COM 2012)
Niagara, ON, Canada
Edited by
42ND ANNUAL HYDROMETALLURGY MEETING
INTRODUCTION
AngloGold Ashanti Brasil (AGA Brasil) has recently commissioned a refractory gold pressure
oxidation plant at the site of the original So Bento operation in Brazil. The design of the So Bento
pressure oxidation facility was based on Sherritt technology; Sherritt carried out the original process
development test work in the mid-1980s, provided a process design package and detailed specifications for
critical pressure oxidation equipment and participated in the training of operators and commissioning of the
plant. The So Bento plant was operated between 1986 and 2007, when the original ore body was
exhausted (Silva et al., 2004). AGA Brasil purchased the facility from Eldorado Gold in 2008, with the
intent of refurbishing the plant to process refractory gold concentrates produced from the nearby Crrego
do Stio mining area.
Sherritt International Corporation has a long history in the development and application of
commercial pressure oxidation and pressure leaching processes. Sherritts development of technology for
the pressure oxidation of refractory gold ores and concentrates commenced in the 1980s in collaboration
with Homestake for application at the McLaughlin project in California. This was followed by several
commercial applications in Canada, Papua New Guinea and Brazil (Berezowsky et al., 1991). More than
thirty pilot plant campaigns investigating the pressure oxidation of refractory gold ores or concentrates
have been conducted by Sherritt since the 1980s, and projects with Sherritt contributions to the process
development studies and/or engineering design account for about half of the commercial plants that have
operated to date with this type of process (Collins et al., 2011a; 2011b).
AGA Brasil contacted Sherritt Technologies, a division of Sherritt International Corporation, in
August 2008 and requested proposals for test work and engineering activities to support the development
of capital and operating cost estimates for the Crrego do Stio Project. The proposed scope of work
included:
A review of preceding mineralogical and batch pressure oxidation studies, conducted by others,
with the Crrego do Stio concentrates, and provision of commentary on the employed methods
and the veracity of the data;
Process development studies, comprising batch test work, to identify the optimum operating
conditions for treatment of concentrates produced from the Crrego do Stio area, including the
Cachorro Bravo and Laranjeiras ore bodies, and a blend of ore samples recovered from both ore
bodies;
Up to 120 hours of continuous pilot plant test work, including integrated operation of acidulation,
pressure oxidation, countercurrent decantation wash and solution neutralization circuits;
Commensurate cyanide leach test work on selected samples from batch and continuous testing to
demonstrate gold extraction from the pressure oxidation solids;
Complementary liquid-solids separation testing to provide data for sizing the commercial
thickeners and filters;
A trade-off study, comprising limited batch testing and preliminary engineering activities, to
compare the treatment of the Crrego do Stio concentrates under operating conditions that could
be applied at the existing So Bento facility with the optimum operating conditions that could be
accommodated using new equipment; and
Preparation of a process design package for the pressure oxidation, solids washing, solution
neutralization and effluent treatment areas.
There was significant incentive to evaluate the treatment of the Crrego do Stio concentrates in
the existing So Bento equipment. Of particular interest was the possibility of using the existing
autoclaves at the So Bento site. The original autoclaves are limited to a maximum operating temperature
of 190C and a pressure of 1 700 kPa(g), but are of sufficient size to allow extended pressure oxidation
retention times for treatment of available Crrego do Stio concentrates.
The original scope of process test work for the Crrego do Stio Project included a limited
program of batch pressure oxidation (POX) tests under So Bento conditions followed by cyanide leach
tests on the POX solids to evaluate gold recovery. All of these tests were to be conducted under the same
methodology as the process development tests which examined higher temperature and pressure POX
conditions, the so called Preferred Conditions case, which would require a new autoclave. However,
following evaluation of the batch test results, Sherritt recommended that the continuous pilot plant
campaign should include a period of operation to test the So Bento conditions and generate the required
data for process comparison. Accordingly, a 48 h period of operations under So Bento POX conditions
was also conducted during the pilot plant test.
The Sherritt process development test program commenced on January 5, 2009, and detailed
engineering activities commenced in March 2010, culminating in start-up of the new commercial pressure
oxidation circuit in January 2012. A chronology of the major events during execution of the project is
provided as Table 1.
Table 1 Chronology of the Crrego do Stio project
Activity
Receipt of feed materials for process development work
Start of Sherritt batch tests
Complete review of previous test work
Issue plan for continuous pilot plant
AGA Brasil personnel on site in Fort Saskatchewan
Continuous pilot plant POX autoclave test
Issue pilot plant results update
Issue trade-off study summary of process test work
Issue final process development test report
Basic engineering
Detailed engineering
Issue autoclave shell specification
Autoclave shell delivered to site
Feed on to autoclave
Date
December 22, 2008
January 5, 2009
January 15, 2009
March 9, 2009
March 23, 2009
March 23 to March 28, 2009
April 3, 2009
May 15, 2009
June 12, 2009
April to August 2009
March 2010 to March 2011
April 1, 2010
January 13, 2011
January 12, 2012
This paper describes the results of batch and pilot plant test work carried out by Sherritt for
AGA Brasil to confirm the amenability of the Crrego do Stio concentrates to treatment by pressure
oxidation for extraction of the contained refractory gold and to determine the technical feasibility of
treating the Crrego do Stio concentrates in the existing, or in a slightly modified, So Bento pressure
oxidation facility. Highlights of the engineering activities, leading up to start-up of the new commercial
facility, are also provided.
PROCESS DESCRIPTION
A block flow diagram of the flowsheet evaluated in the process development studies is shown in
Figure 1.
Gold flotation concentrate slurry is fed to acidulation, along with recycled first wash thickener
overflow solution as a source of acid for decomposition of the carbonates contained in the feed.
Decomposition of the carbonates prior to pressure oxidation limits the quantity of carbon dioxide that may
be evolved in the autoclave. In the commercial plant, CO2 evolution in pressure oxidation would require
an increased vent rate to maintain the required oxygen partial pressure and thereby would reduce oxygen
utilization.
The acidulated slurry is thickened and the underflow slurry is fed to the POX autoclave. Oxygen
is added to each compartment of the autoclave to oxidize the sulphide minerals and liberate the gold. The
flashed POX slurry is fed continuously to the first of a series of CCD wash thickeners. The underflow
slurry from the last wash thickener is the feed to cyanide leaching.
The acidulation thickener overflow solution is forwarded to the solution neutralization circuit,
where the free sulphuric acid and the acid generated by hydrolysis of metals in this step are neutralized
with either limestone or flotation tailings. Metals precipitation is completed by addition of lime to further
increase the pH. The neutralized slurry is thickened, and the overflow solution is forwarded to the CCD
wash circuit to meet the wash water requirements.
Oxygen
Concentrate
Lime; Cyanide
Quench Water
Sulphuric Acid
S
Acidulation
L
Limestone/
Flotation Tails
Lime
Solution
Neutralization
Pressure
Oxidation
Cyanide
Leach
CCD Wash
Gold
Tailings to Impoundment
Figure 1 Process flow diagram for treatment of Crrego do Stio concentrate

FEED MATERIALS
Two different concentrate samples, Cachorro Bravo and Laranjeiras, were received in Fort
Saskatchewan from AGA Brasil on December 22, 2008, as well as a sample of flotation tailings for
solution neutralization tests. Each sample was well mixed to produce uniform feed for testing. In keeping
with the mine plan, the concentrates were blended in a 1:1 weight ratio for the bulk of the batch tests and
for the feed to the pilot plant campaign. The chemical compositions of the individual concentrates and the
1:1 blend are summarized in Table 2. The concentrates were relatively fine, at 88 to 89% passing 27 m.
The blend was prepared as a slurry of 56.0% solids for feed to the pilot plant campaign.
Table 2 Composition of Crrego do Stio concentrates tested during Sherritt pilot plant campaign
Feed
Au
Ag
Al
Sb
As
g/t
g/t
%
%
%
Cachorro Bravo
66.2
1.8
6.3
0.4
4.4
Laranjeiras
28.4
4.9
5.9
3.6
1.1
Blend
47.5
3.5
6.2
2.1
2.8
*
CNAL = non-acid leachable carbon, equivalent to organic carbon
C
%
2.0
2.4
2.3
CNAL*
%
0.8
1.3
1.1
Fe
%
16.2
8.3
12.2
Si
%
17.6
22.2
19.8
S
%
9.0
7.5
8.3
The flotation tailings contained 6.1% Al, 2.4% Ca, 2.1% C (most of which was carbonate),
5.0% Fe, 2.4% Mg and 27.8% Si. The flotation tailings solids were coarser than the concentrates, at 40%
passing 27 m. The neutralizing capacity of the flotation tailings was 0.10 g H2SO4 per gram of solids, or
about one-tenth that of the limestone used. For use in the pilot plant, the flotation tailings were prepared as
an homogeneous slurry of 65.8% solids.
PROCESS DEVELOPMENT STUDIES
The amenability of the Crrego do Stio concentrates to the pressure oxidation process was
evaluated in batch tests, followed by a continuous pilot plant campaign to generate design data.
Acidulation, CCD washing and solution neutralization circuits were operated in an integrated fashion with
the pressure oxidation circuit in the pilot plant campaign. Extensive cyanide leach tests were also
conducted on the pressure oxidation product solids and intermediate solids from the individual autoclave
compartments during the campaign.
Batch Test Program
Acidulation
Four batch acidulation rate tests were conducted on the separate concentrates and ten additional
tests were conducted on the 1:1 blend. The effects of acid addition, temperature and retention time on the
rate and extent of carbonate decomposition were examined. Between 75 and 90% carbonate
decomposition was achieved.
Pressure Oxidation and Cyanide Leaching
Four batch POX rate tests were conducted at 220C with the separate concentrate samples.
Several rate samples were collected during each POX test so that gold extraction vs. sulphide oxidation
curves could be produced. The primary goal of the tests was to evaluate the effect on gold extraction of
chloride removal from the acidulation solids by washing prior to pressure oxidation. It was found that
washing the acidulation solids prior to POX was not necessary, since sulphide oxidation in all cases was
rapid, exceeding 99%, and gold extraction in cyanide leaching typically exceeded 96% for the 40 min POX
solids and 97% for the 60 min POX solids.
Sixteen additional batch POX rate tests were conducted with the 1:1 blend. Test variables were
temperature, pressure and concentrate particle size. For temperatures between 210 and 230C sulphide
sulphur contents of the POX solids were between 0.03 and 0.04 wt% after 40 min retention time, and gold
extractions in cyanide leaching were between 95.7% and 98.5%. The extent of gold extraction increased
with increasing temperature and retention time. Regrinding the feed had no measurable effect on the
ultimate extent of sulphide oxidation or gold extraction. POX conditions of 220C and 60 min retention
time were selected as the base case for the preferred conditions in the pilot plant test, although it was
proposed to also evaluate 230C, and 220C at 90 min retention time.
At 190C (So Bento conditions), sulphide oxidation in the batch tests was slower and gold
extraction in the range of 94 to 95% required a POX retention time of up to 180 min. Similar results were
obtained with solids recycle or addition of calcium lignosulphonate. (The purpose of either solids recycle
or calcium lignosulphonate addition is to disperse elemental sulphur, which is expected to be formed in a
greater proportion at the lower POX temperature.) Regrinding the feed resulted in increased sulphide
oxidation rate but gold extraction following POX was not increased. Based on these results, it was
proposed to operate the So Bento case in the pilot plant with as-received concentrate, i.e., without
additional grinding, with solids recycle, at 190C and with 180 min continuous retention time.
The POX discharge slurry was conditioned at 95C. The purpose of the conditioning step is to
decompose basic iron and/or iron-arsenic sulphate precipitates, which would otherwise increase lime
consumption in the cyanide leach step. Generally, the conditioning step decreased the iron, arsenic and
sulphur contents of the POX solids, confirming the efficacy of this step for treatment of the Crrego do
Stio concentrates, especially for POX at 230C.
Solution Neutralization
Two solution neutralization batch rate tests were conducted with selected solutions that were
produced in the acidulation and POX batch tests. The retention time was 240 min. Neutralization was
conducted in two stages, with addition of either flotation tailings or limestone in the first stage, followed by
addition of lime in the second stage.
As expected based on the acid neutralization capacities of the two materials, limestone was much
more effective than flotation tailings for neutralization in the first stage. The pH achievable with flotation
tailings (pH 2.6) was considerably lower than that with limestone (pH 6.8). As a result, considerably less
lime was required when used with limestone versus the flotation tailings. In both tests, aluminum, arsenic,
iron, manganese and silicon were precipitated to below the detection limits (<0.002 to <0.01 g/L).
Magnesium was also precipitated to either near or below the detection limit (<0.004 g/L).
On the basis of the batch test results, it was decided to operate the pilot plant solution
neutralization circuit with limestone plus lime for the first 4 days and then switch to the flotation tailings
plus lime configuration for the final 24 hours. This plan was consistent with the amount of flotation
tailings available.
Continuous Pilot Plant Test
The pilot plant operations commenced at 1200 h on March 23 and ended at 1500 h on March 28.
In addition, the acidulation circuit was operated for about ten hours over a two day period (March 19 and
20) prior to the start of the continuous campaign, to generate a surge of feed material for start-up of the
pressure oxidation circuit on March 23.
The pressure oxidation operation was divided into five periods, based on variations in chloride
concentration of the quench water , temperature, pressure, retention time, and recycle of oxidized solids to
the autoclave by way of the acidulation circuit. Cyanide leach tests were performed on selected POX
solids samples throughout the campaign.
The POX solids were washed in a countercurrent decantation wash circuit. The recovered
solution was forwarded to acidulation, and the washed solids were sampled for cyanide leach tests.
Following acidulation, the solution was treated in a neutralization circuit.
Acidulation
The acidulation circuit consisted of feed systems for concentrate slurry and recycle solution or
slurry, a set of stirred tank reactors in cascade, and a thickener with a flocculation system. The circuit
processed 1 250 kg of feed slurry containing 700 kg of concentrate solids, and 245 kg of recycle slurry
containing 100 kg of oxidized solids. Approximately 1 500 kg of acidulation thickener underflow slurry,
containing 750 kg of solids, was delivered to the pressure oxidation circuit. About 2 400 L of acidulation
thickener overflow solution was transferred to the solution neutralization circuit.
During the continuous campaign, acidulation was operated in a series of cascading reaction tanks.
The circuit feed was concentrate slurry; after 99 h run time, oxidized recycle slurry from POX conditioning
was also fed to the circuit. The feed solution was synthetic first wash thickener overflow solution for the
first 11 h of operation, until solution was received from the pilot plant wash circuit.
The extent of carbonate decomposition in acidulation, shown in Figure 2 for values calculated
based on analysis of acidulation thickener underflow samples, ranged from 60 to 90% and correlated well
with the free acid concentration in the final reaction tank. A final acidity of 4 g/L H2SO4 was required to
achieve at least 70% carbonate decomposition, and 8 g/L terminal acid was required to achieve greater than
75% carbonate decomposition.
P2
P3
P4
Carbononate Decomposition, %
Decomposition
P5
16
Acidity
90
12
80
70
60
0
0
24
48
72
96
Acidity in Final Reaction Tank, g/L
P1
100
120
Run Time, h
Figure 2 Extent of carbonate decomposition during operation of acidulation pilot plant circuit; variations
in operating conditions are indicated by vertical dashed lines, separating operating periods 1 to 5
The acidulated slurry settled very well in the continuous circuit. The underflow slurry solids
content ranged from 45 to 55%, with an average of 49%.
Pressure Oxidation
The pressure oxidation circuit consisted of feed systems for acidulation thickener underflow slurry
and quench water, the pressure oxidation autoclave, a flashing system, and conditioning tanks to dissolve
basic iron sulphates in the POX solids. The autoclave was a horizontal, multi-compartment vessel,
operated with a double-sized first compartment (C1/C2) and four additional compartments (C3, C4, C5 and
C6).
The pressure oxidation circuit was operated for 120 hours with 99.8% on stream time. The circuit
processed about 1 500 kg of thickened acidulated slurry containing about 750 kg of solids and about
1 100 L of quench water.
The target parameters for each period of autoclave operation are summarized in Table 3. The first
four periods tested the high temperature, preferred conditions case. Periods 1, 2 and 3 were operated at
220C, with the retention time and chloride levels being the target process variations. The temperature was
elevated to 230C in Period 4. The So Bento conditions case was tested in Period 5, at a significantly
lower temperature, 190C, and pressure, 1 650 kPa (gauge); the retention time was 2 to 3 times longer than
in the higher temperature periods, and oxidized solids were recycled, by way of the acidulation circuit, to
prevent agglomeration of any elemental sulphur that could be formed in the autoclave at the lower
temperature.
For each operating temperature the ratio of thickened acidulation product slurry and quench water
was adjusted to achieve a target slurry solids content in the autoclave as predicted by preliminary mass and
heat balances performed prior to the continuous campaign. Prior to the start of Period 5, the acidulation
10
circuit was manipulated to ensure that the transition from fresh concentrate to a 1:1 blend of recycled POX
solids and fresh concentrate was a step change as opposed to a gradual transition.
Table 3 POX pilot plant operating conditions
Operating Condition
Period 1
Period 2
Run Time, h
0 to 24
24 to 42
Temperature, C
220
220
Pressure, kPa(gauge)
2 570
2 570
Retention Time, min*
90
60
Chloride in Quench Water, mg/L
13
13
Solids Recycle Ratio
0
0
*Based on single pass solids retention time in the autoclave
Period 3
42 to 60
220
2 570
60
nil
0
Period 4
60 to 72
230
3 050
60
nil
0
Period 5
72 to 120
190
1 650
180
nil
1:1
Sulphide oxidation profiles across the POX autoclave were developed by collecting samples from
each autoclave compartment during the campaign, as summarized in Table 4. The values provided in the
table are for samples that were collected after the autoclave had reached steady state in each operating
period, rather than average values for all samples collected during the campaign. The autoclave retention
time corresponding to each autoclave compartment could be readily calculated based on the feed rates and
the known internal geometry of the autoclave.
Table 4 Sulphide oxidation profile during POX pilot plant test
Period
1
2
3
4
5
Temperature
C
220
220
220
230
190
C1/C2
89.9
77.7
78.0
82.5
88.6
Sulphide Oxidation (steady state values), %

C3
C4
C5
95.9
99.2
99.4
83.0
90.7
99.0
85.8
97.4
99.3
98.3
99.2
99.3
94.4
98.0
99.1
C6
99.4
99.5
99.4
99.3
99.1
Sulphide oxidation exceeding 99% was achieved in all 5 periods of operation. As expected, the
rate of sulphide oxidation increased with temperature. The retention times required to reach 99% sulphide
oxidation were about 45 and 60 min for operation at 230 and 220C, respectively. When operating at
190C, 99% sulphide oxidation was not achieved until compartment C5, corresponding to about 160 min
retention time (single pass basis) in Period 5.
Cyanide amenability (CNA) tests, which are cyanide leach tests that use small quantities of solids
and do not involve intermediate sampling, were performed on samples of the conditioned solids every two
hours and on a suite of selected samples from the pressure oxidation circuit every six hours. In addition,
carbon in leach (CIL) cyanide leach tests, conducted at higher pulp density with larger quantities of solids
and with intermediate sampling, were performed on a conditioned and washed sample of the POX solids
every six hours. These higher pulp density tests are more useful for defining reagent requirements for the
commercial operation. Nonetheless, as shown in Figure 3, there was very good agreement between the
gold extraction values obtained in the CNA and CIL tests, indicating that the more numerous CNA results
provide a reliable assessment of the trends in gold extraction under the range of POX conditions tested.
Table 5 summarizes CNA gold extraction results obtained during the pilot plant campaign based
on cyanide leaching of samples taken after the autoclave had reached steady state in each operating period.
Samples collected from each autoclave compartment and from the discharge of the conditioning circuit
were tested.
11
Gold Extraction, %
96
Period 1
Period 2
Period 3
Period 4 Period 5
48
72
94
92
CNA
90
CIL
88
0
24
96
120
Run Time, h
Figure 3 Gold extraction in cyanide leaching of pilot plant POX solids following conditioning
Table 5 Gold extraction from POX solids in CNA cyanide leach tests during pilot plant campaign
Period
1
2
3
4
5
Temp.
C
220
220
220
230
190
Gold Extraction in CNA Cyanide Leach Tests (steady state values), %

C1/C2
C3
C4
C5
C6
Conditioned
90 to 93
90 to 94
93 to 95
93 to 95
94 to 95
93 to 94.5
86 to 88
90 to 92
92 to 93
92 to 94
93 to 95
93.5 to 94.5
84 to 88
88 to 89
91
92
93
92 to 93
90 to 91
94 to 95
95
95.5
95.5
95.5
88 to 91
90 to 91
91 to 92
91
90
89.5 to 91.5
Final gold extraction achieved in cyanide leaching when operating the pressure oxidation circuit at
temperatures of 230, 220 and 190C (i.e., for solids collected from compartment C6 or following
conditioning) was about 95, 92.5 to 94.5, and 90%, respectively. Based on the shapes of the gold
extraction profiles for cyanide leaching of solids collected from the individual autoclave compartments,
there was no indication that increased gold extraction could be obtained by extending the autoclave
retention time beyond 60 min at 220 or 230C, or beyond 180 min at 190C.
The effect of varying chloride concentration in the pressure oxidation solution was also
investigated, since it was expected that preg-robbing by organic carbon under POX conditions may
affect gold extraction. Two levels of chloride concentration were tested, approximately 30 and 15 mg/L in
the POX solution before flashing, corresponding to addition of quench water containing about 13 mg/L
chloride or essentially no chloride, respectively. There was very little difference in the results obtained
over this small range in chloride concentration. Nevertheless, there were indications during the test
program that small variations in oxygen distribution and oxidation reduction potential in the autoclave
were influencing gold extraction. It appeared that the preg-robbing effect was diminished by operating
at 230C compared with operating at 220C, since gold extraction in Period 4 (230C) was about 95%,
compared with 92.5 to 94.5% in Periods 1 to 3 (220C).
Conditioning following pressure oxidation did not have a significant impact on gold extraction.
However, significant redissolution of ferric iron, arsenic and sulphate sulphur in the solids did occur in the
conditioning step. The value of the conditioning step was especially evident when operating the autoclave
12
at 230C, as the sulphate sulphur assay of the solids changed from about 3.3% in the final autoclave
compartment to about 2.4% following conditioning. This difference would lead to a decrease in lime
consumption in cyanide leaching of about 15 kg/t compared with not conditioning the solids.
Countercurrent Decantation Wash
The conditioning tank discharge slurry from the pressure oxidation circuit was washed with
solution neutralization thickener overflow solution in a three-stage countercurrent decantation (CCD) wash
circuit to remove the bulk of the acid from the POX solids prior to cyanide leaching for gold extraction.
Overflow solution from the first wash thickener was forwarded to the acidulation circuit to serve
as lixiviant for decomposition of carbonate in the concentrate feed. The underflow slurry from the third
wash thickener was collected for further testing. Every six hours, samples of the third wash thickener
underflow slurry were taken, further washed and subjected to cyanide leaching tests to determine gold
extractions.
The countercurrent decantation (CCD) wash circuit was operated from 10.5 to 120 h run time,
with an on-stream time of 99.3%. The acid concentration in the wash circuit solutions depended on the
feed solution acid concentration and the wash ratio. The acid concentration across the CCD circuit
decreased from about 30 g/L in the circuit feed to between 1.5 and 3 g/L in the entrained liquor with the
third wash thickener (W3) underflow slurry. The product solution, W1 overflow, typically contained about
15 g/L H2SO4.
The POX solids settled well in the CCD wash circuit, to about 40 to 45% solids, and allowed from
91 to 96% of the sulphuric acid and metal salts to be washed from the conditioning tank discharge slurry
during the pilot plant operation. A wash ratio of about 2.5 L of wash solution per L of W3 underflow
entrained solution gave the desired extent of washing in the circuit.
Solution Neutralization
In solution neutralization, acidulation product solution was reacted with limestone (or flotation
tailings) and slaked lime in two stages to neutralize the free acid and precipitate metals. The solution
neutralization circuit consisted of a solution feed tank, slurry feed tanks for limestone or flotation tailings
and lime, five stirred tank reactors in series, and a thickener.
Overflow solution from the solution neutralization thickener was forwarded to the CCD wash
circuit to serve as wash solution. The underflow from the solution neutralization thickener was collected
for further testing.
In the first stage of neutralization, limestone or flotation tailings solids were added as a slurry to
neutralize the sulphuric acid and to hydrolyze and precipitate metals at a target pH of 5. Limestone
consumption was about 25 to 30 g per L of feed solution, or about 0.7 g limestone per g of equivalent acid.
Limestone utilization was calculated at about 93 to 94%, based on assays of carbon in the solids and flow
rates. When flotation tailings were added in place of limestone, the addition rate was about 7.5 g per g of
equivalent acid in the feed solution, and a pH of 3.3 was achieved. Carbonate utilization from flotation
tailings was calculated at about 44% based on assays of carbon in the solids and flow rates.
In the second stage of neutralization, lime was added to precipitate metals to low concentrations at
a target pH of 9. Lime consumption was about 15 to 18 g CaO per L of feed solution when limestone was
added in the first stage of neutralization, but was approximately doubled to 32 g CaO per L of feed solution
when flotation tailings was added to the first stage.
Antimony and arsenic were both precipitated to near completion in the first stage of neutralization
with either limestone or flotation tailings addition to a pH range of about 3 to 5. Significant amounts of
13
aluminum, iron and silicon were also precipitated in the first stage with limestone. Nearly complete
precipitation of aluminum, iron, manganese and silicon occurred in the second stage of neutralization with
lime addition to the range of about pH 8.5 to pH 9. Some magnesium remained in the calcium-saturated
solution after lime addition to about pH 9, and ranged from about 0.2 to 1.3 g/L Mg.
The solution neutralization slurry settled very well. The underflow slurry solids content typically
ranged from 54 to 58% when limestone was added to the first stage of neutralization. The underflow pulp
density increased from about 1 350 g/L (or about 45% solids) without recycle of product slurry to the first
stage of neutralization, to about 1 500 g/L (or about 58% solids) after one day of slurry recycle. The
underflow pulp density and solids content remained fairly similar when flotation tailings were added in
place of limestone; however, the quantity of solids being handled was significantly greater when flotation
tailings were used.
ENGINEERING DESIGN
A trade-off study completed by Sherritt provided preliminary economic information for the
implementation of pressure oxidation technology under various conditions. Further, basic engineering
activities were completed for two cases: a) installation of a new autoclave at high temperature (Period 4 in
Table 3); and b) refurbishment of one existing So Bento autoclave at original conditions (Period 5 in
Table 3). The cost and performance data from these studies supported AGA Brasils steering committee in
their ultimate decision to install a new autoclave.
A review of the So Bento equipment showed that much of the available equipment outside the
autoclave area was in good mechanical condition and could be used, with some refurbishment, to process
the Crrego do Stio concentrates and oxidized slurry. Within the autoclave area, one of the autoclaves
could be used to treat concentrates under the conditions tested during Period 5 of the continuous pilot plant
operation. Some rearrangement of the existing equipment, piping rework and instrumentation upgrades
were deemed to be required to put the plant in working order for this case. However, the higher gold
recovery demonstrated during pilot plant Period 4 offered sufficient economic benefit to justify the
additional cost of new equipment. The additional time to design and procure a new autoclave had minimal
impact on the projected startup date, as both cases required new equipment in milling and flotation as well
as refurbishment of existing equipment in the remainder of the plant.
The process design criteria for the Crrego do Stio Project were developed based upon results of
the laboratory and pilot plant test work, information supplied by AGA Brasil, and Sherritts experience and
expertise in similar projects. The pressure oxidation plant was designed for a nominal treatment rate of
60 000 t/a refractory gold concentrate using an operating basis of 24 hours per day, with an annual 85% on
stream time.
The autoclave shell design that was developed during basic engineering was utilized without
modification during the initial stages of detailed engineering, and underwent only a small number of
changes recommended by the fabricator. This allowed the order to be placed for the autoclave shell within
days of receiving approval to proceed, in order to ensure that autoclave delivery would not delay plant
construction.
The refurbishment of feed, discharge and vent handling equipment in the So Bento autoclave
circuit was considered during detailed engineering with the objective of reducing cost and delivery time.
However, in most instances new equipment was specified in order to optimize the equipment layout in the
available space, and to maximize environmental performance. Costs were reduced by reusing some of the
original agitator components and refurbished electrical equipment.
14
CONCLUSIONS
The process development studies conducted for the Crrego do Stio Project demonstrated
significantly improved gold extraction from Crrego do Stio concentrates when processed at 220 to 230C
prior to cyanide leaching compared with pre-treatment at 190C. Overall, the value of continuous piloting
for process demonstration and sound engineering design was confirmed during the project. The following
key parameters were defined, which otherwise were not clearly identified based on batch test results:
Improved gold extraction with POX treatment at 230C compared to 220C;

Lower gold extraction with pre-treatment at 190C, even with solids recycle and very long solids
retention times in the autoclave;
Liquid solids separation testing of pilot plant process slurries confirmed the suitability of existing
thickeners; and
Continuous neutralization confirmed the suitability of the existing tanks.
As a result, following an economic evaluation, AGA Brasil made the decision to build a new
pressure oxidation circuit. The results of the process development work were successfully used by Sherritt
to produce a commercial design for the new pressure oxidation circuit, which was commissioned in
January 2012 and is currently in operation.
ACKNOWLEDGEMENTS
The authors wish to thank the management of AGA Brasil and of Sherritt International
Corporation for permission to publish these results. The significant contributions of the professional and
technical staff of Sherritt Technologies are also gratefully acknowledged.
REFERENCES
Berezowsky, R.M.G.S., Collins, M.J., Kerfoot, D.G.E., & Torres, N. (1991). The commercial status of
pressure leaching technology. JOM, Vol. 43, No.2, February 1991, 9-15.
Collins, M.J., Hasenbank, A., Parekh, B. & Hewitt, B. (2011). Design of the new Lihir Gold pressure
oxidation autoclave. In B.R. Davis and J.P.T. Kapusta (Eds.), New Technology Implementation in
Metallurgical Processes (pp. 101-110), MetSoc. of CIM, Montreal, Canada.
Collins, M.J., Yuan, D., Masters, I.M., Kalanchey, R. & Yan, L. (2011). Pilot plant pressure oxidation of
refractory gold-silver concentrate. In G. Deschenes, R. Dimitrakopoulos and J. Bouchard (Eds.),
World Gold 2011 (pp. 145-155), MetSoc. of CIM, Montreal, Canada.
Silva, L., Guimaraes, R. & Milbourne, J. (2004). Process modifications to the Sao Bento concentrator of
Eldorado Gold. In M.J. Collins and V.G. Papangelakis (Eds.), Pressure Hydrometallurgy 2004
(pp. 781-791). CIM, Montreal, Canada.
15
THE MOBILIZATION AND POTENTIAL IN-AUTOCLAVE RECOVERY OF GOLD DURING

PRESSURE OXIDATION AND LEACHING OF AURIFEROUS SULFIDE MATERIALS
*G.P. Demopoulos, J.-C. Parisien-La Salle, D. Blais
Department of Mining and Materials Engineering
McGill University
Montreal, Quebec, Canada H3A 2B2
(*Corresponding author: George.demopoulos@mcgill.ca)
ABSTRACT
In this work the dissolution, precipitation and adsorption behaviour of gold in acidic iron sulphate
media containing small amounts of chloride ions is investigated via batch laboratory tests and OLI
thermodynamic calculations over the temperature range 25-250C. Chloride ions may be present in
industrial pressure oxidation/pressure leaching (POX/PL) operations due to elevated water salinity levels or
due to intentional addition as is the case of the CESL Copper Pressure Leaching Process. Thermodynamic
calculations show that AuCl4- may form depending on the free Cl-/Au ratio and temperature, its stability
increasing with increasing Cl- concentration and decreasing with increasing temperature. On the other hand
during POX/PL, we know that massive precipitation of iron in various hydrolysis products and compounds
occurs. Hence of interest is the question how AuCl4- that may form during leaching interacts with the iron
precipitation products. Gold(III) chloride was found to co-precipitate with iron(III) (oxy) hydroxides and
arsenates forming in the autoclave but not with natrojarosite. Upon further investigation it was discovered
that activated carbon added in the autoclave (as done in CIL) acts as preferential sink for the mobilized
gold, hence opening the potential for the development of a direct cyanide-free gold recovery process in
acidic sulphate leach reactors.

Niagara, ON, Canada
Edited by
16
INTRODUCTION
The recovery of gold from ores and concentrates has evolved over the years with processing
routes becoming increasingly complex. Given the high value of gold, any reduction in losses during
recovery operations constitutes an important economic benefit. One such loss that needs to be addressed is
the potential solubilisation of gold during pressure oxidation (POX) of refractory sulphidic gold feedstocks.
For example, Agnico Eagle Mines reported a loss in gold recovery due to the formation of a gold chloride
complex (Garofalo, 2009). Gold is known to form complexes in solution, such as gold(III) chloride, if an
excess of chloride ions are present. The fate of such soluble gold chloride during pressure oxidation and the
subsequent neutralization of the acidic discharge slurry will determine if gold is lost or recovered in the
downstream cyanidation operation. Thus it is of interest to know under what conditions gold chloride may
stay soluble or co-precipitate along primary (formed in the autoclave) or secondary (formed during
neutralization) precipitates. Furthermore, the mode of co-precipitated gold, such as adsorption on iron
compounds, like goethite and hematite (Machesky et al., 1990; Nachayev, 1984); substitution in one of the
precipitated phases; or finally chemical reduction to metallic state would have consequences in terms of
gold recovery.
Another process where gold is recovered from the residue generated in an autoclave is copper
pressure leaching. There are two general approaches in pressure leaching of copper: the high-temperature,
or total sulphur oxidation and the medium-temperature approach, exemplified by the CESL process
(Defreyne et al., 2006). Drawbacks of this technology are: in the former case excessive cost due to oxygen
consumption and neutralization of the generated acid; and in the latter case low gold recoveries due to the
formation of elemental sulphur which interferes with cyanidation. Cyanidation remains by far the key
process used worldwide on free-milling ores and on gold recovery systems from autoclave discharge, but
increasingly serious concerns are expressed about the toxicity of cyanide and the risks associated with its
handling and transportation.
For these reasons the behaviour of gold(III) chloride in acidic iron(III) sulphate solutions during
hydrothermal or neutralization treatment was investigated. In particular two types of experiments were
carried out. The first involved atmospheric pressure precipitation of iron(III) (with and without arsenate)
by neutralization to pH 4 in the presence of gold chloride (100 mg/L Au as HAuCl4). This investigation
involved examination of solution composition (iron(III) concentration, Fe/As molar ratio, Cl/Au molar
ratio) and temperature (20-90C). The second series involved autoclave experiments under various
conditions favouring the formation of crystalline iron(III) and arsenate phases and monitoring the
behaviour of gold chloride over the temperature range of 200-250C. The behaviour of gold(III) chloride in
terms of stability (resistance to reduction) in solution is analyzed with the aid of the OLI thermodynamic
package to set the scene for the experimental investigations undertaken. The adsorption of gold chloride on
iron oxides is also covered.
After examining the behaviour of gold chloride during autoclave iron compound precipitation, it
was decided to investigate a new cyanide-free and direct (one-step) concept for the recovery of gold from
refractory gold pressure oxidation and copper pressure leaching reactors-autoclaves. The new process
concept involves the extraction of gold during the actual pressure oxidation/leaching operation in the
autoclave via the use of a small amount of chloride ion addition (if not already present) plus activated
carbon. For maximizing gold recovery the process is designed in such way that favours the precipitation of
iron as sodium jarosite since the latter does not interfere with gold recovery in contrast to hematite (or
ferrihydrite) that does. Under these conditions gold (in the form initially of aurochloride complex) adsorbs
on carbon from which it can be recovered following screening, elution and electrowinning or reductive
precipitation/cementation.
It is the scope of this paper to review the dissolution/adsorption/co-precipitation of gold as
chlorocomplex during iron precipitation occurring in POX autoclaves or in neutralization reactors
following PX and to demonstrate the potential use of activated carbon directly in hot leaching reactors
(atmospheric to pressure) to recover in-situ the mobilized gold.
17
PROCESS AND CHEMISTRY REVIEW

Pressure Oxidation
The pressure oxidation treatment of refractory gold-bearing minerals involves a number of
processing steps as seen in Figure 1 (left). Slurried crushed/ground ore, or concentrate, is fed into a multi
compartment autoclave where it is made to react with oxygen. Oxidized iron, arsenic and sulphur (as
sulphate) are released temporarily into solution where most ions later form precipitates in-situ.
Depending on the operating conditions a wide range of precipitates may form.
Figure 1 (left) General flowsheet for the recovery of refractory gold via pressure oxidation;
(right) General CESL copper pressure leaching process flowsheet
Pressure oxidation may be conducted in either acidic or alkaline media. Acidic media remains the
prominent route used in industry, whereas alkaline oxidation may be applied industrially in special cases.
For proper oxidation the autoclave operating temperature should be above 180C to ensure complete
oxidation of all sulphides present to the sulphate form of sulphur. Elemental sulphur forming at lower
temperatures is undesirable as it interferes with the oxidation process and the downstream recovery of gold
by cyanidation (Demopoulos & Papangelakis, 1989). After pressure oxidation the solids and liquids are
separated and the solids are sent to cyanidation to recover the gold, which was liberated during pressure
oxidation (POX). The liquid, which still contains dissolved iron (and arsenic), is neutralized to completely
precipitate all the metals from solution. As in POX, stable gold complexes can react with compounds that
form during neutralization.
Pressure Leaching of Copper
The high temperature total oxidation process described earlier for the processing of copper
concentrates is essentially the same (from a gold recovery standpoint) with the POX process for refractory
gold ores; hence it will not be discussed further. Instead the medium-temperature (150C) type of copper
pressure leaching process and in particular the CESL (developed by Teck) process (Defreyne et al., 2006)
is described. The key ingredient of the process is the addition of 6-15 g/L chloride as catalyst to accelerate
the leaching kinetics of chalcopyritethe most common and difficult to leach copper sulphide mineral. It
is interesting to observe here that despite the presence of this quantity of chloride ions in the CESL
autoclave not dissolution or losses of gold have been reported. This may suggest that if any solubilisation
18
happens, it must be short-lived with gold reporting ultimately to the residue from which it is recovered.
The generalized CESL process flowsheet is shown in Figure 1 (right). The feed, copper flotation
concentrate, is sent to the pressure leaching autoclave. The copper sulphides are fully oxidized and the
copper is solubilised. Any pyrite present reacts only partially because it is a highly noble mineral that
forms a galvanic couple with chalcopyrite. The majority of oxidized iron reports in the residue as hematite
and jarosite. At the same time elemental sulphur is the dominant sulphide oxidation product. A counter
current S/L separation/washing circuit (CCD) separates the copper-containing solution and the goldbearing solids. The copper-containing solution is sent to a copper recovery process (typically consisting of
SX and EW). The washed solids (which may have been previously separated from the elemental sulphur
by flotation) are sent to another autoclave where they are subjected to pressure cyanidation (Barr et al.,
2007) in order to recover gold by dissolution as soluble gold-cyanide complexes. The products from the
second autoclave stage are sent to a carbon-in-pulp (CIP) circuit to recover the leached gold with activated
carbon. The pulp is screened and the gold-loaded carbon is transferred to an elution circuit while the
remaining pulp is sent to a cyanide destruction plant and subsequently disposed in a tailings pond. The
activated carbon is stripped exactly as in the POX process and the gold cyanide solution (eluate) is
electrowon to recover gold.
In-situ Iron Precipitation
The pressure oxidation chemistry and kinetics of pyrite and arsenopyrite are described elsewhere
(Papangelakis & Demopoulos, 1990a, 1999b, 1991; Long & Dixon, 2003). Upon oxidation these minerals
release iron (and arsenic), which precipitate in situ. Depending on temperature, oxygen pressure and
solution composition parameters such as acidity, total sulphate content and presence of co-ions for example
sodium, many products can precipitate, such as hematite, basic ferric sulphate (BFS) and several types of
jarosites that may be stable or metastable (Cheng & Demopoulos, 2004). If arsenic is present, then
additionally ferric arsenate compounds may form as recently studied by Gomez et al. (2011).
Gold Dissolution During Pressure Oxidation
During pressure oxidation in sulphate media, generally no or very little complexing ligands (like
halide ions) are present, hence the common understanding is that refractory gold remains in the elemental
state if already present as such or simply converts to that as soon as it is liberated. It is conceivable that
temporarily solubilised gold is reduced in-situ on oxidized mineral product surfaces via short-term
adsorption or not and reports with the residue solids. Gold is subsequently recovered from these residues
by cyanidation under an oxidizing environment. However in the presence of significant amounts of
complexing agents like chlorides, arising from either brackish process water or the ore itself can lead to
greater gold solubilization and possible losses.
A classic example of gold solubilisation, which caused serious complications, was at the Lihir
POX plant in Papua, New Guinea. In this case chlorides caused the solubilisation of gold within the
autoclave and the subsequent plating of gold inside the discharge nozzle (Ketcham et al., 1993). More
recently gold losses due to solubilisation of gold as a result of chloride complexation was reported by
Agnico-Eagle (Garofalo, 2009).
Gold has two oxidation states: aurous (Au1+) and auric (Au3+). These are stabilized only upon
complexation with strong ligands. Thus the solubilisation of gold in cyanide solutions occurs via the
formation of the cyano-aurous complex Au(CN)2-, while in the presence of halide ions gold is solubilised
in its auric form as Au(Cl)4- (Demopoulos et al., 1989; Liu & Nicol, 2002).
The importance of complexation in rendering gold soluble can be evaluated by referring to
appropriate reduction potentials and Pourbaix diagrams. Equation 1 gives the standard reduction potential
corresponding the Au3+/Au(s) couple. When this potential is compared to that of oxygen/water couple
(Equation 2) it becomes clear that gold in its elemental state is the most stable form.
19
Au3+ + 3e- Au(s) e = 1.498 V
(1)
O2 + 2H+ + 2e- H2O e = 1.23 V
(2)
With the presence of chloride ions as a complexing agent, the potential required for the oxidation
of gold does change and allows for the lixiviation of the metal since its standard reduction potential now
(0.99 V) is less than that of oxygen (1.23 V).
AuCl4- + 3e- Au(s) + 4Cl- e = 0.99 V
(3)
It is interesting to report here that with increasing temperature the reduction potential of the
Au(Cl)4-/Au couple decreases making the oxidation of gold possible even by the Fe3+/Fe2+ couple as it can
be deduced from the data plotted in Figure 2 (Liu & Nicol, 2002).
Figure 2 Reduction potentials of the Au(Cl)4-/Au, O2/H2O and Fe3+/Fe2+couples as a function of

temperature, [Fe3+] = [Fe2+] = 0.1M (Liu & Nicol, 2002)
The possible dissolution of gold during pressure oxidation as a result of the presence of chlorides
and the relative stability of gold(III)-chlorocomplexes as a function of temperature and chloride ion
concentration was studied recently in our laboratory using the OLI thermodynamic software package
(StreamAnalyzer Version 3.0). Some of the calculations are presented in Figure 3; the calculations were
made for 5 10-4 M of AuCl3 (corresponding to approximately 100 mg/L Au). According to this data, the
concentration of stable soluble gold complex decreases upon a temperature rise, but increases upon raising
the excess chloride ion concentration. For example we calculated that the solubility limit of the gold (III)
chloride complex before it is reduced to metallic gold for the case of 0.0715M HCl (or 2.3 g/L Cl) solution
is 5 10-4 (or 100 mg/L) Au at 227C. Although in industrial systems this may be much lower due to the
presence of other reducing agents such as unreacted sulphides, nevertheless these numbers serve to
substantiate the notion that solubilisation (even if partial or temporary, i.e. metastable) of gold can occur
hence the importance of considering its deportment and possible in-situ recovery.
20
Figure 3 The effect of temperature on gold (III) chloride complex concentration for various added
amounts of excess chloride (as HCl)
Adsorption of Gold (III) Chlorocomplexes
During the in-situ precipitation of iron oxides (and iron arsenates) in the POX autoclave or
neutralization reactors, soluble species (cations or anions) may co-precipitate via adsorption (Demopoulos,
2009). In this section, the possible co-precipitation of AuCl4- via adsorption on iron precipitates is
considered as well as reference is made to previous studies involving carbon adsorption of gold(III)
chlorocomplexes.
Adsorption of Gold(III) Chloride on Iron Precipitates
Complexes of gold including gold(III) chloride may adsorb on iron (hydroxy)oxides via
chemisorption. The formation of surface complexes on an oxide involving anions (as, for example,
arsenate species (Demopoulos, 2009; Yongfeng & Demopoulos, 2005) and AuCl4-) is described in
Equation 4:
/XOH + A3- + H+ OA2- + H2O
(4)
Reports of gold chloride adsorption on iron oxide surfaces do exist. Thus according to Karasyova
et al. (1998) gold(III) chloride adsorbs on hematite via inner sphere coordination. But in addition to
complexes, colloidal gold has been reported to adsorb on iron oxide particles due to electrostatic attraction.
This phenomenon is known as mutual coagulation or heterocoagulation (Enzweiler & Joekes, 1991). This
type of electrostatic interaction may lead to re-encapsulation hence constituting a possible cause of gold
losses during pressure oxidation processes. This solubilisation-encapsulation phenomenon apparently is
observed in natural mineralization processes theorized to be responsible in the genesis of refractory gold
ores (gold encapsulated within iron sulphides upon cooling) (Ranet al., 2001). In this case the adsorption
mechanism of gold(III) chloride on the surface of iron sulphides (see pyrite) is of electrostatic
(physisorption) type followed by reduction on the mineral surface as represented by Equation 5 (Mycroft et
al., 1995).
FeS2 + 5AuCl4- + 8H2O Fe3+ + 2SO42- + 16H+ + 5Au(s) + 20Cl-
(5)
By extrapolating this geochemical information to the case of pressure oxidation of refractory gold
ores, it may be deduced that partially oxidized sulphides (e.g. pyrite or arsenopyrite) plus in-situ forming
hematite or other oxidized products can cause equivalent to preg-robbing effect if chloride ions are present.
21
Adsorption of Gold(III) Chloride onto Activated Carbon

Conventionally in gold mining, the gold(I) cyanide complex Au(CN)2- adsorbs onto activated
carbon via Van der Walls forces, i.e., via physisorption (Adams, 1995; Lagerge et al., 1999). This
adsorption is reversible and at high temperature, the gold complex can be stripped off the activated carbon.
However, in the case of gold(III) chloride adsorption onto activated carbon (Sun & Yen, 1993; Huges &
Linge, 1989), chemical reduction occurs on the surface of the activated carbon resulting in metallic gold
formation and apparent production of carbon dioxide as described by Equation 6:
4AuCl4- + 3C + 6H2O 5Au(on carbon) + 12H+ + 16Cl- + 3CO2 E = 0.796 V
(6)
It has been further established that the adsorption/chemical reduction of gold chloride onto
activated carbon is diffusion-controlled (Sun & Yen, 1993; Huges & Linge, 1989).
RESULTS
Four types of experiments were conducted: (1) neutralization tests involving iron sulphate
solutions containing a small amount of soluble gold chloride to monitor its co-precipiation behaviour;
(2) autoclave precipitation experiments involving similar solutions; (3) carbon adsorption tests involving
dilute gold chloride solutions over the temperature range 20 to 95C; and (4) pressure leaching/oxidation
tests involving pyrite and cemented gold as model refractory gold material in the presence of activated
carbon. A sample of results from these tests is presented here.
Gold (III) Chloride Co-precipitation During Neutralization
During the neutralization of autoclave discharge solutions, base is added in order to precipitate the
residual iron left in solution. During this process any soluble gold could react with the forming solids. In
order to study the behaviour of gold(III) chloride during precipitation of iron, various neutralization tests
were performed. Initially, acidic solutions with various ferric (added as a sulphate salt) concentrations were
treated. In all these solutions approximately 5 10-4 M (100 mg/L) Au (as HAuCl4) plus 0.05MHCl was
added to provide for a Cl/Au molar ratio equal to 100. The tests involved a gradual increase of pH with the
addition of MgO (3M) until the target precipitation pH (pH 4). The behaviour of gold during a typical test
with an initial iron concentration of 0.3M is shown in Figure 4 (left). It can be seen that the gold
concentration variation parallels that of iron. At low pH levels, before iron begins hydrolyzing (< 30
minutes) for all practical purposes gold can be said to remain in solution. That no gold precipitates when
iron stays in solution was further verified by agitating a solution of pH 1.2 with 0.15M dissolved iron and
the same Cl/Au content, for one hour. No gold concentration drop was observed.
0.65
0.60
0.2
0.35
0.30
pH<4
0.25
pH4
Gold concentration
Iron concentration
0.20
0.1
0.15
0.10
Gold concentration (mmol/L)
0.45
Iron concentration (M)
0.50
0.40
22C
22C Repeat
60C
90C
0.5
0.3
0.55
0.4
0.3
0.2
0.1
0.0
0.05
0.0
0.00
0
20
40
60
80
Time (minutes)
100
120
-10
10
20
30
40
50
60
70
Time (minutes)
Figure 4 (left) Iron and gold concentration profiles during co-precipitation experiment at pH 4; (right)
effect of temperature on gold (III) chloride co-precipitation with iron (0.15M)
22
However, upon reaching pH 4 (at ~35 min), complete iron precipitation (apparently as
ferrihydrite) occurred, accompanied by partial co-precipitation of gold(III) chloride. The gold uptake
occurs apparently over a short period of time and then plateaus at a gold concentration of 0.17 mmol/L.
The mechanism by which gold co-precipitates could be attributed to either reduction of gold(III) into
metallic gold, or adsorption of gold(III) chloride onto the surface of ferrihydrite or the incorporation of
gold in the structure of ferrihydrite. As there are no other ions present in solution to act as reducing agents
for gold(III) chloride the more likely mechanism for the loss of gold is via adsorption. The adsorption of
gold(III) chloride to goethite via inner-sphere bidentate surface complex formation has been reported in
literature (Machesky et al., 1990). The present results, upon further analysis were found to involve indeed a
similar mechanism. Thus for example we found a linear correlation between the relative surface area of the
ferrihydrite precipitate and the amount of gold(III) chloride removed from solution.
The effect of temperature on gold co-precipitation at fixed iron concentration is reported in Figure
4 (right). The plotted data reveals that the loss of gold increases with increasing temperature. Not only is
the amount of gold removed affected (as deduced from the final gold concentration) but also the kinetics of
gold co-precipitation.
In order to determine the mechanism by which gold co-precipitates, diagnostic leaching on the
produced precipitates was performed. By independently digesting solids obtained from iron and gold coprecipitation experiments in a non oxidizing acid (3M HCl) and in aqua regia (AR) a distinction between
metallic gold and adsorbed gold was made. The diagnostic leaching results (in the form of dissolved gold
concentration) are reported in Table 1. As it can be seen there is no difference in the gold concentration in
HCl and AR. Therefore, as was hypothesized in the previous section, no reduction to metallic gold occurs
during gold(III) chloride co-precipitation with ferrihydrite.
Table 1 Diagnostic leaching results obtained from iron and gold co-precipitation solids
Temperature
22C
60C
90C
HCl
(mmol/L)
0.067
0.117
0.129
AR
(mmol/L)
0.066
0.121
0.127
Gold(III) Chloride Behaviour During Autoclave Precipitation

The possible preg-robbing effect of precipitated iron phases on gold(III) chloride complexes
under pressure oxidation conditions was investigated for the cases of hematite and jarosite precipitation.
Thus in this study hematite precipitation from sulphate solutions was carried out at 200C in the presence
of 100 mg/L Au (5 10-4 M HAuCl4) plus 0.05 M HCl (Cl/Au molar ratio = 100).
As it can be seen in Figure 5 (left) all gold was found to coprecipitate with hematite. After
characterization of the gold/hematite precipitate, using the diagnostic leaching technique mentioned earlier,
it was concluded that at least 50% of gold was present in the precipitate as adsorbed gold(III) chloride
species and the rest in metallic state. The adsorption of gold(III) chloro-complexes onto the surface of
hematite is suggested to be described by the following reaction (where =FeOH symbolizes the surface of
iron (hydroxyl)oxide:
=FeOH + AuCl4- FeOHAuCl3 + Cl-
(7)
It is interesting to note that similar results to hematite were also observed in the case of the three
iron-arsenate phases: scorodite, FAsH and BFAS (Gomez et al., 2011) although in this case substitution
rather than adsorption is suspected.
23
Concentration (Au:mmol/L, Fe/Na:M)
0.6
0.5
0.4
0.3
0.2
Gold concentration
0.1
0.4
Gold Jarosite 1
Gold Jarosite 4
Gold Jarosite 3
Iron
Sodium
0.2
0.0
0.0
0
20
40
60
80
100
10
20
30
40
50
60
Time (minutes)
Tim e (m inutes)
Figure 5 Gold concentration change during hydrolytic precipitation of hematite (left) and jarosite (right)
at 200C
In contrast to hematite, no gold was found to co-precipitate in the tests favouring the formation of
natrojarosite, again at 200C. This is clearly seen with the data (triplicate tests) plotted in Figure 5(right).
In other words in this case, gold(III) chloride was neither adsorbed nor apparently chemically reduced.
This finding was utilized in evaluating the in-situ recovery of solubilised gold(In the presence of small
amount of chloride ions) by activated carbon as described later.
However, the mechanism responsible for the reduction of part of the gold chloride to metallic gold
during autoclave precipitation of hematite is still elusive. As per OLI theoretical calculations, the stability
(resistance to reduction) of gold tetrachloride ions decreases with increasing temperature on one hand and
increases with increasing excess chloride ion concentration on the other. Thus as per theoretical
calculations made, a 100 mg/L Au (as AuCl3) concentration is supposed to remain stable in solution at
200C, when the excess chloride ion concentration is 100 times higher as was the case with the tests of
Figure 5. The fact that gold was nevertheless reduced in the actual experiment may reflect error with the
thermodynamic data on which the theoretical OLI calculations are based on. This is not unlikely given the
inevitable uncertainty with high temperature data extrapolation. Another possible cause for this behaviour
may have been the presence of a reducing agent, such as ferrous ions. Given the small concentration of
gold (5 10-4 M) it would take three times as much iron, see Equation 8, to be present as ferrous, which
corresponds to approximately 0.4-0.5% of the 0.15M ferric sulphate used, not an unrealistic scenario.
AuCl4- + 3Fe2+ Au + 3Fe3+ + 4Cl-
(8)
Carbon Adsorption of Gold(III) Chloride

Atmospheric adsorption experiments were performed with a solution containing 1.5 10-4 M
Au(III) and 0.05 M chloride concentration at pH of 1.5. Tests were done at three different carbon loadings
(10, 20 and 30 g/L) and at three different temperatures (20, 60 and 95C).
The variation of soluble gold(III) concentration with time for the room temperature test is shown
in Figure 6 (left). As it can be seen complete gold removal was achieved within a few minutes of contact.
The kinetics was found to increases with increasing carbon loading as well as temperature but somewhat to
slow down with increasing chloride background concentration. The beneficial effect of temperature on
gold chloride adsorption (in the form of first-order plots) is shown in Figure 6(right). From these plots,
an activation energy of 8.69 kJ/mol was determined consistent with previous assertions of a diffusioncontrolled process (Huges & Linge, 1989).
24
Figure 6 (left) Adsorption kinetics of gold(III) chloride on activated carbon at 20C ; (right) First-order
adsorption kinetic plots (10 g/L carbon) at 20, 60 and 95C
Upon detailed XPS characterization of gold-loaded carbon surfaces it was determined the
mechanism of adsorption to be complex involving a redox reaction. Thus it was found for example at
room temperature 45-50% of gold loaded on carbon was in the form of AuCl and the remaining as metallic
gold. The amount of metallic gold increased with increasing temperature (from 55% at RT to 70% at
200C). At the same time the amount of Au(I)Cl increased with increasing chloride concentration
reflecting the apparent increase in complex stability.
Carbon-in-autoclave
Gold Recovery
In this part of the investigation, tests were performed involving carbon addition in autoclave in
order to evaluate the extent of in-situ gold recovery in a simple pressure oxidation-leaching system. In a
typical carbon-in-autoclave test a simulated refractory feed material was used consisting of ground pyrite
as model sulphide mineral along with metallic gold deposited in the starting slurry by cementation. The
starting solution contained as well different amounts of free chloride and sodium ions. The presence of
adequate chloride and sodium ion concentrations was required to ensure the solubilisation/adsorption of
gold and suppression of hematite formation in view of the results reported in Figure 6. The presence of
sodium favours the formation of jarosite instead of hematite thus avoiding the losses of gold due to
adsorption on the latter.
Some representative results are summarized in Table 2. In this series of tests, a 300 mL capacity
titanium Parr autoclave, with a Pyrex liner, was used. The Pyrex liner was required to avoid the loss of
gold by plating/cementation on the metallic titanium surfaces. To minimize further gold losses (due to
cementationmore on this issue later) all internal metallic parts, including the stirrer, were removed. Tests
were conducted at two temperatures corresponding to the medium (CESL) and high temperature (POX)
processing options. Typical conditions were: 53.3 g/L pyrite (80% -38 m), 30 mg/L metallic gold, 40 g/L
carbon, initial pH 1.5, and P = 10 atm. In each test 75 mL of solution was used in which variable amounts
of Na2SO4 and NaCl were added. Once the target temperature was reached, oxygen was supplied to the
autoclave and oxidation was allowed to take place for 2 hours, after which the solution was quickly cooled
and immediately screened with a sieve of 80 m size. The solution was analyzed for gold; the final residue
(oxidation product) was digested in aqua regia, and then analyzed to determine its gold content (loss). The
activated carbon was analyzed via neutron activation, which yields results in the ppb scale.
Upon review of the results summarized on Table 2, it can be seen that there was partial reporting
of gold on activated carbon varying from 37.8% (Test 1) to 75.6% (Test 4). Test 1, performed at 155 oC,
was associated with about 20% of the gold remaining with the residue. Of the remaining gold, 3% was in
solution and only 38% was recovered (captured) by the activated carbon. Some 40% was unaccounted
for. This unaccounted type of gold was thought to have been partially lost during sample handling and
25
analysis but the majority to have plated on internal autoclave surfaces-a hypothesis verified later in the
next series of tests. Interestingly the solution (approximately 40% of the total) that collected outside the
liner due to evaporation and subsequent condensation upon cooling carried no soluble gold at low chloride
concentration. It can be seen conditions that favour jarosite precipitation (confirmed by XRD) like sodium
concentration and seeding resulted in higher gold recoveries. Comparison of Test 3 to Test 1 reveals that
gold recovery on carbon increased with temperature. This indicates an endothermic mechanism behind
gold adsorption on carbon, i.e. a similar behaviour with that observed over the temperature range 2295C mentioned earlier. This behaviour is the opposite of that exhibited in conventional gold adsorption
practice that involves gold-cyanide complexes, where elevated temperatures are known to promote desorption. This observation proves that the mechanism is not based on physisorption but rather on a
endothermic chemical reaction that as shown by XPS characterization leads to reduction of gold(III) into
gold(I) and metallic gold. Interestingly enough gold loss in the residue was again limited to 3% but 22% of
gold remained unaccounted meaning that it was deposited on internal autoclave surfaces. The results serve
as proof-of-concept of the effectiveness of in-situ carbon adsorption during pressure leaching/oxidation
or atmospheric leaching for that matter!
Table 2 Summary of results from selected pressure oxidation experiments (300 mL Ti autoclave)
TEST 1
TEST 2
TEST 3
TEST 4
TEST 5
Sodium1 (g/L)
8.5
6.8
8.5
10.2
4.3
Chloride (g/L)
2.5
2.5
2.5
Temperature (C)
155
155
200
200
200
Jarosite seed (g/L)
6.7
Gold left in solution (%)
2.9
3.2
4.4
2.6
3.6
Gold lost in residue (%)
18.9
1.9
3.2
21.8
37.8%
64.6%
70.2%
75.6%
46.6
CONDITIONS
RESULTS
Gold recovered on carbon (%)

2
Unaccounted gold (%)

40.4
30.3
22.2
21.8
28
This is total sodium including sodium sulphate and sodium chloride additions.
2
Assumed to have plated on metallic surfaces inside the autoclave; this assumption is verified in the
next series of tests.
1
Gold Plating on Metal Surfaces

As noted above a significant amount of gold (20-30%) was unaccounted, i.e., it was neither found
to be on the carbon, in the solution or in the precipitated residue. This unaccounted gold was determined to
have plated out of solution on internal autoclave surfaces via electrochemical coupling similar to
cementation reactions. It would be interesting to know if such plating takes place in brick lined industrial
autoclaves (highly unlikely). Nevertheless, in similar systems to the present one, like the CESL and
PLATSOL processes (where chlorides are added in the autoclave but not activated carbon) no similar
losses due to plating are reported, implying that this may not be a serious obstacle.
Carbon-in-autoclave Testing Using a Glass Pressure Reactor and a Real Concentrate
After the Ti autoclave experiments yielded results where some of the gold found to deposit/plate
on metal surfaces, it was decided to fully test the carbon-in autoclave concept by employing a glass
autoclave with no metal parts. Because of the limited pressure rating of the glass autoclave, tests were run
26
only at 155C. There were three tests, two employing the standard synthetic pyrite/gold feed while the third
test involved pressure leaching of a copper/gold concentrate. Gold occurrence (22.9 ppm content) in the
latter material had the following distribution: 35% liberated gold, 55% gold occurring in non-copper
sulphides, 9% gold occurred in copper sulphides, and the remaining in silicates. The concentration of pyrite
(or concentrate) used in this series of tests was half (26.65 g/L) of that used in the previous series of tests
(53.3 g/L), while the reaction time was longer than 2 hours used in the previous tests. This was deemed
necessary due to lower partial oxygen pressure allowed with the glass autoclave and the inevitable
associated slower kinetics. The obtained gold recovery results are summarized in Table 3. First it is noted
that in Test 1G, there was a significant fraction (~25%) of gold found in the solids. This was thought to be
due to incomplete reaction as evident by the presence of unreacted pyrite in the final solid product. By
extending the reaction time to 4 hours complete oxidation occurred leading to 97% gold recovery on
carbon. The concentrate test yielded in turn 95% recovery. Hence these results clearly prove the capability
of activated carbon to capture gold quantitatively in the autoclave under pressure leaching conditions.
Table 3 Glass autoclave test results (experimental conditions: 26.65 g/L pyrite or Cu conc; 30 mg/L gold
in Tests 1 and 2 and 0.6 mg/L in Cu conc test; 155C; 4 atm O2; 40 g/L carbon; 5 g/L Cl)
Test
Time
(h)
Cl
(g/L)
Na
(g/L)
%Au in
solution
% Au
solids
%Au in
carbon
1G
10.2
1.07%
23.33%
75.60%
2G
10.2
0.87%
0.00%
97.87%
Cu conc
4.90%
0.00%
95.86%
6.67
CONCLUSIONS
In this work, the behaviour and carbon adsorption of gold(III) chloride during pressure leaching
and precipitation of iron (and arsenate) under hydrothermal processing or neutralization of acidic sulphate
solutions has been investigated.
MgO slurry neutralization of ferric sulphate solutions containing 100 mg/L (5 10-4 M) Au with a
molar ratio of Cl/Au of 100 was found to result in ferrihydrite precipitation over the entire temperature (2290C) and concentration range (0.075, 0.15, 0.3M) tested. Along with ferrihydrite it was found gold
chloride to co-precipitate via adsorption. No evidence of reduction of the gold chloride complex to metallic
gold was found. The amount of gold co-precipitated increased with the initial concentration of iron and
temperature. The increased gold uptake with initial iron concentration was correlated to the available
surface area of ferrihydrite.
At elevated temperatures and pressures, several precipitates form depending on the autoclave
operating conditions. Gold chloride was found to exhibit different co-precipitation behaviour depending on
the phase and condition of precipitation. In the case of hematite formation 96% of the soluble gold was
found to co-precipitate at 200C and above 99% at 225 to 250C. Approximately half of the gold chloride
adsorbs on the surface of hematite and the other half is reduced to metallic state. Similar results were
observed in the case of the three iron-arsenate phases: scorodite, FAsH and BFAS although in this case
substitution rather than adsorption is suspected. The partial reduction to metallic gold may have involved
trace amounts of ferrous iron. However, under conditions (high sodium concentration) favouring the
formation of natrojarosite no loss of gold from solution via adsorption or reduction was observed.
Given the above findings, it becomes apparent that gold chloride complexes that may form
(depending on the Cl/Au ratio and the prevailing oxidizing conditions) during pressure oxidation or
pressure leaching (like the CESL process) operations may either stay in solution and report to the
neutralization solids (as adsorbed species), or precipitate in situ in the autoclave. In the latter case part of
the gold may be in metallic form hence recoverable in the subsequent cyanidation step. However the
27
remaining gold (as adsorbed or incorporated via substitution) may be lost if not properly diagnosed and
recovered.
In view of the above observed behaviour of gold(III) chloride in an acidic iron sulphate
environment, it was decided to evaluate the possibility of gold adsorbing on activated carbon under
pressure oxidation-leaching conditions. First, the adsorption of gold(III) chloride on activated carbon was
studied as a function of temperature (20-95C). The initial gold(III) chloride adsorption at 20, 60 and 95C,
yielded increasing adsorption profiles with increasing temperature. XPS analysis of gold-loaded carbon
samples obtained with a low (0.05M) and high chloride (1M) concentration at 20 and 95C revealed the
presence of gold in part as Au(I) chloride and in part as metallic gold. It was observed that the amount of
Au(I) decreased with increasing temperature and increased with increasing chloride ion concentration.
Following the atmospheric pressure adsorption tests, carbon-in-autoclave (CIA!) tests were
carried out involving pressure oxidation of pyrite at 155 and 200C in order to evaluate/determine the
deportment of gold at varying conditions. Two initial observations were made with these experiments,
firstly that the oxidation product hematite results in a preg-robbing effect due to gold chloride adsorption
and secondly that not all of the gold could be accounted for due to apparent deposition on metallic
surfaces. In order to prove finally the validity of the carbon-in-autoclave concept without the undesirable
occurrence of gold plating, pressure oxidation experiments in a low pressure glass autoclave were
attempted at 155C. Due to the lower pressure of oxygen applied (4 atm vs. 10 atm for the Ti autoclave),
the kinetics were much slower hence the reactions were allowed to proceed for longer time (3-4 hours) to
obtain total oxidation of pyrite and dissolution of gold. These low pressure oxidation experiments yielded
recoveries above 95% (compared to the best titanium recoveries of approximately 75%) for both
pyrite/gold synthetic feed as well as a real copper/gold concentrate.
It is obvious that more work is needed to investigate the full technical feasibility of the CIA
concept by paying particular attention to the elimination of the plating problem, the ability of carbon to
resist fragmentation in strongly agitated and oxygenated slurry environment, as well as the effect of various
impurities.
ACKNOWLEDGEMENTS
The help of Mario Gomez with the XPS analysis of the gold-loaded carbon samples is
acknowledged.
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Liu, J.Q., and Nicol, M.J., 2002. Thermodynamic and kinetics of the dissolution of gold under pressure
oxidation conditions in the presence of chloride. Canadian Metallurgical Quarterly, 41, p. 409415.
Long, H., and Dixon, D. G., 2003. Pressure oxidation of pyrite in sulphuric acid media: a kinetic study,
Hydrometallurgy, 73, pp. 335-349.
Machesky, M., Andrade, W.O., and Rose, A.W., 1990. Adsorption of gold(III)-chloride and gold(I)thiosulfate anions by goethite. Geochimica et Cosmochimica Acta, 55, p. 769-776.
Mycroft, J.R., Bancroft, G.M., McIntyre, N.S., Lorimier, J.W., 1995. Spontaneous deposition of gold on
pyrite from solutions containing Au(III) and Au(I) chloride. part 1: a surface study. Geochimica et
Cosmochimica Acta, 59(16), p. 3351-3365.
Nechayev, Y., 1984. The effects of solution composition on the adsorption of gold(III) complexes on
hematite. Geochemistry International, 21(4), p. 87-93.
Papangelakis, V.G., and Demopoulos, G.P., 1990a. Acid pressure oxidation of arsenopyrite: part 1,
reaction chemistry. Canadian Metallurgical Quarterly, 29, p. 1-12.
Papangelakis, V.G., and Demopoulos, G.P., 1990b. Acid pressure oxidation of arsenopyrite: part 2,
reaction kinetics. Canadian Metallurgical Quarterly, 29, pp. 13-20.
Papangelakis, V.G., and Demopoulos, G.P., 1991. Acid pressure oxidation of pyrite: reaction kinetics.
Hydrometallurgy, 26, pp. 309-325.
Ran, Y., Fu, J., Rate, A.W., Gilkes, R.J., 2001. Adsorption of Au(I, III) complexes on Fe, Mn oxides and
humic acid. Chemical Geology, 185, p. 33-49.
29
Sun, T.M., and Yen, W.T., 1993. Kinetics of gold chloride adsorption onto activated carbon. Minerals
Engineering, 6(1), p. 17-29.
Yongfeng, J. and Demopoulos, G.P, 2005. Adsorption of arsenate onto ferrihydrite from aqueous solution.
Environ. Sci. Technol., 39, p. 9523-9527.
31
KINETICS OF THE CESL GOLD PROCESS

*E. Asselin1, P. Sauve2, H. Salomon-de-Friedberg2
1
University of British Columbia, Materials Engineering

6350 Stores Road
Vancouver, Canada V6T 1Z4
(*Corresponding author: edouard.asselin@ubc.ca)
2
CESL Limited
12380 Horseshoe Way
Richmond, Canada V7A 4Z1
ABSTRACT
Residues from the CESL Copper process were leached using the CESL Gold process. The
kinetics of reaction were confirmed to be fast with over 50% of the gold consistently extracted within 2
minutes of leaching. Final gold extractions under the conditions tested here were between 80-90%
obtained within 90 minutes. A model for the CESL Gold process was developed. This model is slightly
different based on whether the copper concentrate leach residue was ground or unground prior to leaching:
the gold leaching rate constant is approximately twice as fast for the ground samples. Unground residues
had a P80 of 13 m whereas ground residues had a P80 of 10 m. The model predicts a 43% decrease in
leaching time for ground residue versus unground residue to achieve the same extraction under otherwise
identical conditions. The model was more accurate for the ground samples.
= 2.39 10 CN O Au Au, gt h (unground residues)
= 4.61 10 CN O Au Au, gt h (ground residues)

Niagara, ON, Canada
Edited by
32
INTRODUCTION
Tecks CESL Process (Jones,
(
1996)) was developed to provide an economically attractive
alternative to traditional copper smelting. It has since evolved to also deal with copper concentrates
containing valuable impurities such as nickel and undesirable ones, such as arsenic, while reducin
reducing
downstream costs. Effective recovery of gold and silver is essential to the economics of the CESL Process.
The Brook Hunt 2007 copper concentrate assay data (Wood
(Wood-Mackenzie,
Mackenzie, 2007
2007)) were examined to
determine the ratio of gold plus silver value relative to
to the contained copper. As indicated in Figure 1
below, nearly two-thirds
two thirds of concentrates have 10% or more of their total value tied up in their precious
metals content.
Figure 1 Histogram indicating the number

number of concentrates aassociated
ssociated with a particular
icular fraction of their
value present as contained precious
recious metals
etals (assumes Cu at $3.5/lb, Ag at $1/g, and Au at $50/g)
CESL has extensively examined the recovery of gold and silver at bench, pilot and demonstration
scale, which has culminated in the present
present CESL Gold Process (Barr et al., 2007
2007).
). The process targets the
precious metal contained in the leach residues produced in the copper portion of the flowsheet. This
residue has two primary components which influence downstream processing. The major iron
iron-rich
rich fraction
wt%) of the residue is a mixture of various forms of iron oxide precipitates including hematite and
(~75 wt%)
jarosite (Sahu
(Sahu and Asselin, 2011).
2011). The iron fraction ranges from amorphous to crystalline in nature
depending on the compound precipitated,
precipitated, upstream operating conditions and feed material composition.
The lesser, but by no means less important, fraction is a mixture of elemental sulphur and unreacted
ulphides (principally pyrite).
sulphides
Elemental sulphur formed during the oxidative leach
leach of the copper concentrate reacts with cyanide
to form thiocyanate (SCN-) making a traditional cyanide leach approach too costly. Since the SCN
formation reaction strongly depends
depend on contact time with the CESL residues ((Po, 2007) short contact times
were preferred. This factor guided the development work towards the eventual room temperature, pressure
cyanidation process which results in near complete gold dissolution in 90 minutes. A recent CESL gold
nstration campaign treating
treating 1.5 t/d of residue from the copper oxidation step achieved an average
demonstration
gold extraction of 91% (96% maximum).
Work was undertaken to develop a mathematical model of the gold leaching step. The purpose of
the model is to assist in process optimization
optimization as well as identify the critical scale
scale-up
up parameters. This
model is presented herein.
33
EXPERIMENTAL
The feed material used in these tests was copper concentrate leach residue. This residue had been
continuously produced when leaching Robinson copper concentrate (open pit copper mine, Nevada)
through the continuous demonstration scale pressure leach autoclave operated under standard CESL
conditions. The typical leach conditions were a temperature of 150C, a total pressure of 200 psig (PO2 of
ca. 130 psig), and a retention time of 60 minutes. Surfactant was added to aid in the dispersion of molten S
that forms as a byproduct of the process.
A homogenized sample of these copper residues, in preparation for subsequent cyanidation
testwork, was first slurried at room temperature with tap water and hydrated lime to a solids concentration
of ~265 g/L at a pH of 10.5 to 11. A stock solution at pH 11 containing 50 g/L NaCN was also prepared
separately.
The room temperature, batch cyanidation trials were conducted in the first compartment of a 20 L,
0.2 m diameter, stainless steel continuous pressure vessel with four separation weirs. The first
compartment was isolated from the remainder of the vessel by extending the existing weir to the roof of the
autoclave using a Teflon seal. This effectively converted the first compartment to a 4 L active volume
batch vessel.
The copper residue slurry was first pumped into the compartment to provide 1 kg of dry
equivalent solids (~21% moisture). The agitator (with a single 10 cm diameter, 6 bladed axial impeller)
was adjusted to a speed of 300 rpm and the vessel pressurized to the target pressure using pure oxygen.
The slurry was allowed to equilibrate with its oxygen environment for 30 minutes to ensure oxygen
saturation before any cyanide was introduced to the system. At t = 0, the requisite amount of NaCNbearing solution was then pumped into the compartment using a high-pressure diaphragm pump. Slurry
samples were taken at 2, 5, 10, 15, 30, 60 and 90 minutes, collected in a 150 ml sample bomb, and quickly
(2 minutes under vaccum) filtered. The solids were washed. Filtrate, wash water and solids were sent for
gold assay. Solutions were assayed at CESL by ICP-AES and residues were assayed externally by fire
assay. These samples provided the basis for the kinetic leach curves discussed in the sections that follow.
At the conclusion of each test, the slurry remaining in the compartment was vacuumed out and the
compartment was then flushed with pH 11 solution which in turn was removed. The compartment was now
ready for the next test.
Twenty-one tests were performed in the apparatus described above of which 14 are discussed in
this paper. There were three variables that were varied throughout the test work: initial CN- concentration,
oxygen partial pressure, and the degree of grinding. Cyanide concentration throughout a given test was
monitored as active cyanide, which is defined as:
[CN-]a = [CN-]WAD 1.64 x [Cu]
(1)
where concentrations are in mg L-1, [CN-]WAD is the weak-acid dissociable cyanide concentration and 1.64
represents the mass ratio of cyanide to copper assuming the cuprous tetra-cyanide complex is dominant.
Three separate initial active cyanide concentrations were tested ([CN-]a = 2650, 2330 and 1990
mg L-1), three oxygen pressures (200, 300, 400 psig or 13.6, 20.4 and 27.2 atm), and both ground and
unground residue were evaluated. The feed size of the unground residues (8 samples) was P80 = 13 m.
Six residue samples were batch ground with a Netzsch pilot plant mill to a particle size of P80 = 10 m.
Oxygen concentration was assumed to be the saturation concentration. This is consistent with
measurements and methods used by Ling et al. (1996), albeit for much lower concentrations of oxygen and
much longer residence times. Saturated oxygen concentration was calculated using the Tromans model for
oxygen solubility (Tromans, 1998) in pure water. This work does not account for minor changes in
solubility associated with dissolved salts such as cyanide.
34
The test matrix for the samples is presented

presented in Table 1.
Table 1 Test matrix used for model development
Test Number
Ground?
[Au]s,0, g t-1 a
PO2, atm b
13.6
1
20.03
NO
20.4
2
10.25
NO
13.6
3
15.15
NO
20.4
4
18.40
NO
27.2
5
9.04
NO
13.6
6
17.65
NO
20.4
7
18.48
NO
27.2
8
12.07
NO
13.6
9
20.90
YES
20.4
YES
10
15.71
27.2
YES
11
12.50
13.6
YES
12
12.50
20.4
YES
13
12.25
27.2
YES
14
13.30
a
Au head assay for each sample b Gauge Pressure c Calculated
[O2], mg L-1 c
557
835
557
835
1114
557
835
1114
557
835
1114
557
835
1114
[CN-]initial, mg L-1
2650
2650
2320
2320
2320
1990
1990
1990
2320
2320
2320
1990
1990
1990
RESULTS
Experimental Measurements
The active cyanide concentration was not controlled but measured as samples were taken. The
cyanide concentration decayed logarithmically as a function of time as is apparent from Figure 2. This
Figure also demonstrates the rapidity with which cyanide is consumed: approximately 25 to 45% of the
initial cyanide dose is consumed within the first 2 minutes of reaction (0.033 h).
Figure 2 Active cyanide concentration as a function of time and vary

varying
ing initial cyanide addition at
constant oxygen concentration
concentration of 835 mg L-1 for leaching of unground samples
Gold extraction as a function of time is shown in Figure 3 for experiments at constant oxygen
concentration of 835 mg L-1 (filled markers represent ground samples)
samples). Over 60% of the Au is consistently
recovered within 10 minutes of
of the start of reaction. Gold
Gold extractions at 90 minutes and [O2] = 835 mg L-1
35
were in the range of 80 to 87%. The unexpectedly poor result at the highest cyanide level (Test 2) might
be explained by the sample simply running out of available gold: no gold dissolved from 15 minutes
onwards and this sample had the second lowest value of [Au] s,0 (Table 1).. For example, su
sulphur
lphur or other
encapsulation may have limited solution access to the gold. The kinetics of extraction appear to be initially
faster for the ground samples but final extractions are similar and even appear to be slightly lower for the
data shown in Figure 3. It should be noted here that because of the very rapid kinetics of the CESL Gold
process, the time required for sample collection and solids separation was a critical parameter believed to
be responsible for experimental error, particularly at the early stages (first 22-10
10 minutes) of the reaction.
Thus comparison of the relative kinetics of ground vs. unground samples aatt short reaction times is made
with a certain degree of uncertainty.
Figure 3 Gold extraction as a function of time and initial cyanide concentration at constant oxygen
concentration of 835 mg L-1. Unfilled markers
markers are unground samples, filled markers are ground samples
Figure 4 Gold extraction as a function of time and oxygen concentration at fixed initial cyanide
concentration of 2320 mg L -1
here, final gold extractions appear to be
Figures 3 and 4 also show that, under the conditions used here
lowest at the highest concentration of oxygen. These data are presented in another way in Figure 5 where
concentr
for the 10 or 90 min samples. A minimum is
gold extractions are plotted against oxygen concentration
36
observed (with two exceptions)

generally observed
exception ) at the highest oxygen concentration. This extraction behaviour
may simply be related to inaccurately low head grade assays for the high
high-oxygen concentration tests
(Table 1) but may also be the result of the complexity of the residues treated through the CESL Gold
process.
Figure 5 Final gold extraction as a function of oxygen concentration, initial cyanide concentration and
residue grinding
Model Development
Ling et al. (1996) and de Andrade Lima and Hodouin (2005) have presented eexcellent
xcellent reviews and
procedures for the development of industrially
industrially relevant gold leaching models. De Andrade Lima and
Hodouin (2005) presented a lumped rate equation similar
similar to that proposed by Ling et al. (1996), but which
unted for ore particle size. Since the present work did not study a wide range of particle sizes, the
accoun
model of Ling et al. (1996) was used here in its generic form:
form
(2)
here kAu is the rate constant for gold cyanidation, [Au]s is the concentration of gold in the ore and [Au] s,s,
where
is the unleachable gold in the ore (or the gold concentration in the oore
re at infinite leaching time).
Integration of Eq. (2) yields the following expression for [Au]s at any time t of tthe leach:
(33)
here [Au]s,0 is the ore gold concentration at time t = 0. Since the cyanide concentration during the leach
where
was not kept constant in the present work, the term [CN-] t of Eq. (3) was integrated using the trapezoid
rule. It is also important to note that the cyanide concentration used here was not the typical free cyanide
concentration but rather the active cyanide concentration as described in Eq. (1). [Au]s was initially
calculated
calculated based on the gold head assay ([Au]s,0 presented in Table 1), the unleachable gold [Au]s, = 1.78 g
ing values for kAu , , and based on literature
literature. The model
t-1 (set by inspection and by best fit) and assuming
estimates of [Au]s were then compared to the measured values and an error was calculated. A least squares
error minimization algorithm was then used to arrive at best fit values for the rate constant and reaction
orders.
37
separately
tely in the model development. However,
The unground and ground samples were treated separa
as can be seen from the following equations (4
(4 and 5,, respectively
respectively),
), the models for both are identical
except for the rate constant, which is roughly doubled for the ground samples.
(44)
(55)
( and (5) are second order with respect to gold concentration as in the work of Nicol
Equations (4)
et al. (1984). The
he fitting procedure did not generate the integer 2 for the gold reac
reaction
tion order but the result
was sufficiently close (1.96 and 2.01 for equations 4 and 5, respectively) to merit rounding to 2. This was
similar in the case of the oxygen and cyanide reaction orders
orders,, which were also rounded to 1 with no
significant difference in the error.
error. The rate constant, kAu, is three orders of magnitude smaller than that
obtained in previous work (de Andrade Lima & Hodouin, 2005; Ling et al., 1996) using a similar model
formulation. This result may reflect sulphur encapsulation
encapsulatio n of the gold but does not necessarily infer any
fundamental mechanism.
Model Validation
predicted extractions are compared to the measured extractions in Figure
Figures 6 and 7 for
The model--predicted
the unground and ground samples, respectively.
respectively There is a lot of sca
scatter
tter on either side of the ideal
prediction for the 22-10
10 min data points in Figure 6.
6 The scatter decreases substantially for data collected
from 30-90
30 90 minutes of leaching time. In particular, at the 2 min sampling time, it appears as though the
model under
under predicts extraction for 4 out of 7 points. This is likely related to experimental error.
The model results are much better for ground residue samples (Figure 7). This difference in
model fit between ground and unground residue samples is likely a re
reflection
flection on the difficulty associated
with obtaining representative head and slurry samples from the unground residues before and during the
leach. The sum of squared errors of prediction (SSE) of gold extraction as a function of residue type and
time of sampling is shown in Figure 8. Errors decrease exponentially as time progresses and the model
predictions are considerably better for the ground samples.
Figure 6 Comparison of model predicted extractions with measured extractions at different sampling
times for unground CESL residues
38
Figure 7 Comparison of model predicted extractions with measured extractions at different sampling
times for ground CESL residues
Figure 8 Sum of squared errors of prediction for gold extraction at each sampling time for ground and
unground residues
predicted extraction curves at constant cyanide (1000 mg L -1) and oxygen concentration
Model-predicted
-1
(835 mg L ) are shown in Figure 9 for [Au]s,0 = 20 g t-1 and [Au]s, = 1.78 or 1 g t-1. Thes
Thesee curves
demonstrate that ground residues can achieve the same extraction as unground residues in 43% less time.
As would be expected, lower values of unleachable gold result
resu lt in higher final extractions.
CONCLUSIONS
CESL Gold pressure leaching of CESL Copper concentrate leach residues was performed under a
variety of conditions. Kinetics of reaction are fast with over 50% of the gold extracted in 2 minutes.
Under the conditions tested here, final gold extractions were typically in the range of 80
80-90%.
90%. A model for
the CESL Gold process was generated. The reaction appears to be second order with respect to gold and
first order with respect to cyanide and oxygen. Residues samples were leached in the ground and unground
condition. Ground residues have a gold leaching rate constant roughly double that of the unground
39
residues. The model adequately predicts

predicts extraction for ground residue samples at most time intervals. The
model is less accurate for unground residue samples, which probably reflects experimental error.
Figure 9 Comparison of model predicted extractions for ground and unground residues at different values
of [Au]s,. Constant values of [CN-] (1000 mg L-1) and [O 2] (835 mg L-1) and [Au]s,0 = 20 g t-1
REFERENCES
Barr, G., Grieve, W., Jones, D.L., Mayhew, K., 2007. The new
ew CESL gold pprocess. In: Proceedings of the
Conference Castlemaine, Victoria
Victoria, Australia
Australia:: Alta
2007 ALTA Copper International Conference,
Metallurgical Services.
de Andrade Lima,
Lima, L.R.P. and Hodouin, D., 2005. A lumped kinetic model for gold ore cyanidation.
Hydrometallurgy,
Hydrometallurgy 79, 121-137.
121
Jones, D.L., 1996. CESL Copper Process.
Process Paper presented at RANDOL Copper Hydromet Roundtable,
Vancouver,, Canada.
Ling, P., Papangelakis, V.G., Argyropoulos, S.A. and Kondos, P.D., 1996. An improved rate equation for
cyanidation of a gold ore. Canadian
Can
Metallurgical
Metall
uarterly, 35, 225
225-234.
Quarterly
Nicol, M. J., Fleming, C. A., and Cromberge, G., 1984. The absorption of gold cyanide onto activated
carbon. II.. Application of the kinetic model to multistage absorption circuits. Journal of the
Afr
itute of Mining
ing and Metallurgy, 84, 70
70-78.
Southern African
Institute
Po, F., 2007. SCN formation rate from Tiger and CESL elemental sulphurs (Internal Report)
Report). Richmond,
BC, Canada: CESL Limited.
Sahu, S.K., Asselin, E., 2011. Characterization of residue generated
enerated during medium temperature
emperature leaching
eaching
halcopyrite concentrate
oncentrate under CESL conditions. Hydrometallurgy
Hydrometallurgy, 110, 107-114.
of chalcopyrite
Wood Mackenzie Brook Hunt, 2007. Metals Concentrates Service.
41
ENHANCING CIL GOLD EXTRACTION BY HARD PARAFFIN WAX BLANKING OF

DOUBLE REFRACTORY ORE PRE- OR POST-PRESSURE OXIDATION (POX)
*G. Van Weert1, J. Jiang2, O. Wang3, Y. Choi4
1
ORETOME Limited
16668 Humber Station Road
Caledon East, ON, Canada L7E 0Z1
(*Corresponding author: oretome@sympatico.ca)
2
Barrick Technology Center

323 Alexander Street
Vancouver, B.C., Canada V6A 1C4
3
Process Research ORTECH

2350 Sheridan Park Drive
Mississauga, ON, Canada L5K 2T4
4
Barrick Gold Corporation
BCE Place, Canada Trust Tower
161 Bay Street, ON, Canada M5J 2S1
ABSTRACT
As part of a general review of processing double refractory ores through Barrick Golds
autoclaves / CIL facility at Goldstrike, blanking the preg robbing native carbon in the process solids with
hard (m.p. 55 - 60 oC) paraffin wax was studied, specifically in relation to pressure oxidation. The
improvement in CIL gold extraction was found to depend on the wax addition point, with hot, dry
contacting of the ore in the presence of wax - prior to POX - yielding the largest, most consistent
improvement in gold extraction.

Niagara, ON, Canada
Edited by
42
INTRODUCTION
Double refractory gold ores present two barriers to gold extraction. The first is generally a
physical barrier: the gold is encapsulated or dispersed in a matrix which is impervious to the gold lixiviant.
In most cases, including Carlin Trend, NV, deposits, this involves a pyrite or arsenopyrite matrix, although
minor gold may also be dispersed in competent silica (quartz) or iron oxides. Gold can be rendered
accessible by oxidative destruction of such sulphide matrices. At Goldstrike this is practised by roasting
and autoclave oxidation (Thomas, 1994). It is the latter route to which this paper refers.
The second barrier refers to the actual gold recovery. Gold may be extracted from the pressure
oxidized solids with cyanide, forming a gold cyanide complex. One characteristic of this complex is that it
adsorbs on graphitic surfaces. This is taken advantage of on a large scale by gold millers, who use manmade activated, i.e., graphitized carbon particles to remove the gold from solution during leaching: the
Carbon-In-Leach, or CIL process. The gold cyanide bearing carbon particles are larger than the ore solids
and can be separately recovered by screening. Goldstrike uses the CIL technology to recover gold.
The second barrier becomes problematic when the ore naturally contains graphitic or
carbonaceous material, hereafter referred to as native carbon (versus the man-made activated carbon). This
material may also adsorb gold cyanide in competition with the activated carbon. Since the native carbon is
ground with the ore it is much smaller than the activated carbon. Any competition between the two carbons
may produce a loss of gold from the pregnant leach liquor to the process tailings. This phenomenon is
called preg robbing. Goldstrike ores come from the Carlin trend, which is known for the occurrence of
native carbon (Adams & Burger, 1998; Schmitz, Duyvesteyn, Johnson, Enloe & McMullen, 2001; Tretbar,
2004).
A general review of processing double refractory ores through Barrick Golds autoclaves / CIL
facility at Goldstrike was started in 2009. Test work at Process Research ORTECH suggested that either a
more active activated carbon be pursued or developed (Van Weert & Choi, 2012), or a better means to deactivate native carbon in-process be researched for treating Carlin Trend ores. This paper discusses the
latter approach, which involves coating the native carbon with low vapour pressure, molten paraffin wax.
Figure 1 illustrates the effect of wax treating a severely preg robbing Goldstrike ore (BR-22). Without wax,
the gold content of the CIL residue can actually increase when loaded carbon is used. The native carbon in
this ore will readily deplete loaded activated carbon. Hot wax treatment can reverse the gold loss. What
one operator calls preg robbing, may be a minor drawback to others. The samples described in this work
were preg robbing to an extent that virgin activated carbon needed to be used to compare behaviour; as
illustrated in Figure 1 the native carbon in some Carlin trend ores can desorb gold cyanide from loaded
plant carbon (Van Weert& Choi, 2011). Other ores described in the literature are much less preg robbing
and this influences the efficiency of hydrocarbon blanking. The addition mentioned for two operating
systems was 200 - 300 g diesel oil per tonne ore. Additions used in this work were at least 10 times higher.
Carlin trend ores are not the only gold ores with native carbon; such ores occur not infrequently.
The Carlin trend ores are more unique in that they are double refractory. Single refractory gold ores, i.e.,
preg robbing ones, are generally shunned by gold millers for the process problems they cause and hence
are not purposely explored for by geologists. Nevertheless, the literature refers to testwork and operations
where native carbons were de-activated. The most common method is treatment with diesel oil. The terms
blinding and blanking are both used to describe this technology. For this paper the term blanking is
preferred; the word blinding already has several connotations in gold milling, such as screen-, filter
cloth-, or even activated carbon-blinding.
BLANKING PRACTISES
Although there are literature references (Kazakoff & Mortimore, 1999), none of these go into
detail as to how the diesel oil is applied and what problems are generally encountered. Simplified
descriptions of mixing ore and oil are given without a ringing endorsement of the technology. One would
43
suspect that the handling of diesel oil could

ould result in a number of unsuitable Mill conditions in terms of
personnel hygiene,
hygiene, such as hydrocarbon vapours, accretions on equipment, fire hazards (welding), particle
agglomeration (CIL screens
screen blinding) and blanking of the activated carbo
carbonn itself in the CIL circuits. In
personal communications with current and former Mill operators rubber deterioration was mentioned as a
big concern as it limited the choice of mill and pump linings. It is interesting to note that the Fosterville
gold mine in Australia, while treating a similar ore as the co-owned
owned Stawell mine, adopted a heated leach
process on CIL tailings. There is no mention of hydrocarbon blanking in the literature abstract
Binks&Wemyss, 2011).
2011
(Binks&Wemyss,
Figure 1 Gold in cyanide leach residue

residue using various types and amounts of activated carbon. The
Goldstrike (GS) carbon was derived from coconut shells and plant loaded to approx. 1200 g Au/tonne. The
Norit carbon was the extruded type, as received. CIL leaching was done by standard bottle roll. BR-22
22 is
the most preg robbing, double refractory ore at Goldstrike. More detai
details
ls in Van Weert and Choi (2011)
The use of liquid paraffin oil could probably overcome some of the diesel oil negatives. However,
itt was conceptualized that going to hard wax applied above its melting point would have the potential to
overcome all real and perceived negatives associated with diesel or liquid paraffin oil for blinding
carbonaceous (preg robbing) matter, especially in double refractory gold ore slated fo
forr treatment by
pressure oxidation. Flowsheets with pressure oxidation (POX) contain a thermal window where solid wax
becomes molten, offering a means of distributing liquid wax and thus blanking native carbon. In the colder
CIL section of the plant,
plant the paraffin
raffin wax will
w have reverted to the solid state
state. Critically,, solid wax has a
low vapour pressure under POX conditions (see Flammability
Flammability).For
For a double refractory ore the pressure
oxidation step provides a number of options, outlined in Figure 2.. Wax can be contacted with ore during
the preheating of autoclave feed (pre-POX).
(pre POX). Molten wax could also be injected directly into an autoclave
compartment (in-POX)
(in POX). By excluding
xcluding the oxygen phase in the last compartment (or in aan oxygen-free
free
dedicated autoclave)
autoclave) concerns about flammability may be alleviated. Alternatively, wax could be added
during the cooling of the autoclave discharge (post-POX).
(post POX). A final option involves milling, i.e.
i.e.,
comminuting ore and wax in a suitable mill at approx.75 oC (also classi
classified
fied as pre
pre-POX
POX in this paper).
ariants of the latter involve dry tumbling of wax and already ground ore at approx. 75 oC or final fine
Variant
grinding of coarse ground ore with wax before POX feed preparation
preparation (not shown)
shown).
44
ORE
DRY
HOT
GRIND
PRE-HEAT
SLURRY
WAX ADDITION POINTS
POX No O2
COOL
SLURRY
CIL
Figure 2 Array of possible hard paraffin wax addition points

HARD WAX BLANKING OF ACTIVATED CARBON
In the planning of this work it was assumed that the wax blanking characteristics of preg robbing
carbonaceous matter in Goldstrike ores are similar to those of commercial activated carbon. The early
exploratory work on the blanking of native carbon was therefore done with NORIT 3515 activated carbon
to evaluate hard wax addition procedures and rates. Near complete blanking results were obtained by using
60 wt% wax to treat dry activated carbon (see Figure 3). This pointed to dry grinding or dry contacting of
preg robbing ore at approx. 1wt% carbonaceous matter with <1 wt% paraffin wax at the mildly elevated
temperature usually associated with dry grinding. Although simple, such a procedure was not feasible in
the current Goldstrike POX/CIL facility. The early work was concluded with wax blanking tests on a
variety of ore types from the Goldstrike operation, utilizing subsequent gold cyanide spiking tests to
determine changes in the ores preg robbing characteristics. Results (Van Weert, Jiang, Wang & Choi,
2012) pointed in the same direction, i.e., to achieve consistent blanking of these ore types, the wax must be
allowed to contact the dry ore for some time at elevated temperature; in this work between 65 and 150 oC.
The higher temperature may allow the use of less paraffin wax.
The ore at Goldstrike, however, is double refractory; gold is both locked into pyritic sulphides and
subject to adsorption onto native carbon during cyanide leaching after POX. To reduce the results of this
early test work to industrial practise at Goldstrike, a number of steps were required. First of all, the efficacy
of wax blanking should be judged on the basis of actual cyanide extractions, not preg rob numbers. This
meant subjecting the ore to autoclave oxidation, after wax blanking, followed by a CIL leach. More recent
wax blanking test work also explored in-POX addition, i.e. injection of liquid wax into the first autoclave
compartment, or into the slurry feeding to it. This appeared the best option to advance the paraffin wax
blanking technology at a gold mill with existing equipment, such as Goldstrike. Unfortunately, simulation
of this at batch-benchtop scale is difficult, the weight of wax needed at the <1 wt% level is so small that the
wax could be lost unknowingly. Continuous pilot autoclave operation studying the effect of agitation,
power input and impellor wear is called for to generate process parameters.
Autoclave discharges of double refractory ores could also be blanked after cooling to approx.
85 oC. Results may be erratic, however, based on the present testwork (Tables 1 and 2).
45
Figure 3 Blanking of Norit 3515 activated carbon with various amounts of hard paraffin wax,
followed by an adsorption test to measure gold cyanide uptake vs time (Van
Van Weert, Jiang, Wang & Choi,
2012).
2012 . Full blanking occurred between
between 30 and 60 wt% wax addition
BLANKING HIGHLY PREG ROBBING, DOUBLE REFRACTORY GOLDSTRIKE ORES
re
wax, it was conceptualized that to get
of the early blanking work with paraffin wax
In a 2009 review
around flammability issues, the last compartment in an autoclave could be made oxygen free by venting
the O2 bearing gases and recompressing with N2, removing most of the concerns about paraffin wax
flammability. As an alternative,
alternative multiple autoclaves might feed into a separate
separate, N2 purged autoclave for the
post
, but at POX temperature (approx. 220 oC).Wax
Wax could also be added to the
wax blinding process post-POX,
autoclave discharge after partial pressure letdown, at about 170 oC, orr after final discharge at 85 oC (see
ure 2).
2 It was therefore decided to have another look at the various pre- and post
post-POX
POX options for wax
Figure
addition. High and low gold grade ores with various levels of preg robbing activity were bench (alkaline)
ed and treated with paraffin wax under a variety of conditions
conditions,, followed by bottle roll CIL gold
POX-ed
extractions.
extractions Only
ly a summarized version of this testwork is presented here.
igher gold
gold, high
Att least six ore types have been tested for wax addition in dozens of tests. Higher
carbonate, preg robbing feeds available at PRO for testing were MP
MP-44 and BR
BR-24. The latter was severely
preg robbing, no wax POX/CIL gave only 45%
% gold recovery. Results on two lower grade gold ores are
also reported: BR-22
BR 22 and Composite #5. BR-22
BR 22 is probably the most preg robbing ore at Goldstrike; when
its autoclave discharge is cyanided for 24 hours before activated carbon is added for aanother
nother 24 h CIL only
0.3% of the contained gold is recovered. Using 5 g/L
g/ cyanide and 30 g/
g/L carbon recovered 2.5% of the
gold. Most
M of the blanking and CIL equilibrium benchtop testwork
work has been carried out with this material
(see also Figure
Fig
1).. Composite #5 is a high sulphide ore and POX discharge liquors would have a pH of
about 1.5. All other reported POX testwork was done without pre
pre-acidification,
acidification, i.e.
i.e., under neutral pH
alkaline) POX conditions.
condit
The Tables show the CIL results on POX slurries using the following PRO test
(alkaline
conditions (exceptions are noted in the Tables):
Table
Feed.
POX.
CIL.
200 mesh, dry grind

-200
Bench test: 2 L autoclave, 2 hours at 225 oC, 100 psi O 2, 35 wt% slurry, 500 rpm
Bottle roll: four days, pH=11, 0.5 g/L
g/ NaCN, 170 rpm, virgin Norit 3515
3515@
@ 5 g/
g/L.
46
Table 1 Bottle roll CIL results on samples of higher gold grade preg robbing ore from two Goldstrike ore
zones (not necessarily representative of the entire zone). Addition of small amounts of wax on benchtop
scale is problematic at best. However, gold recovery to carbon is enhanced by 35- 40% for the moderately
preg robbing BR-24 sample. Removal of organics in the POX slurry had no discernible effect
POX
Test
#
BR-24
Test Particulars
Gold, g/t
Calc.
Head
CIL
tails
Gold
Extr.
%
POX
Test
#
17
No wax.
8.2
4.53
44.8
BLANKS
40
34
21
No wax, Carbon
pretreat of POX
slurry.
10.1
4.63
54.1
26
1.94
80.6
58
In-POX
56
60
13
14
15
16
0.25 wt% wax at

start of POX.
10.0
Gold
Extr.
%
CIL
tails
No wax, wet grind.

As per SGS
procedure for
POX/CIL (no wax).
No wax, C pretreat
of POX slurry to
remove dissolved
organics.
No wax, (dry grind).
8.2
9.4
3.51
4.19
64.8
55.3
9.1
3.08
64.1
9.6
3.25
66.2
0.25% wax, added

to dry feed to
autoclave.
As 56, 1% wax.
9.6
1.56
83.8
10.0
1.70
83.0
9.9
1.40
85.9
10.0
3.05
69.4
10.0
1.76
82.4
POX, no vent,
1% wax, hold 30
min.
As POX 13,
vent.
8.2
1.78
8.1
1.39
82.8
27
As POX 13,
hold 120 min. no
vent.
As POX 14,
hold 120 min.,
vent.
8.6
1.68
80.5
28
7.9
2.06
74.8
43
As Pox 28, 0.25%

wax.
9.1
1.54
83.2
44
As POX 43, 700

rpm.
As POX 27, wet
grind.
As POX 45, 700
rpm.
9.1
5.20
43.1
9.7
1.86
80.8
10.1
1.53
84.8
9.5
1.58
83.4
46
31
Gold, g/t
Calc.
Head
57
Post-POX
78.4
25
45
19
MP-4
Test Particulars
2h hot roll after

dry grind, 1%
wax.
1% wax to slurry
at 90 C, hold 15
8.2
1.36
83.4
8.4
1.76
79.0
Pre-POX
29
1% wax after POX

and vent, held for
120 min.
1% wax after POX
and vent, held for
30 min.
As POX 27, no
vent.
As POX 19.
47
Table 2 Blanking results for severely preg robbing Goldstrike sample BR-22 and high sulphide
Composite #5. For the latter, a standard POX may be insufficient to oxidize all sulphides; results could be
erratic due to incomplete sulphide oxidation. Ceraline 694 is a low volatility (at 200 oC) polymer, tested to
explore flammability issues. Carbon used: Virgin Norit 3515
POX
Test
#
117
155
120
1-4
BR-22
Test Particulars
Gold, g/t
Gold
Extr.
Calc. CIL
%
Head Tails
1 h POX, no wax,
As 117
2h POX. Add 3x reg. C in
CIL
As 117, 24h CN, no Norit,
then 24h standard CIL
109 1 h POX, then inject 0.25%

wax, hold 30 min at 225 C
500 rpm
110
As POX 109, 700 rpm
113 As POX 110, but add and
hold wax at 80 C, (2 h POX)
114
2 h hot roll, 1% wax, 2 h

POX, 96 h CIL
115 As POX 114, 1 h POX, 24 h

CIL
165 As 115 + MWing after hot
roll
166
As 165, 0.25% wax
156
As 115, hot mill
220
1% Ceraline 694
POX
Test
#
Composite #5
Test Particulars
All dry ground
BLANKS
34.0
1
no POX, no wax,
n/a
2
Standard POX, No wax
37.3
54
POX @700 rpm, 2 h, no wax,
no venting
0.3
4
no POX, wax injected, 30 min,
230 C, 500 rpm
Post-POX
65.3
6
1% wax after 2h POX at 230 C,
vent, held for 120 min. 500 rpm
3.4
n/a
3.1
2.28
2.66
1.97
3.4
3.39
3.5
1.2
3.3
3.3
1.30
2.61
66.1
20.5
3.4
1.15
38
39
51
Pre-POX
66.5
30
3.4
1.76
60.1
35
3.5
0.97
72.6
32
3.3
3.3
3.6
0.90
0.97
1.23
73.0
70.6
64.1
12
24
Gold, g/t
Calc. CIL
Head Tails
Gold
Extr.
%
2.4
4.3
2.5
2.29
2.71
0.97
5.9
36.9
61.3
2.5
2.28
9.4
2.4
0.44
81.6
As POX-6, held 30 min.

As POX 12, no vent
2.0
2.6
0.52
1.08
74.1
57.8
As Pox 6, 0.25% wax

As POX 38, 30 min
As POX 39 , 700 rpm
2.4
2.3
2.9
0.66
1.01
0.60
72.2
55.5
79.2
2 h hot roll at 70 C
1% wax, then
2h POX, 24 h CIL
As POX-30, 2% wax
2.9
0.69
76.0
2.5
1.02
59.1
3.3
2.02
39.6
Beaker test, 95 C, 1%
wax, 2h POX, 24h CIL
OBSERVED EFFECTS OF WAX ADDITION

Results for BR-22, -24, MP-4 and Composite #5 are presented in four groups: Blanks, in-POX,
post-POX and pre-POX. The description under Test particulars gives summary details. In-POX and prePOX have to deal with paraffin wax actually being present during sulphide oxidation, i.e., in the slurry or
in the slurry and the freeboard gases. There have been a number of effects observed when paraffin wax was
injected into the oxidized slurry in the laboratory autoclave and held under agitation for 30 or120 minutes
at 230 oC:
1.
2.
3.
Gold recovery on carbon is improved compared to the blank (no wax post POX). This was
observed for all six ore types tested. The average improvement was 10-20 %, but 20-40% for MP4 and BR-24.
Longer holding times of the wax/slurry mix at 230 oC appear to help.
More intense agitation, particularly at 85 oC, appears to help.
48
4.
Venting the O2 gas and re-pressurizing at 230 oC before wax injection appears to help gold
recovery, compared to no-venting. The results are not conclusive, however, and an explanatory
mechanism is not apparent.
It is clear that post-POX, in-autoclave addition of wax offers a higher gold recovery, but the
cost may be high in terms of lost production from using part of the autoclave volume for blinding, and
from the increased steam consumption needed to offset the effects of venting, if indeed required. Agitation
of the slurry to effect good slurry/wax contacting under high temperature conditions may turn out to be less
of a challenge however, than adding wax to the autoclave discharge at approx. 85 oC. That option appears
to be particularly sensitive to good mixing. The erratic results are ascribed to dispersion issues (see BR22), although changes in hydrophobicity of native carbon during POX cannot be ruled out.
As mentioned already for post-POX, re gold recovery, in-, post- and pre-POX additions of wax
have all reported noticeable improvements as can also be deduced from the results in Tables1 and 2. Hot
roll wax addition (pre-POX) has consistently given the highest gold extractions for all Goldstrike materials
tested, but that alternative is academic for the Goldstrike autoclave plant. Hot-grind or -roll addition would
require dry grinding instead of wet, a capital intensive change for an existing operation.
EFFECT OF MOLTEN WAX EMULSIFICATION
To fit better with the existing process at Goldstrike, the post-POX, post autoclave option was
further explored using a variety of wax products at Barrick Technology Center on acidic and alkaline
autoclave discharges of several Goldstrike ore types. Contacting times and agitator power input were
varied at 90 oC with little effect on gold recovery. Better results were obtained with a commercial wax
emulsion, but this appeared more due to the presence of an emulsifier than to the improved dispersion of
the wax. The effect of surface agents on blanking preg robbing ore constituents has been described in detail
(Buckingham & Robles, 1992, Adams & Burger, 1998). Activated carbon, however, is also blanked by
emulsifiers, hence their dosage and the regeneration of surfactant laced activated carbon becomes critical.
Stable wax/water emulsions were produced by adding small amounts of commercial emulsifier
(Tweet-20). These emulsions were used to blank Goldstrike autoclave discharge #2, a medium preg robber,
described in more detail elsewhere (Van Weert & Choi, 2011). There is no question that emulsified wax
results in blanking, even on post-POX discharges. However, when the same quantity of Tweet-20 is added
without wax, similar results are obtained.
A small number of additional tests were carried out at PRO on the post-POX, post-autoclave
option with machine dispersed molten paraffin wax (no emulsifiers). It was postulated that dispersion of
wax before dosing would carry lower operating costs for this option than dispersion in the mineral slurry.
Mechanical dispersion (Silverton) and ultrasound dispersion (Hielscher) were both tested. It was noted that
the wax dispersions coalesced in seconds and blanking tests with such dispersions had to be carried out
without delay. This proved difficult with the small bench top equipment and minor amounts of wax used in
batch mode. It was visualized that by mounting a wax/water homogenizer directly above, and discharging
in the autoclave discharge tank, much more efficient use of the wax could be achieved without having to
resort to the use of emulsifiers. One set of results on ultrasound mixed wax is given in Table 3. Dispersion
by standard agitation actually gave a lower gold extraction, a good example of the erratic nature of that
procedure. U/S emulsified wax gave an encouraging result, using Norit 3515 as the carbon. As earlier work
has shown, plant loaded activated carbon gives lower gold recoveries from the leach liquor (Van Weert &
Choi, 2011).
49
Table 3 Gold adsorption by various carbons from a severe preg robbing autoclave discharge before and
after blanking with 0.25 wt% hard paraffin wax
Test #
GSAC 17
GSAC
GSX 12
GSX 21
GSX 22
GSX 23
GSX 24
Test Particulars: Goldstrike autoclave discharge #2 (Spring 2010)

Blanking agent: Sasol Wax #4257.
BLANK tests, with no-wax
As received , CIL, Norit 3515
Bottle roll cyanidation (i.e. no CIL) No Carbon
(Post-POX) blanking tests, with 0.25 wt% wax
Add 0.25% wax, 85 oC, 1h,500 rpm Norit 3515
Add 0.25% wax, 85 oC, U/S emulsified Norit 3515
As GSX 21, GS virgin act. carbon
As GSX 21, GS regenerated AC
As GSX 21, GS loaded AC
Gold, g/t
Calc.
CIL
Head
Tails
Gold
Extr.
%
3.2
3.0
1.22
2.80
62.2
7.4
3.0
3.3
3.2
2.8
3.2*
1.33
0.87
0.88
0.90
1.25
55.6
75.4
72.7
67.4
60.9*
*Gold extraction calculated by assuming the Goldstrike discharge #2 sample to be 3.2 g/t Au.
OTHER CONSIDERATIONS ON THE USE OF HARD PARAFFIN WAX
Supply/Market
Hard paraffin wax is a refined product of slack wax, which in turn is a byproduct of heavy oil
processing by refineries. The supply of heavy oils is increasing; the demand for hard waxes is not, at least
not to the same degree. One may expect price stability. At the time this testwork was done, coastal
refineries offered slack wax at approx. US$ 1000 / tonne. Hard wax is used extensively in the food industry
for packaging.
Flammability
Prudence demands that passing a flammable material through an oxidizing process step requires a
HAZOP study. In the spring of 2007 a study was commissioned with Prof. Michael Misovich of Hope
College on wax vapour pressure under POX conditions and whether such a paraffin concentration in the
autoclave freeboard vapour would be within flammability limits. Whereas the gas concentration of paraffin
wax was calculated to be very low, the molecular weight of wax is very high. There is also a lack of
information on hydrocarbon flammability in concentrated steam / CO2 environments. It was concluded
flammability may be borderline and should be explored experimentally.
The vapour pressure of the two Sasol samples available were subsequently measured in a
modified TGA setup at 225 oC. It appears that highest mp Sasol wax has only a minor vapour pressure
below 225 oC (it becomes measurable at 275 oC). These measurements suggest that POX at 200 oC is fully
compatible with Sasol wax # R4257 (mp 63 oC).The presence of activated carbon lowered the evaporation
rate. Whether native carbons in Carlin Trend ores have the same effect could not be measured with
equipment at hand.
DISCUSSION
Earlier, exploratory work on the blanking of preg robbing carbon used activated carbon to define
hard wax addition methods and rates. Dry conditions and up to 60 wt% wax proved optimum. This pointed
to dry grinding or dry contacting, not available or feasible in the Goldstrike POX/CIL facility. Therefore,
follow-up testwork focussed on in- and post-POX wax addition. These would be the least disruptive
options for the Goldstrike plant to apply paraffin wax blinding. All it would require for, say in-POX, is the
50
injection of liquid wax into the first autoclave compartment, or in the slurry feeding to it. Unfortunately,
simulation of this at batch benchtop scale is difficult; the weight of wax needed at the 0.25 wt% level is so
small that the wax could be lost unknowingly. Continuous pilot autoclave operation studying the effect of
agitation, power input and impellor wear is therefore called for to evaluate this route.
This in-POX option requires the presence of wax in a POX environment and raises the issue of
flammability of wax and/or its decomposition products acting as contaminants. Flammability has not been
an issue for the presence of ammonia in autoclave processing of nickel sulphides, or for elemental sulphur
vapour when autoclave processing of zinc sulphides. No adverse effects were observed in any of our tests.
A proper HAZOP study is required, however, to justify piloting. Blanking double refractory feeds with
hard wax may also become accepted as an industrial technology, for instance by stipulating 200 oC as an
(initial) POX operating maximum. There are low vapour pressure man-made meltable polymers available,
likely at higher cost. One was tested. These could extend the POX operating temperature. Finally, a
separate N2 blanketed pressure vessel post-POX, post-autoclave operating at POX temperature or after the
first stage of pressure letdown (170 oC) is an alternative if the associated loss in production, or increase in
capital costs is acceptable.
The final, least promising option appears to be blanking the autoclave discharge after cooling to
approx. 85 oC. Results with this variant have been erratic. This may have been due to mixing, low wax
fluidity, or changed hydrophobicity of the preg robbers in the ore. Mixing near the boiling point at
atmospheric pressure invites cavitation. This is hard to detect at benchtop scale. Low wax fluidity may
have resulted in the formation of wax/native carbon agglomerates in incidental testwork on acidic
autoclave discharges at Goldstrike. Therefore, the possibility that fresh wax at this stage may collect, even
blank some of the newly liberated gold particles cannot be overlooked. However, the gold in Goldstrike
ores is predominantly submicroscopic and may not be hydrophobic. There is no direct evidence for gold
coverage by wax, although some tests with additional wax (1 wt% vs 0.25 wt%) have given slightly lower
gold extractions.
In summary, hard paraffin wax addition offers a means of using POX/CIL technology for treating
double refractory gold ores, possibly limited to a max.200 oC POX operating temperature. For the ores
tested, blanking appears most effective when carried out early in the process, on dry ore. This also gives
the maximum length of time for ore/wax contacting. Following a hot ore/wax tumbling procedure, CIL
gold recoveries increased by 20-40% for severely preg robbing ores. In similar tests (not reported) on
single refractory, i.e.,preg robbing gold ores not requiring POX, direct cyanidation became possible. Due to
dosing problems with small wax additions, continuous hot grinding and POX pilot plant trials appear
needed to reduce these results to industrial practice and determine optimum gold recovery as a function of
grind and wax addition parameters. It is assumed that activated carbon contamination during CIL will not
be an issue with the use of hot paraffin wax, as compared to diesel oil; this was not experimentally verified.
ACKNOWLEDGEMENT
The authors thank Barrick Gold Corporation for the financial support of this testwork as part of its
search for strategic process solutions, and for its permission to put these early results in the public domain.
REFERENCES
Adams, M.D. &Burger, A.M. (1998). Characterization and blinding of carbonaceous preg-robbers in gold
ores. Minerals Engineering, 11, 919-927.
Binks, M. and Wemyss, P.(2011). Fosterville gold mine heated leach process. Abstract at
www.ausimm.com.au/metplant2011.
51
Buckingham, L. and Robles, A.T. (1992). Utilization of surfactants in recovery of gold employing carbon.
Proceedings of the 24th Canadian Mineral Processors Conference, Ottawa, ON, Jan 1992, Paper
9.
Kazakoff, J. &Mortimore, A. (1999). The Kumtor Gold Mill startup and startup challenges. Proceedings of
the 31st Annual Canadian Mineral Processors Operators Conference, Ottawa, ON, Jan 1999,
Paper 23.
Schmitz, P.A., Duyvesteyn, S., Johnson, W.P., Enloe, L. & McMullen, J. (2001). Adsorption of
aurocyanide complexes onto carbonaceous matter from preg-robbing Goldstrike ore.
Hydrometallurgy, 61,121-135.
Thomas, K.G. (1994). Research, engineering design and operation of a pressure hydrometallurgy facility
for gold extraction. Doctoral Thesis, Delft University of Technology, 123-171.
Tretbar, D. (2004). Preg-Robbing carbon in the processing of gold-bearing ores: Definitions, analytical
methodology and characterization, Geological Society of America, Abstracts with Programs,36,
No. 4, 23.
Van Weert, G. & Choi, Y. (2012).The limitations of activated carbon in CIL circuits: Handling preg
robbing solids. Proceedings of the 44th Annual Canadian Mineral Processors Operators
Conference, Ottawa, ON Jan. 17-19, 2012, 315-327.
Van Weert, G. & Choi, Y.(2011).CIL gold extraction from preg robbing autoclave discharges. Proceedings
of the 50th Conference of Metallurgists Gold 2011, Canadian Inst. of Mining, Metallurgy and
Petroleum, Montreal, QC, Oct. 2011, 619-630.
Van Weert, G., Jiang, J., Wang, O. & Choi, Y. (2012). Simulating the blanking of pregrobbers in gold ores
by treating activated carbon with hard paraffin wax. Presented at the T.T.Chen Symposium, TMS
Annual Meeting, Orlando, FL, March 11-15, 2012.
53
ALKALINE PRESSURE OXIDATION OF PYRITE IN THE PRESENCE OF SILICA:

A SURFACE STUDY
A. Dani , *V.G. Papangelakis
University of Toronto
200 College Street
Toronto, Canada M5S 3E5
(*Corresponding author: vladimiros.papangelakis@utoronto.ca)
ABSTRACT
Alkaline pressure oxidation, particularly in the presence of trona as additive, can be used to
oxidize high carbonate refractory gold ores as it prevents the formation of CO2 in the autoclave. However,
the presence of silica in the ore can lead to the encapsulation of pyrite due to the solubility of silica in
alkaline solutions and its subsequent re-precipitation on the reacting pyrite surface, leading to the
formation of a passive layer. This fundamental study investigates the chemical composition and thickness
of the passive layer on a rotating pyrite disk using XPS and SEM, as a function of process conditions at
230C, in an aqueous slurry containing silica sand, sodium carbonate and calcium carbonate under 100 psi
of oxygen overpressure.

Niagara, ON, Canada
Edited by
54
INTRODUCTION
Alkaline pressure oxidation (POX) has been used successfully to treat high carbonate refractory
gold ores, which contain carbonates in addition to sulphides, most notably at Mercur and Goldstrike mines
operated by Barrick Gold. There are several advantages to using alkaline POX over its acid counterpart,
especially due to high carbonate content. First, it eliminates the production of CO2 in the autoclave without
resorting to pre-acidification, which allows for high oxygen utilization. Second, alkaline POX suppresses
the formation of elemental sulphur and intermediate sulphur oxyanions (such as thiosulphates and
dithionates), which reduce gold recovery. Third, the use of sodium hydroxide or salts prevents the
formation of anhydrite scale by forming soluble sodium sulphate. Other advantages are the use of cheaper
materials of construction and the formation of non-acidic residue that do not require further treatment prior
to cyanidation (Thomas, 2005).
Sodium carbonate in particular is a promising reagent for alkaline POX because it was shown to
significantly accelerate the kinetics of pyrite oxidation by molecular oxygen, when compared to other
reagents such as sodium hydroxide, sodium borate and calcium hydroxide. This has been attributed to the
following factors: a) the faster oxidation kinetics of Fe2+-CO3 complexes compared to Fe2+ oxidation,
b) the buffering effect of carbonate ions on the acidic pyrite surface, and c) the increased solubility of
oxidizing Fe(III) species due to carbonate complexation (Caldeira, 2010).
On the other hand, a competing effect of decreased oxidation has been observed in the presence of
silica due to passivation of the pyrite surface. Silica is present in Goldstrike autoclave feed to the order of
80%. Operations that use whole ore as feed to autoclaves experience reduced pyrite oxidation extents and
as a consequence, reduced gold recoveries. Previous work in our research group showed a 50% drop in
iron oxidation in the presence of silica, compared to that in the absence of silica. Pyrite oxidation increased
with the addition of sodium carbonate until a maximum at 77% stoichiometric (w.r.t. pyrite) sodium
carbonate, and then decreased with further addition. Passivation of the pyrite surface was visible as a dense
coating around pyrite particles containing up to 13 wt% silicon (Peters, 2011). The passivation effect was
attributed to increasing solubility of silica with alkalinity, making it available for precipitation on the pyrite
surface as iron silicates (Descostes et al., 2002; Iler, 1979):
FeS2 + 7.5 O2 + 4H2O = Fe2O3 + 4H2SO4
2FeS2 + 7.5 O2 + 5H2O = 2FeOOH + 4H2SO4
SiO2 + 2H2O = Si(OH)4(aq)
The precipitation of silicic acid as iron silicates happens on the pyrite surface due to the availability of iron
and can be represented by the general equation:
ySi(OH)4(aq) + x(Fe2O3, FeOOH) + nH2O = (Fe2O3,FeOOH)x(Si(OH)4)y.nH2O
The competing effects of accelerating pyrite oxidation and increasing silica solubility make
sodium carbonate concentration the dominant factor in controlling the growth of the passive layer. This
paper investigates the effect of varying sodium carbonate concentration on the thickness of the passive
layer. In order to isolate the effect of sodium carbonate on passive layer growth, other variables, surface
geometry and hydrodynamics, were kept constant by providing a single, uniformly accessible pyrite
surface available for oxidation. This was achieved by constructing a rotating disk with an embedded pyrite
cube.
EXPERIMENTAL SET-UP
Natural pyrite cubes (99.4% pure, approx. 4 cm 4 cm 4 cm, sourced from La Rioja, Spain)
were obtained from the Geode Gallery (Roseville, IL, USA). These cubes were cut into smaller, uniform
1.5 cm 1.5 cm 1.5 cm cubes using a Buehler Isomet 5000 linear precision diamond saw, polished to
6 m fineness using Buehler MetaDi diamond suspensions, cleaned in 3M hydrochloric acid and rinsed in
55
DI water before being used in experiments. A 5 cm diameter PTFE disk was machined with a 1.5 cm
1.5 cm 1.5 cm cubic hole in the centre. The pyrite cube was wrapped in Teflon tape, embedded in the
hole and held in place with two SS-316 screws. The disk was attached to the bottom of the impeller shaft
via a stainless steel base and rotated at 300 rpm during operation. All experiments were carried out in a 2 L
Parr titanium autoclave, at 230C, under 100 psi of oxygen overpressure in 1.2 L of DI water. Calcium
carbonate and silica sand were added in large excess of their solubilities (24 g and 22.6 g respectively) to
maintain saturation levels in the solution.
Experimental Procedure
The autoclave was loaded with reagent grade sodium carbonate solution, calcium carbonate and
silica sand, and the pyrite sample mounted in its disk. After sealing, the autoclave was evacuated to remove
air from the headspace to prevent premature oxidation. Using two 2 kW band heaters, the vessel was
heated to 230 C before 100 psi of oxygen gas was introduced inside. The system was maintained at
temperature and pressure for 1 hour. Process control was maintained using a LabView script. Following
the experiment, the pyrite sample was rinsed in DI water to remove adsorbed ions from the oxidized
surface and stored under acetone.
The oxidized surface was then analyzed for its chemical composition using X-ray Photoelectron
Spectroscopy (XPS) (Thermo Scientific) and for its thickness using Scanning Electron Microscopy (SEM)
(JEOL JSM6610-Lv).
XPS was carried out with a monochromatic Al K- source, with 400 m spot size and flood gun
for charge neutralization. The surface was sputter-cleaned with Ar+ ions for 5 to 10 minutes prior to
acquiring surveys and high resolution scans of Si 2s, S 2p, Al 2p, Fe 2p, Na 1s, O 1s and C 1s spectra (Si
2s spectra replaced Si 2p spectra for quantification due to interference of Fe 3s with the latter). The carbon
1s spectra was used for calibration, with adventitious carbon at 284.6 eV used as the reference peak.
Quantification was done using Gaussian-Lorentzian peaks and Shirley backgrounds in Thermo Scientifics
Avantage software.
In order to measure product layer thicknesses, one surface normal to the oxidized surface was
ground and polished progressively down to 6 m fineness, which gave a clear cross-section of the oxide as
well as the bulk pyrite visible under SEM. Imaging was performed under backscatter electron
compositional mode with an accelerating voltage of 20 kV. Energy Dispersive X-ray Spectroscopy (EDS)
was used to identify the pyrite-oxide interface as well as for elemental analysis of the product layer.
RESULTS
As shown in Figure 1, SEM results showed the average thickness rising to a maximum of
25.23 m for 2.5 g/L Na2CO3, before declining down to nearly the same as that for a system with zero
sodium carbonate. The trend proved that sodium carbonate clearly has a positive as well as a negative role
in pyrite passivation.
Average thicknesses were calculated from SEM micrographs as the area of the product layer
divided by the total length of the cube (xtot), tave = t dx / xtot. The area of the product layer and the
corresponding length of the cube were measured in the freeware image editing software GIMP 2. The
product layer was seen to be uniform on the outer surface and somewhat uneven at the pyrite-oxide
interface. Given that the pyrite surface was polished before oxidation, the outer oxide surface has to
correspond to the initial surface, which means that the product layer formed from outside and developed
inwards as the pyrite surface receded. This indicates that the oxidation takes place via a shrinking core
mechanism, as seen in Figure 2. The shrinking core mechanism has been observed for pyrite oxidation at
lower temperatures (Chuang et al., 1980; Evangelou, 1995), so this observation is consistent with earlier
studies.
56
Figure 1 Change in average product layer thickness with sodium carbonate concentrations
Figure 2 A cross-sectional view of the product layer (dark phase) formed over bulk pyrite (bright phase)
in 10 g/L Na2CO3. A shrinking pyrite core with the product layer coating it can be seen
The detection of significant amounts of aluminum in the product layer led to the analysis of
reagents for aluminum content, since no aluminum compounds were added explicitly to the system. X-Ray
Fluorescence (XRF) showed that the silica sand contained 0.887% wt. aluminum (as Al2O3), probably as a
feldspar impurity, while pyrite contained 0.073% wt. The presence of aluminum affected the results
markedly, since large quantities of aluminum seem to have leached from sand and re-precipitated as
aluminosilicates on the pyrite surface.
XPS was also performed on the oxide surface to determine the chemical composition of the
surface. The presence of aluminum and iron ions is known to decrease the solubility of silica (Gallup,
57
1998) due to the formation of silicates and the decrease in the activity of water (which in turn is caused by
the hydration of iron and aluminum). This was confirmed by XPS spectra, which showed the formation of
silicate and aluminosilicate species in every case. In the absence of sodium carbonate, aluminum species
dominated the product layer and silicon species were negligible. The introduction of sodium carbonate
drastically increased the presence of silicon as silicates and reduced the precipitation of aluminum species
(Table 1 and Figure 3).
Table 1 Total Al/Si mol ratios at various Na2CO3 concentrations
Na2CO3
(g/L)
0
1.25
2.5
10
Al/Si molar ratio

87.54
0.265
0.676
0.197
It was also evident that passivation due to anhydrite formation was not an issue even in the
absence of sodium carbonate, as sulphates were not detected in significant amounts on the surface, with or
without sodium carbonate (Figure 4). Anhydrite was likely formed away from the acidic pyrite surface and
in the bulk alkaline solution. The product layer was dominated instead by silicates, aluminum
oxides/aluminosilicates and iron oxides. Si 2s spectra showed that silicon was present as silicates and not
silica, which confirmed that silica was dissolving and re-precipitating because of the lower solubility of
silicates compared to silica (Figure 5). Iron spectra could not be used to determine iron chemistry because
of the effect of sputtering on iron oxides. Ar+ sputtering has been shown to reduce Fe(III) to Fe(II) oxides
(Paparazzo, 1986) and has almost certainly altered the iron chemistry in the present study. Fe 2p 3/2
spectra were dominated by lower binding energy peaks that correspond to Fe(II) species. The
predominance of Fe(II) could be either due to the incomplete oxidation of pyrite or its re-reduction by Ar+
sputtering. Based on the results by Peters et al. (2010), re-reduction due to sputtering seems the more
plausible explanation.
Figure 3 Al 2p scans of product layers formed at various Na2CO3 levels; note the prominence of
Al in the absence of Na2CO3
58
Figure 4 S 2p scans showing the absence of sulphates on the surface, due to the lack of peaks beyond
166 eV; peaks at 162 eV are sulphides from the pyrite surface
Figure 5 Si 2s peaks around 155 eV showing the increase in silicate levels with increase in Na2CO3 levels
which can be attributed to the increasing solubility of SiO2
59
Flashing
It was suspected that the formation of the passivating silicate layer may have occurred as the
autoclave cooled down rather than at temperature, due to the decreasing solubility of silica with decreasing
temperature. To confirm this hypothesis, tests were run in which water was flashed from the system at
temperature before the bomb was allowed to cool down, thus preventing any precipitation from solution
during cool-down. This was achieved by withdrawing water from the bottom of the reactor via a dip tube.
The results, when compared to a conventional cool-down, with water inside the system, showed that there
was no appreciable change in chemical composition (Figure 6). The product layer thickness, however, was
slightly greater when compared to a conventional cool-down (Figure 7). EDS analysis of the cross section
revealed that concentration of silicon was relatively constant from the pyrite-oxide interface to the outer
edge, which would not be the case if silicates precipitated after the oxide (Figure 8 and Table 2). It was
therefore concluded that the product layer, including silicates, was formed at process temperature and not
during cool-down.
Figure 6 Si peaks are near identical with or without flashing water

CONCLUSION
Pyrite oxidation in alkaline media produces a uniform passive product layer consisting of silicates
that can hinder pyrite oxidation. The product layer is dominated by silica, aluminum oxide and
aluminosilicates as a result of aqueous silicic acid and aluminum hydroxide reacting with iron ions to form
insoluble precipitates. The competing effects of promoting pyrite oxidation and promoting the dissolution
of silica produced a maximum product layer thickness at 2.5 g/L of sodium carbonate. Growth of the layer
starts at the exposed pyrite surface and progresses into the particle. The product layer was shown to form at
230C and not as a result of cooling down.
ACKNOWLEDGEMENTS
The authors would like to thank Barrick Gold Corp. for funding this project and SI Ontario for
XPS analysis.
60
Figure 7 Cross section of the product layer after flashing water at temperature. The average thickness,
12.68 m, is slightly greater than the corresponding thickness without flashing (8.87 m)
Figure 8 SEM cross-section of the oxide layer after flashing, with EDS analysis performed on points
across the layer
61
Table 2 EDS elemental analysis of the product layer after flashing showing an even distribution of Si
across the layer, indicating that the silicates grew along with the oxides during the oxidation process
Spectrum
1
2
3
4
5
6
C
14.46
15.98
4.91
6.95
5.20
6.25
8.50
35.31
26.11
28.00
Elemental wt%
Na
Si
0.71
1.21
1.22
4.12
3.27
3.73
S
45.74
45.51
33.91
0.44
0.37
Fe
39.80
38.51
51.46
52.92
64.98
60.45
REFERENCES
Caldeira, C.L., Ciminelli, V.S.T, and Osseo-Assare, K., 2010. The role of carbonate ions in pyrite
oxidation in aqueous systems. Geochimica et Cosmochimica Acta 74, pp. 1777-1789.
Chuang, K.C., Chen, M.C., Greer, R.T., Markuszewski, R., Sun, Y., and Wheelock, T.D., 1980. Pyrite
oxidation by wet oxidation in alkaline solutions, Chemical Engineering Communications 7, pp.
79-94.
Descostes, M., Beaucaire, C., Mercier, M., Savoye S, Sow J, Zuddas, P, 2002. Effect of carbonate ions on
pyrite (FeS2) dissolution. Bulletin de la Socit Gologique de France 173(3), pp. 265-270.
Evangelou, V.P., and Zhang, Y.L., 1995. A Review: Pyrite oxidation mechanisms and acid mine drainage
prevention. Critical Reviews in Environmental Science and Technology 25(2), pp. 141-199.
Gallup, D.L, 1998. Aluminum silicate scale formation and inhibition (2): Scale solubilities and laboratory
and field inhibition tests. Geothermics 27(4), pp. 485-501.
Iler, R.K, 1979. Chemistry of Silica Solubility, Polymerization, Colloid and Surface Properties, and
Biochemistry. Wiley, New York.
Paparazzo, E, 1986. XPS analysis of iron aluminum oxide systems. Applied Surface Science 25, pp. 1-12.
Peters, S., 2009. An investigation of the role of sodium carbonate and silica in the neutral/alkaline pressure
oxidation of pyrite. MASc Thesis, Dept of Chemical Engineering and Applied Chemistry,
University of Toronto, Toronto, Canada.
Thomas, K.G, 2005. Pressure oxidation review. In: D. Adams and B.A. Wills (Eds.), Developments in
Mineral Processing, vol. 15, pp. 346-369.
63
GOLD EXTRACTION FROM PYRITIC ORES THROUGH SIMULTANEOUS

PRESSURE LEACHING/OXIDATION
*J.L. Valenzuela G.1, L.S. Quiroz C.1, J.R. Parga T.2, P.J. Valenzuela G.3,
P. Guerrero G.1
1
Universidad de Sonora, Departamento de Ingeniera Qumica y Metalurgia

Hermosillo, Sonora 83000, Mxico
(*Corresponding author: jvalen@iq.uson.mx)
Instituto Tecnolgico de Saltillo, Departamento de Metalurgia y Materiales

Saltillo, Coahuila, Mxico
3
Minas de Oro Nacional, Mulatos, Sonora, Mxico
ABSTRACT
Pressure oxidation is a hydrometallurgical pre-treatment process used for refractory auriferous
sulfide ores. In the work reported here, a refractory pyrite ore sample from the Mulatos mine, Sonora,
Mexico was characterized. The sample was subjected to atmospheric cyanidation, and simultaneous
pressure oxidation and cyanidation under different conditions of temperature and pressure. The mineral
characterization showed that pyrite is the main species in the sample. The gold extraction tests were carried
out in an 1-litre Parr pressure vessel at a temperature range of 90-120 C, a pressure range of 87.5150 psi
(using oxygen), and a cyanide concentration range of 0.8-1.2 %wt. The gold extraction results showed that
diffusion through product layer is the rate controlling step.

Niagara, ON, Canada
Edited by
64
INTRODUCTION
In hydrometallurgical precious metals extraction, the most commonly used process is sodium
cyanide leaching, as shown in the next reactions involving gold and silver (Fleming, 1992; Marsden &
House, 2006):
4Au(s) + 8CN-(aq) + 2H2O(l) + O2(g) 4Au(CN)2-(aq) + 4OH-(aq)
(1)
4Ag(s) + 8CN-(aq) + 2H2O(l) + O2(g) 4Ag(CN)2-(aq) + 4OH-(aq)
(2)
Refractory auriferous ores or concentrates often contain gold and silver locked inside other
sulfide phases such as pyrite. This renders cyanidation ineffective, so oxidative pre-treatments are used in
order to convert the sulfide minerals into porous oxide minerals and make cyanidation work more
efficiently. Reaction (3) shows the oxidation of pyrite in alkaline media and the formation of the porous
oxide (Koslides & Ciminelli, 1992):
2FeS2 (s) + 15/2 O2 (g) + 8H-(aq) Fe2O3 (s) + 4SO42-(aq) +4H2O(l)
(3)
A process of simultaneous chemical pressure oxidation and cyanide leaching for a flotation
concentrate produced in the mine of Bacs, Durango, in Mexico, gave good results (Parga et al., 2007). In
the study presented here, it was intended to use this treatment for a refractory pyrite mineral from the
Mulatos mine in Sahuaripa, Sonora, Mexico, modifying variables such as pressure, temperature and
cyanide concentration to find the best conditions for oxidation and leaching.
MATERIALS AND EXPERIMENTAL SETUP
An ore sample was obtained from the Mulatos mine (designation SAS-1), a silicified sulfide
containing gold and silver. The sample was ground, and the size fraction 4553 microns was selected for
further work. The mineral was characterized using X-ray diffraction, scanning electron microscopy, atomic
absorption spectroscopy, and energy dispersive X-ray spectroscopy, in order to determine the elements and
mineral species in the sample. The sample was then subjected to metallurgical tests including agitated
leaching, hot cyanidation and fire assay to determine gold extraction percentages.
The experimental setup consisted of a 1-liter Parr pressure vessel equipped with a heating jacket,
stirring and in and out gas control valves as shown in Figure 1. The mineral was mixed with water to form
slurry, to which the leaching reagents were added and the whole mixture was put into the reactor. Pure
oxygen was used to elevate the pressure of the vessel, sodium cyanide was used as a leaching agent and
limestone was used to maintain the pH above 11, to avoid the formation of hydrocyanic acid, which is
volatile and poisonous; this occurs at pH lower than 9.5, by the reaction:
H+ + NaCN HCN + Na+
(4)
The tests were carried out with a fully stirred reactor. Once the time of reaction had passed, the
contents of the reactor were vacuum filtered to separate solids and solution for chemical analysis. The gold
extraction percentage was calculated based on the results obtained.
65
Figure 1 Parr pressure vessel used in experiments, equipped with heating jacket and cooling coil for
temperature control
Mineral Characterization
The characterization results indicated the presence of pyrite (FeS2) as the main mineral
component, as well as quartz. The sample contains gold, silver and other elements in the quantities shown
in Tables 1 and 2. XRD and EDS analyses confirmed the presence of pyrite and quartz as main species, as
shown in Figures 2 and 3.
Table 1 Fire assay and atomic absoprtion spectroscopy results for sample SAS-1
Au (g/t)
4
Ag (g/t)
23
Cu (% wt.)
0.029
Fe (% wt.)
6.33
Pb (% wt.)
0.061
Zn (% wt.)
0.0068
Table 2 Gold and sulfur content, and reagent consumption for sample SAS-1
Au (g/t)
Extraction Au (%)
Assay
Consumption (kg/t)
Calculated
S
(% wt.)
Head
Tailing
Head
Assay
Calc
CaO
NaCN
3.97
1.65
3.96
57.4
58.43
4.98
0.86
16.32
The SEM and XRD results show high contents of iron, sulfur and silica, which are in the pyrite
and quartz species. As shown in the microphotograph in Figure 2, the white, shinier particles contain large
amounts of Fe and S.
66
Figure 2 Scanning electron microscopy and energy dispersive X-ray spectroscopy images of sample
SAS-1
d=3.36415
SAS_1
400
d=1.63377
d=1.67135
d=1.81790
d=1.97899
d=1.91537
d=2.12659
d=2.70832
d=3.12729
d=3.57523
d=7.15589
100
d=2.28058
d=2.23693
d=2.21156
200
d=2.45529
d=2.42249
d=4.25261
Lin (Counts)
300
0
10
20
30
40
50
2-Theta - Scale
Figure 3 X-ray difraction results for sample SAS-1; the spectrum indicates the presence of pyrite (FeS2)
and quartz (SiO2)
67
RESULTS AND DISCUSSION

Leaching Tests
Ambient temperature leaching tests as well as the hot
h cyanidation tests carried out at temperatures
80C showed relatively low Au extraction. The conditions for the ambient temperature leach tests
4080C
were: slurry density 30% wt. solids, 300 mg/L cyanide concentration, pH 10.5 (using CaO), 72 h
leaching time, particle size at p80 4.76 mm (3/16 (100% -9.52
9.52 mm or -3/8).
). The hhot cyanidation
conditions were: 1% wt. cyanide concentration,
concentration, 10 kg/t
g/t CaO added for pH control, temperature 40
4080C,
0C,
slurry density 30% wt.
w solids, 2.5 h leaching time, particle size -55 microns (270
270 mesh).
imultaneous pressure oxidation and cyanidation tests were carried out at pressure 87.5
87.5 50 psi,
Simultaneous
perature 90120C
90 0C and cyanide concentration 0.81.2
0.8
temperature
%wt.t., pH higher than 11, and 1 h leaching time
SAS-1
Figure 4 Ambient temperature leaching results for sample SAS
SAS-1
Figure 5 Hot cyanidation results for sample SAS
68
Figure 6 Gold extraction

xtraction versus temperature at different pressure
pressures for an initial cyanide concentration of
0.8 %wt

1.0 %wt
Comparing the atmospheric leaching results (Figures 5 and 6) to the simultaneous pressure
oxidation and cyanidation results (Figures 79),
7 , it is obvious that pressure oxidation and cyanidation yields
greater Au extraction in a much shorter time. A similar effect has been observed in hydrometallurgical
operations where pressure oxidation and cyanidation are carried out separately
separately.. In that case, the gold
extraction is directly affected by the oxidation of the sulfides, increasing from 20% to 70% (Li et al.
al.,
2006).
The experimental results show that the effect of temperature on gold extraction is greater than the
effect of pressure. It is possible that the reaction time of 1 hour, considered sufficient for a case already
studied by Parga et al.,
al. 2007, may not have been enough to form the porous oxide product layer seen for
pyrite in alkaline solution as reported by Koslides & Ciminelli,, 1992, due to the differences in mineralogy.
It is worth
wo th mentioning that it is possible that due to these partia
partiall oxidation conditions, oxygen pressure did
not show a greater effect in the extraction percentage.
69

1.2 %wt
100
Go lExtraccin
d Ex trade
ctioro,
on %%
90
80
70
60
50
110C
40
90C
30
120C
20
10
0
0
20
40
60
80
100
Leaching
Tiempo, time,
min min
Figure 9 Gold extraction in simultaneous pressure oxidation and cyanidation as a function of

oftime and
temperature. Test conditions: 0.8% w
wt. NaCN, 87.5 psi
A Process Kinetics Model
om kinetic tests are shown in Figure 9, displaying the extraction of ggold
ld at three
Results from
different temperatures. These results were analyzed using the shrinking core model assuming control by
diffusion through a product layer (Sohn & Wadsworth,
Wadsworth 1986;; Ballester et al.
al., 2007).. The characteristic
equation of that model is:
2
2
1 (1 ) 3 = kt
3
where is the fraction reacted of the ore and t is extraction time.
(5)
70
A plot of the left hand side of Equation (5) against time can be fit by linear regression to a straight
line with a slope equivalent to the kinetic constant k (Figure 10)
10).. The constant k can be further used to
calculate the activation energy of the oxidation/cyanidation process
process.
0.25
1-2/3-(1-)^(2/3)
0.2
y = 0.002x + 0.019
R = 0.941
90C
0.15
y = 0.001x + 0.017
R = 0.842
0.1
110C
120C
Lineal (90C)
Lineal (110C)
0.05
Lineal (120C)
y = 0.000x + 0.001
R = 0.952
0
0
10
20
30
40
50
60
70
Leaching
Tiempo,
mintime, min
Figure 10 Plot of the left hand side of Equation (5) against tim
time, (shrinking
shrinking core model with control by
diffusion through a product layer
layer)
The activation energy is calculated from an Arrhenius plot (Figure 11)
11). The
he value of the
activation energy indicates whether the process is controlled by diffusion of rea
reactants to the particle surface
or by another mechanism.
mechanism The
he Arrhenius equation (Equation 6)
6), in its logarithmic form
form, indicates that the
data of the kinetic constant k against the inverse of absolute temperature gives us a line, the slope of which
gives us the activation energy (E
Ea) of the process over the universal gas constant (R),, and ultimately
expressing Ea can be calculated in
in kJ/mol.
ln k = ln A
Ea 1
R T
Figure 11 Arrhenius plot for the calculation of activation energy
(6)
71
The regression coefficient of the kinetic model, for temperatures of 90 and 110C is relatively
low, around 0.62 to 0.70 for 90 min of leaching time. However, in model fits for the first 60 min, at these
two temperatures, the agreement is better with shrinking core control of diffusion through the porous
material formed by oxidation of the particle.
The values of the slopes k for the equations of the diffusion controlled model and the three
different temperatures are shown in Table 3.
Table 3 Calculation of the activation energy according to the Arrhenius equation, with k values from the
diffusion through product layer model
T, C
k, 1/min
T, K
1000/T
ln k
(-Ea /R)
Ea, kJ/mol
90
110
120
0.0008
0.0011
0.0023
363
383
393
2.753
2.609
2.543
-7.130
-6.812
-6.074
-4.574
38.03
CONCLUSIONS
This simultaneous pressure oxidation and cyanidation, under moderate pressure conditions, has
shown considerable improvement in gold extraction percentage in comparison to atmospheric leaching..
Under ambient temperature cyanidation, gold dissolution was around 38-39%, increasing to 5054% under hot cyanidation at 40 80C. Under simultaneous pressure oxidation and cyanidation at 87.5
psi, the gold dissolution reached 81-86%. The optimum leaching conditions were determined as: T =
90C, P = 87.5 psi, [NaCN] = 8 g/L, t = 1 h, pH > 11 and constant stirring.
The kinetic analysis of leaching data shows that the rate controlling step of the pressure oxidation
and cyanidation process is diffusion through an oxidized product layer. Given that the activation energy
values is about 38 kJ/mol, one may further speculate that surface reaction also plays some role in the
process rate.
ACKNOWLEDGEMENTS
Acknowledgements and appreciations are extended to the Department of Chemical Engineering
and Metallurgy of the University of Sonora, to the company Minas de Oro Nacional for their collaboration
with sample supply and metallurgical assays, and to the Proyecto de Fortalecimiento Institucional PIFI
2011 from SEP in Mexico.
REFERENCES
Ballester, A., Verdeja, L.F., & Sancho, J. (2007). Metalurgia Extractiva, Vol.1 Fundamentos. Madrid:
Editorial Sntesis, p. 182 -191
Fleming, C.A. (1992). Hydrometallurgy of precious metals recovery. Hydrometallurgy, 30, 127-162.
Koslides, T., & Ciminelli, V.S.T. (1992). Pressure oxidation of arsenopyrite and pyrite in alkaline
solutions, Hydrometallurgy, 30, 87-105.
Li, J., Dabrowski, B., Miller, J.D., Acar S., Dietrich, M., Levier, K.M., & Wan, R.Y. (2006). The
influence of pyrite pre-oxidation on gold recovery by cyanidation. Minerals Engineering, 19, 883895.
72
Marsden, J.O., & House, C.I. (2006). The Chemistry of Gold Extraction (pp. 147-177). Littleton, Colorado,
USA: SME.
Parga, J.R., Valenzuela, J.L., & Cepeda, T.F. (2007). Pressure cyanide leaching for precious metals
recovery, JOM 59, pp. 43-47.
Sohn, H.Y., & Wadsworth, M.E. (1986). Cintica de los Procesos de la Metalurgia Extractiva (pp. 167194). Mxico: Editorial Trillas.
Modeling
75
SIMULATING THE IRON(III) PRECIPITATION RATE DURING MEDIUM TEMPERATURE

CHALCOPYRITE OXIDATION IN BATCH AND CONTINUOUS AUTOCLAVES
J.D.T. Steyl
Anglo American
Technical Solutions, Research
8 Schonland Street
Johannesburg, South Africa
(johann.steyl@angloamerican.com)
ABSTRACT
This paper presents a phenomenological model of the rate of iron(III) precipitation in batch and
continuous autoclaves at medium temperature operating conditions. The rate expressions are based on
information obtained from the literature and experimentation at low and high pulp densities. Special
allowance is made for the formation of surface nuclei, which appears to be promoted at a higher iron(III)
precipitate surface area, especially in suspensions of lower terminal acidity. This leads to the formation of
secondary particulates and provides the required link to simulate high pulp density leaching-precipitation
systems, using low pulp density batch precipitation data. In particular, the model allows direct application
of the simulation to the autoclave oxidation of iron-containing copper sulfide concentrates and provides a
good estimation of the relative precipitation rate of hematite, the preferred product, compared to
hydronium jarosite. Some interesting mechanistic understandings of iron(III) precipitation in autoclaves are
further elucidated.

Niagara, ON, Canada
Edited by
76
INTRODUCTION
The objective of this work is to describe the rate of iron(III) precipitation and the relative amounts
of hematite compared to hydronium jarosite precipitation during batch and continuous chalcopyrite
oxidation under medium temperature (MT) (~130 to 160C) autoclave conditions. Published information
has not yet revealed sufficient mechanistic insights about this sparingly soluble salt system under these
conditions. The rate expressions in this paper are based in part on current literature information,
supplemented by qualitative experimental observation at low pulp density conditions, in particular the
high-resolution backscatter electron (BSE) images and particle size distributions (PSDs) of the precipitates.
A summary of this work and insights from the literature are presented first, after which the behaviour of
iron(III) in high pulp density leaching systems is used to derive a phenomenological expression of the
effect of existing iron(III) precipitate surface area on the precipitation rate. The overall regression
encapsulates all the experimental results, i.e., those obtained in both batch and continuous autoclave
configurations (Steyl, 2012a).
REVIEW AND THEORY
Background
The nature of iron(III) hydrolysis and precipitation is complex and still poorly understood. Firstly,
like any crystallisation process, both thermodynamic and kinetic aspects are important, i.e., the
thermodynamics determine the solution speciation and saturation concentration, while the precipitation rate
depends on the driving force, e.g., supersaturation, surface type and area. Figure 1a illustrates that the two
most important factors determining iron(III) precipitation are temperature and hydrogen ion concentration.
One of the complexities associated with iron precipitation is its tendency to generate acid, i.e., the
hydrolysis process itself affects the intrinsic acidity of the particle environment.
3.0
m
ssiu
100
jaro
site
50
Goethite
(S
)
O4
2.0
1.5
1.0
0.5
Fe3+
H)
(O
Fe
2.5
140C
200C
Hematite
Fe2O3
150
Fe(III) (mol/kg)w
a
a
Pot
Temperature (C)
200
(
6
H)
(O
(H
SO
)2
Aqueous (140C)
e3
)F
O)
H)(S 4
Fe(O
Aqueous (200C)
0.0
pH
SO4 (mol/kg)
Figure 1 Major stability areas in the Fe(III)-S-H2O system: a) Schematic diagram at 0.5 mol/L Fe2(SO4)3
(Miller, 1986); b) Isotherms at 140 and 200C (data of Posnjak & Merwin, 1922)
In general, higher temperatures favour phases with fewer waters of hydration, while increased
saturation levels (at higher acidities) incorporate more sulfates into the crystal structure (Figure 1b). The
most common iron phases encountered in pressure oxidation systems are: goethite (FeO(OH)), hematite,
(Fe2O3), jarosites (general formula XFe3(SO4)2(OH)6, where X may be Na+, NH4+, H3O+, etc.), and basic
ferric sulfate (BFS) (Fe(OH)SO4). Various factors determine the precipitation rate and precipitate
composition in hydrometallurgical processes (Cheng & Demopoulos, 1997). From a thermodynamic
perspective, jarosites are more stable at lower pH, while goethite is favoured at higher pH and lower
temperature (Figure 1). Higher temperature favours hematite formation, while BFS only forms under more
77
severe acidity (< pH 0) and temperature (> 170C) conditions. Tozawa and Sasaki (1986) have shown that
the addition of metal sulfates, e.g., copper or zinc sulfate, may extend hematite stability to higher acid
levels by reducing the free hydrogen ion concentration, i.e., the solution thermodynamics underpin the
stability of the precipitated phase. Hematite is the preferred phase, both from environmental (relatively
inert towards weathering) and economical viewpoints, e.g., low metal losses, faster liquid/solid separation,
higher wash efficiencies, lower tailings neutralisation requirements and smaller residue storage ponds.
Since only small amounts of potassium and sodium are usually present in copper sulfide
concentrates, hematite formation would be expected to dominate under MT autoclave conditions. However,
the above figures only refer to thermodynamic time frames and neglect the metastability of phases such as
hydronium jarosite, (H3O)Fe3(OH)6(SO4)2. High supersaturation is most likely to produce metastable
phases, which would then convert to the thermodynamically preferred phase over time. According to the
data of Posnjak and Merwin (Figure 1b), the transition point between hematite and stable hydronium
jarosite at 140C lies around 0.3 mol/kg H2SO4 and 0.1 mol/kg Fe(III), which is only marginally different
from the conditions experienced in a typical MT autoclave (see later). The conversion of metastable
hydronium jarosite to stable hematite would therefore be slow and the jarosite phase could for all practical
purposes be considered stable (while in the autoclave). This statement is particularly relevant to MT
chalcopyrite oxidation since this mineral typically requires acid concentrations higher than 0.15 to 0.2
mol/kg H2SO4 in order to oxidise at acceptable rates (Steyl, 2004), while the system is self-compensating
in that more hydronium jarosite is produced at higher acidities (Dreisinger et al., 2003).
The Driving Force of Precipitation (Bulk Perspective)
Oswalds rule of stages (Shnel & Garside, 1992) implies that the thermodynamically stable
phase will be preceded by that of several metastable precursor phases. This is also the case in autoclaves
due to the rapid leaching and oxidation of iron, which lead to high initial iron(III) supersaturation. The
relative rates of the following two reactions are most important in context of the overall model:
Fe 2 O 3 (s) + 3H 2 O (aq) {Fe 2 O 3 3H 2 O}(s) 2Fe(OH)3o(aq)
(1)
(H 3O)Fe3 (OH) 6 (SO 4 ) 2 (s) {(H 3O)Fe3 (OH) 6 (SO 4 ) 2 }(s) FeH(SO 4 ) o2 (aq) + 2Fe(OH)3o(aq) + H 2 O (aq) (2)
where the two complex species FeH(SO4)2 (Casas et al., 2005) and Fe(OH)3 act as surrogate species for
different iron(III) sulfate and hydroxide species, respectively (Steyl, 2012b). The {Fe 2O33H2O} and
{(H3O)Fe3(OH)6(SO4)2} phases represent the metastable precursor hematite and amorphous hydronium
jarosite phases, respectively. Since the free energies of formation of these phases are unknown, their
solubility products are estimated from their stable analogues, i.e., assuming nominal hematite ( Hem), Fe2O3 (Liu et al., 2003), and hydronium jarosite (Jar) (Majzlan et al., 2004) compositions, respectively:
o
K sp,
Hem = exp
o
K sp,
Jar = exp
(G oFeH(SO
(2G oFe(OH)o G oHem 3G oH 2O )
o
4 )2
Rg T
+ 2G oFe(OH)o + G oH 2O G oJar )
3
Rg T
2
a Fe(OH)
o
3
a H3 2O
o
{K sp,
Hem }
a H3 2O
(3)
2
o
= a FeH(SO )o a Fe(OH)
(4)
o a H O {K sp, Jar }
2
4 2
Unity activity coefficients are conveniently assigned to the two iron(III) surrogate species, i.e., the
interactions of these neutral inner-sphere complexes with the surrounding solution are assumed weak at
higher temperatures. The supersaturation ratio, S (Shnel & Garside, 1992), which artificially caters for the
nucleation and growth of both the initial amorphous phases and the stable phases forming during the later
stages of the leaching process, may then be expressed as follows (Steyl, 2012a):
78
S 2Hem =
S 4Jar =
a FeH(SO
o
4 )2
2
a Fe(OH)
o
3
o
{K sp,
Hem }
2
a Fe(OH)
o aH O
2
3
o
{K sp,
Jar }
m 2Fe(OH)o
o
K sp,
Hem
a H3 2O
1
o
K sp,
Jar
m FeH(SO
o
4 )2
(5)
m 2Fe(OH)o a H 2O
(6)
This simplified treatment therefore makes no distinction between the metastable and stable phase
solubilities and implicitly assumes that the conversion of the metastable to the stable phase at some
reaction front has an insignificant impact on this bulk precipitation driving force. These ratios are linked by
an equilibrium reaction between the two aqueous iron(III) surrogate species, imbedded within a Pitzer ioninteraction framework of the background electrolyte, H2SO4-M(II)SO4-H2O (Steyl, 2012b).
Figure 2 represents the calculated solubilities of the hematite and hydronium jarosite phases. For
the sake of maintaining internal consistency, the thermodynamic data of all the species partaking in these
iron(III) equilibria are based on the values of Liu et al. (2003). The choice of the Fe(OH)3 species is
convenient, but cognisance has to be taken of the fact that this species rather arbitrarily represents a host of
possible complex species at lower acidities (< 0.15 mol/kg H2SO4), demanding from the dominant
FeH(SO4)2 species to assume thermodynamic values unique to this study. The G25C value of the
FeH(SO4)2 species is therefore treated as an adjustable parameter, i.e., to best represent the hematite
solubility data of Reid and Papangelakis (2006). The calculated hydronium jarosite solubility value of 0.11
mol/kg Fe(III) at 140C and 0.3 mol/kg H2SO4, i.e., corresponding to the 4.6 kJ/mol uncertainty in the
standard thermodynamic values of Majzlan et al. (2004), is close to the average measured value of Posnjak
and Merwin (PM) (1922) of 0.13 mol/kg Fe(III) (Figure 2). Although the model underpredicts the jarosite
solubility at higher acidities, no conclusions can be drawn without generating more data using modern
measurement techniques. Nevertheless, Figure 2 suggests that hydronium jarosite is metastable in
comparison to hematite, particularly under typical batch and continuous autoclave conditions (< 0.3 mol/kg
H2SO4). This statement neglects, however, consideration of various surface properties (discussed below).
Fe(III) (mol/kg).
0.20
170C
PM (1922; 140C)
150C
H-Jarosite
130C
130C
150C
170C
Hematite
0.15
0.10
GJar, HJar
4.6 kJ/mol
0.05
0.00
0.05
0.15
0.25
0.35
0.45
0.55
0.65
0.75
H2SO4 (mol/kg)
Figure 2 Calculated solubilities of -Fe2O3 and H-Jar (GJar and HJar varied 4.6 kJ/mol; Majzlan et
al., 2004). The closed symbols represent the measured Fe2O3 solubilities (Reid & Papangelakis, 2006)
The Solid/Solution Interface

The material-specific interfacial energy of the surface ( = G/a; J/m2) accounts for the work
required to achieve the formation of unit surface area. Surface structures are less stable than bulk structures
and therefore require more energy to be created. This is a collective property, as it depends on crystal
79
morphology, structure, and in particular, particle size. It is most reliable if derived from experimental
measurements under well-controlled conditions, but no such values could be found for hematite or
hydronium jarosite. However, based on the inverse relationship between the interfacial energy and the
solubility (log C*) (Shnel & Garside, 1992), a higher interfacial energy would be expected for hematite
than for hydronium jarosite. This is also reflected by the high apparent surface enthalpy of hematite in
comparison to hydroxide and oxyhydroxide polymorph surfaces (Diakonov et al., 1994; Marchand &
Rancourt, 2009; Navrotsky et al., 2008). The formation of a high number of small hematite particles would
therefore be expected in a region of spontaneous nucleation, which follows from crystallisation theory
(e.g., Randolph & Larson, 1988) and has been confirmed experimentally at low acidities (see next section).
In contrast to hematite, the lower comparative interfacial energies of hydronium jarosite and other
metastable phases tend to form larger surfaces (see images in the next section). This follows directly from
the Gibbs-Thomson (GT) relationship (Shnel & Garside, 1992), which may be expressed as follows:
SL
L
= exp OD
L
S
(7)
where S refers to the supersaturation with respect to the equilibrium at infinite particle size and LOD is the
Ostwald diameter of the particular phase. The supersaturation experienced by a particle of finite size L, SL,
would therefore be lower than envisaged by the above thermodynamic formulations. The already slow
conversion of jarosite to hematite (in hydrometallurgical terms) could therefore be decelerated further in
the 0.15 to 0.30 mol/kg H2SO4 range, which justifies the treatment of hydronium jarosite as a stable phase
under typical MT autoclave leaching conditions. This assumption is also in agreement with Zerella et al.
(1983), who found that higher temperatures (>150C) and/or significant neutralisation (< 10 g/L H2SO4 at
150C) are required in order to rapidly convert hydronium jarosite to hematite.
A PHENOMENOLOGICAL MODEL BASED ON LOW PULP DENSITY TEST RESULTS

Since supersaturation is difficult to control in this sparingly soluble system, the phenomenological
model is based on qualitative energy-dispersive X-ray (EDX) spectroscopy results and BSE images.
Experimental
b
Sample valve
Non-return valves
From HP pumps
(solution feed)
Cooling coils
(removed)
Sampling
system
Filter
medium
Dip tube
Pressure relief
Autoclave
Pressure filter
Steam
Filtrate
collection
Figure 3 Schematic diagram of the batch test arrangement: a) Parr 2-litre autoclave; b) Pressure filter
80
This study utilised a standard 2-litre Parr autoclave (Figure 3a). The internal pressure of the
autoclave was used to obtain representative solid and solution samples via a pressure filter (0.4 m
polycarbonate membrane) (Figure 3b). The autoclave was charged with the required amount of water and
background salts, and then heated. The measuring tube of the high pressure (HP) feeding system was then
charged with the required amount of dissolved iron(II) sulfate and sulfuric acid, and pumped into the
autoclave. The overpressure was increased to the setpoint gauge pressure using pure oxygen, while the
impeller speed was increased to 1000 rev/min, signifying the start of the kinetic test. Iron(III) precipitation
was therefore driven by the rate of iron(II) oxidation, which is quantitatively known, in addition to the rate
of interfacial oxygen gas/liquid mass transfer (Steyl, 2012a).
The filter cake was split into three parts: one part (washed with propanol solution) was dried in an
oven at 40C and the total iron, copper (or zinc) and sulfur contents were determined. The second part was
immediately subjected to PSD measurement, while the third part (washed with propanol solution and dried
in the atmosphere) was used to produce the BSE images of the precipitated particles. EDX spectroscopy
was used to estimate the sulfur/iron (ST/Fe) mass ratio, i.e., to qualitatively identify the dominant iron
precipitate phases. Selected samples were also analysed by X-ray powder diffraction (XRD).
Data Interpretation
A total mass balance is used to determine the water loss during sampling, which, in turn, is used to
back-calculate the aqueous species concentrations in the autoclave at temperature. In order to determine
the normalised amounts (wt %) of hematite (WHem) and hydronium jarosite (1 WHem), a constant average
sulfur value is assumed to be present as adsorbed sulfate on the hematite polycrystals. The ranges
suggested by Dutrizac and Chen (2009), Sugimoto and Wang (1998), Umetsu et al. (1977) and Zerella et
al. (1983) average at 2% S, which is applied as a fixed constituent of the hematite phase. Antlerite,
Cu3(SO4)(OH)4, is the only crystalline phase identified by XRD analysis in the copper sulfate system at
low acidity (Figure 4b), while all residual zinc is assigned to basic zinc sulfate, ZnSO4.2Zn(OH)2, in the
zinc system. All sulfur, not present as these salts and adsorbed sulfate, is assumed to be present as the ideal
hydronium jarosite end member. The solid phase iron balance then (iteratively) yields the idealised
hematite content, while the extent of precipitation, Xppt, is based on the residual amount of total iron left in
the solution and the original amount of iron(II) injected at the start.
Apparent Surface Interactions, Morphologies and Precipitation Mechanisms

The experimental programme covered numerous tests (Steyl, 2012a) of which only a few selected
results are presented here. Besides the background salts, small amounts (0.05 g/L) of the surfactants
sodium lignosulfonate (LS) and Quebracho (QB) were added upfront in order to approximate the solution
environment during leaching (Steyl, 2004). The particle morphologies of the hematite and hydronium
phases are quite distinct (see images below), which lends qualitative support to the main assumptions of
the phenomenological model.
Hematite Precipitation in the Low Acid Regime (< 5 g/L H2SO4 and Fe(II) initially)
A low and narrow acid concentration window could be maintained by limiting the initial acid and
iron(II) concentrations to less than 5 g/L. Figures 4a and b present the typical results of these tests at
155C. Different oxygen partial pressures (pO2 refers to pure water), within the typical ranges applied
during MT oxidation, result in similar hematite contents (Steyl, 2012a). Similar insensitivities are also
prevalent between the zinc and copper systems, suggesting that differences in the rate of iron(II) oxidation
at these high temperatures and low acidities have an insignificant impact on the nucleation rate, i.e., at least
as can deduced from the sample data at short reaction times. Differences in supersaturation ratios under
these conditions are therefore relatively inconsequential in comparison to the results at higher acidities,
resulting in nano-aggregates of similar sized (0.1 to 0.2 m), spindle-like particulates (Figure 4a). An
average characteristic size of around 0.15 m is therefore adopted, notwithstanding the fact that these
particulates are not spherical and transform into nano-aggregates and agglomerates of different overall
81
sizes over time. The low sulfur content (ST/Fe ratio < 6 wt %), the characteristic deep red colour of these
residues, as well as the qualitative XRD analyses (Figure 4b) confirm that hematite is the primary (> 85 wt
%) iron(III) phase produced under these low initial acid conditions.
Intensity (counts)
1900
1700
1500
1300
b
Antlerite, Cu3(SO4)(OH)4 - Orthorhombic
Hematite, syn--Fe2O3
1100
900
700
500
300
100
10
500 nm
20
30
50
40
2-Theta - Scale
Figure 4 Residues at 155C: a) BSE image after 5 min (700 kPa pO2), initially 3.5 g/L H2SO4 and Fe(II),
15 g/L Zn; b) XRD pattern after 2.5 min (1000 kPa pO2), initially 4 g/L H2SO4, 3 g/L Fe(II), 15 g/L Cu
Hydronium Jarosite Precipitation in the High Acid Regime (> 20 g/L H2SO4 and 10 g/L Fe(II) initially)
The BSE image of the residue produced at high initial acidity (Figure 5a) not only illustrates the
significant differences in hydronium jarosite particle size and general morphology in comparison to
hematite (Figure 4a), but also suggests that hydronium jarosite precipitation is driven by growth. This
results in smooth individual crystallite surfaces but many different orientations, most likely due to a
twinned growth mechanism under these relatively high supersaturation conditions. The XRD diffractogram
(Figure 5b) confirms that crystalline hydronium jarosite formation dominates at longer reaction times (25
min) in this high acid environment.
a
Intensity (counts)
3 m
Hydronium Jarosite,
syn-(H3O)Fe3(OH)6(SO4)2
4000
3000
2000
1000
0
10
20
30
40
50
60
2-Theta - Scale
Figure 5 Residues at high acidity, starting with 20 g/L H2SO4, 10 g/L Fe(II), 15 g/L Cu at 1000 kPa pO2:
a) BSE image after 45 min at 140C; b) XRD pattern after 25 min at 150C
Comparatively small spherical hematite particles are visible after 15 minutes (4% Xppt; Steyl,
2012a), indicating that initially the system is close to a cusp (which depends strongly on the prevailing acid
concentration). This phase appears to be present as dispersed particulates on the jarosite surface after 20
minutes (Figure 6a). Qualitative EDX spot analysis at the top position on the image (Figure 6b1) yields a
ST/Fe ratio of about 11 wt %, strongly suggesting that this dispersed surface coat comprised small
82
hematite-like particulates. In contrast, the (lower) spot analysis of the crystalline phase (Figure 6b2) reveals
a considerably higher ST/Fe ratio of about 33 wt %, confirming the presence of the comparatively larger
and more crystalline hydronium jarosite phase.
b1
EDAX ZAF (Standardless)

ST/Fe ~ 11 wt %
b2
EDAX ZAF (Standardless)

ST/Fe ~ 33 wt %
10 m
Figure 6 Residues at high acidity, starting with 20 g/L H2SO4, 10 g/L Fe(II), 15 g/L Cu at 1000 kPa pO2:
a) BSE image after 20 min at 150C; b) EDX analyses at different particle locations
As the acid concentration increases over time, eventually no hematite-like particulates are
detected on any surfaces, e.g., after 25 minutes (12% Xppt and ST/Fe ratio of ~39 wt %; Steyl, 2012a) the
precipitation mechanism is primarily driven by hydronium jarosite crystal growth, as confirmed by the
XRD diffractogram (Figure 5b) and which is also in line with the GT relationship (Equation 7). Besides the
general increase in the overall particle size due to hydronium jarosite growth, the PSDs in Figure 7 confirm
the complex particle interactions in these precipitation systems. The particle masses and numbers (based on
unit mass water) in Figure 7, as well as the initial two peaks merging into one, suggest agglomeration.
These polycrystalline structures are often also remnants of the initial (amorphous) conglomerates (see next
section). Most importantly, a general increase in particle mass transpires due to hydronium jarosite growth
under these high acid concentrations. A topochemical reaction boundary assumption (translating into an
idealised surface area) is therefore the logical premise of the phenomenological model, despite the clouded
relationship between the precipitation rate and the observed PSDs.
20
15 min
2.51 g (11010)
20 min
3.67 g (2 109)
25 min
6.14 g (2 109)
Volume (%).
15
10
0
1
10
100
Particle size (m)
Figure 7 PSD (Malvern MasterSizer 2000), particle mass and number (in parentheses) at 150C, 1000
kPa pO2 and 15 g/L Cu after 15, 20 and 25 min, starting with 20 g/L H2SO4 and 10 g/L Fe(II)
83
Simultaneous Hematite and Hydronium Jarosite Precipitation in an Intermediate Acid Regime

The intermediate acid regime is more typical of the conditions experienced during the initial stage
of precipitation in a batch leaching reactor. The initial particle conglomerates consist of comparatively
bright (higher average atomic number) hematite nano-aggregates, often surrounded by what appears to be
precursor hydronium jarosite structures (Figure 8a). This suggests that the initial drop in acidity (due to
iron(II) oxidation) promotes hematite formation, which then acts as a substrate surface for the hydronium
jarosite precursor phase. In other cases (circled), hematite appears on the outer surfaces, either due to
agglomeration or as a result of a role reversal between the two phases, i.e., hematite nucleation catalysed
by other precipitate surfaces (also see Figure 6a). With an increase in jarosite crystallinity over time, the
initial conglomerates transform into more compact aggregate structures (Figure 8b). This particular test is
insightful in that the hematite content remains relatively constant over time (65 to 68 wt %). Despite an
increase in the acid concentration due to the advancing precipitation reactions, both jarosite growth and the
continuous formation of dispersed hematite particulates are sustained (Figure 8b). The comparatively
bright hematite particulates (circled) are visible on the outer proximity of the amorphous structures, again
suggesting that these surfaces could catalyse secondary hematite nucleation. Contact angle calculations
(e.g., Mersmann et al., 2001a) might confirm this, but it is outside the scope of this study due to the
unknown interfacial energies of the amorphous (and other) phases.
3 m
5 m
Figure 8 BSE images, starting with 12.5 g/L H2SO4, 4 g/L Fe(II), 15 g/L Cu at 150C (1000 kPa pO2):
a) After 15 min (13% Xppt, 65 % WHem); b) After 20 min (23% Xppt, 68 % WHem)
Phenomenological Modelling Framework and Batch Simulation Performance at Low Pulp Densities
Based on the above evidence, it is reasonable to assume that hematite and hydronium jarosite
precipitation are strongly interrelated, demanding a simplified approach. The phenomenological model
assumes that each particle remains in contact with the surrounding solution and retains its identity, i.e.,
agglomeration is neglected. MT chalcopyrite oxidation typically yields a significant proportion of
elemental sulfur (~60%; Steyl, 2004), causing the initial fast iron dissolution process to be accompanied by
a drop in acid concentration. This is the reason why iron(II) was utilised in the above tests. Due to the
relatively high interfacial energy, hematite nucleation is accompanied by rapid growth, which, in turn,
causes the supersaturation to dissipate rapidly, leading to a large number of small particulates of
characteristic size, LHem. The precipitation rate (mol Fe/kg.min) of primary particles, Rprim, is then:
3
K
em
Hem
R prim = k Hem L3Hem J prim = k Hem L3Hem k prim exp
(2 ln S Hem ) 2 T
(8)
where the proportionality constant, kHem (mol Fe/m3), translates the one-dimensional size increase into an
iron(III) molal concentration decrease and the pre-exponential efficiency factor, kprim (1/kg.min), is
84
assumed to be a weak function of the temperature. The exponential functionality follows directly from
fundamental precipitation theory (Shnel & Garside, 1992; Mersmann et al., 2001a).
The previous section suggests that hydronium jarosite precipitation is often kinetically favoured
above hematite precipitation under typical leaching conditions. Preferential growth along particular crystal
planes within the amorphous precursor structures leads to different initial growth phenomena (Figure 8a).
As highlighted above, attempting to simulate such phenomena, as well as the agglomeration effects, is not
warranted in the context of a phenomenological model, especially since a wide range of supersaturation
ratios and associated growth mechanisms could be valid over the course of a leaching-precipitation
process. The topochemical reaction boundary assumption then leads to:
(9)
R Jar = k Jar a Fe G Jar
where kJar is the proportionality constant (mol Fe/m2) and GJar the average linear growth rate (m/min).
This equation assumes that the overall jarosite precipitation rate, RJar, depends on the total precipitate
surface area, aFe (m2/kg H2O). No distinction is therefore made between growth on existing jarosite and
barren hematite substrate surfaces. This assumption is based on the strong adsorption of the sulfate ion on
hematite (noted earlier). It further assumes that all particles maintain their shape as they grow and that the
growth rate does not vary with particle size, i.e., comply with McCabes law (Mersmann et al., 2001b), so
that the calculated particle size, L, and total surface area in the batch reactor are respectively as follows:
L = L Hem + (G Jar t)
and
a Fe =
a L2 N L
(10)
where a is the area shape factor and NL is the particle number in size class L. The rapid conversion of
hydronium jarosite to hematite at low terminal acidities (Zerella et al., 1983) also needs to be accounted for
and is assumed to be driven by the solubility difference between the hematite and jarosite phases. The
relative saturation ratio, Fe = [Fe*Jar]/[Fe*Hem] 1, is utilised for this purpose and is a non-linear function
of the hydrogen ion concentration (Figure 9a). The net jarosite growth rate then is as follows, assuming an
Arrhenius response and a linear dependence on the relative supersaturation ratio, Jar = SJar 1:
G Jar = G +Jar G Jar = k G exp
E a, Jar 1
E a, Jar/Hem 1 1
1
ln Fe

Jar k G exp
R g T Tr
Rg
T Tr
3.5
log Fe
2.5
2.0
Xppt (%), WHem (%)
3.0
100
130C
140C
150C
160C
1.5
1.0
0.5
0.0
(11)
WHem
4.0 g/L H2SO4
3.5 g/L Fe(II)
80
130C
60
8.5 g/L H2SO4
4.5 g/L Fe(II)
40
130C
140C
20
Xppt
15 g/L H2SO4
7.5 g/L Fe(II)
0
0.0
0.1
0.2
+
0.3
[H ] (mol/kg)
0.4
0.5
10
20
30
40
50
60
Time (min)
Figure 9 Simulating low pulp density batch precipitation at various acidities: a) Calculated log Fe vs. H+
molality in the H2SO4-Fe2(SO4)3-H2O system ; b) Measured (points) vs. simulated (lines) Xppt and WHem
values at 1000 kPa pO2 in 15 g/L Cu (boxed values refer to the initial acid and iron(II) concentrations)
85
At artificially low acidities, the characteristic hematite particulate size is assumed to be a weak
linear function of Fe, i.e., LHem = 0.125 + 104Fe, yielding a rounded value of 0.15 m at ~0.075 mol/kg
H+ (in the 130 to 160C range). Neither this variation nor the conversion rate expression (GJar) have a
significant bearing on the model performance under typical leaching conditions. Figure 9b illustrates that it
provides a reasonable estimate of the hematite and jarosite precipitation rates at lower pulp densities.
Different growth rate models have been tested but the best regressions are obtained with Equation (11)
(Steyl, 2012a). No conclusions can be drawn from this apparent linear dependence on Jar since small
changes in the thermodynamic model tend to overshadow the impact of the different growth rate models.
This emphasises the need to develop more thermodynamic (including speciation) data for iron(III) in
mixtures with sulfuric acid and metal(II) sulfates at typical autoclave temperatures.
SIMULATING THE PRECIPITATION RATE IN HIGH PULP DENSITY LEACHING SYSTEMS

Despite the success of the above framework in simulating the precipitation rate when starting with
relatively dilute iron(II) solutions, the model consistently underpredicts the rate in batch and continuous
leaching systems (Steyl, 2012a). Ambiguity exists between the different modes of precipitation under
typical autoclave conditions since surface nucleation is not easily differentiated from continuous growth in
sparingly soluble systems, especially when accompanied by the rapid formation of nano-aggregates and
agglomerates. This grey area is explored below, with the objective of simulating (high pulp density)
leaching systems on a phenomenological level.
Secondary Hematite Nucleation

Randolph and Larson (1988) indicated that the energy of contact nucleation is important and
smaller particles (< 100 m) would not be expected to be instrumental in producing secondary nuclei. A
power-law rate expression is often used to describe such mechanisms, which is typically proportional to the
pulp density (mass) and also related to the degree of mechanical agitation. Shnel and Garside (1992)
indicated that secondary nucleation could become relevant during the precipitation of sparingly soluble
substances when large crystals are brought into contact with a solution at lower supersaturation, either via
the above contact-type mechanism or due to particle fracturing, e.g., of dendrites. Based on the above BSE
images, these kinds of secondary nucleation mechanisms would not be expected to be prominent during
iron(III) precipitation under typical autoclave leaching conditions. Therefore, the term secondary
nucleation in this study refers to a true surface nucleation mechanism, where hematite nuclei are formed
due to solid/solution interactions and lead to new particles.
Although growth on seed particles is more likely in the case of jarosites, it is unclear at what point
(in the degree of supersaturation) secondary nucleation would start to dominate over a continuous growth
mechanism. Interestingly, the precipitation rates of different jarosites usually increase in a linear manner
with the pulp density of the initial seed material present (Dutrizac & Jambor, 2000). Itou et al. (2006)
studied, among other parameters, the effect of seed material on the mechanism of scorodite (FeAsO4.xH2O)
precipitation. They found that the effect of seed is not to precipitate scorodite directly but rather to provide
reaction sites for crystallisation. First, an amorphous scorodite phase precipitated on such reaction sites,
and only later were well-crystallised single crystals observed on the seed surface. Papangelakis et al.
(1996) studied particle morphologies from acid pressure leaching of limonite ore (> 240C) and proposed
that small hematite particles form rapidly, probably via a secondary nucleation mechanism.
The assumption is made that secondary nucleation rapid growth of hematite becomes relevant
when enough surface area is available in supersaturated solutions, especially at lower acidity levels. The
overall hematite precipitation rate, RHem (mol Fe/kg.min), follows from Equation (8) and the secondary
nucleation rate, Jsec (number/kg H2O.min), is described (phenomenologically) by Equation (13):
R Hem = k Hem L3Hem J Hem = k Hem L3Hem (J prim + J sec )
(12)
86
J sec = k sec ( f (a Fe ) ln Fe ) exp
E a,Hem 1
1

Hem
R g T Tr
(13)
The relative supersaturation ratio, Hem = SHem 1, represents the overall driving force to form
hematite particulates of characteristic size, LHem. This equation assumes an Arrhenius response of the rate
constant, ksec (number/m2.min), to temperature change, while the bracketed pre-exponential function
(reaction frequency) captures the catalytic effect of the precipitate surface area. The relative saturation
ratio, Fe, accounts for an increased surface nucleation rate via hematite-like surfaces, as compared to
hydronium jarosite surface structures. Either way, the nucleation rate seemingly stretches beyond a linear
response in the total iron(III) precipitate surface area. A catalytic enhancement factor, , is therefore
defined, which results in an approximately linear response of the surface nucleation rate to the precipitate
pulp density, Fe (kg/kg H2O), of a typical average particle size, i.e.:
f (a Fe ) = a Fe Fe
(14)
Examples of catalytic surface effects on reaction kinetics can be found in the literature. For
example, Tamura et al. (1976) described the heterogeneous oxidation rate of iron(II) in close-to-neutral
solutions as an autocatalytic reaction, with an apparent first-order dependence on the precipitated mass
concentration of ferric hydroxide. Sugimoto and Matijevic (1980) studied the rate of iron(II) hydroxide
conversion to magnetite. Iron(III) centres on the surface of iron(II) hydroxide gave rise to the magnetite
nuclei and the conversion extent followed sigmoidal profiles over time. Unlike classical autocatalysis
reactions, a transition-type variation of the surface activity as a function of the total available area would
be expected to be governed by different processes. For example, even at high supersaturation ratios, supply
limitations of hematite growth units might manifest as an apparent efficiency drop at high exposed surface
areas: the following versatile transition function is adopted in the phenomenological model:
log a p 3 log a p 3
log a = p1 + p 2
p4
p4
10
7.5 %
2.5 % (Fe)
High Fe batch &

continuous tests
Equation (15)
Sigmoid 1
Sigmoid 2
Sigmoid 3
1.0 %
Low Fe
batch tests
0.5 %
3.5
2
2.5
2.0
p5
(15)
Equation (15)
Linear function
3.0
17
100
4.0
(a) 10 (m /kg)
Factor,
1000
1.5
1.0
0.5
0.0
0.01
0.1
a 10
15
1
2
(m /kg)
10
20
30
40
50
Pulp density, Fe (g/kg)
Figure 10 Transition functions with reference to monosized spherical particles (LHem = 0.15 m):
a) Enhancement factor () vs. particle surface area; b) Term a vs. precipitate pulp density (Fe)
Indicative enhancement factors vs. surface area plots are compared in Figure 10a, while Figure
10b illustrates that this transition function can yield a relatively linear relationship (in comparison to
typical sigmoidal functions) between the nucleation rate (at constant temperature and supersaturation) and
typical precipitate pulp densities (1 to 5 wt %) for monosized spherical particles (in this case, hematite
87
particulates of 0.15 m). The higher the acid concentration due to the advancing precipitation reactions, the
smaller the values of Fe and Hem, and the comparatively less significant the role of secondary nucleation
would become. This trend is qualitatively in line with the above discussions, because the higher the driving
force of hydronium jarosite growth, the lower the tendency of its precursor phases to yield secondary
hematite nuclei. The above secondary nucleation rate expression (Eqn. 13) is therefore most dominant at
lower acidities and in the presence of high iron(III) precipitate surface area.
Application of the Phenomenological Model to Batch and Continuous Leaching Systems

The secondary formation of hematite particulates provides the required link to simulate high pulp
density leaching-precipitation systems using low pulp density batch precipitation data. Although the above
secondary nucleation rate framework is speculative, the general formulation of this phenomenological
model is justified due to the current lack of thermodynamic and mechanistic knowledge. Based on the
current methodology, the continuous autoclave simulation is readily dealt with via the time- and spaceaveraged population balance around each compartment (Randolph & Larson, 1988), using an iterative
calculation scheme in order to simplify the population balance equation:
j
j
L Fe
j -1
j
(16)
+ BL, j
where LFe is the overall particle size (m), is the average residence time (min) and j is the particle
number density distribution (1/kg.m) exiting compartment j. The symbol j refers to the mean hydronium
jarosite velocity vector, while the formation rate of new hematite particles, BL,j (1/kg.m.min) of
characteristic size (LHem), is assumed to occur instantaneously on entering the reactor:
WHem (%).
80
60
40
20
0
0
10
20
30
40
Reaction time (min)
50
60
dJ Hem (S Hem , a Fe , Hem , Fe , T) j
(17)
dL Hem ( Fe ) j
80
Sim
Sim
Sim
Sim
WHem (%), [H2SO4] (g/l)
Hem
Acid
Fe(II)
Fe(III)
[H2SO4, Fe] 10 (mol/kg)
100
B L, j =
and
5
60
C #1+2
4
3
40
[Fe] (g/l)
j = G Jar ( Jar , Fe , T) j
2
20
1
0
0
0
30
60
90
120
Average residence time (min)
Figure 11 Experimental (points) vs. simulated (lines) trends during chalcopyrite concentrate oxidation
(~7 wt %; d90 7 m) at 150C and 700 kPa pO2: a) Batch operation, starting with ~30 g/L H2SO4, 5 g/L
Fe(III), Fe(II), Cu and Zn; b) Continuous pilot operation, feeding ~35 g/L H2SO4, 5 g/L Fe(II), Cu and Zn
Figures 11a and b compare the measured and simulated behaviour of iron in batch and continuous
reactors, respectively, confirming a generally reasonable simulation performance. It should, however, be
emphasised that these simulations include reactions that impact on the net oxidation and precipitation rates
of iron. For example, although the homogeneous oxidation rate of iron(II) is accurately simulated (Steyl,
2012a), the extent of iron(III) reduction on each of the mineral surfaces is unknown and may not even be
88
constant over time. Furthermore, the above precipitation scheme does not consider the re-leaching of
precipitated iron(III) phases, e.g., the possible re-dissolution of small hematite particulates as the acid
concentration increases over time. These aspects need to be addressed in future modelling exercises.
CONCLUSIONS
The phenomenological model developed in this study provides an estimate of the complex
processes taking place during iron(III) precipitation in MT autoclaves. It assumes that the primary
nucleation rate of hematite dominates the formation of new hydronium jarosite particles due to the higher
hematite interfacial energy, and hence supersaturation, especially as the acid concentration drops during the
initial stages of sulfide mineral oxidation. Due to the relatively high interfacial energy, the formation of
these hematite nuclei is accompanied by rapid growth, which, in turn, causes the supersaturation to
dissipate rapidly, leading to a large number of small particulates of similar size. On the other hand,
crystalline hydronium jarosite growth occurs under conditions of higher acid concentration, and hence
lower relative supersaturation, i.e., where nucleation on existing surfaces leads to a continuous growth
mechanism. The overall hydronium jarosite growth rate is strongly dependent on the number of hematite
particulates, which allows simulation of the relative precipitation rates of these two phases over typical
fluctuating acid concentrations during chalcopyrite oxidation in batch and continuous autoclaves.
The formation of secondary hematite nuclei appears to be promoted at a higher precipitate surface
area, especially in suspensions of lower terminal acidity. This surface nucleation, accompanied by rapid
growth, leads to the formation of secondary hematite particulates and provides the required link to simulate
high pulp density leaching-precipitation systems using low pulp density batch precipitation data. Although
the theoretical framework is highly simplified, this modelling exercise has helped to elucidate some
interesting mechanistic understandings of iron(III) precipitation in MT autoclaves. More experimental data
of the thermodynamics, speciation and precipitation rate of iron(III) in mixtures with sulfuric acid and
metal(II) sulfates are required in order to expand our understanding of this sparingly soluble salt system.
ACKNOWLEDGEMENTS
The author gratefully acknowledges the financial support of Anglo Operations Ltd. Prof. Alison
Lewis (University of Cape Town) and Max Pelser (Anglo American, Technical Solutions) are thanked for
their valuable comments. Mr. Sibusiso Mdlalose is thanked for assisting with the experimental work.
NOTATION
a
a
BL
Ea
G
G
J
Particle surface area

Species activity
Particle (L) birth rate
Activation energy
Linear growth rate
Gibbs free energy
Nucleation rate
k
k, K
Ksp
L
m
N
R
Rate constant
Proportionality constants
Solubility product
Particle size
Molality
Number of particles
Precipitation rate
Rg
S
t
T
Tr
W
Xppt
Gas constant
Supersaturation
Time
Temperature
Reference temperature
Weight percent
Precipitation extent
Area shape factor

Interfacial energy
Enhancement factor
Fe
Fe
Precipitate pulp density

Relative supersaturation
Relative saturation ratio
Num. density distribution

Average residence time
Mean velocity vector
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91
USE OF NUMERICAL METHODS, SCALE-UP AND LAB TESTS

IN THE DESIGN OF HPAL AUTOCLAVES
J. Jung, W. Keller, A. Zucht
EKATO RMT GmbH
Kaeppelemattweg 2
Schopfheim, Germany 79650
ABSTRACT
The agitator design for nickel high pressure acid leach autoclaves (HPAL) is critical with regard
to the process result, i.e., the recovery rate. Further considerations during the design phase are the
avoidance of acid hot spots which reduce the lifetime, due to corrosion of the wetted parts, including
components manufactured from titanium. Besides the process knowledge to design HPAL autoclaves, tools
such as, Computational Fluid Dynamics (CFD) supplemented by lab testing allow the design of optimized
agitation systems. This paper describes the effect that different feed point locations have on instantaneous
blending of the reactants. Furthermore, experiments and CFD show where abrasion issues might occur and
how to obtain information about the static and dynamic forces acting on internals. We show how
simulations can be validated by lab testing to ensure that the CFD models are applied in an appropriate
way.

Niagara, ON, Canada
Edited by
92
INTRODUCTION
Agitated systems in hydrometallurgical processes have to comply with multiple process tasks and
in many cases have to withstand extreme operation conditions such as pressure up to 50 bar, elevated
temperatures of up to 250C and exposure to very acidic or alkaline environments and abrasive ores. The
process tasks range from instantaneous mixing of reactants, homogeneous suspensions of up to 65% wt.
solids with coarse and heavy particles, enhancing the solid-liquid mass transfer for leaching, dispersing
large volumes of reactants (gas-liquid, liquid-liquid mass transfer) and moreover to transport generated
heat e.g., from exothermic reactions through the vessel walls or internal heat exchangers if required. For
economies of scale, agitator systems have reached sizes of 5000 m for large open leach tanks with
impeller diameters of approx. 6 m, while autoclaves nowadays have exceeded 5.5 meters in diameter with
a power demand for a single compartment drive between 300 - 400 kW. In parallel all process industries
require a more efficient use of resources, to generate less by-products and higher yields, while ore-bodies
tend to be less qualitative and new process routes (e.g. direct leach) are developed. Besides all these facts
the mixing solution must be robust and economic. In this paper we want to address our approach in the
development and designing of HPAL agitation equipment.
OVERVIEW OF METHODS
Numerical Methods
Computational Fluid Dynamics (CFD) is a common tool in the fluid processing industry and for
equipment manufacturers. Today the design of a modern agitator system not only includes the agitator, the
vessel and baffles but also the geometry and location of internals like feed and discharge pipes, spargers,
heat exchangers, etc. Another paradigm change is that CFD is used in the design phase sometimes even
before lab or pilot tests are carried out so as to reduce the number of tests to a necessary minimum and to
save time and money in the development process. CFD is often misunderstood as a tool only for simulation
and visualization of flow fields or to describe the hydrodynamics of different impellers. The main efforts
and costs for CFD are to carry out the spatial discretization and to build up the so-called grid, which
consists of many millions of small cells which represent the fluid continuum of the agitation system. The
grid structure and the geometry of the surrounding mechanics have to be as detailed and precise as
necessary and the quality of any computation is pre-determined by the quality of modelling. Once the
computation is done and the Navier-Stokes equations converge, a complete set of physical data is
generated. The next step is to analyse the data, e.g., by visualization tools, and to interpret the numbers and
their importance on the process result. We will talk about this later and give examples for a broad range of
practical uses. Another important topic that we will discuss is the impact that CFD has on mechanical
engineering for modern agitator design. The static and dynamic forces acting on agitator, vessel and the
internals can be calculated very precisely by using the pressure loads created by the flow field. The next
step is to take this data for Finite Element Analysis (FEA), which allows determination of the local stresses
of mechanical parts and the deflections of structural components. Potential weak points are evaluated
quickly and, if necessary, mechanical redesign can be done instantly. Furthermore, the stochastic changes
of turbulent flow fields induce dynamic loads, which can cause resonance phenomena and accelerate
fatigue break. As a result, components must not only be designed for static but also for dynamic loads,
which is done by carrying out a Modal Analysis. In Table 1 we illustrate the state of the art for CFD
calculations used in typical industrial mixing applications, as described by Rohn et al. (2012).
Table 1 Overview of CFD for industrial mixing applications
CFD standard
applications
Blending
Velocity distribution
fields
Pumping rate, Power
input, Ne-number
Pressure on vessel walls
and internals
Suspending
Assessment of particle
distribution over the
vessel volume by
analysing the flow fields
Dispersing
Qualitative results for
dispersion capabilities
of an impeller design by
analysing
93
Table 1 - (continued)
CFD standard
applications
Blending
Pressure drop
Concentration
distributions
Suspending
or by simulating a
single particle (e.g. offbottom suspending).
Dispersing
local power dissipation
and local shear rates
(single phase model)
Limits in the industrial

use of CFD
Common tools provide

good and reliable results
Calculations have to be
verified and validated
by lab or pilot tests.
Modelling multiple
phases is not yet
standard
Lab Test Methods

Classical calculation methods and lab tests for scaling-up still have a key role for development
and design of agitation processes. Most methods and physical models have been well known for decades.
On the other hand, measurement devices become more and more accurate, easy to handle and
economically feasible: take for example viscosity measurement. Voluminous tests can be planned and
analysed with Design of Experiment programs in combination with dimensional analysis. These tools
reduce the number of test runs dramatically and facilitate the interpretation of huge data sets. Before going
to production scale, lab tests (either in-house or on customer site) help to evaluate or validate the basic
mixing tasks and to obtain key figures based on the agitation system so that the industrial scale can be
designed. Typically this is done with dimensional analysis/dimensionless numbers and proven correlations.
Lab tests are done with their scaled-down pendants and in many cases with so-called model substances.
Tests with the original product make sense if the product characteristic is complex or very much dependent
on other variables, e.g., temperature and shear rate. Processes with chemical reactions, crystallization or
liquid-liquid dispersing have many influencing variables and although lab tests can be done under the same
conditions, additional scaling effects have to be discussed in detail with the customer. Table 2 gives a small
overview of lab tests for different industrial mixing applications.
Table 2 Overview of lab test methods for different mixing tasks
Blending
Pumping rate,
mixing time,
Momentum
balance for
addition (feed and
discharge points),
Residence time
distributions
Suspending
Off-bottom,
homogeneity over
suspension height,
draft tube designs
(e.g., crystallizer)
Dispersing
Dissolving salts
(mass-liquid mass
transfer), droplet
size distribution
(liquid-liquid)
Gassing
kla measurements
(gas-liquid-mass
transfer)
oxygen utilization
flooding point
reactions with e.g.,
O2 (pure, air), H2 or
CO2
Heat-transfer
Heat transfer
measurements
over jacket or
via internal heat
exchanger
elements
Typical vessel sizes for lab tests are 50 litre and one cubic meter scale. For force measurements
and continuous running trials we also use a 30 m test pit.
OPTIMIZATION OF SLURRY AND ACID FEED POINT LOCATIONS
Industrial HPAL autoclaves typically have 6 8 compartments, see Figure 1. The performance of
the first compartment is key to the overall process efficiency. Slurry and highly reactive acid for leaching
are pumped into this compartment. As Forschner et al. (2004) stated, one basic mixing task is to get the
fresh acid and the slurry immediately into contact to quickly obtain high leaching rates and to provide a
uniform residence time distribution (RTD) of the solids and acid to prevent short-circuiting over the weir,
which would lower the compartment leaching efficiency. In this regard, the following compartments are
less critical as the leaching rates get lower as the reactants are already premixed. Another important task of
the first compartment is to prevent fresh and undiluted acid from getting in contact with the vessel walls,
94
the agitator or other mechanical components, which are made of titanium. Acids of low pH-values cause
corrosion that in combination with the abrasion by solids reduces lifetime. Besides the costs for
maintenance and repair, additional downtime is a risk for operators of industrial autoclaves.
Figure 1 Nickel leach autoclave with 6 compartments, first compartment shown by the dotted line
Test Set-up
The tests were carried out in a transparent acrylic glass autoclave with a compartment filling
volume of approximately 80 litre. The agitator, baffles and the weir were scaled-down geometrically equal
from production scale. Two geometries, A and B, of feed points for the slurry and acid feed lances were
studied. Geometry A represents the basic set-up. Figure 2, picture A shows the positions of the two acid
and the two slurry feed pipes. Picture B shows the lance positions of the optimized solution with respect to
advanced mixing efficiency.
Geometry A
Geometry B
Figure 2 CFD model A and B with different feed pipe positioning
The tests were run at steady-state condition. Therefore slurry and acid were pumped constantly by
a diaphragm and a hose pump through the lances into the first compartment of the autoclave and the flows
were discharged via the first weir and an overflow behind the second compartment. The positive
displacement pumps supplied a constant flow rate and with additional pulsation dampers behind the outlet
of the pumps, a very uniform pulse-free flow was obtained. Homogenous alkaline and acidic solutions
were used as model substances for the slurry and acid. Inside the vessel, a neutralisation reaction took
95
place and the different pH indicators for slurry and acid were decolorized or changed their colour as
function of the pH value. The pH values of the two solutions were adjusted to obtain a neutral mixture (pH
= 7). The incoming slurry flow was red and when being neutralized with the acid it changed to yellow. The
pH indicator of the acid flow was blue and changed to transparent when reacting with the slurry.
Scaling
As scale-down criteria to adjust the flow feed rates (slurry and acid) and the diameter of the
nozzles we looked at the following two dimensionless numbers and the ratios of C1 and C2 of the
production scale.
Iimp.
= C1
I
(1)
jet
R const.
> C2
( 2)
The dimensionless number 1 represents the ratio of the impulse flow rate induced by the impeller
Iimp and the impulse flow rate Ijet created by the free jet of the feed flows, when leaving the nozzle. The
physical principle is the basis for many designs and has been applied successfully. The dimensionless
number 2 describes the mean residence time R versus the mixing time of the fluids. The aim was to hold
the residence time constant, which means we pumped the same volume specific amount of slurry and acid
through the test autoclave as designed for production scale. It is important to mention that the mixing time
is always an EKATO design factor, C2, smaller than the mean residence time. However, not all
dimensionless numbers can be held constant by scaling. This can be explained easily in the Penney
diagram as presented by PENNEY (1971), see Figure 3. The abscissa shows the scale (volume size 1.0
refers to the production scale P) and the ordinate shows the ratio of power per volume of the production to
lab scale. The bold lines show the effect scaling has with respect to volume specific power input for
different constant dimensionless numbers. The black line (P L) shows the scale-down for a constant
impulse flow rate ratio.
Figure 3 Penney diagram for scaling-down
96
Based on the dimensionless number Iimp/ Ijet, which describes the mixing behaviour of the feeds,
the agitator speed for the lab test scale was set to 183 min1. Depending on the mixing task, dimensionless
numbers must be chosen correctly for scaling to be able to compare lab test results with the production
scale.
Results for Geometry A
The test results for geometry A showed a segregation of acid. The volumes in CFD are called isosurfaces. An iso-surface indicates a constant concentration value. Figure 4 shows two iso-surfaces, one for
an acid concentration of 8% (light gray) and second for a slurry concentration of 91.6% (black). Simply by
the sizes of the two clouds the efficiency of fast mixing can be studied and comparisons of different feed
point locations can be made. In this case we also investigated local acid hot spots, which should not be
permanently in contact with the walls or other mechanical parts inside the vessel. The composition of the
perfect (unreacted) mixture would be 7.9% acid and 92.1% slurry. A constant value of 8.0% acid and a
deviation of only 0.1% with regard to the perfect mix do not seem to be much. But as a consequence, 1.3%
of the incoming acid stream on the light gray iso-surface is not mixed with slurry and represents a
significant excess of acid.
Figure 4 Feed pipe geometry A CFD simulation and usage of iso-surfaces
Acid
Acid
Picture A
Picture B
Figure 5 pH indicator 1: blue-transparent to visualize the acid concentration inside the test autoclave
97
The results from lab tests are in good agreement with the results obtained by CFD. The pictures in
Figure 5 show the acid flow only with indicator 1, which illustrates the acid concentration. The acid shortcircuiting at the overflow of the weir and the size and location of the acid hot spot was observed during the
lab tests as well as by the analysis of the CFD data.
In the next step, indicator 2 was added to the acid and slurry feed tanks. The pictures in Figure 6
show the slurry indicated by the red cloud. Slurry, which is blended with acid, is neutralised and vice versa.
The indicator 2 changes its colour from red to yellow. The blue colour of indicator 1 (for acid) is still
noticeable, as the pale yellow and dark blue results in a dark green tone.
Slurry
Acid
Slurry
Picture A
Picture B
Figure 6 Mixture of two indicators: Indicator 1 blue-transparent (acid),

Indicator 2 red-yellow to visualize the slurry concentration inside the test autoclave
Results for Geometry B
By changing the geometry of the pipe positions for the acid and slurry feed, we observed a
minimum of segregation of the two flows and CFD predicts a much faster mixing, see Figure 7.
Figure 7 Feed pipe geometry B - CFD simulation and use of iso-surfaces,

acid concentration 8.0% and slurry concentration 91.6 % as for geometry A
98
As the pictures in Figure 8 show, we again found the lab tests in good agreement with the results
obtained by CFD.
On the left hand side the slurry flow is indicated and on the right hand side the acid, which is
quickly mixed and diluted. Although it looks as if the agitator was imbedded it is only surrounded by the
acid. In a nutshell, geometry B leads to an improved process and mechanically feasible design.
Acid
Slurry
Figure 8 Mixture of two indicators: pH indicator 1 - blue-transparent for visualization of acid,

pH Indicator 2 - red-yellow to visualize the slurry concentration inside the test autoclave
FORCES AND DYNAMIC STRESS (FATIGUE) ON INTERNALS
Internals in agitated vessels are numerous in function and shape:
Baffles direct the flow of the fluid and suppress rotation of the liquid content inside the vessel.
Heat exchangers have the function to heat or cool the product and to keep the product temperature
constant for continuous operation. Common designs are tubes close to the walls, horizontal tube or
parallel plate bundles.
Feed units add the liquid or gaseous educts, as done by rings, lances, or dip pipes including the
mechanical fixation. Discharging the product can be done via an overflow, down comers or
discharge locations close to the bottom area.
Measuring devices, like for temperature, pH-value, liquid level monitoring and others.
Fixing elements for agitator, intermediate or bottom bearing and deflection rings.
In all of the cases mentioned above, the fluid motion by agitation creates hydraulic forces and
static and dynamic loads on these internals. The classical formula to calculate the drag force resulting by
the flow around an object is given by:
Fdrag =
cW
A v2
2
( 3)
Values of drag coefficients cw can be found in standard fluid mechanics textbooks and the product
density and the cross section A of the body are known. To obtain the flow velocity v, although it seems
to be trivial, it is much more complex because of local variations in intensity and flow direction (xyz
vector). CFD gives detailed information about the local flow field around and along the component and
with the local velocity vectors the pressure field acting on the component can be calculated. This set of
data must then be used for Finite Element Analysis (FEA) to calculate stresses and deformations. By
experiments, the results can be validated in two ways. One is to measure at discrete points the flow
velocities, e.g., by anemometers, and second to measure, e.g., with strain gauges, forces and resulting
bending moments and compare these results with CFD and FEA.
99
Figure 9 shows a cross-section of the horizontal vessel with the EKATO EPAL impeller, baffles,
acid feed pipe and anemometers for flow velocity measurement. In Figure 10 we compare the measured
axial flow velocities and the flow velocities calculated with CFD and find both results in close agreement.
Rohn et al. (2012) derived an easy functional correlation for vertical vessels from measurements and CFD
calculations to describe the flow field as a function of the impeller diameter ratio d2/d1 and the variable x.
We found in the horizontal vessel that the local flow profiles vary even more, because the flow symmetries
in a vertical vessel do not exist for a horizontal vessel.
Figure 9 Test set-up horizontal vessel for measuring forces and flow velocities
Flow field calculated with CFD (right hand side)
Figure 10 Comparison of measured and calculated velocity curves (CFD) as function of 2x/d1
Besides the static loads, vibrations in mechanical components can be excited by the blades
passing or by the vortex detachment of the flow behind a body according to the theory of Karman as
described by Truckenbrodt (1968). Both physical phenomena have been studied in detail and formulas to
calculate both frequencies are known. Again the frequencies can be compared with numerical calculations,
which are obtained by Modal Analysis of the FEA model. The natural frequency of a component must not
be equal or close to the excitation frequencies. Vessel internals such as baffles, heating and cooling coils or
100
feed and discharge pipes are mainly excited by the so-called blade passing frequency, if the ratio of
impeller to vessel diameter is large, or in other words, if the component is close to the impeller.
fb = n J
(4)
The blade passing frequency fb is derived by multiplication of the agitator shaft speed n and the
number of impeller blades J. For example, an four bladed impeller running at 75 min1 creates a passing
frequency of 5.0 Hz. The frequency exited by oscillation of shedding vortices can be expressed with the
following equation:
fk =
St u
d
(5 )
where St is the dimensionless Strouhal number, fk is the frequency of vortex shedding, d is the
characterising hydraulic diameter and u the velocity of the fluid around the component. Strouhal numbers,
like drag force coefficients, can be found in standard fluid mechanics textbooks. As the blade passing
frequency and the frequency exited by oscillation of shedding vortices lead to different results, it is
important to use the correct model for the mechanical design.
ABRASION ISSUES
To get information about potential wear areas in the autoclave, we used CFD data and compared
them with the results of abrasion tests in our lab scale autoclave. Abrasion occurs mainly by two
mechanisms. The first is by impacting particles (impingement) and the second effect is wear by sliding and
grinding of particles that move parallel to the metal surface, as discussed before by Keller (2007).
Minimizing abrasion by agitation could be a measure, but in many cases it would be compromising the
mixing task. Other possibilities are to optimize geometries or change the position of an internal, if possible.
We advise clients to protect potential wear areas by coating or lining or simply by reinforcing these areas
and as an additional service we provide customers and vessel manufacturers with more detailed
information. Abrasion is a very complex matter, which is subject of numerous studies and publications. A
comprehensive overview is given by MENG (1995). For practical use we propose therefore the following
method.
M abrasion~ umtip
(6 )
This proportionality describes, that the abrasion rate M is a function of the fluid velocity u around
a body or along a surface, which is related to the impeller tip speed. The exponent m is typically found
between 2.5 and 3.0, which means that areas exposed to zones of higher flow velocities will erode
disproportionately faster. The abrasion rate can be expressed as the loss of mass over time and is measured
e.g., by abrasion tests with slurries at production conditions, see also EKATO Handbook of Mixing
Technology. For the modelling of the impact and slide erosion with CFD, the calculated local hydraulic
pressures and local shear rates were used, where the results of the CFD calculations were validated by the
abrasion rate trials.
Test Set-up
To prove the validity of CFD for abrasion studies, we designed an additional test method. We
took the acrylic glass test autoclave with lance geometry B. For modelling the solids and the effect of
abrasion, multiple runs with different sands and glass beads were conducted. The solid content was 15
volume percent in water. All components like impeller, shaft, compartment wall and baffles were painted
with a three colour layer of acrylic lacquer. The metal was pre-treated with a primer and then coated in the
colour sequence yellow, red and blue (top-layer). The time span for one test run was approximately 24 h
and the product temperature of the water-glass-sand slurry was 18 22 C. In this study the bottom area of
101
the autoclave was of special interest and we installed therefore an additional plate on top of the acrylic
glass bottom in the cylindrical part of the vessel, see Figure 11 (left side).
The results in Figure 11 (right side) and the comparison with CFD figure 12, show, that the
amount and position of abrasion can be explained well by visualization of the pressure loads and wall shear
rates obtained from CFD. However, the tests were carried out with a shaft speed of 500 rpm, which was a
compromise between getting the same tip speed as in the production scale and to prevent gas entrainment
by vortexing.
Figure 11 Test set-up for abrasion measurements (left hand side) test results (right hand side)
Figure 12 Pressure and wall shear obtained from CFD calculations, dotted line indicates the area of the
bottom plate used for the abrasion rate lab tests
Improved Agitator Design
Further potential risk for abrasion might be at the impeller. Standard impeller geometries as the
pitched blade turbine and Rushton turbine are not optimal. Specifically, with pressure oxidation autoclaves
(POX) high power inputs are required to ensure high mass transfer rates. Modified flat blade disc turbines
with planar blades provide sufficient power input at acceptable tip speeds. Despite these efforts to
minimize tip speed, impact erosion can be detected coming from vortices on the low pressure side. Down
time for maintenance and even repair is the consequence. Keller (2007) presented with the EPOX-R an
102
impeller that reveals significantly reduced impact erosion while maintaining the high power number of a
flat blade disc turbine. Tests and CFD simulation lead to this patented design, which is shown in Figure 13.
Figure 14 shows significantly reduced abrasion of the curved blade (left hand side) compared to
the planar blade of the Rushton turbine (right hand side). Two pronounced vortices on the low pressure
side of the Rushton turbine cause zones of high wear at the blade and the blade holder. In contrast, in case
of the EPOX-R the media flows parallel to the impeller blade, thus vortices and consequently wear
mechanisms are suppressed. The method of using multiple coloured layers and CFD calculations (here
single flow paths) have been used successfully for the development of impellers with an optimized
geometry in terms of abrasion issues.
Figure 13 EKATO EPOX-R for pressure oxidisation applications with high specific power input
and a high potential for abrasion
EPOX-R lab test result
CFD results
Rushton Turbine lab test results
CFD results
Figure 14 Standard Rushton turbine and EKATO EPOX-R

CONCLUSIONS
CFD, lab tests and scale-up form a powerful bundle for designing agitated systems. We have
discussed in this article the optimization of slurry and acid feed point locations, the importance of how to
determine forces acting on internals and abrasion issues inside the vessel and at impellers. The results
obtained from CFD, from experiments and other calculations show that CFD can be used over a wide range
of applications successfully. Like any experiment, CFD experiments have to be planned carefully, which
means the input variables must be determined and the output variables measurable. In fact, a CFD run can
be described as a virtual experiment, which gives a numeric result. Although these models still have
limitations for certain applications, they have two remarkable advantages: CFD simulates at production
scale and with each simulation a complete set off physical properties is calculated simultaneously for every
point inside the vessel. Parameter studies can be repeated with the same model even in a later project phase
with other input values, because the model is established and can be up-loaded again. However, real
experiments will not disappear! CFD engineers, as well as process specialists and lab staff must work
therefore hand in hand to set-up correct models, internally and externally, to validate results and to find the
correct answers for the real world.
103
REFERENCES
EKATO Handbook of Mixing Technology. Edition 1990, pages ME.9 ME.10
Forschner, P., Houlton, D., Kassera, V., Klepper, R., & Krebs R. (2004). Design of horizontal vessels
operated as CSTR - Basic mixing tasks, RTD, productivity. Chemical Engineering & Technology
27(3), 282-286.
Keller, W. (2007). POX Autoclaves New advantages in impeller design for highly abrasive ores. In:
Proceedings of ALTA Copper 2007 International Conference. Castlemaine, Victoria, Australia:
Alta Metallurgical Services.
Meng, H.C., Ludema, K.C. (1995), Wear models and predictive equations: their form and content. Wear,
181-183.
Penney, W. R., (1971). Recent Trends in Mixing Equipment. Chemical Engineering, 86-98
Rohn, N., Stadthaus, M., & Himmelsbach, W. (2012). Numerische Methoden zur Auslegung von
Rhrsystemen. Chemie Ingenieur Technik 84(4), 432-446.
Truckenbrodt, E. (1968). Strmungsmechanik. Springer Verlag, 409-413.
105
CHEMICAL MODELING IN PRESSURE HYDROMETALLURGY USING OLI

*V.G. Papangelakis1, A. Anderko2, G. Moldoveanu1,
M. Carlos1, G. Azimi3
1
Department of Chemical Engineering and Applied Chemistry

200 College Street, Toronto, Ontario M5S 3E5, Canada
(*Corresponding author: vladimiros.papangelakis@utoronto.ca)
2
OLI Systems, Inc.
108 American Road
Morris Plains, NJ
07950 USA
3
Department of Mechanical Engineering

Massachusetts Institute of Technology
77 Massachusetts Avenue, Cambridge, MA 02139-4307, USA
ABSTRACT
OLI Analyzer is a software package that uses the powerful Mixed Solvent Electrolyte (MSE)
model to simulate the behavior of multicomponent electrolyte solutions from infinite dilution to the limit of
fused salt, and from temperatures below the freezing point up to near critical temperature of the mixture.
The software also allows the creation of thermodynamic parameters for new chemical systems unavailable
yet in public-domain or commercial software databanks. This communication reviews the basics of the
model and provides some examples of modeling hydrometallurgical applications with emphasis on high
temperature applications, including calcium sulfate scale formation in autoclaves, high temperature pH
inference and iron control.

Niagara, ON, Canada
Edited by
106
INTRODUCTION
Modeling of electrolyte systems has been of particular interest to various industrial processes,
such as separation processes (e.g., solution crystallization, extractive distillation, seawater desalination or
bio-separations), environmental applications (e.g., gas treatment, wastewater treatment or chemical waste
disposal) and hydrometallurgy (e.g., pH control and neutralization, iron control, scaling and fouling of
equipment). Using a chemical model, time-effective predictions of various properties of electrolytes can
be obtained, which is beneficial not only during process monitoring, but also during process optimization
and process scale up. As a result, pilot scale studies can sometimes be eliminated where budgetary
constraints exist. Development of such a powerful model requires the use of a speciation-based model, in
which solution chemistry is explicitly addressed (as compared with some models that treat electrolytes
either as undissociated or fully dissociated systems), despite being computationally challenging. In
addition, as a feature of electrolyte systems, speciation equilibria inherently influence the phase equilibria
due to complex formation, ion pairing, and acid-base reactions. Therefore, how the electrolyte solutions
behave at various conditions may differ significantly due to the non-ideality, which must be carefully
addressed to obtain a model that is applicable to a wide range of conditions such as concentration,
temperature, pressure and solvent system.
A speciation-based thermodynamic model has been developed by OLI Systems for mixedsolvent electrolyte solutions (Wang et al., 2002). This model was able to reproduce simultaneously vapor
liquid equilibria, solidliquid equilibria, speciation, caloric and volumetric properties of electrolytes in
aqueous, organic or mixed (organicwater) solvents. The model is valid for salts from infinite dilution to
the fused salt limit and for various completely miscible inorganic systems (such as acidwater mixtures)
over the whole concentration range. Also, the model is capable of representing phase equilibria in
multicomponent inorganic systems containing multiple salts and water or a salt, an acid and water (Wang
et al., 2004; Wang et al., 2010).
OLI Analyzer software package is a powerful application based on the above-mentioned
speciation-based thermodynamic model that enables reliable estimation of properties and chemical
equilibria in concentrated electrolyte solutions of interest to hydrometallurgical applications. This userfriendly software features single point equilibrium calculations, multiple point survey calculations for trend
analysis of temperature, pressure, pH and composition effects, and simple mix and separate capability.
The calculations provide vapor, liquid, solid, and 2nd liquid phase separations for a fully speciated model.
Properties such as pH, oxidation-reduction potential, viscosity, density, enthalpy as well as compositions
are reported; isothermal, adiabatic, bubble and dew point, set pH, vapor fraction and custom calculations
are available.
Furthermore, OLI also incorporates a built-in regression facility in its software to allow creation
of new chemical databases or optimization of the existing database to expand the reliability of the model to
chemical systems or process conditions of interest. Experimental data (including solubility, density, heat
capacity, water activity, etc.) can be used to fit the model through regression of binary interaction
parameters and standard-state properties of the species involved. Optimization of the parameters is the key
for obtaining satisfactory binary and ternary models which can then be extended to predict the properties of
multicomponent systems.
This communication reviews the basics of the MSE model and provides some examples of
modeling high-temperature hydrometallurgical applications; in particular, examples from calcium sulfate
scale formation in heaters and reactors during recycling of process solutions, high-temperature pH
inference in pressure acid leach (PAL) process, and iron control are presented.
THERMODYNAMIC FRAMEWORK
As described above, the speciation-based model, as implemented by OLI, requires solving
chemical equilibria involved in the system of interest. For a chemical reaction,
aA + bB + = cC + dD +
107
(1)
the equilibrium composition can be determined from:

(2)
where xi is the mole fraction of species i, i is the activity coefficient of species i, R is the ideal gas
0
constant, and T is the temperature. In Eq. (2), the standard free energy term, G , is given by:
(3)
where i0 is the standard-state chemical potential of species i, the sum is over all species participating in the
chemical reaction, and i is the stoichiometric coefficient of species i in Eq. (3) with positive and negative
values for the species on the right-hand side and left-hand side of the equation, respectively. A
comprehensive model is also employed, widely known as Helgeson-Kirkham-Flower-Tanger (HKFT)
equation of state (Helgeson and Kirkham, 1974, 1976; Helgeson et al., 1981) to calculate the standard state
chemical potential, i0, at a given temperature and pressure in order to solve the speciation equilibria. In
addition, the parameters used in the model for various aqueous ions, ion pairs, and neutral species for both
inorganics and organics are readily available in the literature or can be estimated (Shock and Helgeson,
1988, 1990; Shock et al., 1989; Shock et al., 1997; Sverjensky et al., 1997).
Solving speciation equilibria by using Eq. (2) has to be accompanied by calculating the activity
coefficient of each participating species in the reaction. The activity coefficient is a parameter which
accounts for the non-ideality (i.e., excess properties) of electrolyte solutions, and is defined by the excess
Gibbs free energy of the solution, Gex:
(4)
,,
where ni is the number of moles of the solution constituents (species i), and j is any other species.
As part of the MSE model, the activity coefficient model covers the full concentration range from
infinite dilution where electrostatic forces dominates, to more concentrated solutions where mixed
contribution from electrostatic forces, as well as the forces relevant in short range (interactions between all
neutral molecules) and mid-range (interactions between ions or ions and molecules) cannot be neglected.
In order to take full advantage of the MSE model, the Gibbs excess free energy is calculated as a
summation of the interactions in all three ranges (Wang et al., 2002):

(5)
The long range contribution is described by Pitzer-Debye-Hckel expression (Pitzer, 1973; Pitzer,
1980) that was chosen because it has been tested to give satisfactory predictions up to the fused salt limit
(Achard et al., 1994; Chen et al., 1982; Chen and Evans, 1986; Pitzer and Simonson, 1986), as well as for
MSE system (Achard et al., 1994; Liu and Watanasiri, 1996; Pinho and Macedo, 1996). As for the middle
range contribution, a second virial coefficient-type expression is used which involves the use of binary
interaction parameters for each ion pair or ion-molecule pair. Finally, the short range contribution employs
the UNIQUAC model due to the following advantages: (i) small temperature dependence of the parameters
which reduces the number of parameters used, (ii) applicability for any molecular size including polymers,
and (iii) possible extension of the model to UNIFAC, to improve its predictive nature. The UNIQUAC
model is relevant for mixed-solvent chemical systems. For electrolyte systems at concentration levels
108
encountered in hydrometallurgical operations, the biggest contribution comes from the specific-interaction,
ionic strength dependant mid-range contribution which is shown in Eq. (6) (Wang et al., 2002):
(6)
where interaction parameters Bij(Ix) = Bji(Ix) and Bii = Bjj = 0.The functionality of Bij (Ix) is shown in Eq. (79) (Wang et al., 2004):
= + +
bij= b0,ij+ b1,ijT + b2,ij/ T
(8)
cij= c0,ij+ c1,ijT +c2,ij/ T
(9)
(7)
with bij and cij as the adjustable parameters which are a function of temperature (the temperature dependent
variables were chosen due to their effectiveness in reproducing experimental data), and a1 is a constant set
at 0.01. The detailed mathematical expressions for the short and long range contributions are provided in
the original paper (Wang et al., 2002).
PRESSURE HYDROMETALLURGY APPLICATIONS
Modeling of Calcium Sulfate Solubility in High Temperature Laterite Pressure Acid Leach Solutions
The PAL process has been used to treat nickel laterite ores due to its fast kinetics, high extraction
of Ni and Co and in-situ removal of Fe and Al impurities (Whittington and Muir, 2000). The leach process
is followed by a neutralization step in which limestone is added to increase the pH of the solution in order
to remove the soluble iron. Counter-current decantation (CCD) follows in which solid-liquid separation
takes place. The solution containing base metals is further purified by solvent extraction and the resulting
process water is treated by lime addition, which removes the remaining impurities in order to meet the
environmental regulation. The process water, which is recycled to the leaching step, is usually saturated
with calcium and it causes scaling inside the preheater as well as the autoclave. Other sources of calcium
include the laterite ore or the process water used. Scaling occurs because of the transformation of
CaSO4.2H2O (gypsum) to CaSO4 (anhydrite) at temperatures greater than about 40C, depending on the
sulfate concentration, in which the solubility of anhydrite reduces significantly with temperature, as can be
seen in Figure 1.
This scaling effect can cause significant problems in PAL process as it reduces the effectiveness
of heat transfer equipment. In the long run, scaling can also cause corrosion and wearing out of
construction materials. It causes the industry to lose considerable amount of money and time since the
scale removal needs to be done mechanically. In order to reduce the amount of scaling, knowledge of the
solubility of CaSO4 in the PAL process solutions is required. More recently, such solubility study was
conducted experimentally (by using synthetic PAL solutions of H2SO4, NiSO4, MgSO4, Al2(SO4)3 and
NaCl) and modeled using OLI to find out the effect of H2SO4, metal sulfates (Mg and Ni) as well as
chloride at elevated temperatures on the solubility of CaSO4 (Azimi & Papangelakis, 2010). New
interaction parameters (as per Eq. 7) were developed by fitting the MSE model on calcium sulfate
solubility data in binary and ternary systems. The model was then used to predict high temperature
calcium sulfate behavior in multicomponent solutions, as follows
109
Figure 1 OLI-determined phase transition diagram of CaSO4 in H2O. The solid and dashed curves show
the stable and metastable phases, respectively, at each temperature (Azimi et al., 2007)
It can be seen in Figures 2 to 4 that at the temperature relevant to the PAL process, and contrary to
a common ion effect expectation, the solubility of CaSO4 increases with H2SO4 concentration due to the
formation of HSO4- ion (from a decrease in the second dissociation constant of H2SO4), which, in fact,
reduces the SO42- in the system. However, in agreement with common ion effect, the solubility
decreases with increasing concentration of other metal sulfates; whereas it increases with chloride ion
increase due to complex formation (Williams-Jones & Seward, 1989). The effect of chlorides in PAL is
important because during ore preparation, the use of bore water or sea water will have an effect on the
scaling potential. To prevent any anhydrite scaling, calcium must be removed from the recycled process
solutions prior to entering the preheating system to decrease its concentration to the level corresponding to
the preheater, or autoclave temperature as well as composition.
Figure 2 Anhydrite solubility vs. NiSO4

concentration in CaSO4-H2SO4-NiSO4-MgSO4Al2(SO4)3-H2O solution; from Azimi &
Papangelakis (2010); the lines represent OLI
prediction
Figure 3 Anhydrite solubility vs. MgSO4

concentration in CaSO4-H2SO4-NiSO4-MgSO4Al2(SO4)3-H2O solution; from Azimi &
Papangelakis (2010); the lines represent OLI
prediction
110
A)
B)
Figure 4 Anhydrite solubility vs. temperature in pure water and in 0.22M H2SO4 solutions in comparison
with that in laterite PAL solutions containing MgSO4-NiSO4-Al2(SO4)3 at various A)H2SO4, B) chloride
concentrations. Solid curves are OLI model predictions while the dashed line shows gypsum solubility at
25C (from Azimi & Papangelakis, 2010; and Azimi, 2010)
Prediction of pH in High-temperature Nickel Laterite Pressure Acid Leach Process Solutions
As mentioned earlier, the PAL process has been used to recover base metals (Ni and Co) from
lateritic ores (Krause et al., 1997; Whittington & Muir, 2000). However, the efficiency of the PAL process
depends on the type and composition of the laterite. While limonitic laterite is rich in Fe (40%) but low in
Mg (2%), saprolitic laterite is rich in Mg (10-20%) and contains less Fe (10-25%). Because iron
precipitates in-situ during the autoclave pressure leach, a substantial portion of the acid added is recovered.
However, the high magnesium content in saprolitic ore dissolves during the leach and consumes a
significant amount of acid, which renders this process inefficient (even though saprolites contain more Ni
than limonites). Thus, PAL is efficient only in recovering limonitic ore (with acid consumption of around
200 kg/t dry ore), or a blend of saprolitic and limonitic ore (with acid consumption of around 400 kg/t dry
ore) (Whittington & Muir, 2000). The question that often arises is what is the optimum acid dosage for a
given and often variable ore composition. Excess acid leads to unnecessary consumption of lime, gypsum
formation, and increased impurity levels, whereas acid deficit leads to incomplete extraction of pay metals
Ni and Co. Free acid measurement at room temperature, however, does not reflect the activity of hydrogen
ion (pH) during the high temperature process, which truly controls the kinetics and equilibria (Rubisov et
al., 2000).
Previous studies suggested that high temperature behavior of divalent metal sulfates can be
approximated with that of MgSO4 (Baghalha & Papangelakis, 1998) because of fairly similar ionic
properties (i.e. hydration, conductivity, complex formation, etc). Furthermore, high extraction of Ni and
Co are achieved when the pH of the leach solution at the leach temperature is maintained at 1 by acid
addition, regardless of the ore composition (Papangelakis et al., 2004). More recently, a flow-through
electrochemical cell containing an yttria-stabilized zirconia (YSZ) sensor for direct high temperature insitu measurement of pH in PAL solution was used (Jankovic & Papangelakis, 2010) to test the above
postulations. The experimental results were compared with the OLI MSE prediction calibrated
independently using the solubility data of Al, Mg and Ni under acidic sulfate solutions (Liu &
Papangelakis, 2005).
In Figure 5, the pH measurement of industrial PAL solution (containing equivalent Mgtotal = Mg +
Ni + Co + Mn) and synthetic solution (containing Mg = equivalent Mgtotal from the respective industrial
PAL solution) are compared with the theoretical pH calculated by OLI MSE. In all cases, the predicted pH
was in a good agreement with the experimental pH measurement. In addition, both the pH of synthetic and
that of industrial PAL solution at different equivalent Mg concentrations as well as free H2SO4
concentration were comparable with one another, validating the first postulation that the behavior of metal
111
sulfates can be approximated with that of MgSO4. Moreover, the pH of both the industrial PAL solution
and the synthetic solution lie approximately around 1 which validates the second postulation that acid is
added to PAL process in order to maintain constant pH at 1 at the process temperature, regardless of ore
composition and solubility issue.
A)
B)
Figure 5 Variation of pH as a function of H2SO4 concentration at different MgSO4 concentrations for

pressure acid leach solutions as well as synthetic solutions. The lines represent theoretical pH values
(calculated with OLI). Solid lines refer to solutions containing no Al, whereas dashed lines represent
solutions under Al saturation (with hydronium alunite). Symbols refer to experimental measurements at A)
various MgSO4 and H2SO4 concentrations, and B) constant MgSO4 and various H2SO4 concentrations
(from Jankovic & Papangelakis (2010))
Figure 6 Variation of free H2SO4 as a function of equivalent-Mg at various temperatures.The lines

represent theoretical values (calculated with OLI). Symbols refer to experimental data at: () 245C
(Tuffrey et al., 2009); (& Papangelakis, 2000); () 260C
(Jankovic & Papangelakis, 2010); (
270C (Rubisov & Papangelakis, 2000). Figure from Jankovic & Papangelakis (2010)
The OLI model was also utilized to calculate acid addition for maintaining pH at around 1 as a
function of equivalent Mg concentration in solution for temperatures between 250C and 270C, as seen in
Figure 6. Experimental data from various industrial PAL processes were used to validate the goodness of
OLI prediction. These results are also consistent with a recent publication on the Moa, Cuba PAL
operation (Chalkley et al., 2010). The construction of Figure 6 is not straightforward because several
parameters need to be accounted for, such as conversion of the concentration units to g/L by solution
density values predicted by OLI. The free sulfuric acid concentration at the specified pH (0.8 to 1.2) is
calculated using OLI Analyzer by trial and error. Also, in using industrial data, the amount of Fe and Al in
the CCD solutions reflect dissolution of hematite (assuming all Fe exist as Fe(III)) and hydronium alunite
112
during cooling of the solution according to reactions (10) and (11), respectively.
Fe2O3(s) + 3H2SO4(aq) Fe2(SO4)3(aq) + 3H2O(l)
(10)
2H3OAl3(SO4)2(OH)6(s) + 5H2SO4(aq) 3Al2(SO4)3(aq) + 14H2O(l)
(11)
Due to the additional acid consumption during flashing and cooling of the solution prior to
measuring free acid, the measured values are often lower than those at temperature. In spite of these
uncertainties, a fairly good and consistent agreement was achieved between the measured and predicted
free H2SO4 concentrations, thus the generated OLI MSE model can be used to control acid additions in the
PAL process, and by extension in other pressure hydrometallurgical operations.
Modeling of Hematite and Sodium Jarosite Solubility in Sulfuric Acid Solutions at Elevated
Temperatures
Iron is a common impurity in hydrometallurgical processes that needs to be removed prior to the
recovery of base metals. During autoclave leaching of nickeliferrous laterites using H2SO4, iron which is
mainly present as goethite dissolves followed by in-situ precipitation of hematite according the hydrolysis
reaction (Chou et al., 1977; Georgiou & Papangelakis, 1998) as seen in reaction (12):
Fe2(SO4)3(aq) + 3 H2O(l) Fe2O3(s) + 3H2SO4(aq)
(12)
The main advantage of hematite precipitation is the recovery of sulfuric acid which is used in-situ
for the leaching process. In addition, hematite is the preferred iron product because it is compact, easily
washed, thermodynamically stable and commercially saleable (Dutrizac & Riveros, 1999).
The knowledge of hematite solubility in H2SO4 solution is particularly important in monitoring
and optimizing the efficiency of iron removal. Hematite solubility had been extensively studied in H2SO4
solutions at elevated temperatures (Liu et al., 2003; Sasaki et al., 1993; Umetsu et al., 1977), but reliable
and accurate solubility data at high temperatures is difficult to find due to sampling errors during the
solubility measurement. Reid and Papangelakis (2006) have measured and modeled the solubility of
hematite in H2SO4 solutions from 130C up to 270C and also in the presence of MgSO4, addressing
several aspects of experimental designs to eliminate the errors made by previous researchers: precise
temperature control to avoid solution super-saturation, elimination of contamination of iron from using
stainless steel materials by using titanium equipment, equilibrium approach from hematite dissolution route
to avoid excess colloid formation during iron precipitation, use of Ti passivators to avoid generation of
ferrous ions, and in-situ filtration at equilibration temperature to remove any solid particles. An OLI MSE
model was fitted on the new binary and ternary hematite solubility data by Reid and Papangelakis (2006)
and the fitting results were compared with the literature data provided by previous investigators, as
mentioned above.
Figures 7 and 8 show that the OLI model is in a good agreement with Reid and Papangelakis
(2006) in fitting the solubility of hematite in the high temperature binary Fe2O3-H2SO4 system. Solubility
of hematite increases with decreasing temperature and increasing H2SO4 concentration. Umetsu et al.
(1977) reported higher solubility due to indirect sampling (after cooling the autoclave to 100C) which
causes further hematite dissolution. Sasaki et al. (1993) also reported higher solubility data because of
hydrolytic precipitation approach (which causes the formation of small size colloidal particles (Flynn,
1984; Matijevi et al., 1975)) and the absence of in-situ filtration (which causes the colloids to dissolve at
low temperature). In addition, Liu et al., (2003) reported higher solubility due to lack of titanium
passivation which causes reduction of Fe (III).
Figure 7 Hematite solubility in H2SO4 solutions

from 130C up to 170C. The symbols are
literature solubility data, and the lines are OLI
model fitted to Reid and Papangelakis (2006)
values
113
Figure 8 Hematite solubility in H2SO4 solutions

from 230C up to 270C. The symbols are
literature solubility data, and the lines are OLI
model fitted to Reid and Papangelakis (2006)
values
Figure 9 Hematite solubility in H2SO4 solutions containing MgSO4 at 250C. The symbols represent
literature data while the lines represent OLI fitting
Figure 9 shows a comparison between the solubility of hematite with no Mg and under the
presence of saturated kieserite (MgSO4.H2O). Solubility of hematite decreases in the presence of MgSO4
due to an increase in the sulfate ions which promotes bisulfate formation according to reactions (13) and
(14):
MgSO4(s) Mg2+(aq) + SO42-(aq)
(13)
SO42-(aq) + H+(aq) HSO4-(aq)
(14)
The decrease in the H+ concentration will shift the equilibrium for reaction (12) toward hematite
precipitation, thus reduces its solubility.
114
Figure 10 Sodium jarosite solubility in H2SO4

solutions from 70C up to 110C. The symbols
represent solubility data taken from Sasaki et al.
(1998) and the lines represent OLI fitting
Figure 11 OLI Predicted solubility of sodium

jarosite and hematite in solutions containing H2SO4
and Na2SO4 at 150C. The symbols represent the
transition points between the hematite and sodium
jarosite lines at the same Na2SO4 concentrations
Aside from hematite, jarosite compounds (XFe3(SO4)2(OH)6) are also relevant to hightemperature processes, especially if monovalent cations (e.g., Na+, K+, NH4+) and moderate acid
concentrations exist in the leach solution. Jarosite precipitation has the benefits of easy washing and
filtration, as well as alkali and sulfate removal (Dutrizac & Jambor, 2000; Paktunc & Dutrizac, 2003), but
it produces high volume waste, has no value and sometimes considered as hazardous waste (Lahtinen et al.,
2006), thus hematite precipitation is preferred. In this study, the MSE model was fitted on sodium jarosite
solubility from 70C up to 110C (Sasaki et al., 1998) as seen in Figure 10, and was then used to predict
the transition point between sodium jarosite and hematite at 150C at various Na2SO4 concentrations.
Based on Figure 11, hematite and sodium jarosite are stable below and above the transition point,
respectively. Furthermore, sodium jarosite precipitation is favored more at higher K2SO4 concentrations,
as the transition point from hematite to sodium jarosite occurs at lower sulfuric acid concentration.
Sodium jarosite solubility decreases with an increase in Na2SO4 concentration due to common ion effect,
as observed also by Stoffregen (1993).
CONCLUSIONS
OLI has developed a sophisticated thermodynamic model for MSE systems capable for
simultaneous calculations of phase equilibria, speciation, enthalpies, heat capacities and densities for
estimation of physicochemical properties of interest to high pressure (and atmospheric pressure)
hydrometallurgical applications.
Examples of applying OLI to actual pressure hydrometallurgical applications relating to calcium
sulfate scale formation in heaters and autoclaves during recycling of process solutions, optimization and
control of acid additions in PAL operations, and prediction of hematite solubility in sulfate solutions at
high temperature were presented. For all the systems involved in this study, the model has been proven to
reproduce experimental data with good accuracy. The developed high temperature OLI model can
potentially be used by the industry to: control the anhydrite scaling by reducing calcium content below its
solubility limit prior to recycling the PAL process solution back to preheaters and autoclaves, calculate the
sulfuric acid addition in PAL in order to maintain pH around 1 for high Ni and Co extraction, and to
monitor the efficiency of in-situ iron removal during PAL as either hematite or jarosite, in which the acid
consumed is recovered.
ACKNOWLEDGEMENT
This work was supported by Vale Canada, Barrick Gold, and OLI Systems.
115
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Process Development
121
INFLUENCE OF IRON ON THE COMPLEXATION AND OXIDATION OF QUEBRACHO:

AN INVESTIGATION ON THE STABILITY OF SULFUR DISPERSING AGENT
*L. Tong1, D. Dreisinger2, B. Klein1, J. Li1
1
NBK Institute of Mining Engineering

University of British Columbia
6350 Stores Road, Vancouver, BC, Canada V6T 1Z4
(*Corresponding author: lbtong@mining.ubc.ca)
2
Department of Materials Engineering

6350 Stores Road, Vancouver, BC, Canada V6T 1Z4
ABSTRACT
The oxidation of Quebracho was evaluated by acid-butanol assay, which indicates depolymerization of Quebracho. Anthocyanidin, an oxidation product of Quebracho, is stable at 95C for up
to 2 h. The ionization, complexation, and oxidation properties of Quebracho were discussed.
Complexation of metal-Quebracho occurs at ambient temperature. The formation of complex precipitates
is influenced by the acidity of the solution. Temperature is another important parameter that influences the
oxidation and the complexation of Quebracho. Quebracho-ferric complex precipitate forms at 90C, 0.1
mol/L H2SO4. The formation of Quebracho-metal complex in the leach solution is a possible reason for the
consumption of Quebracho. Quebracho molecules adsorption on the mineral surface is reduced by
consumption of Quebracho, resulting in poor sulfur dispersing effect in the leaching process.

Niagara, ON, Canada
Edited by
122
INTRODUCTION
Quebracho is used as a sulfur dispersing agent (SDA) in the pressure leaching of zinc concentrate
as stated in U.S. Patent No. 3,867,268 (1975). It prevents the zinc sulfide particles from being coated with
molten sulfur, thus preventing the inhibition of the zinc leaching reaction. Recently, the sulfur dispersing
effect of Quebracho was investigated in the oxygen pressure leaching of nickel concentrate. The oxygen
pressure leaching of pentlandite can be represented by reactions 1-3.
Fe4.5 Ni4.5 S8 + 4.5O2 + 18 H + 4.5 Ni 2+ + 4.5 Fe 2+ + 9 H 2O + 8S
(1)
4 Fe 2+ + O2 + 4 H + 4 Fe3+ + 2 H 2O
(2)
Fe4.5 Ni4.5 S8 + 18 Fe 3+ 4.5 Ni 2+ + 22.5 Fe 2+ + 8S
(3)
The adsorption of Quebracho on the nickel concentrate surface was investigated at pH 3.5-4.7.
Sulfuric acid was used to adjust the acidity of the system. Electrostatic interaction is a possible adsorption
mechanism. However, the adsorption study was investigated at ambient temperature. Quebracho is more
likely to adsorb chemically on the nickel sulfide mineral surface under the following pressure leaching
conditions: 150C, low pH, and high ionic strength (Tong & Dreisinger, 2009a). The concentration of
Quebracho was determined by acid-butanol method. The presence of iron in the mineral slurry influences
the accuracy of acid-butanol assay. Therefore, the influence of iron on the adsorption mechanism of
Quebracho on the nickel concentrate surface cannot be detected by the acid-butanol method.
The effect of Quebracho was evaluated by interfacial studies. Quebracho decreased the work of
adhesion in liquid sulfur-pentlandite-aqueous solution systems (Tong & Dreisinger, 2009b). The
interfacial study indicated that Quebracho is an effective SDA in leaching. The leaching study proved that
Quebracho has an effect on increasing nickel extraction from nickel concentrate (Tong & Dreisinger,
2009c). The extraction of nickel increased from 15%, without addition of SDA, to 83% with addition of
Quebracho under the following leach conditions: 150C, 690 kPa oxygen overpressure, 0.5 mol/L H2SO4,
250 g/L concentrate (-44 m), 2 h. The effect of Quebracho is believed to be influenced by the oxidizing
conditions during leaching. Quebracho is possibly consumed (oxidized) in the autoclave as the leaching
process proceeds.
It is important to understand the stability of SDA under pressure leaching conditions. In the
pressure leaching of chalcopyrite, SDA was found not to affect the subsequent solvent extraction process,
due to the decomposition of SDA during pressure oxidation (Dreisinger, Steyl, Sole, Gnoinski, & Dempsey,
2003). Lignosulfonate was degraded by ferric ions to produce ferrous and degraded lignosulfonate, with a
half-life of approximately 10 min under oxidative pressure leaching conditions (Dreisinger, Peters, Talaba,
DeGraaf, Owusu, & Swiniarski, 1990). However, detailed information about the degradation of
lignosulfonate under leaching conditions is not available. The influence of oxygen and ferric on the
stability of lignosulfonate deserves further study under pressure leaching conditions.
The information on the properties of SDA under low temperature and low pressure conditions is
also necessary. For instance, o-phenylenediamine (OPD), a SDA, is unstable in aqueous solution at
ambient temperature. The changes of the UV-spectra of OPD solution after conditioning with nickel
concentrate indicated the chemical changes of OPD. The literature indicated that OPD is easily oxidized to
form 2,3-diaminophenazine (DAP) and other byproducts. DAP is a common product of the oxidation of
OPD in the presence of ferric ions (Nemeth & Simandi, 1994, 1982).
The main objective of this investigation was to study the influence of temperature, sulfuric acid,
and metal ions on the behavior of Quebracho under low temperature (up to 90C) and low pressure
conditions. The structure of Quebracho was reviewed. The ionization of Quebracho and the complexation
of Quebracho with iron and nickel were evaluated. The formation of metal-Quebracho complex was
123
studied by UV method. The oxidation of Quebracho was indicated by acid-butanol assay. Anthocyanidin,
an oxidation product of Quebracho was also evaluated in this study.
EXPERIMENTAL
Materials
Quebracho (Orfom grade 2 tannin) was obtained from Chevron Phillips Chemical Company LP.
It contained 85-95% sulfited Quebracho and 5-15% water. Nickel (II) sulfate hexahydrate, A.C.S. reagent,
was obtained from Sigma Aldrich. A standard solution of sulfuric acid (0.5 mol/L), obtained from Fisher
Scientific, was used to adjust the acidity of solution. Hydrochloric acid, iron (II) sulfate heptahydrate, 1butanol, and reagent grade ferric sulfate were also obtained from Fisher Scientific.
Treatment of Quebracho in Heavy Walled Tube
The stability of Quebracho was studied at 90C by using 35 mL heavy walled test tubes. The
Quebracho, ferric sulfate, and nickel sulfate solutions were prepared separately before testing. Mixed
solutions of Quebracho and metal-sulfate solution were prepared right before each test. About 16 mL
mixed solution was transferred to the test tube, capped and heated for 30-120 min. After treatment, the
Quebracho solution was cooled in cold water and filtered. The Quebracho solution was then ready for
acid-butanol assay to determine the concentration of Quebracho.
Acid-butanol Method
The acid-butanol assay was used to determine the concentration of Quebracho in aqueous solution.
It is a common method to determine the concentration of condensed tannins in plant tissues (Waterman &
Mole, 1994; Porter, Hrstich, & Chan, 1986). The preparation of butanol solution reagent includes the
following three steps: (1) 50 mL concentrated hydrochloric acid was added to a 1 L volumetric flask; (2)
0.7 g ferrous sulfate heptahydrate was added into the flask and fully dissolved in the concentrated acid; (3)
1-butanol was added into the volumetric flask to make 1 L solution. 2 mL Quebracho solution and 14 mL
butanol reagent were added into a heavy walled test tube, capped, and mixed. For a blank sample, 2 mL
deionized water and 14 mL butanol reagent were added into the heavy walled test tube, capped, and mixed.
The mixed samples were conditioned in a water bath at 95C for 1 h. After cooling, the sample was
transferred into a clean quartz UV 1 cm cell, and the absorbance measurement was obtained at a
wavelength of 550 nm. The measured value was the Quebracho concentration left after treatment.
Infrared Spectrum of Quebracho
The infrared spectra of Quebracho were obtained using a Perkin-Elmer System 2000 Fourier
transform infrared (FTIR) spectrophotometer. Fifty scans were run to collect the infrared spectra in the
wavenumber range from 4000 to 400 cm-1. The spectral resolution was 0.5 cm-1.
DISCUSSION
Characterization of Quebracho
Structure of Quebracho
Quebracho is a condensed tannin. Condensed tannins, also known as proanthocyanidins (PAs),
are polymers or oligomers of flavan-3-ol (catechin) and/or flavan-3, 4-diol units (Dykes & Rooney, 2006).
Fig. 1 shows the repeat unit of PAs (Schofield, Mbugua, & Pell, 2001). For B-type proanthocyanidins, the
basic units are linked mainly by C4C8 and/or C4C6 interflavan bonds. For A-type PAs, the flavan-3ol units are linked by an additional ether bond between C2C7 and/or C2C5. The flavan-3-ols differ on
the number of hydroxyl groups on the B rings and the nature of the stereochemistry of the asymmetric
124
carbons on the C rings. PAs can be classified, according to the differences in hydroxylation patterns, into
10 subgroups: (1) profisetinidins (3,3,4,7-hydroxyl); (2) prorobinetinidins (3,3,4,5,7-hydroxyl); (3)
procyanidins (3,3,4,5,7-hydroxyl); (4) propelargonidins (3,4,5,7-hydroxyl); (5) prodelphinidins
(3,3,4,5,5,7-hydroxyl); (6) proguibourtinidins (3,4,7-hydroxyl); (7) proteracacidins (4,7,8-hydroxyl); (8)
promelacacidins (3,4,7,8-hydroxyl); (9) proapigeninidins (4,5,7-hydroxyl); and (10) proluteolinidins
(3,4,5,7-hydroxyl) (He, Pan, Shi, & Duan, 2008).
Figure 1 The basic repeat unit of condensed tannin

Quebracho is a traditionally important commercial source of condensed tannins. Profisetinidins
and prorobinetinidins comprise the major tannins found in Quebracho. In sulfited Quebracho, a sulfite or
sodium sulfite group is introduced on the C1 of the flavonoid structure and causes the opening of the
heterocyle ring. Sulfitation of tannins is known to increase tannin extraction yield from tree barks, as well
as to lower the molecular weight of tannins (Hoong, Paridah, Luqman, Koh, & Loh, 2009). Fig. 2 shows a
possible structure of sulfited Quebracho. This figure shows the presence of fisetinidin and robinetinidin in
the structure of Quebracho, as well as the sulfonate group. Changes were made based on reaction shown in
Fig. 2 (a). Fig. 2 (b) is a combination of previous studies (Hoong et al., 2009; Pasch, Pizzi, & Rode, 2001).
The MW of Quebracho could be as high as several thousand. Fig. 2 (b) does not show the exact number of
the repeat units, as well as the connection of those units in the molecule. Pasch et al. (2001) found that the
structure of Quebracho is almost completely linear.
(a)
(b)
Figure 2 A possible structure of sulfited Quebracho: (a) sulfitation of tannin;
(b) sulfited Quebracho
125
Infrared Spectrum of Quebracho

Fig. 3 shows the infrared spectrum of Quebracho. The qualitative analysis of the infrared
spectrum of Quebracho is based on band assignments to functional groups in previous studies (Colthup,
1950; Iskra & Kielkowska, 1980; Arshad, Beg, & Siddiqui, 1969). The strong peak at 3407 cm-1 is due to
the vibrations of OH groups. The peak at 2923 cm-1 and the shoulder at 2849 cm-1 are due to CH groups.
The peaks at 1616, 1521 and 1453 cm-1 are due to aromatic skeletal vibrations. The band at 1373 cm-1 is
assigned to the phenolic OH bending vibrations. OH and ether groups contribute to the bands ranging from
1285 to 1038 cm-1. The peak at 975 cm-1 is due to OH out-of-plane bending. The peaks at 1038 and 651
cm-1 are characteristic of sulfonate groups. The infrared spectrum of Quebracho indicates the presence of
both hydroxyl and sulfonate groups.
Figure 3 Infrared spectrum of sulfited Quebracho

UV-Vis Spectrum of Quebracho and Anthocyanidin
The UV-Vis spectrum of Quebracho and anthocyanidin is shown in Fig. 4. Quebracho has a peak
at 280 nm in its UV-Vis spectrum, which comes from the A ring of the repeat unit (Fig. 1). There is no
peak in the 300-550 nm range, due to the lack of conjugation between the Quebrachos A rings and B rings
(Santos-Buelga & Williamson, 2003). The interaction of Quebracho and metal ions can be studied by
recording the spectrum of metal-Quebracho complex. The advantage of this method is that the UV-Vis
spectrum can be recorded at a low concentration of Quebracho (0.1 g/L).
Fig. 4 shows the formation of anthocyanidin after acid-catalyzed cleavage of Quebracho tannin.
The formation of anthocyanidin is influenced by temperature, reaction time, and impurities present in
solution. The acid-butanol assay was used to study the stability of Quebracho in this study by measuring
the concentration changes of Quebracho before and after treatment. When the butanol reagent- supernatant
= 14:1 (refer to line 4 in Fig. 4), the wavelength of the maximum absorbance (max) is smaller than 550 nm.
The yield of anthocyanidin is influenced by the amount of water added into the butanol reagent as shown in
Fig. 4. In this study, the ratio of the butanol reagent and Quebracho solution is 7, and the adsorption was
recorded at 550 nm. Fig. 4 indicates that acid-butanol method is suitable to measure a high concentration
of Quebracho due to the low absorbance of anthocyanidin.
126
Figure 4 UV-Vis spectra of Quebracho and its oxidation product

(1)100 mg/L, pH 2.2; (2) 50 mg/L, pH 2.2; (3) 2.0 g/L Quebracho, butanol reagent: supernatant = 7:1; (4)
2.0 g/L Quebracho, butanol reagent: supernatant = 14:1; (5) butanol reagent: supernatant = 7:1, without
Quebracho
Ionization of Quebracho
In the Quebracho-H2O system, Quebracho is dissociated and has negative charge on the molecule.
The charge density is influenced by the pH of the Quebracho solution. Sulfonate and hydroxyl groups are
reported to exist in the Quebracho molecule. The pKa values of the sulfonate group, first phenolic, and
second phenolic groups are 1.5, 8.0, and 11.4 respectively (Ratinac, Standard, & Bryant, 2004; Last &
Cook, 1952). The dissociation of the functional groups in Quebracho is represented by reactions 4-5.
R OH R O + H +
(4)
R SO3 Na R SO3 + Na +
(5)
Interactions of Heavy Metals with Quebracho at Ambient Temperature

Iron-Quebracho Interaction
When ferric sulfate was mixed with Quebracho (without the addition of sulfuric acid), the color of
Quebracho solution changed into blue-black and the solution became turbid. The influence of pH (1.3-3.2)
and ferric-Quebracho ratio on the formation of ferric-Quebracho complex was investigated. The results are
illustrated by their UV-Vis spectra as shown in Fig. 5. The sulfuric acid concentration, ranging from 0
mol/L to 0.1 mol/L, had no influence on the UV-Vis spectrum peak at 280 nm. Ferric has great influence
on the UV-Vis spectrum. At pH 1.3, the peak of the spectrum increases with the concentration of ferric
ions, which indicates the formation of iron-Quebracho complex. At pH 3.2, the peak of the UV-spectrum
decreases with the concentration of ferric ions due to the formation of precipitate. This indicates that pH
influences the product of iron-Quebracho complex. Therefore, if the slurry pH is high enough Quebracho
will be consumed by iron instead of adsorb on the sulfide mineral surface.
127
The interaction of Fe3+ with Quebracho tannin, shown in reaction 6, reveals that iron-tannin
complex requires a certain pH level before it can form. The ferric ions react with Quebracho tannin to
form blue-black iron tannate complex (Brune, Hallberg, & Skanberg, 1991; House & Van Campen, 1994;
Slabbert, 1992; Mila, Scalbert, & Expert, 1996). The precipitated complex formed by ferric and
Quebracho is an amorphous solid. The ferric-tannin complex shows different colors depending on metal to
ligand ratio and pH: green (1:1), blue (1:2), red (1:3) (Rahim & Kassim, 2008). Reaction 7 represents the
formation of three ferric-tannin complexes. Fig. 6 shows the structure of FeR+ and FeR2- complex.
H 2 R + Fe3+ FeR + + 2 H +
(6)
nH 2 R + Fe 3+ FeRn32 n + 2nH +
(7)
Figure 5 Influence of acid concentration on the UV-Vis spectra of Quebracho-ferric sulfate mixture
128
(a)
(b)
Figure 6 The structure of ferric-Quebracho complex: (a) FeR+; (b) FeR2-; R- the repeat unit of Quebracho
Nickel-Quebracho Interaction
Ni2+ ions form NiR and NiR22- complex species with catechol-type ligands as shown in reactions 8
and 9 (Slabbert, 1992).
H 2 R + Ni 2 + NiR + 2 H +
(8)
2 H 2 R + Ni 2 + NiR22 + 4 H +
(9)
Figure 7 (continued on next page) Influence of sulfuric acid on the UV-Vis spectra of Quebracho-nickel
sulfate mixture
129
Figure 7 Influence of sulfuric acid on the UV-Vis spectra of Quebracho-nickel sulfate mixture
The influence of pH (1.3-5.4) and nickel-Quebracho ratio on the formation of nickel-Quebracho
complex was investigated. The results are illustrated by their UV-Vis spectra. Fig. 7 shows the UV-Vis
spectra of mixed nickel sulfate and Quebracho solution. It indicates that small amount of nickelQuebracho complex formed at pH 5.3-5.4. No precipitation was observed in this solution. Fig. 7 also
shows the UV-Vis spectra of mixed nickel sulfate and Quebracho solution in the presence of 0.1 mol/L
sulfuric acid. Nickel (II) ions have no influence on the spectra of the Quebracho solution. This indicates
that the formation of nickel (II)-Quebracho complex is not likely at pH 1.3.
The formation of ferric-tannin complex was observed at pH 3.0-3.2, while no precipitate was
observed at pH 5.3-5.4 in the mixed nickel-tannin solution. This indicates that the formation of iron-tannin
is more likely than the formation of nickel-tannin complex.
Acid-Butanol Assay
Oxidation of Quebracho Reaction
Figure 8 Acid-butanol reaction of condensed tannin
130
The concentration of Quebracho was measured by acid-butanol method as shown by Fig. 8. Note
that the terminal unit does not give a colored anthocyanidin product structure. More information on the
oxidation of proanthocyanidins to yield anthocyanidin pigments upon oxidative cleavage can be found in
the literature (Schofield et al., 2001). The acid-butanol reaction of Quebracho yields fisetinidin and
robinetinidin. The structure of anthocyanidins is shown in Fig. 9.
Figure 9 Structure of anthocyanidin

Influence of Metal Ions on Acid-Butanol Assay
The influence of ferric and nickel concentrations on the formation of anthocyanidin was studied,
and the results are shown in Fig. 10. The addition of Ni2+ up to 2.0 g/L into the tannin solution had no
negative impact on the acid-butanol assay of Quebracho tannin. Ferric concentrations, when present in the
tannin solution up to 1.5 g/L, have a great influence on the determination of the concentration of
Quebracho tannin.
The influence of ferric concentration and conditioning time on the formation of anthocyanidin was
investigated and the results are shown in Fig. 11. In the absence of ferric ions, 1 h reaction time is enough
for the Quebracho assay purpose. In the presence of ferric ions, and while increasing the reaction time
from 1 h to 2 h, more anthocyanidin was found in the solution. This indicates that anthocyanidin is pretty
stable under the following conditions: 0.1 mol/L H2SO4, 1.5 g/L Fe3+, 95C.
Figure 10 Influence of iron and nickel concentration on the acid-butanol assay results:
Quebracho: 1.5 g/L, sulfuric acid: 0.1 mol/L
131
In the presence of 1.5 g/L ferric concentration, about 30% Quebracho tannin could not be
measured by the acid-butanol assay method. The influence of iron on the acid-butanol assay is discussed as
follows: (1) Small amount of iron catalyzes the oxidation of Quebracho. Iron favors the formation of
anthocyanidin; (2) The oxidation of Quebracho is faster when more iron is present in the solution; (3) Iron
interacts with Quebracho, such that the more iron is present, more difficult it is to transfer Quebracho into
anthocyanidin; (4) Iron interacts with anthocyanidin and decreases the adsorption at 550 nm (refer to Fig.
4). Points (3) and (4) are more likely in this study.
Figure 11 Influence of time on acid-butanol assay: Quebracho: 1.5 g/L, sulfuric acid: 0.1 mol/L, 95C
Interactions of Heavy Metals with Quebracho at 90C
Influence of Sulfuric Acid on the Stability of Quebracho
A calibration curve of Quebracho was obtained in the absence of sulfuric acid. A second curve
was then obtained with sulfuric acid included. The equations obtained from these two curves were then
used as a standard to calculate the concentration of Quebracho. The results are listed in Table 1. The
addition of sulfuric acid into Quebracho solution influenced the formation of anthocyanidin.
Table 1 Calibration curves of Quebracho in the absence or presence of sulfuric acid
R2
Sulfuric Acid Concentration
Calibration Equation
mol/L
c:ppm
Abs=3.5810-4c
0.998
0.1
Abs=3.8810-4c
0.999
Influence of Metal Ions on the Stability of Quebracho

Thermal treatment and acid treatment have no great influence on the stability of Quebracho, based
on acid-butanol assay as shown in Fig. 12. Nickel sulfate, up to 2.0 g/L, has no significant impact on the
stability of Quebracho. Ferric concentration had a considerable influence on the stability of Quebracho.
Iron was used as a catalyst to the de-polymerization of Quebracho in the acid-butanol assay process.
However, more iron resulted in a lower adsorption peak at 550 nm, which is either due to the fast oxidation
of anthocyanidin, or due to the formation of iron-anthocyanidin compound.
132
Figure 12 Influence of acid and metal ions on the stability of Quebracho: 1.5 g/L, 90C
Influence of Iron-Quebracho Complexation on the Sulfur Dispersing Effect of Quebracho
Quebracho was evaluated as a sulfur dispersing agent in the pressure leaching of nickel
concentrate. Results show that it must adsorb on the sulfide mineral surface, which decreases the work of
adhesion in the liquid sulfur-sulfide mineral-nickel sulfate system. Quebracho improved nickel extraction
from 15% to 83% from the bench scale pressure leaching test work in the previous study (Tong, 2009).
Table 2 shows the properties of leach solution at ambient temperature. Degradation of Quebracho was
believed to be an important explanation for the limited effect of SDA under leaching conditions. Table 2
shows that more than 10 g/L of ferric ions were present in the leach solution. The complexation of ferric
ions and Quebracho occurred during the leaching process, preventing the adsorption of Quebracho onto the
nickel sulfide mineral surface. Therefore, fresh Quebracho is needed for successful sulfur dispersion during
the oxygen pressure leach process.
Table 2 Properties of leach solution at ambient temperature, leaching conditions: 150C, 690 kPa oxygen
overpressure, 0.5 mol/L H2SO4, 250 g/L nickel concentrate (-44 m), 2 h (Tong, 2009)
SDA
Ni
Cu
Fe
H2SO4
Ferrous
5 kg/t
g/L
g/L
g/L
g/L
g/L
None
4.1
0.8
11.2
31.1
0.47
Quebracho
23.0
3.5
29.4
32.1
0.98
CONCLUSIONS
The structure of Quebracho was reviewed in this study. Profisetinidins and prorobinetinidins
comprise the major tannins in Quebracho. The IR spectrum of Quebracho confirms the presence of
hydroxyl and sulfonate groups.
The complexation of ferric and nickel (II) ions with Quebracho was studied. At ambient
temperature, pH is a critical factor in influencing the formation of metal-Quebracho complex. The
formation of ferric-tannin complex is much easier than the formation of nickel-tannin complex.
133
The oxidation of Quebracho was evaluated by the de-polymerization of Quebracho using the acidbutanol method. Anthocyanidin, the oxidation product of Quebracho, is stable for up to 2 h at 95C.
Thermal treatment up to 90C and acid treatment up to 0.1 mol/L sulfuric acid had no significant
influence on the stability of Quebracho, based on acid-butanol assay. Nickel sulfate, up to 2 g/L, had no
great impact on the stability of Quebracho. On the other hand, ferric concentration had a considerable
influence on the stability of Quebracho. Iron was used as a catalyst to the de-polymerization of Quebracho
in the acid-butanol assay process. However, more iron resulted in a lower adsorption peak of 550 nm,
which is either due to the fast oxidation of anthocyanidin, or due to the formation of iron-anthocyanidin
compound.
ACKNOWLEDGEMENTS
The authors acknowledge Chevron Phillips Chemical Company LP for providing the Quebracho
sample. The contributions on the structure of condensed tannin and its assay methods from other
researchers are also acknowledged.
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137
ADVANCES IN THE USE OF POLYTETRAFLUOROETHYLENE DURING MEDIUM

TEMPERATURE PRESSURE OXIDATION OF CHALCOPYRITE
*E. Guerra
Bharti School of Engineering
Laurentian University
Sudbury, ON, Canada
(*Corresponding author: eguerra@laurentian.ca)
ABSTRACT
Previous studies on the effect of polytetrafluoroethylene addition during chalcopyrite leaching
under conditions similar to those of the CESL process have reportedly resulted in complete leaching of the
copper without the need for grinding of the flotation concentrate. However, these studies employed a pulp
density of only 1% and finely sized PTFE particle that required the use of high impeller rotation rates that
are not sustainable at an industrial scale. This paper explores the performance of 1/8 diameter balls of
PTFE, that readily sink in the leach solution, on leaching performance at impeller rotation rates and ore
pulp densities more typical of industrial practice. Possible routes for separation of the PTFE from the leach
residues and their regeneration for recycling back to the leaching stage are also discussed.

Niagara, ON, Canada
Edited by
138
INTRODUCTION
Chalcopyrite, CuFeS2, is the most important primary sulfide source of copper. While
pyrometallurgical smelting of chalcopyrite remains the only widely accepted route for treating chalcopyrite
concentrates, several medium temperature pressure oxidation processes are claimed to be economically
feasible (Muir & McDonald, 2007). Among these, the CESL process has been extensively piloted and
demonstrated at the prototype scale. The overall process chemistry of the CESL process may be
summarized as follows (Marsden & Wilmot, 2007):
4CuFeS2 + 5O2 + 4H2SO4 4Cu2+ + 4SO42- + 2Fe2O3 + 8S0 + 4H2O
(1)
4CuFeS2 + 17O2 + 2H2SO4 4Cu2+ + 10SO42- + 4Fe3+ + 2H2O
(2)
Though copper extractions of over 95 % are achieved, the CESL process requires extra grinding
of the concentrate (Muir & McDonald, 2007). This is because leaching is conducted at temperatures
around 150 C, where the elemental sulfur produced is molten and grows thicker on the minerals surfaces
as oxidation progresses, creating an increasingly large barrier for mass transport. In addition, the sulfur is
sticky and tends to cause the mineral particles to agglomerate, effectively halting further oxidation of the
particles that end up embedded within the agglomerates. Consumable surfactants, such as ligin sulfonate,
have been shown to be effective at avoiding agglomeration, but they are not effective at removing sulfur
from the minerals. Hence, their use does not obviate the need for fine grinding.
Polytetrafluoroethylene, commonly referred to PTFE or Teflon, is a promising candidate as a
solid sorbent for molten sulfur in medium temperature pressure oxidation processes. PTFE has excellent
chemical resistance and has been shown to be wetted by pure molten sulfur in synthetic leach solutions
under hydrothermal conditions (Guerra, Mathew & Papangelakis, 2010). Studies on pressure oxidation
kinetics of nickeliferous pyrrhotite (Guerra & Shepherd, 2011) and chalcopyrite (Nuo & Guerra, 2012)
flotation concentrates have shown that addition of PTFE can markedly increases oxidation rates and
ultimate extractions. However, the aforementioned studies employed low pulp densities and relatively fine
granular PTFE particles that required the use of high impeller rotation rates, which are not sustainable at an
industrial scale. Hence, this study was undertaken to test the effect of relatively large particles of PTFE,
which will readily sink in the aqueous solutions, on the kinetics of chalcopyrite pressure oxidation under
mixing conditions and pulp densities that are closer to those proposed for an industrial installation of the
CESL process. However, a larger size fraction of the flotation concentrate, relative to the CESL process,
was to be employed based on the presumption that in order for the use of PTFE to be economical the
increased capital costs associated with its use (cost of PTFE and large autoclaves and ancillary equipment)
would need to be offset by obviating the need for added grinding of the flotation concentrate.
EXPERIMENTAL METHODS
The chalcopyrite used for this study was the +106 m fraction of a copper flotation concentrate
from Xstratas Strathcona Mill (Sudbury, Canada). The copper content in concentrate was measured to be
32.6 % (close to the theoretical value of 34.6 % for pure CuFeS2) using a Varian 730-ES series ICP-OES
unit after acid digestion. Chalcopyrite was also verified as the principle copper mineral in the concentrate
by XRD analysis using a Philips 1728 Powder Diffractometer with Siroquant software. Each experiment
employed a 5 % ore pulp density (50 grams of concentrate with one litre of synthetic leach solution).
While a 10 % pulp density is more typical, the 5% value was selected in order to test relatively large PTFE
to chalcopyrite weight ratios (2, 4, and 8) without exceeding the recommended 1.2 L maximum solution
volume of the autoclave employed in the study (a 1.8L titanium autoclave, floor stand model, Parr 4574,
equipped with a temperature/speed controller, Parr 4843). The PTFE was added in the form of 1/8
diameter balls (U.S. Plastic Corp.). The leach solution was prepared using ACS grade chemicals to a
composition of 2.5 g of ferric sulfate (Sigma-Aldrich), 20.0 g of sodium chloride (BDH Chemicals), 51.8 g
of 96.5 % sulfuric acid (Stanchem), and ultrapure deionized water from a Barnstead ROpure LP system
equipped with a NANOpure II polishing filter.
139
The experimental procedure was to place the ore, which was sealed in a glass test tube using a
natural gas-oxygen torch, the leach solution, and either 100 g, 200 g, or 400 g of PTFE into the autoclave
and heat it to 145C without stirring. Once the temperature had stabilized, a pressure of 100 psi was
applied using compressed oxygen through a dual stage pressure regulator. At this point stirring was
initiated at a rotation rate of 700 rpm to crack the glass ampoule and release the chalcopyrite sample into
the leach solution. After 90 minutes the oxygen was shut off and the autoclave contents were rapidly
cooled (to less than 35 C within ten minutes) using tap water passed through the internal cooling coils
within. Once cooled, the PTFE was screened from the autoclave discharge using a No. 16 sieve (1.18 mm
opening). The resulting slurry was then immediately vacuum filtered to generate a clarified solution and
mineral residues fraction. The filtrate was analyzed for copper by Atomic Adsorption Spectroscopy, using
a Perkin Elmer model 3110 at a wavelength of 324.8 nm.
The results of the leaching experiments are illustrated in Figure 1. By inspection, copper
extraction appears to increase linearly as the PTFE to chalcopyrite weight ratio is increased. Since the
PTFE added was monosized, the surface area of the added PTFE was directly proportional to its mass and
so the results suggests that the mechanism by which PTFE increases copper extraction is, not surprisingly,
topological. Extrapolation of the trendline to 100% copper extraction indicates that a PTFE to chalcopyrite
weight ratio of 24.5:1 would result in complete chalcopyrite oxidation within 90 minutes. Assuming this
ratio would be similar for an ore pulp density of 10%, then addition of 2450 g of 1/8 PTFE balls are
required per 100 g of concentrate. This may seem like an unreasonably large amount of PTFE to add, but,
in fact would only correspond to the addition of a little over a litre of PTFE per litre of slurry, which would
roughly double the autoclave size requirement compared with a CESL process that uses consumable
surfactants and fine grinding. That said, it would obviously be advantageous to reduce the PTFE
requirement and thereby reduce the capital costs as well as heating and material handling costs. While
simply reducing the size of the PTFE particles seems like a logical solution this is not practical with pure
PTFE since, as mentioned in the introduction, this would necessitate the use of much more vigorous
mixing conditions that would lead to unreasonably high power and maintenance costs. One possible
solution may be to employ PTFE pellets that contain a denser inorganic. In this regard, hematite, Fe2O3,
seems to be a good candidate as a filler material since it is relatively dense, having a specific gravity of
around 5.0, and since it is a byproduct of the process it is cheap and posses no risk of contamination of the
leach solution.
Though the effectiveness of PTFE in accelerating leaching kinetics has been established, the
downstream processes for recovering and regenerating the PTFE have not yet been addressed. A
schematic flowsheet for PTFE-assisted chalcopyrite leaching, illustrated in Figure 2, contains unit
operations for PTFE-Sulfur / Residues-leach solution Separation and PTFE/ Sulfur Separation. After
the leaching experiments the PTFE balls were easily screened from the leach residues and so this seems the
most likely method for separating the PTFE-Sulfur fraction from the autoclave discharge in an industrial
setting. However, the best method of separating the PTFE from the sulfur adhered to its surface is not as
clear. In this study the sulfur/mineral residues were simply dissolved from the PTFE balls by placing them
in a beaker of aqua-regia overnight. Though they retained a slight brown color and odor of aqua-regia,
which could only be removed by soaking them in deionized water for several days, this procedure at least
appeared to confirm that the PTFE balls could be fully regenerated. However, in an industrial setting, the
sulfur would be a valuable by-product that would need to be collected and not simply dissolved away. In
zinc pressure leaching processes, hot filtration is employed to create an elemental sulfur product. Since the
softening temperature of PTFE is around 260 C it should be able to withstand the conditions of hot
filtration, so this proven technology is the most likely way to recovery sulfur from the PTFE-Sulfur
residues. However, this method would still leave behind a residue that contains gold and other unreacted
sulfides (Krysa, 1995). This residue may be dissolved using a hot acid leach, as was done in this study, or
it may be possible to use a hot caustic leach to convert the residual elemental sulfur to thiosulfate and
concomitantly leach the gold (Fang & Wei, 2003) along with the other residual sulfides. Further research in
this area is needed.
140
Figure 1 Copper extraction after pressure leaching for 90 minutes in a leach solution containing
2.5 g/L Fe2(SO4)3 , 20 g/L NaCl, 50 g/L H2SO4, at an impeller rotation speed of 700 rpm, at 145 C and
100 psi O2 pressure, as a function of PTFE to chalcopyrite weight ratio
Chalcopyrite
Concentrate
PTFE Assisted
Pressure Oxidation
PTFE
PTFE/ Sulfur
Separation
PTFE-Sulfur
Raffinate
PTFE-Sulfur /
Residues-leach
solution Separation
Cu SX-EW
Sulfur Product
Residues
Residues / leach
solution
Separation
PLS
Copper Product
Figure 2 Schematic flowsheet of PTFE assisted chalcopyrite leaching
141
CONCLUSIONS
Coarse PTFE has been demonstrated as an effective catalyst for pressure oxidation of chalcopyrite
under CESL process type conditions. However, the required ratio of 1/8 PTFE balls to concentrate that is
necessary for complete oxidation of chalcopyrite is projected to double the size requirements of the
autoclave. The use of hematite as a filler material within PTFE pellets was suggested as a way to decrease
the requirement of PTFE by allowing the use of smaller pellets with higher specific surface areas.
Screening of the autoclave discharge was demonstrated to be a relatively easy way of recovering
the PTFE-Sulfur fraction from the leach residues. Hot filtration was proposed as the most likely method
for separating sulfur from PTFE to generate a sulfur product in an industrial setting. However, further
work is needed to verify the suitability of the use of hot filtration. Research is also required to determine
the most suitable method to clean the PTFE surface from precious metals and unreacted sulfides.
ACKNOWLEDGEMENTS
The author wishes to thank Dr. David Tisdale, Xstrata Nickel, for the copper concentrate sample
and NSERC for financial support. The author would also like to acknowledge the support of the Canadian
Foundation for Innovation for a grant which helped establish the Hydrometallurgical and Electrochemical
Engineering Research Laboratory at Laurentian University, where this research was conducted.
REFERENCES
Fang, Z-H. & Wei, S. (2003). Gold leaching with elemental sulfur in alkaline solutions under oxygen
pressure, Transactions of the Nonferrous Metals Society of China, 13(1), 195-198.
Guerra, E., Mathew, R. J., & Papangelakis, V. G., (2010). Interfacial Phenomena in the SulfurPolytetrafluoroethylene System under Hydrothermal Conditions, Minerals Engineering, 23(14),
1113-1119.
Guerra, E., & Shepherd, J. L. (2011). The Effect of Polytetrafluoroethylene on Pressure Oxidation of
Nickelferrous Pyrrhotite, Hydrometallurgy, 106(3), 179-182.
Krysa, B. D. (1995). Zinc pressure leaching at HBMS, Hydrometallurgy, 39(1-3), 71-8.
Marsden, J. O. & Wilmot, J. C., (2007). Medium-temperature Pressure Leaching of Copper Concentrates
Part I: Chemistry and Initial Process Development, Minerals and Metallurgical Processing, 24(4),
193-204.
Muir, D. M. and, & McDonald, R. G. (2007). Pressure Oxidation Leaching of Chalcopyrite Part II:
Comparison of Medium Temperature Kinetics and Products and Effect of Chloride Ion,
Hydrometallurgy, 86(3), 206-220.
Nuo, J., & Guerra, E. (2012). The Effect of Polytetrafluoroethylene on Pressure Oxidation of Chalcopyrite;
In S. Wang, J. E Dutrizac, M. L. Free, J. Y. Hwang, J.Y., & D. Kim (Eds.), T. T. Chen Honorary
Symposium on Hydrometallurgy, Electrometallurgy and Materials Characterization (pp. 207215). Hobokken, NJ: John Wiley & Sons, Inc.
143
HYDROTHERMAL PRODUCTION OF GALLIUM OXIDE

L. Becze1, *E. Peek1, C.J. Ferron1, G. Evans2, K. Reading2
1
Neo Performance Materials

625 Neal Drive
Peterborough, Ontario, Canada K9J 6X7
(*Corresponding author:epeek@neomaterials.com)
2
Neo Gallium Compounds

3225 South 625 Road
Quapaw, Oklahoma, USA 74363
ABSTRACT
Gallium oxide is an important semiconductor material used in optoelectronic devices (flat panel
and solar cell) catalysts and sensors. One of the methods to produce -Ga2O3 is the so-called hydrothermal
route. It is practiced by Neo Gallium Compounds and comprises of two steps: (1) the production of mainly
gallium-oxy-hydroxide in a pressure vessel by reacting metallic gallium with water at 200-220 oC and (2)
the calcination of gallium-oxy-hydroxide at 700-750 oC to convert it into -Ga2O3. This paper describes
this pressure hydrometallurgy process supported with relevant thermodynamic data and presents the
characteristics of the -Ga2O3 powder produced for commercial purposes.

Niagara, ON, Canada
Edited by
144
INTRODUCTION
Gallium is a relatively new metal, having been predicted by D. Mendeleev in 1871, discovered by
P.E. Lecoq de Boisbaudran in 1875, and first commercially produced in the USA in 1943. Gallium is not
rare, being more abundant in the earth crust than antimony, bismuth, molybdenum, silver and tungsten.
However, few gallium minerals exist in nature, and the dispersion of gallium within other minerals add to
the complexity of its recovery. In practice, gallium is found in dispersed state primarily in bauxites and in
some sphalerites, and, to a much smaller extent, in some coals. At present, a very large proportion of the
primary gallium in the world is recovered as a by-product of aluminum plants, mostly Bayer plants, where
gallium is extracted from a bleed of the Bayer liquor (Roskill, 2011). In 2011, world production of primary
gallium was estimated at 200 metric tonnes. In addition, there is a significant contribution of recycling to
the overall yearly availability of the metal.
Gallium exhibits fairly remarkable properties: it is liquid above 29.76 oC, can be supercooled, and
with its high boiling point (2204 oC), is the metal with the widest liquid range. Gallium is magnetic, and is
an excellent conductor of both heat and electricity. Gallium also displays a marked anisotropic electrical
conductivity (Roskill, 2011). All these properties render gallium almost irreplaceable in the semiconductors (GaAs, GaN, GaSb, GaP wafers) and the optoelectronics industry (flat panel, solar cell).
Neo Performance Materials, through its Rare Metals Division, is a fully integrated gallium
producer, with a primary gallium plant in Germany (50% owned), a recycling plant in Peterborough,
Canada, and a refining plant in Blanding, Utah, USA (C.J. Ferron, 2011). In Figure 1 a schematic overview
of both the primary and secondary gallium production routes has been provided.
Figure 1 Schematic diagrams both for primary and secondary gallium production
145
The company also operates gallium tri-chloride production plants in Quapaw, Oklahoma, USA,
and, just starting, in Hyeongok, South Korea. The gallium output of the company, in addition to gallium
tri-chloride, is gallium metal of various grades (4N to MBE grades), and other value-added products such
as gallium nitrate and gallium oxide. Depending on the market requirements Neo employs several
treatment routes to produce gallium oxide. One of the routes utilized is a high temperature pressure
oxidation of gallium metal (hydrothermal route). This paper describes the process, reviews the
thermodynamic data available and discusses some of the control parameters to achieve the product
characteristics demanded by the market.
DESCRIPTION OF HYDROTHERMAL PRODUCTION ROUTE
There are multiple production routes for gallium oxide both worldwide and within Neo
Performance Materials. The explanation for the different production routes is largely driven by customer
needs, i.e. their specification for particle size, particle shape, surface area, mineralogy and chemical
composition determines the cost effective use of gallium oxide in the diverse, high-tech production lines of
the various electronic consumer goods. Within Neo we produce gallium oxide via both atmospheric
precipitation and the hydrothermal route. The autoclave process was commercialised at our subsidiary
Gallium Compounds in Quapaw, Oklahoma, USA. The flow sheet of this hydrothermal route, as practised
at Neo Gallium Compounds, is outlined in Figure 2.
Figure 2 Flow sheet of autoclave production of gallium oxide

The hydrothermal route is largely based on a well-known process that was originally developed by
VAW Aktiengesellshaft in Germany (Pfundt et al., 1978). The patent reveals that a polytetrafluorethylene
(PTFE) lined autoclave is operated at 220 C for 5 hours using a Ga to H2O weight ratio of 2.5 to 8. The
autoclave production of gallium oxide at Neo is a batch process in which 5N gallium metal and de-ionised
water are heated in a pressure vessel under similar conditions to those referenced in the patent to convert
more than 99 % of the gallium into a gallium oxy-hydroxide precipitate. A visual representation of the
autoclave at Neo Gallium Compounds is provided in Figure 3.
To sustain pressure vessel operability and integrity the evolved hydrogen and some steam are
periodically vented from the pressure vessel. It can be calculated that theoretically ~480 litres of hydrogen,
a flammable and explosive gas under certain circumstances, are generated per kilogram gallium converted.
This underlines the need for both safety awareness and periodic, controlled venting of the autoclave
freeboard when pursuing this production route. Designing an autoclave with a very high pressure rating to
146
contain the hydrogen inside the vessel is not deemed an economic option by Neo for the purpose of gallium
oxide production. The intermediate product, mainly gallium oxy-hydroxide, is harvested as a wet cake
and/or slurry from the batch autoclave. Due to the distinct density difference between water, gallium oxyhydroxide and gallium the harvesting of each component can be done visually as unique layers of product.
Unreacted gallium and impure gallium oxy-hydroxide is recycled. To generate a customer, compliant
gallium oxide product calcination is performed in an electric furnace, as shown in Figure 4, at 700-750 C,
where the oxy-hydroxide is converted into a crystalline gallium oxide phase.
Figure 3 Autoclave production of gallium oxide
Figure 4 Pictures of the furnace (left) and crucibles (right) used for calcination of gallium hydroxide
Upon request from Neo Gallium Compounds an investigation was started into the optimization of
both the hydrothermal and calcination reaction. Optimization was defined as identifying operating cost
reduction opportunities per kilogram of gallium oxide produced. Our primary focus was residence time.
147
Due to Neo Performance Materials laboratory facility constraints our study commenced with the
calcination stage. The autoclave stage is subject to future process review.
Experimental Procedures for the Calcination Study
For morphological characterization of the gallium oxide samples, a Variable Pressure Scanning
Electron Microscope (VP-SEM; Hitachi SU6600) was used.
The size distribution of the particles was determined using a laser scattering particle size
distribution analyzer (model CILAS-1064), which can measure particle size distributions over a wide range
of sizes from 0.04 to 500 m in slurry form.
The structural OH/H2O content of the gallium oxy-hydroxide samples was determined by thermogravimetric analysis (model TGA Q500) from TA instruments. The acquisition was done between 25 C
and 900 C with a heating rate of 10 C per min. The purge gas was nitrogen.
Prior to the surface area measurement (BET) the samples were degassed under flowing UHP
grade nitrogen for two hours at a temperature of 200 C in a Micromeritics FlowPrep 060. The nitrogen gas
adsorption measurements were taken at relative pressures of 0.05, 0.1, 0.15, 0.2, and 0.25 of Po using a
Micromeritics TriStarII instrument.
The thermodynamic data (standard free energy and enthalpy) were calculated by HSC Chemistry
(version 5.11).
Thermodynamic Considerations for Gallium Oxy-hydroxide Precipitation
The oxidation of gallium metal and its subsequent precipitation (Equation 1) in the form of
gallium oxy-hydroxide is highly exothermic (Ho<0) and spontaneous (Go<0) between 100 and 300 oC,
as predicted by HSC Chemistry software and as shown in Figure 5. The higher the temperature the more
spontaneous the reaction becomes.
Ga (l) + 2H2O (l) = GaOOH (s) + 1.5H2 (g)
(1)
Figure 5 Autoclave: change of standard free energy (left) and enthalpy (right) versus temperature
The dehydration of gallium oxy-hydroxide (Equation 2) into gallium oxide is endothermic
(Ho>0) and spontaneous (Go<0) above ~175 oC, as predicted by HSC Chemistry software and as shown
in Figure 6. The higher the temperature the more spontaneous the reaction becomes.
148
2GaOOH (s) + Heat Ga2O3 (s) + H2O (g)
(2)
Figure 6 Calcination: change of standard free energy (left) and enthalpy (right) versus temperature
Characterization of Gallium Oxide Product Produced via Hydrothermal Route
The gallium oxy-hydroxide intermediate product obtained in autoclave precipitation is subjected
to calcination at 700-750 C and aims at removing its free moisture along with structural H2O and OH
content according to equation 2.
Figure 7 Thermo-gravimetric analysis of 3 autoclave discharge samples (5944, 5945, 5946)

High temperature dehydration of a compound, such as used at a very large scale for the production
of alumina, is a very common process in our industry. Dehydration reactions can be divided into several
categories, the most frequent being: loss of constitutional water, loss of crystallization water and loss of
water extraneous to the lattice (adsorbed), such as zeolites (Berg, 1970). Dehydration reactions are
149
reflected by a clearly endothermic peak on a differential thermal analysis (DTA) curve. The thermogravimetric analysis (TGA) curve of typical autoclave products at Neo has been show in Figure 7.
The initial weight loss (20-120 oC) is clearly indicative of the evaporation of the sample moisture.
The variability in free moisture is linked to the product collection technique employed after each autoclave
run. The only other significant weight loss occurs around 425 oC, and corresponds to a weight loss of 7.1%
(5946), 5% (5944) and 0% (5945), respectively. The first two samples are fairly close the theoretical
weight loss of 8.8% for the complete dehydration of GaOOH, as compared to the theoretical weight loss of
20.6% for the complete dehydration of Ga(OH)3. However, sample 5945 shows no weight loss at all, which
suggests that the autoclave is capable of making gallium oxide.
Based on similarities with the hydrothermal dehydration of iron and aluminum, it is postulated
that Ga(OH)3 is not stable under autoclave conditions and that the products characterised via the TGA are a
mixture of GaOOH and Ga2O3. The formation of Ga2O3, presumably the -Ga2O3 species (see Figure 8), is
postulated to be a function of residence time, temperature and seeding inside the autoclave. The act of
recycling off-spec product, i.e. gallium oxy-hydroxide contaminated with small metallic gallium prills, will
raise the residence time of the autoclave solids at Neo into the 10-20 hours range at temperatures exceeding
200 C. Thermodynamics and these TGA results indicate that this allows gallium-oxide formation, which
is consistent with the literature (Roy, 1952).
Figure 8 - Transformation relationships amongst the forms of gallium and its hydrates (Roy, 1952)
The gallium oxide product was examined by scanning electron microscope (SEM) and can be seen
in Figure 9. Due to the uncontrolled nucleation mechanism the product is quite inhomogeneous
consisting of a mixture of rod shape and agglomerated particles. Upon characterizing it by particle size
analysis a monodental distribution was observed by which D10, D50 and D90 were 1.95, 14.79 and 36.33m
respectively. The PSD curve can be seen in Figure 10. The typical BET surface area was also determined
and was 17.5 m2/g.
150
Figure 9 Typical SEM images of the Ga2O3 product obtained upon calcination of gallium hydroxide
Figure 10 Typical particle size distribution of the Ga2O3 product

Optimization of the Calcination Furnace
The calcination of the gallium oxy-hydroxide/gallium oxide mixture was historically carried out at
700-750 C for 9 hours. A thorough thermo-gravimetric (TGA) study aimed at optimizing the calcination
furnace performance and achieving considerable cost and energy savings was undertaken. Optimum
residence time is a parameter specific to the geometry of the commercial calcination furnace. The
experimental conditions and the obtained measurement data are summarized in Table 1. The TGA curves
of samples 5932, 5933 and 5934 (3 hours calcination) can be seen in Figure 11. These are the only samples
which did not meet the product, market qualification of less than 1% water content.
According to this TGA study, in which the crucibles were emulated at three different autoclave
product depth levels, 9 hours of calcination of gallium hydroxide can be reduced to 5 hours at 750 C
resulting in approximately 40% electricity cost and 40% operational time reduction to produce a kilogram
of Ga2O3 product having less than 1% water content. The optimised residence time was successfully
validated using the commercial calcination furnace.
151
Table 1 Experimental conditions of calcination and obtained weight loss of Ga2O3 powders
Sample
ID
5932
5933
5934
5935
5936
5937
5938
5939
5940
5941
5942
5943
Duration of
calcination (h)
3
3
3
5
5
5
7
7
7
9
9
9
Location of sample in
crucible
Top
Middle
Bottom
Top
Middle
Bottom
Top
Middle
Bottom
Top
Middle
Bottom
Weight loss
wt%. H2O
0.03
2.19
4.04
0.22
0.42
0.44
0.25
0.40
0.82
0.21
0.41
0.58
Cost and time

saving (%)
66.6
0
0
44.4
44.4
44.4
22.2
22.2
22.2
0
0
0
Figure 11 TGA (thermo-gravimetric analysis) curves for various Ga2O3 samples

(Sample # 5932, 5933 and 5934)
Product Quality
Figure 12 SEM images of various shapes of Ga2O3 produced in atmospheric precipitation routes
at Neo Performance Materials
152
The authors recognise that optimisation of the autoclave conditions is a key process variable that
can contribute towards the quality of the gallium oxide. The hydrothermal route offers kinetic advantages
and allows the use of an environmentally friendly reagent, i.e. water. At the same time autoclave
technology is more capital intensive and complex (in terms of both engineering and laboratory simulation)
than atmospheric hydrometallurgy, since it generates hydrogen. It should therefore come as no surprise that
Neo Performance Materials decided to optimise gallium oxide product quality using atmospheric
precipitation technology first. Using our in-house hydrometallurgical expertise we are able to control
particle morphology and size as exemplified in the pictures shown in Figure 12.
Some of these products are available commercially, whereas others await a suitable market
demand. Although these products were created via the atmospheric route, we are optimistic the
hydrothermal route will offer similar or superior quality gallium oxide powders. We envision the
hydrothermal route to have environmental and production rate advantages that could justify its capital
investment.
CONCLUSIONS
The hydrothermal production of gallium oxide generates at 200-220 C an autoclave product
consisting of a mixture of most likely gallium oxy-hydroxide and -Ga2O3. In order to create the high
chemical purity gallium oxide that the market demands, it is essential to employ 5N gallium and de-ionised
water. A calcination stage at 700-750 C is required to produce the desired -Ga2O3. It has been
demonstrated that thermo-gravimetric analysis is a useful tool for optimising the calcination and
dehydration conditions of the autoclave residue. Consequently, the Neo Gallium Compounds operation was
able to increase its calcination capacity by 40%, while reducing electricity consumption by 40% at constant
gallium oxide output.
ACKNOWLEDGEMENT
The authors acknowledge the thorough TGA study conducted at McGill University, Center for
Self-Assembled Chemical Structures.
REFERENCES
Berg, L.G., 1970. Differential Thermal Analysis, R.C. Mackenzie Ed., Academic Press, Volume 1, pp.
346-349.
Ferron, C.J., 2011. Recycling Ga, In and Re at the Rare Metals Division of Neo Material Technologies,
Recycling Metals from Industrial Waste, Short Course and Workshop, June 21-23, 2011, Golden,
Colorado.
Pfundt, H., Fuchs, M., and Voib, P., 1978. Method for the production of gallium oxide. US Patent
4,081,523.
Roskill, 2011. Gallium: Global Industry Markets and Outlook, 8th Edition, pp. 4-11.
Roy, R., Hill, V.G., and Osborn, E.F., 1952. Polymorphism of Ga2O3 and the System Ga2O3-H2O, Journal
of the American Chemical Society, 73 (4), pp. 719-722.
153
SYNTHESIS OF Li2TiO3 POWDERS BY A HYDROTHERMAL PROCESS

*Y.J. Li1, L. Li1, C. Xu 1, V.G. Papangelakis 2, L. Kong 1
1
School of Metallurgical Science and Engineering, Central South University

932 South Lushan Road
Changsha, Hunan, 410083, P. R. China
(*Corresponding author: yunjiaoli6601@hotmail.com)
2
Department of Chemical Engineering and Applied Chemistry

200 College Street
Toronto, Ontario, Canada M5S 3E5
ABSTRACT
The Eh-pH diagram of lithium-titanium-water system at 25C, 100 C and 200 C was constructed.
It shows that there exist thermodynamic stability areas of Li2TiO3. This indicates a thermodynamic possibility
for the formation of Li2TiO3 in aqueous solution. A hydrothermal process has been applied for the preparation
of Li2TiO3 using TiCl4 and LiOHH2O as raw materials. The prepared samples were examined with X-ray
diffraction, scanning electron microscopy and thermo-gravimetric analysis and differential scanning
calorimetry. The results show that temperature and washing condition have significant effects on the phase
composition of the product. Phase-pure Li2TiO3 powders were obtained at 200C with Li:Ti molar ratio of
2.0.

Niagara, ON, Canada
Edited by
154
INTRODUCTION
Lithium-containing ceramics enriched in 6Li, such as Li2O, LiAlO2, Li4SiO4, Li2ZrO3 and Li2TiO3,
are considered as tritium breeding materials (Saito et al., 1998; Roux et al., 1998; Johnson et al., 1998;
Hoshino et al., 2002). In view of its admirable properties: low-activation, good thermal stability and
thermal conductivity, excellent tritium release performance and reasonable lithium atom density (Kopasz et
al., 1994; Roux et al., 1996; Saito et al., 1998; Wu et al., 2008), Li2TiO3 is recognized as one of the most
promising candidates of tritium breeding materials. Meanwhile, Li2TiO3, as the precursor of H2TiO3-type
lithium absorbent, receives more attention as the development of extracting lithium from salt lakes (Zhong,
2004; Zhang, 2010).
Several synthetic techniques have been applied to prepare Li2TiO3 powders, such as solid-state
methods (Lulewicz and Roux, 2002; Ramaraghavulu et al., 2011; Mandal et al., 2012), sol-gel processes
(Deptula et al., 2002; Lee, 2008) and solution combustion routes (Cruz et al., 2006; Jung et al., 2006; Sinha
et al., 2010). A solid-state method may produce a series of problems, including impurity contamination and
difficulty in morphology control of the obtained powders, although the process involved is simple. The solgel process is prolonged and usually demands for multi-step reactions, while solution combustion route
requires plenty of energy and easily causes product contamination by the fuel used. Owing to its
environmentally benign and highly suitable characteristics in fabricating materials, hydrothermal
technology has been widely used and became a powerful tool in the field of material synthesis (Yoshimura
and Byrappa, 2008). For example, ZnO in the form of bulk single crystals, fine particles and thin films,
which is an attractive photoelectric material, was successfully synthesized by hydrothermal process
(Sekiguchi et al., 2000; Ohshima et al., 2004). A hydrothermal technique was also used to the preparation
of carbon nanotube, which possesses outstanding mechanical, structural and electric properties (Bernholc
et al., 1997), and is superior to the commonly used method (Gogotsi and Libera, 2000). There, it provides
an option for preparing Li2TiO3. Laumann et al. (Laumann et al., 2010) synthesized cubic -Li2TiO3 by
hydrothermal reaction at 180 C for 18 h, using TiO2 powder, comprising of anatase and rutile, and lithium
hydroxide in de-ionized water. However, the prepared -Li2TiO3 is extremely unstable with a maximum
lithium loss of 75% when treated in bathing experiment.
From our previous study (Chen et al., 2008; Li et al., 2009; Li et al., 2010; Qiu et al., 2010), it
was found that a trace amount of Li2TiO3 appeared as an impurity phase in the synthesis of spinel Li4Ti5O12
via in-situ hydrolysis with TiCl4 and LiOH.H2O as raw materials. It indicated an opportunity for the direct
preparation of Li2TiO3 from aqueous solution. However, there is little literature on the redox potential-pH
diagram of lithium-titanium-water (Li-Ti-H2O) system due to lack of thermodynamic data at high
temperatures for species considered in the system. It makes the synthesis of pure-phase Li2TiO3 in aqueous
solution difficult for lack of thermodynamic data.
In this paper, the potential-pH diagram of Li-Ti-H2O system at 25 C, 100 C and 200 C was
constructed based on our previous study (Qiu et al., 2010). A novel hydrothermal route to prepare Li2TiO3
was proposed and investigated using TiCl4 and LiOH as starting materials.
EXPERIMENTAL PROCEDURES
Preparation of Li2TiO3 Powders
The raw materials were: analytically pure ammonia solution (NH3H2O, Xilong Chemical Co.,
Ltd.), chemically pure TiCl4 (purity98%, Sinopharm Chemical Reagent Co., Ltd.) and LiOHH2O
(purity98.9%, Sichuan Tianqi Lithium Industries, Inc.). The TiCl4 aqueous solution was prepared from
the chemically pure TiCl4 in an ice-water bath with magnetic stirring. A 140 mL sample of 0.5 molL-1
TiCl4 aqueous solution was added dropwise to 245 mL of about 2molL-1 ammonia aqueous solution at
40 C under vigorous stirring, forcing the Ti(VI) to hydrolyze completely to give the intermediate product
of hydrous TiO2. The slurry was vacuum filtered and thoroughly washed with distilled water to remove the
Cl- until it could no longer be detected in the wash liquor with silver nitrate. Then, the white precipitate,
155
which was designated as TiO2 precursor, was mixed with 1.0 molL-1 LiOH aqueous solution in the
stoichiometric ratio of Li:Ti (=2) and reacted at 95 C in a water batch with magnetic stirring or at 200 C
in a 250 mL autoclave for 5 h. The resulting pulp was filtered and washed if required with 150 mL
distilled water then by dried at 90 C overnight to obtain the solid product, namely Li2TiO3 precursor. The
as-prepared Li2TiO3 precursor was then heat-treated at 800 C for 6 h in an air atmosphere to produce the
final Li2TiO3 powder.
Characterization
The thermo-gravimetric analysis and differential scanning calorimetry (TGA-DSC, NETZSCH
STA 449 C), was performed in the temperature range 10 C~1100 C with a constant heating rate of
10 Cmin-1 under atmospheric conditions, to record mass and enthalpy changes of the hydrothermally
synthesized Li2TiO3 precursor in the heat-treatment process. The crystallinity and the phase composition of
the prepared samples were characterized by powder X-ray diffraction (XRD, Rigaku D/max-2500) with a
beam of Cu K-radiation (=1.5418). The tests were conducted with a scanning angle ranging from 10
to 70 and a scanning speed of 8min-1 at ambient temperature.
The phase content (Pc) of the final products, were quantified by using the peak intensities of each
phase identified (Abe et al., 2007; Qiu et al., 2010). Since the strongest X-Ray diffraction peaks of
Li4Ti5O12 and -Li2TiO3 overlapped, the second and third intense peaks were used. The empirical equations
used are (1) and (2) as follows:
Pc(Li2TiO3)=I1100%/(I1+I2)=[I1(-131)+I1(-133)] 100%/ [I1(-131)+I1(-133)+ I2(311)+I2(400)] (1)
Pc(Li4Ti5O12)=I2100%/(I1+I2)= [I2(311)+I2(400)] 100%/ [I1(-131)+I1(-133)+ I2(311)+I2(400) ] (2)
Where, I1 denotes the diffraction peak intensities of Li2TiO3;
I2 denotes the diffraction peak intensities of Li4Ti5O12.
The morphology and the size distribution were examined by scanning electron microscopy (SEM,
JEOL JSM-6360LV) operated at 20kV. The operation parameters were set as, voltage: 20kV, working
distance: 11mm, and high vacuum state.
RESULTS AND DISCUSSIONS
The Potential-pH Diagram of Li-Ti-H2O System
The thermodynamic data of species considered in the Li-Ti-H2O system, which are unavailable in
literature, were estimated based on the well-known empirical relations and models that were described in
detail in paper (Li et al., 2012). The potential-pH diagram for the Li-Ti-H2O system at 25 C, 100 C and
200 C was constructed under the conditions of 0.1 activities of various dissolved species and 1.0 activities
of H2O and all substances in solid state, as shown in Figure 1.
As seen from Figure 1, the thermodynamic stability areas of lithium titanium composite oxides,
such as Li2TiO3, Li4Ti5O12 and Li4TiO4, exist in the Li-Ti-H2O system in temperature ranging from 25 C
to 200 C, and they are adjacent in these diagrams. The span of the predominant area of Li4Ti5O12 is larger,
and it appears to be stable in weakly acidic and alkaline environments. Li4TiO4 is can be found under very
strong basicity at 25 C. The stability domain of Li2TiO3 is between the stability areas of Li4Ti5O12 and
Li4TiO4. This suggests that Li4Ti5O12 and Li4TiO4 could transform into Li2TiO3 in aqueous solution under
specific conditions. With increasing temperature, the equilibrium lines of Li4TiO4/Li2TiO3 and
Li2TiO3/Li4Ti5O12 shift towards lower pH, resulting in their dominant zones moving to the area of lower
pH. The stable area of Li4TiO4 obviously expands, while that of Li4Ti5O12 clearly shrinks due to the
Li4Ti5O12/TiO2 equilibrium line maintaining at almost unchanged. The predominant area of Li2TiO3 is at
higher pH between 13.69 and 14.84 at 25 C, and moves to more moderate pH ranging from 9.60 to 10.53
156
at 200 C. When the process for the preparation of Li2TiO3 is conducted at ambient temperature, the pH
value of about 14, i.e. free OH- activity of about 1.0, in equilibrium state, is needed, suggesting a sufficient
amount of excess LiOH required for providing a strongly alkaline environment. On the other hand, Li4TiO4
may occur in concentrated LiOH aqueous solution. As the reaction is performed at elevated temperature,
the alkaline condition required is not so rigorous, as shown in Figure 1. It is indicated that both pH and
temperature are critical factors for the synthesis of Li2TiO3 in aqueous solution. Obviously, hydrothermal
route is thermodynamically favorable and preferable.
Figure 1 - The superposition diagram of potential-pH diagrams at temperatures of:

25C;
100 C;
200 C
TGA-DSC Analysis of the Li2TiO3 Precursor
Figure 2 shows the TGA-DSC curves of the hydrothermally synthesized Li2TiO3 precursor. As
can be seen, an endothermic peak was presented at 165 C on the DSC plot, which can be attributed to the
removal of absorbed and boned water. Correspondingly, a weight loss of about 7.5% was observed on the
TGA curve in temperature ranging from 10C to 450C, in which the average weight loss ratio is distinct.
The DSC plot shows an exothermic peak between 450C and 750 C, and this was ascribed to the phase
transition of cubic -Li2TiO3 to monoclinic -Li2TiO3. In fact, owing to cubic -Li2TiO3 existing below
300 C, the above-mentioned phase variation occurred in a temperature range (Kleykamp, 2002). A weight
loss of approximately 0.76% was given on the TGA curve, resulting from the elimination of some volatiles
(Laumann et al., 2010). The weight of sample remained constant from 750 C to 1000 C, suggesting that
the product is stable in this temperature range.
157
Figure 2 - TGA-DSC curves of the hydrothermally synthesized Li2TiO3 precursor

Phase Analysis
The XRD patterns of the TiO2 precursor, gained from the TiCl4 aqueous solution neutralized with
ammonia aqueous solution, are shown in Figure 3. It reveals that the obtained TiO2 precursor is amorphous
(Figure 3a), which can be easily transferred to anatase TiO2 after six hours of heat-treatment at 600 C, as
shown in Figure 3b. Compared to well-crystallized rutile and anatase, the amorphous TiO2 is more active
and more favorable chemically. Figure 4 shows the XRD data of the Li2TiO3 precursor (A) obtained by the
hydrothermal technique at 200 C under unwashed condition, and the sample (B) derived from the Li2TiO3
precursor (A) heat-treated at 800 C for 6h. As shown in Figure 4 A, two characteristic peaks of cubic Li2TiO3 occurred, but the intensities of the peaks were very weak. This indicates that the Li2TiO3 precursor
is poor-crystallized cubic -Li2TiO3, which is in a metastable form at low temperatures, and irreversibly
transforms to monoclinic -Li2TiO3 when heat-treated at 800 C (Laumann et al., 2010), as shown in
Figure 4 B.
Figure 3 - XRD patterns of TiO2 obtained from TiCl4 hydrolysis. a: TiO2 precursor; b: TiO2 precursor heattreated at 600 C for 6 h
158
Figure 4 - XRD patterns of the Li2TiO3 precursor synthesized by the hydrothermal process at 200 C. A:
without heat treatment; B: with heat treatment at 800 C for 6 h
Effect of Temperature and Washing Condition
Two Li2TiO3 powder samples B and C were obtained at 200 C and 95 C precursor preparation
temperatures followed by the same heat treatment at 800 C for 6 h. Figure 5 shows the XRD patterns of
the Li2TiO3 powders obtained by the hydrothermal process at 200 C (B) and the atmospheric pressure
process at 95 C (C). When the foregoing precursor synthesis was carried out at 200 C with the
stoichiometric Li/Ti molar ratio of 2 and the precursor kept unwashed, phase-pure Li2TiO3 powders were
obtained with no impurity peaks detected (Figure 5 B). This suggests that the reaction proceeded to
completion. However, when the precursor preparation reaction was performed at 95 C, the product (C)
showed the mixture of monoclinic -Li2TiO3 and Li4Ti5O12, which is another lithium titanium composite
oxide with a lower stoichiometric Li/Ti molar ratio of 0.8. The phase composition of Li2TiO3 in the product
(C) was estimated from equation (1) to be 48.7%. The results demonstrated that the influence of
temperature was notable, and it was in line with the message provided in Figure 1. The reason for the
occurrence of impurity phase of Li4Ti5O12 could be due to some Li detaining in the solution to maintain a
higher pH value for reaching the chemical equilibrium at 95 C.
Figure 5 - XRD patterns of the products obtained at different precursor preparation temperatures. B: 200
C; C: 95 C
159
Figure 6 shows the XRD patterns of the samples obtained from the precursors synthesized at 200
C with Li/Ti molar ratio of 2 and left unwashed (B) or washed with 150mL distilled water (D). As shown
in Figure 6, the powder sample (B), obtained from the unwashed Li2TiO3 precursor, was pure Li2TiO3,
while the sample (D) was mainly Li2TiO3 with a small amount of Li4Ti5O12. The phase composition was
determined by equation (1) and (2) to be 70% of Li2TiO3 and 30% of Li4Ti5O12. A remarkable amount of
lithium in the precursor was lost during washing process due to the equilibrium state changed.
Figure 6 - XRD patterns of the samples obtained under different washing conditions.
B: unwashed; D: washed with 150mL distilled water
Morphology
Figure 7 shows the SEM images of the Li2TiO3 precursor, obtained from hydrothermal reaction at
200 C and left unwashed, before and after heat treatment at 800 C for 6 h. The Li2TiO3 precursor before
heat treatment shows an amorphous morphology and an irregular grain shape, as shown in Figure 7 a and
b, which implies the necessity of subsequent heat-treatment process. The particles in the sample of heattreated precursor are well defined and most have similar and homogeneous size. This suggests that the
green compacts received from the as-prepared powders are capable of sintering to desired density, while
lithium density is a key parameter as tritium breeder material (Deptula et al., 2002).
160
Figure 7 - SEM micrographs of the Li2TiO3 precursor obtained at 200 C and left unwashed.
a: without heat treatment, 3000; b: without heat treatment, 10000; c: with heat treatment at 800 C for
6h, 3000; d: with heat treatment at 800 C for 6h,10000
ACKNOWLEDGEMENTS
The authors wish to thank the financial support from the National Natural Science Foundation of
China (Program No. 51010105015 and 51074194).
CONCLUSIONS
The potential-pH diagram of Li-Ti-H2O system at temperatures of 25 C, 100 C and 200 C are
presented. The diagram shows that there is a thermodynamic stability area for Li2TiO3, and it moves
towards a lower pH with an increase in temperature. A novel hydrothermal technique was used for the
preparation of Li2TiO3 powders. The XRD patterns shows that the TiO2 precursor, obtained from TiCl4
aqueous solution neutralized with ammonia aqueous solution, is an amorphous structure. The Li2TiO3
precursor, synthesized from the TiO2 precursor by the hydrothermal process, is a metastable cubic Li2TiO3 with a low-crystallized structure and can transform to monoclinic -Li2TiO3 after heat-treated at
800 C for 6 h. Pure phase -Li2TiO3 powders were obtained by the hydrothermal process at 200 C for 5 h
under the conditions of Li/Ti stoichimetric ratio of 2. Experimental results show that temperature has a
great effect on the preparation progress. Li2TiO3 precursor preparation at lower temperature of 95 C
resulted in the mixture of Li2TiO3 and Li4Ti5O12 produced. A decrease in lithium content was also observed
on washing. All these experimental conclusions are in good agreement with the information provided in the
potential-pH diagrams. The reasons for the occurrence of the lower lithium content phase Li4Ti5O12 in the
samples, obtained at 95 C or washed with distilled water, were explained by the potential-pH diagrams.
161
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163
EFFECTS OF HYDROTHERMAL PROCESSING ON THE CRYSTALLINITY AND

MORPHOLOGY OF THE PRECURSOR OF In2O3
*Y. Li, Z. Liu, Q. Li, C. Wu, Z. Liu
School of Metallurgical Science and Engineering,
Central South University, Changsha, Hunan, P.R. China, 410083
(*Corresponding author: lyh_csu@163.com)
ABSTRACT
The precursor of In2O3 was prepared by hydrolysis precipitation/hydrothermal method using
In(NO3)3 solution as the feed material and ammonium hydroxide as the neutralizing agent. The crystallinity,
morphology and particle size of the products were characterized by SEM, XRD, BET and LPSA. The results
showed that the hydrolysis product consists of an aggregate of cubic In(OH)3 particles with a short rod
morphology. In the hydrothermal process, the structure, morphology and size of the particles changes through
the mechanisms of Ostwald ripening and phase transition, respectively. When the hydrothermal temperature
was less than 280 , the Ostwald ripening process took place, which changed the morphology of the particles
from short rods to cuboids through dissolution-recrystallization. When the hydrothermal temperature was
higher than 280 , the processes of Ostwald ripening and phase transition took place successively. Firstly,
the morphology of the particles changed from short rods to cuboids through Ostwald ripening, and then, the
phase transition from cubic In(OH)3 to orthorhombic InOOH occurred and the morphology of the particles
changed from cuboids to polyhedron.

Niagara, ON, Canada
Edited by
164
INTRODUCTION
Due to its excellent electrical conductivity and optical transparency, indium tin oxide (ITO) film has
been wildly used in flat-panel display, solar cell, antistatic coating and EMI shielding (Medvedovski et al.,
2008). Indium oxide powder is one of the fundamental materials for preparing ITO film. Along with the
development of ITO targets of both high density and large size, high quality indium oxide powders, such as
single phase, nano-size, spherical morphology and mono-disperse, have been in high demand (Nakashima and
Kumahara, 2002; Betz et al., 2006; Kim et al., 2007).
The main preparation methods for indium tin oxide or indium oxide powders include chemical
precipitation (Nam et al., 2001; Xu and Yu, 2007), melt atomizing-combustion (Chen et al., 2000) and spray
pyrolysis (Ogi et al., 2009). Among them, chemical precipitation has been preferred, since it is simple, easy to
control and suitable for industrial scale-up. In chemical precipitation method, indium oxide powders were
prepared through the following steps: firstly, indium hydrate precursor was precipitated from an indium salt
solution by neutralization using an alkali, such as ammonia; and then, indium oxide (In2O3) powders can be
obtained from the precursor through calcination (Li et al., 2006), or solvothermal method (Lee and Choi,
2005), or hydrothermal processing/roasting (Xu et al., 2005; Chen and Li, 2007), respectively. However, the
indium oxide powders obtained by direct roasting are polycrystalline, dispersable with a wide size distribution
(Liao, 2006). The disadvantages of the solvothermal method are high cost, complicated after-treatment
processes, as well as bad performances of the powders (Udawatte and Yanagisawa, 2000). Therefore, among
three methods of obtaining indium oxide from the hydrolysis precursor, the hydrothermal process/roasting
method is the most feasible to synthesize high quality In2O3 powder with uniform crystallinity and size (Kim
et al., 2002; Zhu et al., 2004; Xu et al., 2005; Xu et al., 2005; Chen and Li, 2007; Seetha et al., 2009).
However, current research on hydrothermal process-roasting method has been limited to the synthesis of a
certain ITO or In2O3 powders under specific conditions. A systematic study on the phase transition, as well as
the change of the morphology and size of the particles in the hydrothermal process is still missing. In this
paper, the effects of hydrothermal processing on the mineralogy, morphology and size of products were
investigated. The results showed that the evolution of crystal structure, morphology and size in the
hydrothermal process was affected through the mechanisms of Ostwald ripening and phase transition
successively. These results are novel and have guidance for improving the hydrothermal process for In2O3
preparation.
EXPERIMENTAL
Materials
Indium ingots (4N) were purchased from the Shaoguan Smelter, Guangdong Province, China.
Reagents of HNO3, NH4OH were of analytical grade, and deionized water was used in all experiments.
Experimental Procedures
0.5 mol/L In(NO3)3 was prepared by dissolving indium ingots into nitric acid. The synthesis experiment
was carried out in a 500 mL three neck flask equipped with mechanical stirrer, which immersed in a
thermostatic water bath. Firstly, 180 mL 0.5 mol/L In(NO3)3 was put into the flask and heated to a
temperature of 50 , then 9% of ammonia was added into the flask at a feeding rate of 1 ml/min until pH
value reached 7.5 and kept stirring for 1h. After the reaction, the slurry was put into a Teflon-lined stainless
steel autoclave of 200 mL capacity to fill with 80 vol.% and sealed, and the autoclave was maintained at a
certain temperature for a given time and then cooled to room temperature. The product was centrifuged,
washed with deionized water and ethanol twice, respectively, and dried at 80 for 24 h in air.
Characterization
The morphology and size were observed on scanning electron microscope (JSM-6360LV). The
crystalline phases were identified by an X-ray diffractometer (Rigaku-TTR ) using a Cu K radiation. The
165
size distributions were measured by a laser diffraction size analyzer (MALVERN, MICRO-PLUS) and
Brunauer-Emmett-Teller (BET) surface area measurements were carried out by N2 adsorption at 77K using a
Quadrasorb SI-3MP instrument.
The Effect of Temperature
The effect of temperature on hydrothermal processing was carried out at 275 , 280 , 290 and
300 for 10 h, and the results are shown in Figure 1, Figure 2 and Table 1. As seen in Figure 1(a), the
precursors are aggregates of short rods particles, and the scales of the major axis and the shorter axis are about
1 micron and 0.2-0.3 microns, individually. The main species of precursor was cubic phase In(OH)3 with a
specific surface area of 120.47 m2/g.
The morphology of the particles changed to cuboids, partly like cubes, and the specific surface area
rapidly decreased below 10 m2/g after treatment at 275 or 280 for 10 h, while the main phase was still
cubic phase In(OH)3 except the improvement of powder crystallinity. This phenomenon can be explained by
the Ostwald ripening mechanism. The precursor, which had large specific surface area and high surface
energy, can be converted to more stable powder with a low specific surface area through a dissolutionrecrystallization mechanism during the hydrothermal process. These changes are beneficial not only due to
the improvement in crystallinity of In2O3 powder, but also the operation of solid-liquid separation and
washing for hydrothermal products.
The XRD of hydrothermal products obtained at 290 and 300 revealed that the main specie was
transformed from cubic phase In(OH)3 into rhombic phase InOOH. At 290 , except for cuboids particles in
the sub-micron size range, there also appeared polyhedron particles with a size of several microns, which
were supposed to be composed of rhombic phase InOOH. It can be also seen from Figure 1(e), the
morphology of products obtained at 300 was all polyhedron, no cuboids particles were observed, which
demonstrated that the phase transformation of In(OH)3 to InOOH was complete.
166
Figure 1 - SEM images of samples prepared at different hydrothermal temperature

(a) Untreated (b) 275 (c) 280 (d) 290 (e) 300
167
Figure 2 - XRD patterns of samples prepared at different hydrothermal temperature

(a)Untreated (b)275 (c)280 (d)290 (e)300
Table 1 - Specific surface area and particle size of samples at different hydrothermal temperature
Temperature
Untreated
275
280
290
300
BET m2/g
D v 0.1
120.47
8.06
7.78
4.28
0.97
0.26
0.25
0.26
0.27
0.23
Particle size m
D v 0.5
0.53
0.38
0.40
0.39
0.43
D v 0.9
1.40
0.62
0.73
1.47
4.48
The Effect of Hydrothermal Time

The effect of time on hydrothermal products was carried out at 270 and 300 , respectively,
and the results are shown in Figure 3 and Figure 6.
168
Figure 3 - SEM images of samples prepared at 275 with different reaction time
(a) 0 h (b) 2 h (c) 4 h (d) 6 h (e) 8 h (f) 10 h
As seen from Figure 3, the morphology of hydrothermal products changed from short rods to
cuboids when treated at 275 for 2 h, and further increase of time had little effect. As seen from Figure 4,
the main species of hydrothermal products was still a cubic phase In(OH)3 even for 10 h.
169
Figure 4 - XRD patterns of samples at 275 with different reaction time

(a) 0 h (b) 2 h (c) 4 h (d) 6 h (e) 8 h (f) 10 h
It can be seen from Figure 5 that the morphology of hydrothermal products was transformed from
short rods to cuboids when treated at 300 for 2 h, and then there was no obvious change except that the
particle size increased a little. The XRD results indicated no phase change (Figure 6). Except for cuboids
particles, polyhedron particles in micron size appeared after 6 hours, and the characteristic peaks of InOOH
was detected in the XRD patterns. The cuboids particles disappeared, meanwhile, only the peak of rhombic
phase InOOH was detected after 12 h, which demonstrated that the phase transition had ended.
170
Figure 5 - SEM images of samples at 300 with different reaction time

(a) 0 h (b) 2 h (c) 4 h (d) 6 h (e) 8 h (f) 10 h (g) 12 h
171
Figure 6 - XRD patterns of samples at 300 with different reaction time

(a) 0 h (b) 2 h (c) 4 h (d) 6 h (e) 8 h (f) 10h (g) 12 h
Mechanism Analysis
The hydrothermal processing of an In(OH)3 precursor could be divided into two steps: firstly, the
morphology changed from short rods to cuboids, the amorphous or low crystalline species in the precursor
disappeared, and the crystallinity of hydrothermal products was improved, which could be explained by the
mechanism of Ostwald ripening. Based on the effect of Gibbs-Thomson (Perez, 2005), Ostwald ripening
generally occurred when the reaction concentration of solution component nearly equal the balance
concentration, in other words, which occurred at the situation of low oversaturation. As seen from Figure 7,
the dimension of growth units was small when oversaturation of solution was low; therefore, the growth units
had a similar crystal growth rate on the different faces of crystal, which resulted in the formation of cuboids
particles (Zhong et al., 2004; Zhong et al., 2005).
Secondly, the process of phase transition occurred when the autoclave temperature increased and
rhombic phase InOOH with polyhedron morphology was obtained, which is spontaneous according to
thermodynamics. The balance between dissolution and crystallization was achieved, and the supersaturation
was close to 1 after Ostwald ripening ended. Therefore, the hydrothermal product remained a cubic phase
In(OH)3 for any further increase in reaction time when the temperature was less than 280 , while it was
beneficial to promote the occurrence of the phase transition. The dimension of growth units was big when
supersaturation of solution was high at high temperature conditions; therefore, the growth units had a different
crystal growth rate on the different faces of crystal, which resulted in the formation of polyhedron particles.
Therefore, the phase and morphology were determined by the supersaturation of indium ions in the aqueous
solution. It was favorable to prepare cubic phase In(OH)3 at the condition of high supersaturation, conversely,
the formation of rhombic phase InOOH.
172
Figure 7 - The evolution diagram of product morphology and structure in hydrothermal processing
CONCLUSIONS
The effect of hydrothermal processing on the structure, morphology and particle size of
hydrothermal products was investigated by using hydroxide precipitation of indium ions as a precursor.
(1) The precursor, prepared by mixing 0.5 mol/L indium nitrate solution and 5 mol/L ammonia solution, was
a cubic phase of In(OH)3 with a morphology of short rods, and the scales of the major axis and the shorter
axis are about 1 microns and 0.2-0.3 microns.
(2) The structure, morphology and particle size were affected by the mechanisms of Ostwald ripening and
phase transition. The product was only affected by the mechanism of Ostwald ripening when temperature was
less than 280 , the particle morphology changed from short rods to cuboids by the way of dissolutionrecrystallization. Although there was no obvious change of particle size, the BET specific surface area
decreased rapidly. On the other hand, the products were influenced by the mechanisms of Ostwald ripening
and phase transition successively when the temperature was higher than 280 . The particle morphology
changed from short rods into cuboids followed by polyhedron, and particles size increased from submicron to
several micron, meanwhile, the mineralogy of the products was changed from cubic phase of In(OH)3 to
rhombic phase of InOOH. The higher the temperature was, the faster the phase transition occurred.
173
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175
PRESSURE LEACHING OF ALKALI-PRETREATED

LIMONITIC LATERITE ORE IN NITRIC ACID
C. Wang1, Y. Zhang1, *Z. Xu2
1
Beijing General Research Institute of Mining and Metallurgy

188 South 4th Ring Road West
Beijing, China 100070
2
Jiangxi University of Science and Technology

86 Hongqi Ave.
Ganzhou,China 341000
(*Corresponding author: xzf_1@163.com)
ABSTRACT
The pressure leaching of alkali-pretreated limonitic laterite ore in nitric acid was studied. The
optimal leaching conditions are as follows: leaching temperature of 458 K, initial nitric acid of 2.44 mol/L,
leaching time of 60 min, liquid to solid ratio of 2:1 mL/g, agitation speed of 500 RPM. Under the above
conditions, the extraction of nickel and cobalt can be achieved as approximate 95% and 80% respectively
while that of iron is as lower as 1%. The leaching residue containing 70% of iron in the form of hematite
and trace amount of chromium is suitable as the raw material for iron-making. The nitric acid in the
leaching solution can be regenerated and further recycled to leach.

Niagara, ON, Canada
Edited by
176
INTRODUCTION
It has been estimated that 60%-70% of the world land-based nickel resources presented in nickel
laterites containing 130 million tons of nickel although these only accounted for about 42% of the world
nickel production (Sudol, 2005; Luo et al., 2010). The nickel resource of laterite has not yet been fully
utilized. Due to the increasing global demand of nickel and the declining global reserves of nickel
sulphides, there is an increasing focus on the processing of the huge reserves of laterite ores today. Nickel
laterite ores can be simply divided into two types, namely, silicate-rich and limonite. The former can be
treated effectively by pyrometallurgical process in which the ferronickel product or nickel/iron sulphide
matte is produced (Monhemius, 1987). The limonitic laterite is rich in iron in the form of goethite which
is the main nickel-bearing mineral and usually contains cobalt associated with a manganese phase (Chang
et al., 2010; Georgiou and Papangelakis, 2004). The limonitic laterite is usually processed by
hydrometallurgical methods, such as atmosphere acid leaching (AL) (Xu et al., 2005; McDonald and
Whittington, 2008), high pressure acid leaching (HPAL) (Chou et al., 1977; Georgiou and Papangelakis,
1998; Rubisov et al., 2000; Whittington and Muir, 2000) and reductive roasting-ammonia leaching (Caron
Process) (Whittington and Muir, 2000; Valix and Cheung, 2002). The AL process can proceed at lower
temperature, thus the operation costs may be very low. But two biggest problems associate with the AL
process, namely, the slow rates of nickel extraction and potentially the significant amount of impurities
such as iron and aluminum in the leaching solutions, which hampers the wide application of the AL
process. The Caron Process uses the pyrometallurgical and hydrometallurgical methods together to obtain
the metallic values, but the overall metal recovery is relatively low, especially for cobalt. In recent years,
the environment-friendly process of HPAL has become increasingly important because it is most suitable
for low-grade ores and leads to high extraction of the valuables. However, the HPAL process needs a
much higher temperature and pressure (503-533 K, 4-5 MPa) to maintain a relatively fast leaching rates,
which results in higher operation costs. Moreover, another serious problem of scale formation in
autoclaves occurs in the HPAL process, for example, in Moa Bay, up to 20 cm scale may build up
resulting in 5 days descale downtime per month. In addition, the iron residues cannot be utilized for ironmaking due to the presence of high content chromium (Ema and Harada, 1987; Owada and Harada, 1987;
Takagi and Furui, 1987).
Our research group cooperated with Institute of Process Engineering, Chinese Academy of
Sciences to develop a new process for the treatment of chromium-containing limonitic laterite ore (Dong
et al., 2009; Qu et al., 2009a, 2009b; Guo et al., 2011). As shown in Figure 1, this new process comprises
two innovative techniques, namely, alkali-roasting pretreatment and nitric acid pressure leaching. Sodium
carbonate (Na2CO3) was used in the alkali-roasting to convert impurities in the ore, such as chromium,
aluminum and silicon to a water soluble form as described by:
Na2CO3 Na2O + CO2
(1)
Na2O + Cr2O3 2NaCrO2
(2)
Na2O + 2NaCrO2 +1.5O2 2Na2CrO4
(3)
Na2O + Al2O3 2NaAlO2
(4)
Na2O + SiO2 Na2SiO3
(5)
2NaAlO2 + nNa2SiO3 Na2OAl2O3nSiO2 + nNa2O
(6)
In subsequent water leaching of the roasting clinker, the impurities of chromium, aluminum and
silicon can be effectively removed because of good water-solubility. Chromium and aluminum can be
further recovered as by-products, such as chromic oxide and alumina.
177
Then the pretreated laterite ore was then leached in nitric acid under relatively mild conditions
(423-453 K, 0.5-1.5 MPa); high extraction of both nickel and cobalt (>95%) and low iron extraction (<5%)
can be achieved. Not only can the scale formation in autoclave be avoided completely but also nitric acid
can be regenerated and further recycled back to the leach. The reaction of nickel, cobalt and iron with
nitric acid in leach are as follows:
NiO + 2H+ Ni2+ + H2O
(7)
CoO + 2H+ Co2+ + H2O
(8)
Fe2O3 + 6H+ 2Fe3+ + 3H2O
(9)
The dissolved ferric ion is easy to hydrolyze and precipitate as hematite in autoclave. The
hydrolysis reaction of iron is as follows:
2Fe3+ + 3H2O Fe2O3 + 6H+
(10)
The objective of this work was to assess the application of nitric acid pressure leaching technique
on the alkali-pretreated limonitic laterite ore from Indonesia.
Limonitic laterite ore
Alkali-pretreatment
HNO3
Pretreated ore
HNO3 solution
Pressure leaching
CaCO3
Ore pulp neutralizing
Leaching residue
Ca(OH)2
Ni/Co hydroxide residue
Ni/Co precipitation
Ca(OH)2
Further processing
Mg removal
Magnesium residue
HNO3 regeneration
Gypsum (CaSO4)
Figure 1 Flow sheet of pressure leaching of alkali-pretreated limonitic laterite ore in nitric acid
EXPERIMENTAL
A chromium-containing limonitic laterite ore from Indonesia was first treated by alkali roasting
and then leached by water to remove chromium and aluminum in the ore. The chemical composition of
178
the pretreated ore is listed in Table 1. As shown in Table 1, the content of chromium and aluminum in the
ore is decreased to 0.36% and 1.27% respectively. X-Ray Diffraction (XRD) patterns before and after
pretreatment are presented in Figure 2 and Figure 3. It can be seen that the mineral structure has been
changed after pretreatment. Iron in the ore originally exists in the form of goethite, hematite, magnetite
and chromite. These minerals are also the main nickel-bearing minerals. After pretreatment, the spectrum
of goethite is weakened and that of hematite disappears completely and a new phase of bunsenite comes
into being. Moreover, most of the minerals in the pretreated ore are present in amorphous form, for
example, iron exists mainly in the form of amorphous oxide. As shown in Figure 4, nickel presents mainly
as fine granular oxides which adsorb on the surface of the amorphous iron oxide.
Table 1 - Chemical composition of alkali-pretreated laterite ore (mass fraction, %)
Component
%
Fe
49.62
250
Ni
0.59
G
H
M
F
S
Ca
0.34
Gothite
Hematite
Magnetite
Alumchromite
Serpentine
Mg
0.36
G
G
100
S
S
H
F
G
Mn
0.18
others
41.229
SiO2
4.97
FS MF
H
M
30
40
G
M
B
N
M
N
40
B
N
Gothite
Magnetite
Bunsenite
Alkali
G
B
G
G
M
MH
MF
S
20
Na
1.03
60
Intensiy
Intensity
Al
1.27
150
0
10
Cr
0.36
80
200
50
Co
0.051
50
60
2( )
Figure 2 XRD pattern of laterite ore
20
0
10
15
20
25
30
35
40
45
50
55
60
65
70
2( )
Figure 3 XRD pattern of pretreated laterite ore
Figure 4 SEM image of nickel oxides on the surface of amorphous iron oxides in pretreated ore
Nitric acid was used for the leaching of the pretreated ore. The nitric acid solution and the ore
were first mixed at a certain liquid to solid ratio and then introduced into the bomb. Afterwards the bomb
was enclosed and heated. The autoclave was operated batchwise for the desired time with temperature and
agitation being maintained throughout. Measurements of the leaching solutions and the leaching residues
were performed at the end of experiments after cooling the autoclave. Both the heating-up rate and the
cooling rate of the autoclave were respectively fixed for each test. The calculation of the metals extraction
was based on the chemical analysis of the leaching residues.
179
RESULTS AND DISSCUSION

Effect of Temperature on Leaching
The effect of temperature on the leaching of the pretreated ore was studied in the range of 433478 K under the following conditions: initial nitric acid of 1.62 mol/L, liquid to solid ratio of 3:1 mL/g,
leaching time of 60 min, agitation speed of 500 RPM. The extraction of nickel, cobalt and iron is
presented in Figure 5.
100
Extraction of metals (%)
80
60
40
Fe
Ni
Co
20
0
430
440
450
460
470
480
Temperature (K)
Figure 5 Effect of temperature on the extraction of nickel, cobalt and iron

As shown in Figure 5, the extraction of iron decreases from 8.6% to 2.4% with the increase of
temperature from 433 K to 458 K, while that of nickel increases sharply from 13.7% to 83.3% and cobalt
from 16.3% to 75.7%. With the further increase of leaching temperature, the extraction of nickel increases
slowly while that of cobalt keeps relatively constant. Thus, the leaching temperature of 458 K is
determined as appropriate. The content of cobalt in the leaching residue can be lowered to approximate
0.011%.
Effect of Initial Acidity on Leaching
The effect of initial nitric acid concentration on the leaching of the pretreated ore was studied
under the following conditions: leaching temperature of 458 K, leaching time of 60 min, agitation speed
of 500 RPM. The extraction of nickel, cobalt and iron at different liquid to solid ratio is presented in
Figure 6.
As shown in the Figure 6, the impurity of iron leached minimally and the leaching behavior of
nickel is similar to that of cobalt irrespective of the liquid to solid ratio, 1.5:1 or 2:1 or 3:1. Under a liquid
to solid ratio of 3:1 mL/g, the extraction of nickel again increases steeply from 15.18% to 96.2% and
cobalt from 31.7% to 76.3% with the increase of initial nitric acid from 1.08 mol/L to 1.92 mol/L. With
the further increase of initial acidity, the extraction of both nickel and cobalt remains relatively constant.
Thus, the initial nitric acid concentration of 1.92 mol/L was initially selected for the liquid to solid ratio of
3:1 mL/g for further study. Nickel and cobalt in the leaching residue contained 0.028% and 0.010%
respectively.
100
100
80
80
80
60
Fe
Ni
Co
40
20
60
40
Fe
Ni
Co
20
Leaching rate, E (%)
100
180
60
40
20
(c) L/S=3:1
(b) L/S=2:1
(a) L/S=1.5:1
0
1.2
1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8
Fe
Ni
Co
1.6
2.0
2.4
2.8
3.2
3.6
cH+ (mol/L)
cH+ (mol/L)
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8
cH+ (mol/L)
Figure 6 Effect of initial acidity on the extraction of nickel, cobalt and iron at different liquid to
solid ratios
Effect of Time on Leaching
The effect of time on the leaching of the pretreated ore was studied in the range of 20 - 120 min
under the following conditions: leaching temperature of 458 K, initial nitric acid of 1.92 mol/L, liquid to
solid ratio of 3:1 mL/g, agitation speed of 500 RPM. The extraction of nickel, cobalt and iron is presented
in Figure 7.
100
90
80
70
60
50
40
Fe
Ni
Co
15
10
5
0
20
30
40
50
60
70
80
90 100 110 120 130
Leaching time (min)
Figure 7 Effect of time on the extraction of nickel, cobalt and iron

As shown in Figure 7, iron is still barely leached under the above conditions. With the increase of
leaching time from 20 min to 60 min, the extraction of nickel is increases from 49.9% to 96.2% and cobalt
from 59.7% to 76.3%. With the further increase of leaching time, the extraction of both nickel and cobalt
maintains relatively stable. Thus, the leaching time of 60 min is considered optimum to leach and lower
the content of nickel and cobalt in the leach residue down to 0.029% and 0.008% respectively.
Effect of Liquid to Solid Ratio on Leaching
The effect of liquid to solid ratio on the leaching of the pretreated ore was studied in the range of
(1.5-5):1 mL/g under the following conditions: leaching temperature of 458 K, initial nitric acid of
1.92 mol/L, leaching time of 60 min, agitation speed of 500 RPM. The extraction of nickel, cobalt and
iron is presented in Figure 8.
181
100
80
60
40
Fe
Ni
Co
20
0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Liquid to solid ratio (mL/g)
Figure 8 Effect of liquid to solid ratio on the extraction of nickel, cobalt and iron
As shown in Figure 8, almost all the iron did not leach in the range of liquid to solid ratios
studied. The extraction of nickel is increased from 45.2% to 96.2% and cobalt from 51.7% to 76.3% with
increasing liquid to solid ratios from 1.5:1 mL/g to 3:1 mL/g. With the further increase of liquid to solid
ratio, the extraction of both nickel and cobalt doesnt change significantly. So preliminarily the liquid to
solid ratio of 3:1 mL/g may be selected for further optimization.
Based on the above, the molar ratio of H+ to metals such as nickel, cobalt and aluminum was
studied further to optimize the liquid to solid ratio and the initial acidity. The molar ratio of H+ to metals
will vary with the initial acidity when the liquid to solid ratio is set at a certain value. The H+ to metal
molar ratio is 3.5 for a liquid to solid ratio of 3:1 mL/g and an initial nitric acid concentration of
1.92 mol/L. The extraction of nickel, cobalt and iron for the molar ratios of H+ to metals of 3:1 and 3.5:1
are presented in Figure 9. As shown in Figure 9, the leaching of iron is always low. With a molar ratio of
H+ to metals of 3:1 and a lower liquid to solid ratio of 2:1 mL/g, the extraction of nickel and cobalt are
95.8% and 76.6% and the content of nickel and cobalt in the leaching residue is 0.032% and 0.014%
respectively. Although the processing capability of autoclave increases with the decrease of liquid to solid
ratio, the viscosity of the slurry increases so that the scale formation in autoclave may become a
possibility. It was concluded that the liquid to solid ratio should not be lower than 2:1 mL/g when the
molar ratio of H+ to metals is 3:1 and the liquid to solid ratio not lower than 3:1 when the molar ratio of
H+ to metals is 3.5:1 based on the operational experience.
100
100
80
80
Thus, the molar ratio of H+ to metals as 3:1 and the liquid to solid ratio of 2:1 mL/g are
determined as appropriate for the leaching of pretreated ore. This corresponds to an initial nitric acid
concentration of 2.44 mol/L.
60
Fe
Ni
Co
40
20
(a) the molar ratio of H+ to Ni, Co and Al of 3:1
60
40
20
Fe
Ni
Co
+
(b) the molar ratio of H to Ni, Co and Al of 3.5:1
1.5
2.0
2.5
3.0
3.5
4.0
Liquid to solid ratio (mL/g )
4.5
5.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Liquid to solid ratio (mL/g)
Figure 9 Effect of molar ratio of H+ to metals on the extraction of nickel, cobalt and iron
182
Effect of Agitation Speed on Leaching

The effect of agitation speed on the leaching of the pretreated ore was studied in the range of
400-800 RPM under the following conditions: leaching temperature of 458 K, initial nitric acid of
2.44 mol/L, liquid to solid ratio of 2:1 mL/g. The extraction of nickel, cobalt and iron is presented in
Figure 10.
100
90
80
70
60
Fe
Ni
Co
15
10
5
0
400
500
600
700
800
Agitation speed (RPM)
Figure 10 Effect of agitation speed on the extraction of nickel, cobalt and iron
As shown in Figure 10, the agitation speed barely affects the extraction of nickel and cobalt
which remains approximately at 96% and 80% respectively. Even when the agitation speed is raised to
800 RPM, the extraction of iron is still limited to 3.4%. The agitation speed of 500 RPM is selected to
ensure the solid and liquid phases are mixed effectively in the autoclave.
Stability of Leaching Technique
Based on the tests above, the optimized pressure leaching technique of alkali-pretreated limonitic
laterite ore in nitric acid is as follows: leaching temperature of 458 K, initial nitric acid of 2.44 mol/L,
leaching time of 60 min, liquid to solid ratio of 2:1 mL/g, agitation speed of 500 RPM. Four repeat tests
shown in Figure 11 indicate that the leaching of pretreated ore in nitric acid can be operated reproducibly
and the extraction of nickel and cobalt are approximately 95% and 80% respectively while that of iron is
limited to about 1%. The content of nickel and cobalt in the leaching residue are typically 0.028% and
0.007%. The ideal separation of the valuables of nickel and cobalt from the impurity of iron has been
achieved.
Fe
Ni
Co
100
90
80
70
0
1
Repeated times
Figure 11 Repeated tests results
183
Treatment of Leaching Solution and Residue

After the precipitation of aluminum from the leach solution through neutralization with calcium
carbonate, the nickel and cobalt values can be recovered by hydroxide precipitation where nickel and
cobalt are concentrated to 25.4% and 2.60% respectively. After precipitation of magnesium from the
solution, the solution contains calcium nitrate which was treated with sulfuric acid to regenerate nitric acid.
The regenerated nitric acid solution of approximate 2.06 mol/L can be recycled to leach.
XRD pattern of the leach residue is presented in Figure 12. As shown in Figure 12, hematite is
the main mineral in the leach residue, which is the hydrolysis product of dissolved iron. The
microstructure of the iron mineral in the leach residue is shown in Figure 13. EDX analysis shows that the
iron mineral contains 70.6% of iron and 26.7% of oxygen and only a small quantity of silicon (2.62%) and
trace amount of chromium. The leaching residue can be sold as hematite product because of its high iron
content.
H
300
H Hematite
T Talcum
Intensiy
250
Iron mineral
200
150
T
H
100
50
20
T
H
25
30
35
40
45
2
50
55
60
65
70
( )
Figure 12 XRD pattern of pressure leach residue

of alkali-pretreated laterite ore
Figure 13 Microstructure of iron mineral

in the leach residues
CONCLUSIONS
The optimal pressure leaching technique of alkali-pretreated limonitic laterite ore in nitric acid is:
leaching temperature of 458 K, initial nitric acid of 2.44 mol/L, leaching time of 60 min, liquid to solid
ratio of 2:1 mL/g, and agitation speed of 500 RPM. This technique can be operated reproducibly and the
extraction of nickel and cobalt is approximately 95% and 80% respectively, while that of iron is limited to
approximately 1%. The content of nickel and cobalt in the leaching residue is as low, 0.028% and 0.007%
respectively. Under these conditions a good separation of the nickel and cobalt values from iron can be
achieved. The iron residue containing 70.6% iron and trace amount of chromium may be sold as hematite
product for iron-making.
The nickel and cobalt values can then be recovered from the leach solution in the form of
hydroxide with nickel and cobalt concentrated to 25.40% and 2.60% respectively. Nitric acid can be
regenerated in the solution through the reaction with sulfuric acid after the removal of such metals as
aluminum, nickel, cobalt and magnesium and the regenerated nitric acid solution can be recycled to leach.
ACKNOWLEDGEMENTS
This work was funded by Major State Basic Research Development Program of China (973
Program) (No. 2007CB613505), National High Technology Research and Development Program of
China (863 Program) (No. 2006AA06Z131) and National Natural Science Foundation of China (No.
50674014). Dr. Zhifeng Xu also wants to express thanks to the support from Jiangxi Province Young
Scientists Cultivating Project of China.
184
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187
LOW-TEMPERATURE PRESSURE LEACHING KINETICS

OF ZINC SULPHIDE CONCENTRATE
Z. Xu1, F. Guo1, *C. Wang2
1
Jiangxi University of Science and Technology

86 Hongqi Ave.
Ganzhou,China 341000
Beijing General Research Institute of Mining and Metallurgy

188 South 4th Ring Road West
Beijing, China 100070
(*Corresponding author: wchy3207@sina.com)
ABSTRACT
The leaching kinetics of zinc sulphide concentrate was studied under total pressures ranging from
0.3 MPa to 0.5 MPa and leaching temperatures ranging from 358 K to 378 K. The apparent activation
energy of leaching reaction under different total pressures was calculated. The results show that for the
extraction of zinc at low-temperature pressure leaching is controlled by an interfacial chemical reaction.
This was supported mineralogical analysis of the leaching residue. The kinetic equation for lowtemperature pressure leaching of zinc sulphide concentrate was further established by quadratic regression
on the basis of shrinking core model.

Niagara, ON, Canada
Edited by
188
INTRODUCTION
The Roast-Leach-Electrowinning Process (RLE) is the primary route for zinc production and
responsible for more than 85% of the total zinc production (Souza et al., 2007). During the roasting of zinc
concentrates, fugitive SO2 causes pollution. The prevention of SO2 emissions from the RLE process can be
one of the challenges to this technology (Deller, 2005). In the 1980s, the Zinc Pressure Leach (ZPL)
process changed the concept of zinc hydrometallurgy, in which zinc sulphide concentrate is directly
leached at approximately 423 K and approximately 0.7 MPa oxygen overpressure and the sulphidic sulphur
is oxidized into elemental sulphur so that the pollution by SO2 is completely avoided. Since 1981, five zinc
plants have adopted the ZPL process either for expansion by integration with existing roasting facilities, or
for the production of zinc without any roasting at all (Collins et al. 1994; Barth et al. 1998). The innovation
of the ZPL process has made the zinc industries more competitive although it needs an autoclave. The
direct leaching technology of zinc is still in development.
In the 1990s, Outotecs Atmospheric Direct Leaching (ADL) technology was proposed
(Fugleberg and Jrvinen, 2002), by which pressure leaching is achieved in special atmospheric leaching
tank. Outotecs ADL process is similar to low-temperature pressure leaching know-how. This technology
has been practiced at an industrial scale since 1998 in Kokkola, Finland and since 2004 in Odda, Norway
(Svens et al., 2003;Takala, 1999). Zhuzhou Smelter Group, the leading Chinese zinc producer, started a
new full-scale application of Outotecs ADL process in 2008 (Haakana et al., 2008). It has been shown that
Outotecs ADL process is the most economical way to produce electrolytic zinc. Compared with the ZPL
process, Outotecs ADL process employs less harsh conditions. The temperature is about 373 K, while the
total overpressure (vapour and oxygen) is equal to or less than 20kPa. Under such conditions, the leaching
reaction of zinc sulphide proceeds much slower than that in the ZPL process and the time required to
extract more than 95% zinc is in the order of 10 (Van Put et al., 1996, 1999) to 20 h, or even higher
(Takala, 1999). Due to this problem, the necessity of kinetic study on sphalerite leaching under low
temperature and low pressure is evident.
The kinetics of pressure leaching of zinc sulphide concentrate has been described by several
authors (Scott and Dyson, 1968; Jan et al., 1976; Niederkorn, 1985; Tozawa and Piao, 1987; Corriou et al.,
1988; Dreisinger and Peters, 1989; Harvey et al., 1993; Owusu et al., 1995; Baldwin et al., 1995; Xie et al.,
2007; Xu et al., 2008). It is agreed that elemental sulphur is the main oxidation product and the iron content
plays a key role during leaching. Many authors have discussed the effect of acid concentration on zinc
dissolution and also observed that the leaching temperature increases the leaching rate, however, the
reported kinetic data are limited in high temperature especially in the range of 403-483 K. Furthermore, the
reaction order with respect to temperature and pressure under low temperature and low total pressure has
not yet determined.
The objective of this work was to assess the effects of temperature (358-378K) and total pressure
(0.3-0.5MPa) on the dissolution kinetics of a zinc sulphide concentrate. The shrinking core model (SCM)
as well as mineralogical analysis methods was used to describe the dissolution kinetics.
EXPERIMENTAL
The chemical composition of a zinc sulphide concentrate is shown in Table 1. The particle size of
the concentrate is 86.9% -74 m. The X-Ray diffraction (XRD) pattern shown in Figure 1 indicates that
sphalerite is the major mineral in the concentrate. Moreover, the concentrate contains some other sulphides
such as pyrite, pyrrhotite and galena and some non-metallic minerals such as quartz, talcum and gypsum.
Quartz and talcum are the original gangue minerals in the concentrate while gypsum is a foreign substance
introduced in the flotation operation. The microstructure of the concentrate is shown in Figure 2.
The leaching tests were carried out in a 1 L titanium lined autoclave. Agitation at 550 RPM was
provided by a magnetically driven twin impeller, which ensured gas-liquid-solid phases are mixed fully.
The autoclave was operated batchwise for the desired period with temperature and pressure being
189
maintained throughout the leaching. The leach solutions and the residues were analysed after the tests were
finished. To ensure the kinetic results being comparable, both the heating rate and the cooling rate of the
autoclave were fixed for each test. The initial sulphuric acid of 1.25 mol/L and a much higher liquid to
solid ratio of 30/1 (mL/g) were selected for the leaching tests to keep the reactant concentration relatively
constant.
Table 1 - Chemical composition of the zinc sulphide concentrate (mass fraction / %)
Element
%
Zn
46.8
Fe
7.62
Pb
2.41
S
28.1
Si
1.96
others
13.1
1000
Sph
Py
Pyrr
Sph
Py
Sph
Py
Sph-Sphalerite
Py-Pyrite
G-Galena
Pyrr-Pyrrhotite
Q-Quartz
C-Calamine
T-talc
Gy-Gypsum
800
CPS
600
Sph
Py
400
Sph
Q
TGy
200
Sph
C
T
Pyrr
Sph
0
0
10
20
30
40
50
60
70
80
Figure 1 XRD pattern of zinc sulphide

concentrate
Figure 2 Microstructure of zinc sulphide

concentrate
RESULTS AND DISSCUSION

Effect of Temperature and Total Pressure on Extraction of Zinc and Iron
The effect of total pressure of 0.3 MPa, 0.4 MPa, 0.5 MPa on the leaching of zinc and iron was
studied at temperatures ranging from 358 K to 378 K and leaching times between 60-420 min. The results
are shown in Figure 3 and Figure 4. The extraction of zinc and iron was fitted by linear regression with
respect to the leaching time. The linear regression equations are presented in Table 2 and Table 3.
Table 2 - Linear relation between zinc extraction and leaching time (60 min t 420 min)
P / MPa
0.3
0.4
0.5
T/K
358
368
378
358
368
378
358
368
378
Linear regression equation

x = 2.09 + 0.06t
x = 1.76 + 0.10t
x = 0.011 + 0.14t
x = 0.51 + 0.08t
x = -0.49 + 0.13t
x = 1.39 + 0.17t
x = -1.57 + 0.11t
x = -1.84 + 0.19t
x = -1.65 + 0.24t
Related coefficient, R
0.98
0.99
0.99
0.99
0.997
0.9998
0.99
0.99
0.99
Leaching rate, k / min-1

0.06
0.10
0.14
0.08
0.13
0.17
0.11
0.19
0.24
190
50
60
358K
368K
378K
Fitted regression line
50
R=0.98
R=0.97
R=0.97
30
30
xFe / %
xZn / %
40
R=0.99
20
R=0.99
20
R=0.99
10
10
0
358K
368K
378K
40
(a) Ptotal=0.3 MPa
(a) Ptotal=0.3 Mpa
60
120
180
240
300
360
420
480
60
120
180
240
300
360
420
t / min
t / min
80
60
50
R=0.9998
30
60
120
180
240
300
360
30
R=0.99
10
(b) Ptotal=0.4 Mpa
R=0.99
20
R=0.99
10
420
480
(b) Ptotal=0.4 MPa
60
120
180
t / min
120
358 K
368 K
378 K
70
R=0.99
60
60
40
R=0.99
(c) Ptotal=0.5 Mpa
60
120
180
240
420
480
300
360
420
R=0.99
40
30
R=0.99
20
20
360
R=0.99
50
R=0.99
xFe / %
xZn / %
300
80
80
240
t / min
358 K
368 K
378 K
100
R=0.9995
40
R=0.997
40
20
358 K
368 K
378 K
50
xFe / %
xZn / %
60
358 K
368 K
378 K
70
480
t / min
Figure 3 The relationship between zinc extraction

and leaching time
10
0
(c) Ptotal=0.5 MPa
60
120
180
240
300
360
420
480
t / min
Figure 4 The relationship between iron extraction

and leaching time
191
Table 3 - Linear relation between iron extraction and leaching time (60min t 420min)
P / MPa
0.3
0.4
0.5
T/K
358
368
378
358
368
378
358
368
378

x = 1.34 + 0.07t
x = -1.62 + 0.09t
x = 5.88 + 0.09t
x = 2.40 + 0.07t
x = 0.53 + 0.12t
x = 6.02 + 0.13t
x = 1.35 + 0.09t
x = 0.86 + 0.15t
x = 1.98 + 0.18t
0.99
0.97
0.97
0.99
0.99
0.9995
0.99
0.99
0.99
Leaching rate, k / min-1

0.07
0.09
0.09
0.07
0.12
0.13
0.09
0.15
0.18
As shown in Figure 3 and Figure 4, the extraction of zinc and iron increase with increasing time
and do not come to equilibrium even at 420 min irrespective of the total pressure. It also can be seen that
the extraction of zinc and iron has linear dependence on the time. As presented in Table 2 and Table 3, the
leaching rates for both zinc and iron increase with increasing temperature under constant total pressure and
they also increase with the increase of total pressure at a set temperature. Moreover, the leaching rate of
zinc is relatively faster than that of iron.
Kinetic Equation for Leaching of Zinc
The heterogeneous reaction for the oxidative leaching of zinc sulphide in sulphuric acid is
represented by Equation 1. When the leaching temperature is lower than the melting point of elemental
sulphur, the oxidation product of elemental sulphur presents in solid state.
ZnS(s) + H2SO4(aq) + 1/2O2 ZnSO4(aq) + S0(s) + H2O(aq)
(1)
Assuming that the reactant concentration (H2SO4) and the particle size of zinc concentrate are
constant during the reaction, the unreacted shrinking core model (SCM) can be applied. When the
interfacial chemical reaction is the rate-controlling step, the following SCM expression can be used to
describe the dissolution kinetics of zinc concentrate:
kC
1 (1 x)1/3 =r A0 t
B r0
(2)
Similarly, when the diffusion of ions through the elemental sulphur layer is the rate-controlling
step, the following SCM expression can be used to describe the dissolution kinetics:
2D C
2
1 x (1 x) 2/3 = s 2A0 t
3
B r0
(3)
where: x = the fractional conversion of zinc, CA0 = the initial sulphuric acidity, B = molar density
of ZnS, r0 = particle radius, kr = chemical reaction rate constant, Ds = effective diffusion coefficient.
The experimental data for zinc leaching were fitted to Equation 2 and Equation 3 at different total
pressures. The results show that only Equation 2 fits well and a plot of 1-(1-x)1/3 versus time under different
total pressures and temperatures is always a straight line as shown in Figure 5, which indicates that the
192
leaching of zinc might be controlled by chemical reaction. The kinetic equations for zinc leaching are
further presented in Table 4.
0.28
0.30
R=0.99
0.25
0.16
1-(1-xZn)1/3
1-(1-xZn)1/3
0.20
0.35
R=0.996
0.12
0.08
R=0.99
60
358K
368K
378K
Fittedregressionline
0.20
R=0.99
0.15
0.3
R=0.98
0.2
R=0.99
R=0.99
0.1
(b) Ptotal=0.4MPa
0.00
0
120 180 240 300 360 420 480
R=0.97
0.4
0.05
(a) Ptotal= 0.3 MPa
0.5
R=0.995
0.10
0.04
0.00
0
0.6
358K
368K
378K
Fittedregressionline
1-(1-xZn)1/3
358 K
368 K
378 K
0.24
60
120 180 240 300 360 420 480
t / min
0.0
0
(c) Ptotal=0.5MPa
60 120 180 240 300 360 420 480
t / min
t / min
Figure 5 Plot of leaching kinetics under different total pressures

Table 4 - Kinetic equations for zinc leaching under different total pressures and leaching temperatures
P / MPa
0.3
0.4
0.5
T/K
358
368
378
358
368
378
358
368
378

1(1x)1/3 = 2.54 10-4t
1(1x)1/3 = 3.88 10-4t
1(1x)1/3 = 5.70 10-4t
1(1x)1/3 = 3.04 10-4t
1(1x)1/3 = 5.23 10-4t
1(1x)1/3 = 7.66 10-4t
1(1x)1/3 = 4.02 10-4t
1(1x)1/3 = 8.38 10-4t
1(1x)1/3 = 1.28 10-3t
0.99
0.996
0.99
0.99
0.99
0.995
0.99
0.98
0.97
Figure 6 presents the Arrhenius plot constructed with the apparent rate constant and the leaching
temperature under different total pressures. As shown in Figure 6, the natural logarithm of the rate constant
(ln k) has a good linear dependence on the reciprocal of the reaction temperature (1/T). The slope of the
Arrhenius line can be calculated as -5742.28 K, -5112.25 K and -5423.14 K under the total pressure of
0.3 MPa, 0.4 MPa and 0.5 MPa respectively. Accordingly, the apparent activation energy of the leaching
reaction can be further calculated as 47.7 kJ/mol, 42.5 kJ/mol and 45.1 kJ/mol under the total pressure of
0.3 MPa, 0.4 MPa and 0.5 MPa respectively. This suggests the leaching of zinc is controlled by an
interfacial chemical reaction as the apparent activation energy is in the range of 40-300 kJ/mol.
-5.4
-5.6
-5.8
lnk
-6.0
-6.2
R=0.97
-6.4
-6.6
-6.8
-7.0
0.00260
0.3MPa
R=0.99
0.4MPa
0.5MPa
0.00265
0.00270
R=0.99
0.00275
0.00280
-1
(1/T) / K
Figure 6 Plot of lnk - (1/T) for zinc leaching under different total pressures
193
Based on the regression equations presented in Table 4, the general kinetic equation under
different total pressures and temperatures can be derived as follows:
1 (1 x)1 / 3 = Kt
(4)
The apparent rate constant K is further assumed as;
K = k 0T a P b e E / RT
(5)
where: k0 = the leaching rate constant, a = the order of reaction with respect to temperature, b = the
order of reaction with respect to total pressure, T = the leaching temperature (K), P = the total pressure
(MPa), E = the apparent activation energy (kJ/mol).
By transforming Equation 5 in logarithmic form, we obtain:
ln k0 + a ln T + b ln P = ln K + E
RT
(6)
, a0 = ln k 0 , x1 = ln T and x 2 = ln P , the following equation is obtained

Assuming, y = ln K + E
RT
after substitution y, a0, x1 and x2 into Equation 6:
y = a0 + ax1 + bx 2
(7)
Considering the apparent activation energy under different total pressures changes only a little, the
average apparent activation energy is taken as 45.1 kJ/mol to simplify the regression calculation. The
kinetic data under different total pressures and temperatures are further analyzed by quadratic regression on
the basis of self-developed regression software and the results are shown in Table 5.
Table 5 - Quadratic regression results
k0
4.6510-49
Coefficient a
17.8
Coefficient b
1.35
Correlation coefficient, R
0.95
F value
64.79
F test is further carried out according to the following equation:

F =
R2 /m
F ( m , n m 1)
(1 R ) /( n m 1)
2
(8)
Taking the significance level as 0.005, the test result of F >> F0.005 (1,7) = 6.11 shows that the
constants are all significant. Thus, the general kinetic equation for zinc leaching between total pressures of
0.3-0.5 MPa and temperatures between 358-378 K is obtained:
1 1 x 1 / 3 = 4.65 1049 T 17.78 P1.35e E / RT t
(9)
where: E = the average apparent activation energy, 45100 J/mol.

As shown in Equation 9, the order of reaction with respect to temperature is much greater than
that to total pressure. Consequently the influence of temperature should be much greater than that of total
pressure on the leaching of zinc.
194
Phase Change of Sphalerite in Leaching

The phase change of sphalerite in low-temperature pressure leaching was studied by mineralogical
analysis of the leaching residue. The microstructure of the leaching residue is shown in Figure 7. It can be
seen that few sulphide minerals exist in the leaching residue, except for pyrite and some residual sphalerite.
The boundary of pyrite is relatively smooth while that of sphalerite is corroded. The oxidation product of
elemental sulphur presents in the form of compact spherules and is separated from the residual sphalerite.
The backscattered electron image as well as the elemental surface distribution as shown in Figure 8 also
shows the relation between elemental sulphur and the residual sphalerite. Thus, it can be concluded that the
diffusion of dissolved zinc ion from mineral surface to bulk solution as well as that of sulphuric acid from
bulk solution to mineral surface is not the controlling step in the leaching of sphalerite under low
temperature and low total pressure because there is no solid elemental sulphur layer on the mineral surface.
Figure 7 Microstructure of leaching residue

Because the leaching temperature is lower than the melting point of elemental sulphur, the solid
elemental sulphur cannot move freely away from where it is produced. Thus, it can be further deduced that
elemental sulphur is mainly produced not on the mineral surface but in bulk solution on the basis of
Figures 7 and 8. This means that the acidic dissolution of sphalerite is possibly the first reaction in leaching
where hydrogen sulphide is produced at mineral surface, then transfers into bulk solution and is oxidized
into elemental sulphur. The production process of elemental sulphur can be presented as the following:
ZnS + H2SO4 ZnSO4 + H2S
(10)
2H2S + O2 2H2O + 2S0
(11)
195
Z nS
FeS2
Figure 8 Backscattered electron image and elemental surface distribution of pyrite and sphalerite in the
leaching residue
CONCLUSIONS
The extraction of zinc and iron has a linear dependence on the time under total pressures ranging
from 0.3 MPa to 0.5 MPa where the leaching temperature ranged from 358 K to 378 K. The leaching rate
increases with the increase of temperature and total pressure and the leaching rate of zinc is relatively
higher than that of iron. The apparent activation energy for zinc leaching is calculated as 47.7 kJ/mol,
42.5 kJ/mol and 45.1 kJ/mol under the total pressure of 0.3 MPa, 0.4 MPa and 0.5 MPa respectively.
The general kinetic equation for zinc leaching under the total pressure of 0.3-0.5 MPa and in the
temperature range of 358-378 K is established by quadratic regression on the basis of shrinking core model
and it is further concluded that the influence of temperature is much greater than that of total pressure on
the leaching of zinc:
1/ 3
1 1 x
= 4.65 10 49 T 17.78 P 1.35 e E / RT t
where: E = the average apparent activation energy, 45100 J/mol.

Based on the mineralogical analysis of the leaching residue, it can be concluded that the acidic
dissolution of sphalerite produces hydrogen sulphide at the mineral surface, the hydrogen sulphide
transfers to the bulk solution and is oxidized into elemental sulphur. Because elemental sulphur is mainly
produced in bulk solution and doesnt form a compact solid layer on mineral surface, the diffusion of
dissolved zinc ions from mineral surface to bulk solution as well as that of sulphuric acid from bulk
solution to mineral surface is not the controlling step. The low-temperature pressure leaching of zinc
sulphide concentrate is controlled by an interfacial chemical reaction.
196
ACKNOWLEDGEMENT
This work was funded by National Natural Science Foundation of China (Project No. 50964004).
Dr. Zhifeng Xu also wants to express thanks to the support from Jiangxi Province Young Scientists
Cultivating Project of China.
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Takala, H., 1999. Leaching of zinc concentrates at Outokumpu Kokkola Plant. Erzmetall, 52 p. 37-42.
Tozawa, K. and Piao, S., 1987. Effect of iron content in zinc sulfide concentrates on zinc extraction in
oxygen pressure leaching with elemental sulfur. Metallurgical Review of MMIJ (Mining and
Metallurgical Institute of Japan), 4 p. 89-105.
Van Put, J.W., Terwinghe, F.M.I.G., and De Nys, T.S.A., 1996. Procd dextraction de zinc de concentrs
sulfures. European Patent EP 0 719 347 B1, July 3 (Assigned to Union Minire SA, Belgium. In
French.)
Van Put, J.W., Terwinghe, F.M.I.G., and De Nys, T.S.A., 1999. Process for the extraction of zinc from
sulphide concentrates. U.S. Patent No. 5,858,315. Washington, DC: U.S. Patent and Trademark
Office.
Xie, K.Q., Yang X.W., Wang J.K., Yan J.F., and Shen Q.F., 2007. Kinetic study on pressure leaching of
high iron sphalerite concentrate. Transactions of Nonferrous Metals Society of China, 17 p. 187194.
Xu, Z.F., Qiu, D.F., and Wang, H.B., 2008. Pressure leaching kinetics of marmatite. The Chinese Journal
of Process Engineering, 8 p. 28-34.
199
TREATMENT OF THOMPSON COPPER/ARSENIC RESIDUE

*T. Xue1, A. Singhal1, I. Mihaylov1, D. Wrana2
1
Vale Base Metals Technology Development

2101 Hadwen Road
Mississauga, Canada L5K 2L3
(*Corresponding author: tao.xue@vale.com)
2
Vale Manitoba Operations

P.O. Box 5000
Thompson, Canada R8N 1P3
ABSTRACT
At Vale's Thompson Nickel Refinery, the copper and arsenic in the nickel electrolyte are removed
by precipitation using H2S, generating a sulphide precipitate containing about 40% Cu, 8% Ni, 2 to 4% As
and 30% S. This residue has been typically stored in impoundment ponds within the plant site. Various
options for reprocessing it have been investigated over the years. One of the options involved oxidative
pressure acid leach, whereby over 95% Cu, Ni and As were extracted. More recently, an atmospheric
alkaline sulphide leaching process for selective removal of 70 to 90% As was developed and mini-plant
tested. After alkaline sulphide leaching, the dissolved arsenic is precipitated as stable basic ferric arsenate
(BFA) with the addition of ferric sulfate, while the low-arsenic Cu/Ni sulfide is suitable for processing in
Vale's operations elsewhere in Canada.

Niagara, ON, Canada
Edited by
200
INTRODUCTION
Vales Thompson Nickel Refinery was commissioned in 1961 and currently it has the capacity to
produce about 56,700 tonnes per year of electrolytic nickel as cathode slab and rounds products. A sulphate
and chloride mixed electrolyte is used in the Thompson refining process and it typically contains 75 to
85 g/L Ni, 50 to 60 g/L Cl, 90 to 120 g/L SO42-, 25 to 30 g/L Na and 8 to 9 g/L boric acid. The main
impurities in the Thompson anolyte are copper, cobalt, arsenic, iron and lead.
The simplified Thompson electrolyte purification flowsheet is shown in Figure 1 (Oliver &
Wrana, 2009, Goble & Chapman, 1986); it consists of precipitation of copper, arsenic and lead with H2S,
followed by nickel replenishment with ground matte and acid and removal of cobalt and iron with Cl2 and
NiCO3.
Matte Anodes
Purified Electrolyte
Ni Cathode
Sale
Tankhouse
Anolyte
H 2S
Ground Matte
H2SO4
Cu/As Removal
Cu/As/Ni Residue
Store in Ponds
Ni Replenishment
Cemented Matte
Recycle to Furnace
Cl2
NiCO3
CoOOH, Fe(OH)3
Further Treatment in Co Plant
Co/Fe Removal
Figure 1 - Simplified thompson electrolyte purification flow sheet

The Thompson electrolyte purification process treats about 9,000 m3/day of anolyte; the
compositions of the anolyte and the purified electrolyte are listed in Table 1.
Table 1 - Typical compositions of thompson anolyte and purified electrolyte, g/L
Electrolyte
pH
Cu
Co
Fe
As
Pb
Anolyte
1.5
0.53
0.23
0.22
0.030
0.0008
Purified
3.0
0.0003
0.022
0.0001
0.0005
0.0002
In the copper arsenic removal process, copper, arsenic and lead as well as some of the nickel in
the anolyte are removed by addition of H2S at about 60oC to form a sulphide precipitate, as expressed by
the following reactions:
CuSO4 + H2S CuS + H2SO4
(1)
2 HAsO2 + 3 H2S As2S3 + 4 H2O
(2)
201
NiSO4 + H2S NiS + H2SO4
(3)
PbCl2 + H2S PbS + 2 HCl
(4)
About 3,000 tonnes of copper arsenic precipitate residue, called Thompson Copper Residue, is
generated every year. This residue is relatively fine, with a particle size (D80) of ~10 m, and its
composition is listed in Table 2.
Table 2 - Composition of thompson copper residue, %
As
Cu
Ni
Pb
Cl
PGM
1.5 to 4
38 to 50
5 to 15
0.1 to 0.3
29 to 33
1 to 2
Trace
Since 1988, Thompson Copper Residue has been stored in two lined ponds at Thompson. Over
the past four years, a significant portion of the residue has been treated at Vales Sudbury Operations.
Currently, about 50,000 tonnes of Thompson Copper Residue is still stored in two ponds at Thompson.
Due in part to depleted ore reserves, Vale recently decided that the Thompson Smelter and
Refinery will be shut down in late 2014, early 2015. Subsequently, the ponds used for storage of
Thompson Copper Residue will be decommissioned and the stored Copper Residue will be treated to
recover copper, nickel and other valuable metals, while arsenic will be rejected as stable and
environmentally acceptable arsenic compounds for disposal.
Various options for reprocessing the Thompson Copper Residue have been investigated over the
years. One of these options involved oxidative pressure acid leach, in which copper, nickel and arsenic
were extracted into solution; the leach residue contained mainly elemental sulphur and small amounts of
precious group metals (PGM). More recently, an atmospheric alkaline sulphide leaching process was
developed for selective extraction of arsenic, and tested by Vale Base Metals Technology Development
(VBMTD) in its hydrometallurgical miniplant in Mississauga. In this paper, the results obtained from these
two processes are presented and discussed.
PRESSURE LEACH PROCESS
Process Description
In the 1990s, VBMTD had carried out extensive work on atmospheric leach of Thompson
Copper Residue, using H2SO4 and O2 (or air with supplemental chlorine). At 80oC and pH 1.5, over 95%
Ni and Cu and ~90% As were extracted in 6 hours from a feed slurry containing 5% solids.
In order to reduce the retention time required for treatment of the Thompson Copper Residue,
VBMTD considered a pressure leach process in 2008; the conceptual process flowsheet is shown in
Figure 2. In the process, the Copper Residue is pressure leached in an autoclave to extract most of the
copper, nickel and arsenic, generating a residue consisting mostly of elemental sulphur with trace amounts
of PGM. To remove arsenic, the leach solution is then treated with FeSO4 and O2 to form stable basic ferric
arsenate (BFA) for disposal in tailings area. Subsequently, copper and nickel could be recovered from the
solution by electro-winning and/or carbonate precipitation.
202
Cu/As Residue
H2SO4, O2
So, PGM
Pressure Leach
FeSO4, O2
FeAsO4. Fe(OH)3
As Removal
Cu/Ni Product
Cu/Ni Recovery
Figure 2 - Conceptual copper residue treatment flowsheet

Bench Scale Testwork
A batch pressure leach test program was carried out using an agitated 2-liter Parr autoclave. The
Copper Residue (feed) that was used for this test work contained about 41% Cu, 11% Ni, 2% As and
29% S. The operating conditions for the batch pressure leach tests and the results obtained are summarized
in Table 3, while Figures 3 to 5 depict the leach kinetics as arsenic, copper and nickel in solution vs. time,
respectively. In all pressure leach tests, the temperature and O2 pressure were fixed at 150oC and 700 kPa,
respectively, while other leach parameters such as the solids content, acid addition and retention time were
varied (Table 3).
Table 3 - Summary of batch pressure leach tests
Test
Solids in Slurry, %
7.3
15
15
H2SO4 Added, kg/t
370
380
580
Temperature, oC
150
150
150
O2 Pressure, kPa
700
700
700
Retention Time, h
1.5
Extraction, %
98 As, 97 Cu,
75 As, 65 Cu,
95 As, 80 Cu
98 Ni, 94 S
96 Ni, 73 S
97 Ni, 85 S
Over 97% Cu, Ni, and As and 94% S were extracted in 1.5 h under the leach conditions of 7.3%
solids, addition of 370 kg/t acid, 150oC and 700 kPa O2 pressure (Test 1). From Figures 3 and 5, it can be
seen that most of the arsenic and nickel were extracted in 1 hour, while longer time was required for copper
extraction (Figure 4). The leach residue contained about 2% As, 5% Cu, 1% Ni and 68% S and the final
solution contained about 40 g/L Cu, 10 g/L Ni, 1.5 g/L As and 30 g/L H2SO4.
When the feed slurry contained more solids (15%) and the acid addition remained at a rate of
380 kg/t (Test 2), the nickel extraction after 2 h was about 96%. However, the arsenic and copper
extractions dropped to about 75% and 65%, respectively. Clearly, the pressure leach conditions were not
sufficient to meet the metal extraction targets; about 73% S oxidized during the leach. The leach residue
contained about 58% Cu, 2% Ni, 0.6% As and 32% S, while the leach solution contained about 45 g/L Cu,
17 g/L Ni, 3 g/L As and 75 g/L H2SO4.
203
4.0
As in Solution (g/L)
3.5
3.0
2.5
2.0
1.5
1.0
Test 1 - 7.5% solids, acid ratio 0.8

Test 2 - 15% solids, acid ratio 0.8
0.5

0.0
0
15
30
45
60
75
90
105
120
Time (min)
Figure 3 - Pressure leach tests: arsenic in solution vs. time

70
Cu in Solution (g/L)
60
50
40
30
20

10

0
0
15
30
45
60
75
90
105
120
Time (min)
Figure 4 - Pressure leach tests: copper in solution vs. time

When the acid addition was increased to 580 kg/t (Test 3), the free acid in the final leach solution
increased from 75 g/L to over 115 g/L. After leaching for 2 h, 97% Ni, 95% As and 80% Cu were extracted.
It was clear that longer retention time would be required to further improve the copper extraction (Figure
4). The results from the batch pressure leach tests indicated that increasing the solid content in leach slurry
to over 10% would adversely affect the extraction of arsenic and copper and the long retention time
required to extract over 90% Cu made this processing option less attractive. As a result, the use of pressure
leach process for treatment of Thompson Copper Residue was not further pursued.
204
22
20
Ni in Solution (g/L)
18
16
14
12
10
8
6
0
0
15
30
45
60
75
90
105
120
Time (min)
Figure 5 - Pressure leach tests: nickel in solution vs. time
ALKALINE SULPHIDE LEACH PROCESS
Process Description
Other researchers had reported the use of alkaline sulphide process for removal of arsenic from
copper concentrates and other materials (Filippou et al., 2007, Anderson, 2005). Recently, VBMTD
developed an alkaline sulphide leach process for treatment of Thompson Copper Residue and the relevant
flowsheet is shown in Figure 6.
Thompson Copper Residue
NaOH/NaHS
Alkaline Sulphide Leaching
Recycle
Cu,NiS Residue
To Sudbury
Air
H2SO4
Fe2(SO4)3
Air/Lime
Oxidation
Precipitation
Basic Ferric Arsenate

To Disposal
Effluent
Figure 6 - Alkaline sulphide leach process for processing copper residue
As shown in Figure 6, in the alkaline sulphide leach process, the arsenic in Thompson Copper
Residue is selectively leached using a NaHS/NaOH solution to generate a As-depleted (Cu,Ni)S filter
205
cake that is well-suited for further processing at Vales smelter in Sudbury, Ontario. A portion of the leach
solution is recycled to the leach process, and the rest is treated by a two-stage solution treatment process,
which includes (a) oxidation using air, and (b) arsenic precipitation to form basic ferric arsenate (BFA)
precipitate for disposal to the tailings area. A similar residue disposal practice has been in use at Vales
operations in Sudbury for many years (Krause, 1992; Xue et al., 2006).
In the oxidation process, air is injected into the solution to oxidize the As(III) and NaHS in
solution to As(V) and thiosulphate (Na2S2O3), respectively. Also, sulphuric acid (H2SO4) is added to
neutralize the residual caustic in solution. Subsequently, ferric sulphate (Fe2(SO4)3) is added to precipitate
the dissolved arsenic as basic ferric arsenate. Meanwhile, lime and air are also added to the arsenic
precipitation step to control the slurry pH, and to further oxidize the thiosulphate (Na2S2O3) in solution to
polythionate (Na2SnO6, where n ranges from 3 to 5) and eventually to sodium sulphate (Na2SO4).
Bench Scale Tests
Alkaline Sulphide Leaching
Bench scale alkaline sulphide leach tests were carried out to assess the effects of various factors on the
arsenic extraction from Thompson Copper Residue, including solids content, arsenic content in the feed,
NaHS and NaOH concentrations in leach solution, recycle of leach solution, temperature and retention
time. In the alkaline sulphide leach process, the main reactions for arsenic extraction are expressed as:
NaHS + NaOH Na2S + H2O
(5)
As2S3 + 12 NaOH 2 Na3AsO3(aq) + 6 H2O + 3 Na2S
(6)
As2S3 + Na2S 2 NaAsS2(aq)
(7)
As2S3 + 3 Na2S 2 Na3AsS3(aq)
(8)
Bench scale tests showed that depending on the arsenic content in the feed slurry (10 to 15%
solids), about 70 to >90% of arsenic in the Thompson Copper Residue was leached in 1 to 2 h at 80oC,
using 50 to 100 g/L NaHS and 100 g/L NaOH in leach solution, which reduced arsenic in the leach residue
to <0.3%. A leach solution containing 3 to 7 g/L As and 0.2 to 5 g/L Ni was generated during the leach.
In the absence of NaHS, the arsenic extraction was significantly lower and very little nickel was
leached. When the addition of NaHS was increased from 10 g/L to 100 g/L, the solution ORP dropped
from about -200 mV to less than -400 mV (vs. Ag/AgCl), and the arsenic extraction was significantly
improved. On the other hand, the addition of 10 - 100 g/L NaHS also resulted in 0.2 to 5 g/L Ni and 10 to
100 g/L S2O32- in the leach solution. Also, the tests showed that a recycle of 50 to 100% of the leach
solution had no detrimental effect on the arsenic extraction, but significantly increased the arsenic
concentration in the discharge solution. Moreover, control of leach temperature at 80oC or higher not only
promoted the arsenic leach kinetics, but also significantly improved filtration characteristics of the
discharge slurry.
Leach Solution Treatment
Following the alkaline sulphide leach tests, extensive bench scale solution treatment tests,
including oxidation and arsenic precipitation as BFA, were carried out. The leach solution typically
contained 4 to 10 g/L As as As(III), up to 5 g/L Ni, over 70 g/L NaOH, over 50 g/L NaHS and 10 to over
50 g/L thiosulphate. In the oxidation stage, air or O2 was added to oxidize the As(III) in solution to As(V)
and the sulphide species in solution to thiosulphate through the following reactions:
Na3AsO3(aq) + 0.5 O2 Na3AsO4(aq)
(9)
206
2 Na3AsS3(aq) + 6 NaOH + 7 O2 2 Na3AsO4(aq) + 3 Na2S2O3(aq) + 3 H2O

2 Na2S + 2 O2 + H2O Na2S2O3(aq) + 2 NaOH
(10)
(11)
The test work concluded that pre-adjustment of slurry pH from over 12 to 10 or less, and the use
of oxygen, rather than air, significantly reduced the retention time required to complete the oxidation
reactions. However, due to the constraints related to the supply of oxygen to the nickel refinery in
Thompson, air was selected as the oxidant. It was also observed that when most of the sulphide species in
solution were oxidized to thiosulphate, the soluble nickel species in solution was precipitated as NiS and
Ni(OH)2.
After oxidation, the solution was further subjected to arsenic precipitation tests. Various factors
that could affect the formation of basic ferric arsenate (BFA) were investigated, including Fe salt used
(ferrous or ferric sulphate), Fe/As molar ratio, pH adjustment and control, temperature and retention time.
The results obtained in this work showed that the arsenic in solution could be effectively precipitated at
60oC with the addition of Fe2(SO4)3 at a Fe/As molar ratio >5 and control of the operating pH in the range
of 4 to 8, through the following reactions:
2 Na3AsO4(aq) + Fe2(SO4)3 2 FeAsO4 + 3 Na2SO4
(12)
Fe2(SO4)3 + 3 H2O 2 Fe(OH)3 + 3 H2SO4
(13)
In the BFA precipitation process, the thiosulphate in solution was further oxidized with air to
thionates (Na2SnO6, where n from 3 to 5) and sulphate, as expressed by the reactions shown below:
3 Na2S2O3(aq) + 2 O2 + H2O 2 Na2S3O6(aq) + 2 NaOH
(14)
4 Na2S2O3(aq) + O2 + 2 H2O 2 Na2S4O6(aq) + 4 NaOH
(15)
Na2S3O6(aq) + 2 O2 + 2 H2O Na2SO4(aq) + 2 H2SO4
(16)
Miniplant Demonstration
Based on the results obtained in the bench scale tests, the alkaline sulphide leach process for
treatment of Thompson Copper Residue was further demonstrated through continuous test work in
VBMTDs hydrometallurgical miniplant. The miniplant leach circuit consisted of two agitated leach tanks
(LT1 and LT2) and a press filter, as shown in Figure 7. The working volume for each tank was 10 L.
NaOH
NaHS
Recycle Solution
Press Filter
NiS/CuS
Feed Slurry
LT1
LT2
Filtrate
Figure 7 - Miniplant leach circuit
207
On the other hand, the solution treatment circuit consisted of 6 tanks (OB1 to OB6), 3 for
oxidation, and 3 for BFA precipitation, as shown in Figure 8. The working volume for each tank was 10 L.
Oxidation
Feed Solution
H2SO4
Fe2(SO4)3
Lime
Filter
Air
OB1
OB2
OB3
OB4
OB5
OB6
BFA
Effluent
Figure 8 - Miniplant solution treatment circuit

The feed slurry that was used in the test work in the miniplant came from Thompson. The Asreceived Copper Residue was washed with water and filtered to recover soluble nickel, and then blended
to form the feed slurry containing about 24% solids. Table 4 shows the composition of the solids and
solution in the prepared feed slurry. The arsenic content in the feed (solids) was 2.4%.
Table 4 - Compositions of solid and solution in miniplant feed, % or g/L
Sample
Solid
Solution
pH
-2.8
Cu
42.0
2.22
Ni
7.96
2.54
Fe
0.89
0.11
Ca
0.21
0.35
Si
1.61
0.03
S
31.6
2.48
As
2.39
0.47
Pb
0.22
<0.01
Cl
1.18
1.27
Leach Campaign
The miniplant leach test consisted of five periods. In these periods, the variable conditions
included NaHS concentration in the leach solution and recycle rate of leach solution. The leach circuit was
operated at a slurry flow rate of ~10 L/h for 160 h, and over 270 kg of feed solids (dry) were processed.
The main results obtained are listed in Table 5, and are also plotted in Figures 9 and 10.
Table 5 - Results obtained in leach campaign (15% Solids, 100 g/L NaOH, 80oC, 2 h )
Period
NaHS, g/L
12
25
25
Recycle of Leach Solution, %
35
30
As Extraction, %
65-70
65-70
70-75
75-78
75-78
As in Leach Residue, %
As in Leach Solution, g/L
0.78
3.6
0.72
4.1
0.66
3.9
0.60
4.1
0.60
4.7
Ni in Leach Solution, g/L
<0.01
<0.01
0.09
0.37
0.37
10.5
13.4
9.6
8.3
11.4
2-
S2O3 in Leach Solution, g/L
In the absence of NaHS (Period 1), 65 to 70% As was leached out, reducing the arsenic in the
leach residue from 2.4 to 0.78%, and resulting in about 3.6 g/L As, <10 mg/L Ni and 10 g/L thiosulphate in
the leach solution. With a recycle of 35% of the leach solution (Period 2), similar arsenic extraction was
208
achieved and the arsenic in the leach residue dropped to 0.72%. However, the arsenic and thiosulphate
concentrations in the leach solution increased to over 4 g/L and 13 g/L, respectively.
Figure 9 - Profile of arsenic extraction (Periods divided by dotted lines)
Figure 10 - Profile of arsenic in leach residue (Periods divided by dotted lines)

During Period 3, addition of 12 g/L NaHS in the leach solution increased the arsenic extraction to
about 70 to 75%, which reduced arsenic in the leach residue to 0.65% and resulted in about 3.9 g/L As, 100
mg/L Ni and 10 g/L thiosulphate in the leach solution. An increase in the NaHS addition to 25 g/L (Period
4) further increased the arsenic extraction to over 75%, which reduced the arsenic in the leach residue to
0.6% and resulted in about 4.1 g/L As, 400 mg/L Ni and 8 g/L thiosulphate in leach solution. In Period 5,
recycle of ~30% leach solution gave similar arsenic extraction to that obtained in Period 4, and there was
209
no significant change to the residual arsenic level in the leach residue, and increased arsenic and
thiosulphate in solution.
Solution Treatment Campaign
The miniplant solution treatment campaign consisted of 4 periods, with a total run time of 74 h.
The operating conditions and the main results obtained in Periods 1, 2 and 4 are summarized in Table 6 (in
Period 3, only the oxidation step was carried out). Over 650 L of leach solution that was generated during
the previous leach campaign was processed, and over 20 kg of BFA precipitate (dry) was produced.
Table 6 - Summary of spent leach solution treatment at 60oC
Period
A1
A2
A4
NaHS Added in Leach, g/L

As in Feed Solution, g/L
25
12
S2O32- in Feed Solution, g/L

Air Rate, L/min/tank
Fe/As Molar Ratio
pH Control in BFA process
3.6
11.3
10
7.2
4.5/6.5
4.3
10.9
10
7.0
4.5/6.5
3.9
13.0
10
7.6
4.5/6.5
Retention Time, h
As in Final Solution, mg/L
10
Total Thiosalts in Final Solution, g/L
10.9
29.2
17.4
As in Final BFA, %
Fe in Final BFA, %
4.2
8.4
7.6
22.1
41.5
39.5
The solutions generated in the miniplant leach process contained 3.6 to 4.3 g/L arsenic, ~10 g/L
thiosulphate and 0 to 20 g/L sulphide. In the oxidation step, the solution ORP increased from <-200 mV to
the range of -200 to 0 mV and the As(III) and NaHS in solution were oxidized to As(V) and thiosulphate,
respectively. The results showed that with the addition of 12 and 25 g/L NaHS in the leach process, after
oxidation, the total thiosalts in solution increased to 17 to 30 g/L.
In the BFA precipitation process, most of the arsenic in the leach solution was effectively
precipitated, from about 4 g/L to 10 mg/L or less in solution, through addition of Fe2(SO4)3 at a Fe/As
molar ratio ~7 and pH controlled in the range of 4.5 to 6.5. The discharge slurry typically contained 3 to
5% solids, and the iron and nickel in the final solution were <10 mg/L each. On the other hand, after the
BFA precipitation process, the discharge solution still contained 10 to 30 g/L thiosalts.
The BFA precipitates were found to be relatively fine, typically with a particle size (D80) of ~5
m. Meanwhile, significant scaling was observed in the precipitation tanks. It is anticipated that recycle of
seed in the BFA process would improve the particle size of the precipitated solids, and also reduce the
scaling rate.
BFA Stability
Standard SPLP stability tests were carried out with the BFA wet cakes collected from the
miniplant test. These BFA samples contained 4 to 8% As and 20 to 40% Fe. The results show that the
arsenic in the final leach solutions ranged from 0.1 to 0.7 mg/L, lower than the limit of 1 mg/L.
The effect of aging of the BFA slurry, i.e., without filtration, on the BFA stability was also
investigated. The results show that in the aging process, the thiosalts in solution, ranging from 10 to 30 g/L,
would gradually oxidize to generate acid, reduce the slurry pH to <3 and result in significant re-dissolution
210
of As, Fe and Ni from the BFA precipitate. For this reason, minimizing the NaHS addition to the leach is
preferred as this will reduce the amount of thiosalts formation. Even more importantly, the BFA product
slurry should be filtered right away to separate the BFA wet cake from the thiosalts-containing effluent in
order to minimize the effect of the thiosalts on the BFA product stability.
CONCLUSIONS
Treatment of Thompson Copper Residue by a pressure leach process was investigated. Batch test
work showed that compared with an atmospheric oxidizing leach with oxygen or air, the use of an
autoclave for leaching the sulphide precipitate improved the leach kinetics for arsenic and nickel
extraction. However, the pressure leach performance was constrained by the low feed slurry density
(<10% solids), slow leach kinetics for copper and a complicated process required for the subsequent
recovery of copper and nickel from the leach solution. As a result, the pressure leach option was not
further pursued.
Instead, an alkaline sulphide leach process was developed and demonstrated in VBMTDs
hydrometallurgical miniplant in Mississauga, Ontario. In this process, arsenic is selectively extracted into
an alkaline leach solution, generating an arsenic-depleted copper nickel sulphide residue that is suitable
for further treatment at Vales smelting operation in Sudbury. The arsenic-containing leach solution is
treated with ferric sulphate to form a stable basic ferric arsenate precipitate for disposal. This processing
option is currently undergoing detailed engineering evaluation for possible implementation for the
decommissioning of the Copper Residue storage ponds after the planned shutdown of the Thompson
Smelter and Refinery.
ACKNOWLEDGEMENTS
The authors wish to thank Vale Base Metals Technology Development Ltd for permission to
publish this paper and their many former and present hydrometallurgy colleagues from both the Thompson
Refinery and VBMTD who have contributed to the development of these processes over the years.
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Filippou, D., et al. (2007). Recovery of Metal Values from Copper-Arsenic Minerals and Other Related
Resources, Min. Processing & Extractive Metall. Rev., 28, p 247-298.
Goble, M. L., & Chapman, J. A. (1986). Electrolytic Nickel Production in Thompson Refinery,
Transaction CIM.
Krause, E. (1992). Arsenic Removal at Incos CRED Plant and Disposal Practice, EPA workshop on
Removal, Recovery, Treatment and Disposal of Arsenic and Mercury, Alexandria, VA, USA, Aug
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Oliver, B. M., & Wrana, D. (2009). Recent and Forthcoming Operational Improvement in Vale Incos
Thompson Nickel Refinery, Hydrometallurgy of Nickel and Cobalt 2009, Sudbury, p 602-610.
Xue, T., et al. (2006). Commissioning and Operation of the Copper Cliff Weak Acid Treatment Plant, Iron
Control Technologies, Eds. J. E. Dutrizac and P. A. Riveros, Montreal, p 415-428.
211
THE CO-PROCESSING OF NICKEL SULPHIDE AND LATERITE MATERIALS USING LOW

OXYGEN PRESSURES
*R. McDonald1, M. Rodriguez2, J. Li1, D. Robinson1, M. Jackson1, T. Hosken1
CSIRO Minerals Down Under National Research Flagship
Australian Minerals Research Centre
7 Conlon Street, Waterford, WA 6152, Australia1
(*Corresponding author: robbie.mcdonald@csiro.au)
Poseidon Nickel Limited
8 Churchill Court, Subiaco, WA 6008, Australia2
ABSTRACT
The addition of sulphidic materials in the leaching of nickel laterites has several potential benefits
that include improvements in the rheological behaviour of the blends, reductions in the sulphuric acid and
steam requirements, sweetening of the nickel grade of the combined feed material, and the option of using
a range of sulphidic materials. The current study examines the oxidative processing of 30% w/w blends of
nickel concentrate and nickel laterite ore at 250oC. In particular, the viability of using low oxygen
overpressures was examined for significant amounts of nickel flotation concentrate, up to 12% w/w.
Further to this the impact of process water quality, in particular the presence of chloride, upon the kinetics
of extraction and the mineralogy of the residue were also investigated. This paper will present the results of
preliminary work in this area.

Niagara, ON, Canada
Edited by
212
INTRODUCTION
The use of sulphidic ore as a source of sulphuric acid during oxidative hydrometallurgical
processing is not a novel idea and can be traced back over forty years (Seidel & Fitzhugh, 1968). A series
of patents pertaining to application of this approach for laterite ores can be subsequently found (ONeill,
1973; Opratko et al., 1974; Rodriguez, 2008a, 2008b; OCallaghan, 2010; Liu et al., 2011) and a few of
articles containing published data (Ferron & Fleming, 2004; Quinn et al., 2009). The use of pyrrhotite
tailings as a source of sulphuric acid has also been employed for the leaching of converter slags (Perederiy
et al., 2011).
It is known that hydrometallurgical operations such as the HPAL plant at Murrin Murrin have
added small amounts of sulphides as either transitional (mixed sulphide/oxide) ore or non-smeltable
concentrate. This can improve the rheology (Rodriguez, 2009) and provide heat credits. However these
plants are generally limited in their ability to add such materials due to their reducing nature and given
under highly acidic conditions that the breakdown potential of the titanium used for the autoclave lining is
significantly reduced. A suitable oxidant must therefore be present to ensure the potential remains
sufficiently high.
Laboratory tests show that it is possible to typically recover around 80% nickel at a grade of 10%
nickel from a nickel sulphide ore (Senior et al., 1995). Grade versus recovery curves indicate it is possible
to increase nickel recovery to around 95% trading off against concentrate grade, a typical drop being by a
factor of around two (Lotter et al., 2003) though subsequent work shows that new approaches to the
optimisation of concentrator circuits are yielding benefits (e.g. Senior & Thomas, 2005; Lotter et al.,
2011).
Poseidons Cerberus orebody, which grades at 2.05% nickel, can generate a higher grade of
flotation concentrate, of around 20% with about 78% nickel recovery which can be increased to about 84%
with accompanying drop in concentrate grade to around 16% (Poseidon Nickel, 2011). Other Poseidon
orebodies have significantly lower nickel grades and result in lower grade concentrates. However, these
also have high sulphide content that can be harnessed for hydrometallurgical processing. Where it is more
difficult to separate the pentlandite and pyrrhotite fractions by depression of pyrrhotite flotation the use of
these concentrates as a source of sulphuric acid may make economic sense, particularly given the nickel
recovery in the flotation circuit can be increased not only through increased recovery of nickel sulphides
but since pyrrhotite normally contains low levels of nickel.
The use of sulphidic materials to generate sulphuric acid requires an oxidant. At Murrin Murrin
the manganese oxide content of the ore combined with head space oxygen are sufficient to provide the
amount of oxidant required. Where the sulphidic content is higher a dedicated source of oxidant (normally
oxygen) and a vessel specifically designed for pressure oxidation is essential.
The current study examines the use of a high-pyrrhotite nickel concentrate as a source of sulphuric
acid for the leaching of a nickel laterite ore. In oxidising the sulphide minerals, the aim was to employ a
low oxygen overpressure that might enable the use of a conventional autoclave and not risk damage to
components, particularly those made from or containing titanium, due to metal fires especially in the
pressure let-down and flash sections. Simultaneously it was important to determine that the leaching
conditions will not enhance the corrosion of the vessel.
MATERIALS AND METHODS
Run-of-mine Bulong laterite was ball milled, wet screened to -500 m and filtered to produce a
filter cake feed material. Poseidon nickel concentrate was dry screened to -75 m to produce feed material.
A series of pulps were leached at 250C using a 1 gallon Parr titanium autoclave in Poseidon site
process water having composition (mg/L) of Mg (330), Na (3060), Ca (110), K (80), SO4 (890) and Cl
213
(6200). Tests using only Poseidon nickel concentrate were run with 10% w/w pulps, whereas most tests
using Bulong nickel laterite and Bulong nickel laterite/Poseidon nickel concentrate blends were run with
30% w/w pulps. The exception was that one of the blend tests was run using a pulp density of 40% w/w. In
most experiments, stirring was performed using a dual pitched blade impeller at a speed of 750 rpm.
The quantity of acid required for the test using only nickel laterite was calculated after drying
(overnight, 110C) and elemental analysis. The laterite pulp was heated to 235oC prior to injection of the
required acid and samples collected during the reaction lasting 90 minutes.
For all experiments the pulps were heated to temperature in an atmosphere of nitrogen. For most
tests employing nickel concentrate and laterite/concentrate blends, these were leached with continuous
oxygen injection into the head space via a Teledyne Hastings Instruments Model HFC-D-302
Flowmeter/Controller with PowerPOD 400 Power Supply/Totaliser. This was performed using a small
oxygen supply overpressure (with total pressure of 4100-4200 kPa) and preset constant oxygen injection
rate. One test with nickel concentrate was performed with a typical oxygen overpressure, 700 kPa,
combined with unmetered oxygen injection. Tests with nickel concentrate and laterite/concentrate blends
were conducted with sampling for 90 and 120 minutes, respectively.
After leaching, the process slurries were filtered and, the residues were washed, repulped,
refiltered and dried. The residues and leach solutions were submitted for elemental analysis by ICP-OES
Free acid determinations were performed using the CaEDTA method (Rolia & Dutrizac, 1984) with
detection of the titration end point using Metrohm Tiamo software, and ferrous iron determinations by
titration with dichromate using barium diphenylamine-4-sulfonate as indicator.
In addition, a selection of residues were mixed with a known amount of fluorite standard and
submitted for XRD. The resultant data was analysed by Quantitative X-Ray Diffraction (QXRD) analysis
using Topas (Brker Advanced X-ray Solutions) software.
MINERALOGY OF THE FEED MATERIALS
The mineralogy of the Bulong nickel laterite ore and the Poseidon Nickel concentrate were
examined by a combination of XRD, SEM/EDS and QEMSCAN analyses. The elemental compositions of
these materials are given in Table 1.
Table 1 Elemental compositions (%) for the Poseidon nickel concentrate and Bulong nickel laterite
Material
Laterite
Concentrate
Ni
Co
Cu
Mg
Mn
Fe
Al
Cr
Si
Na
Ca
1.90
8.11
0.131
0.138
0.011
1.28
3.32
0.651
0.456
0.037
24.6
45.0
2.47
0.318
0.857
0.175
16.8
2.48
0.201
0.082
0.046
0.047
0.170
0.421
0.02
30.3
The Bulong nickel laterite is essentially a blend of limonite and smectite fractions that from
QXRD analysis is indicated to contain 24% goethite, 44% nontronite, 8% maghemite/chromite, 6%
chlorite, 4% quartz, 0.7% talc and 0.3% amphibole (possibly actinolite or tremolite).
The mineralogy of the ore at Poseidons Mt Windarra deposit has been described by Watmuff
(1974). The primary ore comprises major pentlandite with monoclinic pyrrhotite and minor chalcopyrite,
cobaltiferous pyrite and hexagonal pyrrhotite. Traces of sphalerite, galena and ilmenite may also be found.
The gangue minerals include chromite and magnetite spinels, and serpentine, magnesite, talc and minor
chlorite. Weathering of the primary ore results in gradual replacement of the pentlandite and the margins of
pyrrhotite with violarite while unviolaritized pyrrhotite may also be replaced by secondary pyrite and/or
marcasite. The violarite composition can show extensive variation depending upon which zone of the
weathered ore body it is found.
QXRD analysis indicates the nickel concentrate used in the present work contains 36% pyrrhotite,
11% pyrite, 7% pentlandite, 7% violarite, 3% chalcopyrite, 3% talc, 3% quartz, 2% chlorite, 1% amphibole
214
and trace vermiculite. Preliminary SEM/EDS data suggests the following compositions for the
nickel-containing minerals: pyrrhotite Fe0.94Ni0.007S; pentlandite Fe4.20Ni5.28Co0.07S8; violarite
Fe1.67Ni1.88Co0.03S4.
FEED SAMPLE LEACHING
The leaching of Poseidon nickel concentrate at 250oC using an oxygen overpressure of 700 kPa
demonstrated fast release of the nickel and cobalt (Figure 1A) with extractions of 95% and 93%,
respectively, being reached within 5 minutes; a similar result was found for copper extraction. Final
extractions were above 99% after 30 minutes. Even when the oxygen partial pressure is reduced to
approximately 100 kPa, the concentrate still reacts rapidly and nickel/cobalt extractions are still around
99% after 30 minutes (Figure 1B). Alternatively when the rate of oxygen addition is controlled to a fixed
rate of 2.5 g/min the leaching rate, and hence time required to complete the reaction can be controlled
(Figure 1C). This oxygen addition rate corresponds to 11.5 g/min/kg concentrate.
The HPAL of the Bulong nickel laterite sample was conducted using an acid addition of 364 kg/t
dry ore. Rapid initial extraction of nickel and cobalt takes place with extractions reaching 93% and 94%,
respectively, after 60 minutes and about 1% more each after a further 15 minutes (Figure 1D). The final
free acid and ORP values in this test were 46 g/L and 464 mV versus Ag/AgCl, respectively. Iron and
aluminium rejections were both excellent and the final concentrations of these metals were 1120 and
360 mg/L, respectively.
B
Poseidon Nickel Concentrate - low P(O2)
100
80
Nickel
60
Cobalt
Magnesium
Iron
Aluminium
40
Free Acidity
20
0
0
15
30
45
60
Leach Time (min.)
75
Metal Extraction (%) and Free Acidity (g/L)
Poseidon Nickel Concentrate

100
80
Nickel
60
Cobalt
40
Aluminium
Magnesium
Iron
Free Acidity
20
90
15
75
90
D
Bulong Nickel Laterite Blend
100
80
Nickel
60
Cobalt
Magnesium
Iron
Aluminium
40
Free Acidity
20
0
0
15
30
45
60
Leach Time (min.)
75
90
Poseidon Nickel Concentrate - low P(O2), low flow

30
45
60
Leach Time (min.)
100
80
60
Nickel
Cobalt
Magnesium
40
Manganese
Iron
Aluminium
Free Acidity
20
0
0
15
30
45
60
Leach Time (min.)
75
90
Figure 1 - Metal extractions for the leaching of feed materials at 250oC: (A) nickel concentrate with
700 kPa oxygen, (B) nickel concentrate with 100 kPa oxygen, (C) nickel concentrate with oxygen injection
rate of 2.5 g/min and (D) HPAL of Bulong laterite blend using 364 kg acid/t dry ore
215
At both lower oxygen pressure and with controlled oxygen injection, the system becomes less
oxidising and the rate of ferrous iron oxidation is reduced significantly (Figure 2). The effect of lowering
oxygen pressure in decreasing the ferric iron to total iron ratio has also been noted from the pressure
oxidation of pyrite by Long and Dixon (2004). Conversely, the rate of oxidation of ferrous iron in
sulphuric acid solutions has been shown to be proportional to the oxygen partial pressure (Chmielewski &
Charewicz, 1984).
Ferrous iron concentrations and ORP values
30000
550
525
500
20000
475
15000
450
425
10000
Eh (mV Ag/AgCl)
Ferrous iron (mg/L)
25000
Oxygen 700 kPa (Fe(II))

Oxygen 100 kPa (Fe(II))
Oxygen 2.5 g/min (Fe(II))
Oxygen 700 kPa (Eh)
Oxygen 100 kPa (Eh)
Oxygen 2.5 g/min (Eh)
400
5000
375
350
0
15
30
45
60
Leach Time (min.)
75
90
Figure 2 - Ferrous iron concentrations and corresponding ORP values (versus Ag/AgCl) during the
oxidative leaching of Poseidon under various conditions
Once significant metals extraction has occurred, by that time the ferrous iron concentration has
peaked, oxidation to ferric iron then occurs rapidly and the ORP of the system increases. While the final
ORP values are between 450 and 475 mV versus Ag/AgCl these are still somewhat below that when the
oxygen partial pressure employed is 700 kPa. Furthermore both the total and ferrous iron levels are also
higher and as seen from Figures 1B and 1C are still continuing to decrease at the conclusion of the test.
COMBINED PRESSURE ACID LEACHING
The terminology Combined Pressure Acid Leaching (CPAL) was used by Quinn et al. (2009) to
describe the co-processing of mixed sulphide/laterite ores under conditions similar to HPAL using an
oxidant. In this work a sulphide ore was employed and when combined with heap leach PLS and laterite
ore, leaching produced discharge liquors with nickel extraction above 90% and nickel tenors above 10 g/L
after 90 minutes using an oxygen overpressure of 800 kPa. That sulphide oxidation was around 90% after
30 minutes and that laterite leaching significantly slowed between 30 and 60 minutes are probably typical
of the lower temperature employed, 220oC, and may also reflect the extent of liberation of the sulphide
minerals in the sulphide ore sample.
The acronym HPOXAL from High Pressure Oxidative Acid Leaching was used by Perederiy et
al. (2011). This work was conducted at 250oC using pyrrhotite tailings as a supplementary sulphuric acid
source for the leaching of converter slags and gave nickel, cobalt and copper extractions above 90% after
20 minutes that reached 95-97% after 45 minutes using an oxygen overpressure of 630 kPa.
The baseline test conducted in the present study employed a 30% w/w pulp consisting of
10.5% w/w Poseidon concentrate and 19.5% w/w Bulong nickel laterite at 250C. If all of the nickel,
cobalt and copper are assumed to be associated with sulphide, the fraction of sulphide that can be
converted to sulphuric acid is estimated to be 0.83. This corresponds to an effective acid addition of
414 kg/t dry laterite ore. The rate of oxygen injection, 3.125 g/min or 11.5 g/min/kg concentrate, was
calculated to enable complete oxidation of the concentrate to occur within 40 minutes. This was confirmed
by the extraction data presented in Figure 3 which shows high total nickel and cobalt, and low iron
216
extractions after 45 minutes; the nickel and cobalt extractions reach around 98% after 60 minutes (as does
the copper extraction). The extraction of magnesium in particular maps the progress of leaching of the
nickel laterite component given that it contains around 70% of the total magnesium. From the free acidity
data it is apparent that acid is consumed rapidly as it is being generated. The large jump in free acid value
after 30 minutes can be accounted for by the change in dissolved ferrous and ferric levels in solution and
the formation of hematite (with a small amount of alunite/jarosite). The final ORP of the system was
around 475 mV, quite similar to the value obtained for the nickel concentrate alone. The final free acidity
was 55 g/L with iron and aluminium concentrations of 4820 and 440 mg/L, respectively.
CPAL - 10.5% Concentrate, 19.5% Laterite

100
80
Nickel
Cobalt
60
Magnesium
Manganese
Iron
40
Aluminium
Free Acidity
20
0
0
15
30
45
60
75
Leach Time (min.)
90
105
120
Figure 3 - Metal extractions (%) and free acidity (g/L) during CPAL test performed using a pulp consisting
of 10.5% w/w Poseidon concentrate and 19.5% w/w Bulong nickel laterite at 250C
It is interesting to note that a significant fraction of the manganese is dissolved during the heating
up period. At ambient temperatures and under anaerobic conditions the reaction between pyrite and
manganese oxides is reported to be (Schippers & Jrgensen, 2001):
FeS2 + 7.5MnO2 + 11H+ Fe(OH)3 + 2SO42- + 7.5Mn2+ + 4H2O
However, based upon QXRD data it appears that the dissolution of manganese during heating in the
present system is facilitated by pyrrhotite rather than pyrite, given that a small amount of sulfur was also
detected in the t0 sample. Schippers and Jrgensen (2001) also proposed the following reaction:
FeS + 1.5MnO2 + 3H+ Fe(OH)3 + S + 1.5Mn2+
A subsequent baseline test performed using a single gas entrainment impeller rather than a dual
pitched blade impeller to improve oxygen transfer from the head space gave similar results to those shown
in Figure 3 except for slightly lower ferrous iron contents, and therefore iron extractions, up til 45 minutes
of leaching. Similarly, reducing the rate of oxygen injection to 2 g/min or 7.4 g/min/kg concentrate simply
extended the duration of the reaction though still yielding nickel and cobalt extractions of around 98% after
75 minutes.
It is well established that the high extraction of metal values, >95%, from nickel laterites requires
the at temperature pH to be maintained at around 1 irrespective of the feed material (Jankovic &
Papangelakis, 2010). Furthermore the corresponding free acid level is for the most part determined by the
concentrations of nickel and magnesium which buffer the system reducing the concentration of hydrogen
ions. In the absence of equipment to measure the at temperature pH a single test was undertaken with a
lower concentrate to laterite ratio to set a lower limit on this value in order to obtain acceptable
nickel/cobalt extractions. The results from a test that employed just 7% w/w Poseidon nickel concentrate
217
and 23% w/w Bulong nickel laterite, which corresponds to an effective acid addition of 234 kg/t dry
laterite ore, with oxygen injection rate of 2.075 g/min or 11.5 g/min/kg concentrate are shown in Figure 4.
It is clear from the figure that the leaching of the laterite component is still continuing at the
conclusion of the test. The nickel/cobalt (and copper) extractions were around 95%. The high nickel and
magnesium concentrations, 15.2 and 12.4 g/L, respectively, probably meant that at temperature pH was
higher than the target value. The other main outcome of the lower nickel concentrate addition is to lower
the total dissolved iron and given the lower final free acidity, 22 g/L, to produce a liquor with lower iron
and aluminium contents, 1700 and 170 mg/L, respectively.
CPAL - 7% Concentrate, 23% Laterite

100
80
Nickel
Cobalt
60
Magnesium
Manganese
Iron
40
Aluminium
Free Acidity
20
0
0
15
30
45
60
75
Leach Time (min.)
90
105
120
of 7% w/w Poseidon concentrate and 23% w/w Bulong nickel laterite
The high intermediate ferrous iron concentrations encountered are a cause for concern given that
the oxidation of iron and subsequent hydrolysis is required to generate the acid that drives the leaching of
the nickel laterite. The catalysis of ferrous sulphate oxidation by nitrates and nitrites has been studied by a
number of groups (e.g. Kuznetsova et al., 1995). Here the formation of the Fe(NO)+ intermediate is
implicated in the oxidation process (Epstein et al., 1980) while also facilitating the dissolution of NO
(Baldwin & van Weert, 1996). Furthermore the formation of nitrous acid is a pre-requisite for the
formation of NO and this does not become substantial until the free acid level increases.
The study of Baldwin and Van Weert (1996) also indicated that sodium nitrite was a more
effective catalyst than either potassium nitrate or nitric acid. Other catalysts such as dissolved copper
(Dreisinger & Peters, 1989) and pyrite (Littlejohn, 2006) have been demonstrated to enhance ferrous iron
oxidation, the latter relating to enhancement of kinetics in the Galvanox Process.
A single test was conducted with sodium nitrite added to give 2 g/L nitrite to determine if this
could enhance ferrous iron oxidation. The data as shown in Figure 5 are similar within experimental error
to those of Figure 3 indicating that the presence of nitrite did not facilitate ferrous oxidation under the
conditions of the experiment. Upon reflection this is not surprising owing to the low solubility of ferrous
sulphate, and in fact all other divalent metal sulphates present, at high temperature and under conditions of
low free acidity. At 200oC the solubility of ferrous sulphate is 1.25 g/kg H2O rising to 8.02 g/kg H2O when
the acid concentration is 12.2 g/kg H2O; these values decrease in the presence of additional metal sulphates
(Hasegawa et al., 1996). The rapid generation of free acid after 30 minutes is responsible for the
dissolution of the ferrous sulphate enabling ferrous iron oxidation to occur. Further tests are required to
determine if the presence of nitrite facilitates this process.
218
The final test reported in this paper was to examine the effect of increasing the pulp density of the
blend to 40% w/w upon oxygen uptake and reaction kinetics; the extractions data are shown in Figure 6.
Here the effective acid addition was 330 kg/t dry laterite ore. In this test the oxygen addition rate was set at
3.62 g/min or 10.6 g/min/kg concentrate to target a reaction time of 45 minutes for the nickel concentrate.
It was found however that the uptake of oxygen by the system took somewhat longer, ca. 60 minutes, and
therefore the reaction was not largely completed until after 75 minutes. At this time the nickel and cobalt
extractions were 97% and 98% respectively, these values corresponding to nickel and cobalt concentration
in the PLS of 22970 mg/L and 900 mg/L, respectively. The copper concentration in comparison was
2330 mg/L.
CPAL - 10.5% Concentrate, 19.5% Laterite with nitrite

100
80
Nickel
Cobalt
60
Magnesium
Manganese
Iron
40
Aluminium
Free Acidity
20
0
0
15
30
45
60
75
Leach Time (min.)
90
105
120
of 10.5% w/w Poseidon concentrate and 19.5% w/w Bulong nickel laterite with added sodium nitrite
In comparison with the baseline test (Figure 3) it was interesting to note that at higher pulp
density the aluminium tenors were increased by the end of the reaction: 1660 mg/L compared with 440
mg/L. This corresponds with low sodium content in the final PLS, having dropped from a peak value
during the reaction of 2690 mg/L to just 40 mg/L; in the baseline test these values were 3310 mg/L and 660
mg/L, respectively. The driving force for alunite formation is therefore lower.

100
80
Nickel
Cobalt
60
Magnesium
Manganese
Iron
40
Aluminium
Free Acidity
20
0
0
15
30
45
60
75
Leach Time (min.)
90
105
120
of 12% w/w Poseidon concentrate and 28% w/w Bulong nickel laterite
219
OXYGEN UPTAKE DURING CPAL

The aim of using a mass flow controller/mass flow meter to moderate oxygen addition into the
CPAL system was three-fold:
(1)
Determine if the rate of oxygen addition was at least matched by the rate of oxygen consumption;
(2)
Control the rate of concentrate oxidation;
(3)
By controlling the rate of concentrate oxidation, to examine changes in mineralogy that may not
be noted under normal batch pressure oxidation conditions.
B
A
CPAL - 10.5% Concentrate, 19.5% Laterite
CPAL - 7 % Concentrate, 23 % Laterite

250
Actual oxygen addition
200
Oxygen injection (g)
250
Ideal oxygen addition
150
100
50
0
200
150
100
50
0
20
40
60
80
100
120
20
Leach time (min.)
40
60
80
100
120
Leach time (min.)
C
250
200
150
100
50
0
0
20
40
60
80
100
120
Leach time (min.)
Figure 7 - Oxygen additions as a function of leaching time compared with the mass flow controller setting
for CPAL at 250oC for various concentrate-laterite blends and oxygen source pressures (A) 10.5%
concentrate and 19.5% laterite with 4200 kPa; (B) 7% concentrate and 23% laterite with 4100 kPa;
(C) 12% concentrate and 28% laterite with 4200 kPa
For the baseline test using constant oxygen addition rate of 11.5 g O2/min/kg concentrate and
source pressure of 4200 kPa, the rate of oxygen consumption matched the set rate of oxygen addition
virtually right up until all of the concentrate had reacted (Figure 7A). At lower concentrate to laterite ratio
with using constant oxygen addition rate of 11.5 g O2/min/kg concentrate and source pressure of 4100 kPa,
the rate of oxygen consumption fell below the set rate of oxygen addition (Figure 7B). After an induction
period of approximately 10 minutes, the oxygen consumption was approximately constant at a rate of
10.4 g O2/min/kg concentrate. Given that the measurement of autoclave pressure was approximate
(50 kPa), the difference between the two experiments may simply be a function of the oxygen partial
pressure in the head space and therefore lower associated oxygen solubility, which for pure water systems
is approximated by Henrys Law at low partial pressures, even at high temperature (Tromans, 1998). Other
220
groups have established that the reaction kinetics in pressure oxidation systems is first order with respect to
the oxygen partial pressure (e.g. Papangelakis & Demopoulos, 1990).
At higher pulp density, 40% w/w, the rate of oxygen consumption does not match the set rate,
10.6 g O2/min/kg concentrate, at which oxygen could flow into the head space using a source pressure of
4200 kPa (Figure 7C). Again, as in Figure 7B, an induction period is noted after which the rate of oxygen
consumption is essentially constant: 6.9 g O2/min/kg concentrate. As the amount of water in the system
was only around 6% less this decreased consumption confirms that increasing the pulp density reduces the
rate of oxidation as found for other systems (e.g. Khoshnevisan et al., 2012). This is largely due to a
decrease in the volumetric gas transfer coefficient and a significant increase in power may be required to
maintain the value of this coefficient (Mills et al., 1987). Further work is required to examine the
optimisation of gas transfer and how this affects the oxygen partial pressure that must be employed to
obtain acceptable extraction kinetics for the blend of concentrate to laterite employed.
CHARACTERIZATION OF LEACH RESIDUES
The progress of the leaching reactions was also followed by examining the mineralogy of the
leach residues. For the Poseidon nickel concentrate the pyrrhotite reacted rapidly and was consumed within
the first 10 minutes even when the rate of oxygen injection was controlled (11.5 g/min/kg concentrate) as
shown in Figure 8. The pyrrhotite was mostly converted to pyrite and marcasite, with accompanying
formation of hematite, and this has previously been noted by Qian et al. (2011). Thereafter the marcasite
was leached preferentially, leading to a further increase in pyrite content, while the pyrite was mostly
leached after 30 minutes once the free acidity in the system starts to increase rapidly.
Pentlandite and its partially oxidised product violarite are initially present in similar amounts.
Like the pyrrhotite, pentlandite reacted rapidly within the first 10 minutes and based upon solution assays,
the extent of nickel leaching was low. Rather, a significant fraction of the pentlandite was converted to
violarite which has also been previously noted, albeit under milder conditions, by Tenailleau et al. (2006).
Subsequent studies indicated that this process is catalysed by the presence of pyrrhotite (Xia et al., 2007)
and provide a mechanism and kinetics for the replacement of pentlandite by violarite under acidic
hydrothermal conditions (Xia et al., 2009).
Thereafter, the dissolution of violarite took place and a new nickel sulphide intermediate with
cubic structure (space group PA3-) was noted in the 10 to 30 minute samples. In the absence of detail
regarding the composition of this mineral and from the position of the X-ray diffraction peaks it is similar
to, but not identical with, vaesite (NiS2) and/or bravoite (Fe0.5Ni0.5S2). The formation of such species under
conditions of increasing oxidation potential is predicted by the thermodynamic study of Warner et al.
(1996). Chalcopyrite is also present in the concentrate and was mostly transformed to covellite by 30
minutes after which time the copper was leached. This transformation at high temperature is enhanced in
the presence of dissolved chloride ions (McDonald & Muir, 2007) which may also play a role in the
formation of the nickel sulphide intermediate. In both cases the mechanism is currently unclear though the
conversion of pyrrhotite to pyrite and marcasite are indicated to follow a dissolution-re-precipitation
mechanism (Qian et al., 2011) while the formation of covellite from chalcopyrite in the presence of copper
sulphate involves exchange between dissolved copper and iron in the chalcopyrite structure (viz.
metathesis) (Sequeira et al., 2008). In the present study chalcopyrite disappeared under low dissolved
copper concentrations while the appearance of the covellite corresponds to conditions where small but
increasing amounts of dissolved copper are being generated.
The free acidity in the system remained low until 30 minutes and thereafter increased quickly.
Consequently the dominant iron hydrolysis product formed beforehand was hematite with small amounts
of basic iron sulphates. The formation of the basic iron sulphates, at least, are likely to be an artefact of the
washing (with water) and drying process given that iron sulphide minerals are still present in the residues;
in a similar manner small amounts of retgersite/nickel hexahydrite, Ni(SO4).6H2O, are formed from the
residual nickel sulphides.
221
As the free acidity increased rapidly after 30 minutes basic ferric sulphate was formed and for the
remainder of the reaction the system moved toward equilibrium as some of the hematite was dissolved and
basic ferric sulphate formed: the final hematite and basic ferric sulphate contents were 49% and 40%,
respectively. The low jarosite content of 6% was not significantly driven by the sodium content of the
process water which remains at around 3 g/L suggesting that the amount of co-precipitated aluminium is
also low. It is of interest to note when the Poseidon nickel concentrate was leached using an oxygen partial
pressure of 700 kPa, the rapid production of acid resulted in a final residue containing 42% hematite and
50% basic ferric sulphate. This system had also not reached equilibrium as the free acidity was still
increasing at the conclusion of the reaction consistent with the conversion of basic ferric sulphate to
hematite and release of sulphuric acid.
B
A
Poseidon nickel concentrate
Poseidon nickel concentrate

60
35
50
25
Mineral content (%)
Mineral content (%)
30
Pyrrhotite
Pyrite
20
Marcasite
Pentlandite
Violarite
15
Vaesite
10
40
Hematite
30
Basic ferric
sulphate
Jarosite
20
10
5
0
0
0
15
30
45
60
Leach time (min.)
75
90
15
30
45
60
Leach time (min.)
75
90
Figure 8 - Quantitative mineralogy of residues from the leaching of Poseidon nickel concentrate at 250oC
using a fixed oxygen addition rate of 11.5 g/min/kg concentrate: (A) sulfide minerals and (B)
iron-containing hydrolysis products
The reaction of the concentrate-laterite blend gave similar mineralogy to the concentrate system as
seen in Figure 9. Pyrrhotite was oxidised to pyrite and marcasite; pentlandite was oxidised to violarite and
vaesite with the violarite and pyrite being the most stable of the sulphides and therefore the last to leach.
Complete oxidation had occurred prior to collection of the 45 minute sample and, based upon oxygen flow
rates, was concluded in just under 40 minutes.
B
A
Poseidon nickel concentrate + Bulong laterite
Poseidon nickel concentrate + Bulong laterite

60
Pyrrhotite
Pyrite
Marcasite
Pentlandite
Violarite
Vaesite
Mineral content (%)
Mineral content (%)
50
6
Nontonite
40
Goethite
Clinochlore
30
Hematite
Basic ferric
sulphate
Jarosite
20
10
0
0
15
30
45
60
Leach time (min.)
75
90
15
30
45
60
Leach time (min.)
75
90
Figure 9 - Quantitative mineralogy of residues from leaching of Poseidon nickel concentrate (10.5% w/w)
with Bulong laterite (19.5% w/w) at 250oC using a fixed oxygen addition rate of 11.5 g/min/kg
concentrate: (A) sulfide minerals and (B) laterite minerals and iron-containing hydrolysis products
222
Leaching of the main nickel-containing minerals, goethite, nontronite and clinochlore indicated
slow but steady initial leaching of the clay minerals up until 30 minutes. This was confirmed by the
increasing dissolved magnesium content of the leach liquor, and although the nontronite content of the
residue was suggested to be increasing, this simply reflected the transformations of sulphide minerals in the
system along with the change in goethite content. The study of Smith and Kidd (1949) indicates that
goethite conversion to hematite in the presence of 0.1 M acid occurs at around 100oC over a period of
around 8 hours. Clearly this conversion will be faster at higher temperatures, which coupled with reducing
conditions could explain the rapid reduction in goethite relative to nontrontite content, given the latter is
expected to be more readily leached.
The main leaching of laterite minerals occurred after 30 minutes and was substantially complete
by 45 minutes. This corresponded with a sharp jump in hematite content however given that free acidity
was controlled by the leaching of the laterite minerals there was no basic ferric sulphate formation.
Compared to the nickel concentrate there was a somewhat greater amount of jarosite formed which given
the aluminium content of the laterite represented substantial co-precipitation of alunite. Here the material
precipitated before 45 minutes was iron-richer whereas that precipitated subsequently is aluminium-richer
and corresponded to a drop in aluminium concentration from 1160 mg/L to 430 mg/L. The decrease in
sodium concentration was from 3300 to 660 mg/L confirming its role in promoting the removal of
aluminium and stabilising the alunite/jarosite phase(s).
CONCLUSIONS
The present work constitutes a preliminary study to examine the feasibility of co-leaching blends
of nickel concentrate and laterite materials using low oxygen pressures. A mass flow controller/meter was
employed to control the rate of oxygen addition with rough control of the gas supply pressure used to set
the upper limit on the oxygen partial pressure in the system.
The leaching data indicated that at low oxygen partial pressures, estimated to be 250 kPa or less,
the oxidation of the nickel concentrate can be controlled to occur over a period of around 40 minutes with
completion of laterite leaching in just over an hour using a 30% w/w pulp of which 35% of the blend is
concentrate. Under these conditions nickel, cobalt and copper extractions were all around 98%.
Furthermore the rate of oxygen addition into the system corresponded to the rate at which oxygen was
consumed. When the amount of material added as concentrate was reduced to 23%, value metal extractions
of 93-95% resulted after 75 minutes. This is considered to be the lower concentrate to blend percentage
limit for acceptable metal extractions to be obtained from a 30% w/w pulp.
In the systems studied the ferrous iron (and other divalent metal ions) produced are expected to
precipitate in situ during the leaching of the concentrate and this was due to the low acid concentrations
encountered during the early stages of the reaction. Once the acid concentration rose sufficiently, the
ferrous iron dissolved, was rapidly oxidised and subsequently hydrolysed, also enabling the leaching of the
laterite ore to be completed.
Tests conducted using lower gas supply pressure and higher solids concentrations indicated that
oxygen mass transfer needs to be well controlled to ensure that low oxygen pressures can be employed to
allow leaching to occur on an acceptable time scale. Further work is required to optimise the system under
study.
Quantitative mineralogy indicated that components of the nickel concentrate undergo several
oxidative hydrothermal transformations during leaching. Pyrrhotite was transformed to pyrite and
marcasite while pentlandite was transformed to violarite and subsequently a cubic phase that has a mineral
composition somewhere between that of bravoite and vaesite. Chalcopyrite was also transformed to
covellite. The latter is known to be enhanced in chloride-containing systems and this may also explain why
the cubic nickel sulfide phase was detected. Exercising control over the concentrate to laterite ratio ensured
223
that optimum use of the sulphuric acid produced from the concentrate consistent with the estimate that
around 96% of the iron reported to hematite in the final residue.
ACKNOWLEDGEMENTS
The financial assistance of the Goldfields Esperance Development Commission (GEDC),
Poseidon Nickel and CSIRO Minerals Down Under is gratefully acknowledged for support of this project.
Members of the CSIRO analytical team, Milan Chovancek, Tuyen Pham, Bruno Latella and Peter Austin
are thanked for their assistance in providing analytical and XRD data.
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Copper
229
THE MECHANISM OF CHALCOPYRITE LEACHING IN ACIDIC FERRIC/FERROUS

SULFATE MEDIA IN THE PRESENCE OF SILVER-ENHANCED PYRITE
*G. Nazari1, D.G. Dixon2, D.B. Dreisinger2
1
Hatch
2800 Speakman Drive
Mississauga, Canada L5K 2R7
(*Corresponding author: GNazari@hatch.ca)
2

6350 Stores Road
ABSTRACT
The kinetics of chalcopyrite leaching in acidic ferric/ferrous sulfate media under atmospheric
conditions in the presence of pyrite has been investigated. It has been found that pyrite samples from
different sources affect the rate of chalcopyrite leaching differently. A strong correlation between the
amount of silver associated with the pyrite and its effectiveness has been noted. In this study, improvement
of the catalytic properties of pyrite such that all pyrite samples accelerate the rate of copper extraction
regardless of their sources is demonstrated, and a detailed discussion of the mechanisms involved in the
process of chalcopyrite leaching in the presence of silver-enhanced pyrite is presented.

Niagara, ON, Canada
Edited by
230
INTRODUCTION
It is well known that chalcopyrite resists leaching in sulfate media. It has been proved that pyrite
facilitates the leaching of chalcopyrite (Berry et al., 1978; Dixon et al., 2008; Mehta and Murr, 1983;
Muoz et al., 2008; Nowak et al., 1984, Tshilombo, 2004). Considering the catalytic effects of pyrite on
accelerating the kinetics of chalcopyrite leaching, Dixon and Tshilombo (2005) have developed a new
process, known as Galvanox, which has several advantages over other hydrometallurgical processes.
Galvanox runs under atmospheric conditions, so it requires only low-cost leaching tanks. The sulfur
yield at this temperature is high (>95%) which leads to low oxygen consumption and low sulfuric acid
generation. The operating temperature is below the melting point of sulfur which eliminates the use of
surfactants. This process also does not require fine grinding. Reaction 1 shows the overall leaching reaction
in the Galvanox process.
CuFeS2 + O2 + 2 H2SO4 = CuSO4 + FeSO4 + 2 S0 + 2 H2O
(1)
Complete copper recovery from the Galvanox process can be achieved at a considerably higher
rate than other atmospheric ferric sulfate leaching processes (Dixon et al., 2008). Recycling pyrite and
recovering copper from tailings with the Galvanox process have also been evaluated in continuous pilot
leaching campaigns (Dixon et al., 2007).
Recent studies of the Galvanox process have indicated that pyrite samples from different
sources may have different effects on the rate of chalcopyrite leaching (Nazari et al., 2011). Some pyrite
samples accelerate the leaching rate significantly, while others have less effect. A strong correlation has
been noted between the level of silver occurring in the pyrite samples and their effectiveness as catalysts
for chalcopyrite leaching. Recently, the Galvanox process has been improved such that all pyrite
samples accelerate the rate of copper extraction from chalcopyrite significantly. In this process, ground
samples of natural pyrite are pretreated with miniscule amounts of silver ion by soaking the ground pyrite
in a dilute solution of soluble silver salt such as silver nitrate before introducing the pyrite into the leaching
reactor. It was found that the addition of as little as 60 mg of Ag per kg of copper was sufficient to ensure
complete copper extraction within 10 to 15 hours of leaching (Nazari et al., 2011).
Several authors have reported the catalytic properties of silver to catalyze copper dissolution from
chalcopyrite in both chemical and biological leaching systems (Banerjee et al., 1990; Miller et al., 1981;
Price and Warren, 1986). Initially, Snell and Fords (1976) showed that copper extraction from chalcopyrite
increased in ferric sulfate solution by addition of silver as a soluble silver salt. In this work, it was claimed
that the solid residue contained over 90% of the silver. To recover the silver, it was proposed to separate
the elemental sulfur from the solid residue by aromatic liquid extraction to produce a tailings with less than
2% elemental sulfur and then to dissolve the silver using oxygen in a leaching solution containing 80%
sulfuric acid. This reaction occurs at temperatures between 95 and 110C (Snell and Fords, 1976).
Miller and Portillo (1979) proposed the first model to explain the catalytic effect of silver. Based
on this model, the enhanced rate of leaching is due to the formation of an intermediate Ag2S film which
forms on the chalcopyrite surface by an exchange reaction. They have suggested that, under these
conditions, the elemental sulfur forms a non-protective reaction product on the Ag2S crystallites, in
contrast to uncatalyzed ferric sulfate leaching, in which a dense elemental sulfur layer forms on the mineral
surface and acts as a diffusion barrier, thus delaying the oxidation of chalcopyrite by ferric ions. The
following reaction has been proposed for the silver-catalyzed leaching of chalcopyrite (Miller and Portillo,
1981):
CuFeS2 + 4 Ag+ 2 Ag2S(chalcopyrite surface) + Cu2+ + Fe2+
(2)
Ahonen and Tuovinen (1990) have shown that chalcopyrite behaves anodically in the CuFeS2Ag2S galvanic couple. Hence, the copper dissolution rate increases. In the presence of Fe3+, the silver
sulfide film is oxidized to Ag+ and S0:
Ag2S + 2 Fe3+ 2 Ag+ + 2 Fe2+ + S0
231
(3)
The rate of the reaction is controlled by the intermediate electrochemical reaction of the silver
sulfide film with ferric (reaction 3) since the first stage (reaction 2) occurs rapidly. According to a study
by Dutrizac (1994), silver sulfide does not dissolve in sulfate media significantly at temperatures lower
than 100C (Dutrizac, 1994). Increasing the ferric concentration enhances the dissolution of silver sulfide
and hence improves the catalytic effect of silver. However, this also leads to ferric sulfate hydrolysis, and
therefore to iron precipitation (jarosite formation) and sulfuric acid generation:
3 Fe2(SO4)3 + 14 H2O 2 (H3O)Fe3(SO4)2(OH)6 + 5 H2SO4
(4)
Silver is preferentially incorporated into the jarosite structure to form argentojarosite,

AgFe3(SO4)2(OH)6. Hence, silver is trapped in the jarosite structure and loses its activity as a catalyst.
This is one of the main drawbacks associated with silver-catalyzed leaching of chalcopyrite.
Along with reaction 2, in a study by Price and Warren (1986), the following reaction was
proposed to describe the reaction of dissolved silver with chalcopyrite:
CuFeS2 + 4 Ag+ 4 Ag0 + Cu2+ + Fe2+ + 2 S0
(5)
Price and Warren (1986) believed that a change in morphology or conductivity of the sulfur layer
due to the presence of metallic silver enhances the kinetics of chalcopyrite leaching.
At high temperature and high potential, silver sulfide is oxidized and silver ions are released into
solution and subsequently taken up by jarosite. Formation of jarosite increases with increasing temperature,
ferric concentration, and pH. Silver precipitation is rapid, and is complete before ferric precipitation
(Bolorunduro et al., 2003) which leads to the zoning of the silver-rich jarosite in the core of the jarosite. In
order to extract silver from jarosite, the leaching solution has to diffuse through the core of jarosite.
Silver is the most effective catalyst yet proposed for chalcopyrite leaching, but processes requiring
silver are expensive and would typically be avoided in practice, unless the ores themselves contained
sufficient silver (Hiroyoshi et al., 2002). Hence, in spite of extensive research, no commercial process has
been developed successfully which uses silver as a catalyst for copper recovery from chalcopyrite
concentrates (Ballester et al., 2007).
EXPERIMENTAL
Chalcopyrite Leaching
Chalcopyrite leaching experiments were conducted in ferric/ferrous sulfate media in the presence
of silver-enhanced pyrite or natural pyrite. Silver-enhanced pyrite was prepared and leaching experiments
were carried out according to the procedure reported in our previous studies (Nazari et al., 2011, 2012a).
Silver Sulfide Leaching
The silver sulfide formed during chalcopyrite leaching in the presence of silver-enhanced pyrite
was dissolved according to the following procedure. After complete copper extraction from copper
concentrate, the silver in the residue was leached in cupric chloride at pH 0 and 60C, where pH was
adjusted by addition of hydrochloric acid. The process was continued for 10 days.
Ag2S + 2 CuCl2 2 AgCl + Cu2Cl2 + S0
(6)
Then, the sample was filtered and rinsed with distilled water and the solid residue was collected.
The solid sample contained elemental sulfur and silver chloride. The solid residue was treated with sodium
232
thiosulfate to dissolve silver from silver chloride via formation of silver complex ions. However, an
important factor in thiosulfate stability is the pH of the solution. The solution pH was controlled with
sodium hydroxide within the stability region of thiosulfate (pH ~10). This experiment was conducted at
room temperature.
AgCl(s) + 2 Na2S2O32(aq) + S0(s) Na3Ag(S2O3)2(aq) + NaCl(aq) + S0(s)
(7)
The concentration of silver in solution was followed with Atomic Absorption Spectroscopy
(AAS). The dissolution of silver chloride in thiosulfate solution was stopped when the silver concentration
in the solution became constant. The dissolution reaction was complete in just a few minutes. Elemental
sulfur is the sole solid product in this reaction. The solid residue was collected and rinsed with distilled
water. The sample was dried at room temperature. The dried sample was coned and quartered to obtain a
representative sample for analysis. The sample was sent to Acme Labs (Vancouver, BC) for Induction
Coupled Plasma (ICP) analysis to confirm the complete dissolution of silver from sulfur.
Materials
In this study, a copper concentrate containing 27% copper and three different pyrite samples
containing 97.6%, 70.8%, and 98.7% pyrite were used. To obtain the elemental compositions of the
minerals, representative samples were sent to Acme Labs (Vancouver, BC) for Induction Coupled Plasma
(ICP) analysis. The mineralogical compositions of minerals were obtained by quantitative Rietveld X-Ray
Diffraction (XRD) analysis. Mineralogical and elemental compositions of the copper concentrate and the
pyrite sample are summarized in Table 1 and 2, respectively.
Table 1 Rietveld XRD analysis of copper concentrate and pyrite samples
Mineral
Ideal Formula
Copper
Conc (%)
Pyrite #1
(%)
Pyrite #2
(%)
Pyrite #3
(%)
Pyrite
FeS2
15.9
97.6
70.8
98.7
Chalcopyrite
CuFeS2
78
4.0
SiO2
0.6
1.9
0.3
K(Mg,Fe )3AlSi3O10(OH)2
1.8
0.4
Quartz
Biotite
2+
Dolomite
CaMg(CO3)2
1.1
12.2
Plagioclase
NaAlSi3O8 CaAl2Si2O8
2.2
Anhydrite
CaSO4
1.8
Gypsum
CaSO4.2H2O
3.4
0.5
Calcite
CaCO3
0.1
Fe1-xS
2.1
Clinochlore
(Mg,Fe )5Al(Si3Al)O10(OH)8
2.2
Muscovite
KAl2AlSi3O10(OH)2
3.4
Pyrrhotite
2+
233
Table 2 Elemental analysis of copper concentrate and pyrite samples

Element
Copper Conc
Pyrite #1
Pyrite #2
Pyrite #3
Cu
27.00 %
0.13 %
1.8 %
11 ppm
Fe
31.14 %
45.43 %
38.02 %
45.94 %
36.70 %
52.62 %
45.3 %
52.75 %
Mg
0.27 %
0.04 %
1.88 %
< 0.01 %
Co
0.16 %
68 ppm
Pb
0.14 %
48 ppm
< 2 ppm
As
130 ppm
49 ppm
8 ppm
Ag
15.5 ppm
21 ppm
2 ppm
0.4 ppm
Ca
0.47 %
0.56 %
4.05 %
0.16 %
Al
0.51 %
0.02 %
0.41 %
0.08 %
Zn
0.01 %
441 ppm
6 ppm
Si
1.14 %
0.28 %
1.18 %
0.14 %
Results and Discussion

The first test was conducted to observe the rate of copper extraction in ferric sulfate solution at
470 mV (vs Ag/AgCl) in the absence of added pyrite. Figure 1 indicates very slow kinetics and incomplete
copper extraction under these conditions. Under these conditions, only 42% copper extraction was
achieved after 90 hours and leaching proceeded very slowly.
100%
Copper Extraction
80%
60%
40%
20%
0%
0
10
20
30
40
50
Time (h)
60
70
80
90
Figure 1 Chalcopyrite leaching in ferric sulfate media at a potential set point of 470 mV and 80C
The first series of tests was conducted to investigate the effect of adding pyrite from three
different sources in order to obtain a broader understanding of their catalytic properties. The results are
shown in Figure 2 and indicate the catalytic properties of pyrite in accelerating the rate of copper
extraction. Although the kinetics of chalcopyrite leaching increases in the presence of natural pyrite, a long
time is still required for complete copper extraction. These tests were then repeated, but with the addition
234
of silver at a silver-to-pyrite ratio of 100 ppm. The results shown in Figure 2 indicate a significant increase
in copper leaching kinetics. These results also indicate that, in spite of major differences in the catalytic
properties of natural pyrite from different sources, all three silver-enhanced pyrite samples have an
identical catalytic effect on chalcopyrite leaching. Due to this similarity, Pyrite #1 was used in all the
experiments discussed below. Figure 2 reveals the significant improvement on the kinetics of copper
extraction in the presence of silver-enhanced pyrite.
100%
80%
Copper Extraction
Pyrite #1, Ag/Py = 100 ppm

60%
Pyrite #1
Pyrite #2
Pyrite #3
40%
20%
0%
0
20
40
60
80
100
Time (h)
Figure 2 Comparison of natural pyrite and silver-enhanced pyrite at a potential set point of 470 mV, 10
g/L Cu concentrate, and 80C
The effects of several variables such as mass ratio of silver-enhanced pyrite to chalcopyrite,
concentration of silver on pyrite, solution potential, and pulp density on the kinetics of copper recovery
from chalcopyrite using silver-enhanced pyrite were investigated and optimum conditions were determined
(Nazari et al., 2011). It was shown that the silver-enhanced pyrite can be also successfully recycled, and
that the addition of as little as 60 mg Ag per kg contained Cu is sufficient to ensure complete copper
extraction within 10 to 15 hours of leaching.
100%
Copper Extraction
80%
60%
40%
20%
Py/Cp = 2, Ag/Py = 100 ppm, E = 450 mV, Fresh Py

Py/Cp = 2, Ag/Py = 100 ppm, E = 450 mV, 1st Py Recycle
Py/Cp = 2, Ag/Py = 100 ppm, E = 450 mV, 2nd Py Recycle
0%
0
10
Time (h)
Figure 3 Effect of higher pulp density at a constant pyrite-to-chalcopyrite ratio of 2, an initial silver-topyrite ratio of 100 ppm, a potential set point of 450 mV, at 70 g/L Cu concentrate, and 80C
235
In this study, a model was proposed to explain the role of silver-enhanced pyrite on accelerating
the rate of chalcopyrite oxidation in the Galvanox process. In this model, rapid and complete copper
extraction was attributed to the galvanic interaction between pyrite and chalcopyrite. Pyrite has the highest
rest potential of all common sulfide minerals (Majima, 1969). The rest potential of pyrite is considerably
higher than that of chalcopyrite. In the presence of pyrite and chalcopyrite in the leaching slurry, the
surface of pyrite particles acts as a cathode whereas the chalcopyrite surface acts as both anode and
cathode. Due to the increase of the cathodic surface area, the electron consumption through ferric/ferrous
reduction increases. Since the anodic surface area is not affected in the presence or absence of pyrite, the
rate of chalcopyrite oxidation must increase to compensate for the increased rate of ferric reduction. Hence,
the rate of copper extraction increases.
However, an important factor in any galvanic process is an electrical contact between the couple
to ensure the transport of electrons from one mineral (anode) to the other (cathode). Pyrite and chalcopyrite
are both semiconductors. Hence, in the Galvanox process, at the beginning of the leaching process, when
pyrite and chalcopyrite are in contact in the leaching slurry, galvanic interaction can occur. As chalcopyrite
leaching continues, a sulfur layer forms around the chalcopyrite surface. The morphology of chalcopyrite
residue has been shown in previous studies confirming the formation of this layer around chalcopyrite
(Nazari et al., 2012a; Viramontes-Gamboa et al., 2007). This sulfur layer has extremely low conductivity
which does not allow the transport of electrons. Hence, pyrite and chalcopyrite are no longer in electrical
contact. Since the overall reaction rate is limited by electron transfer through the non-conductive sulfur
layer, a modification of this layer is required in order to accelerate the rate of leaching.
During the Galvanox process, in the presence of silver-enhanced pyrite, it has been shown that
a very small amount of silver slowly dissolves in the ferric sulfate leaching solution and reacts with the
sulfur around chalcopyrite to form silver sulfide. The presence of silver sulfide in the sulfur residue was
confirmed in our previous study (Nazari et al., 2012b).
In this study, it is hypothesized that even a very miniscule amount of silver sulfide decreases the
resistivity of the sulfur layer significantly. Although the amount of silver sulfide is very low and the sulfur
layer does not become very conductive, it does become conductive enough to allow the transport of
electrons at a rate sufficient to support the leaching reactions. With a conductive path between pyrite and
chalcopyrite, the galvanic interaction between these minerals can now occur.
In order to better understand the role of pyrite and chalcopyrite as a galvanic couple and the role
of silver in increasing the conductivity of the elemental sulfur layer, the following series of experiments
was designed.
Copper concentrate was sieved through a No. 270 mesh (53 m) screen, and only the portion that
passed through the sieve was used in this study. Similarly, the pyrite sample was sieved through No. 45
(354 m) and No. 60 (250 m) mesh screens. Only the portion with particles larger than 250 m and
smaller than 354 m was used.
The first test was run using natural pyrite at a pyrite-to-chalcopyrite ratio of 2. Copper extraction
was complete after 200 hours. The second test was run under identical conditions, but the pyrite was
pretreated with silver to a ratio of 100 ppm. Under these conditions, copper extraction was complete after
27 hours. Tests were then performed where the leaching was stopped after 1 hour, 5 hours, and 10 hours.
After stopping the experiment, pyrite and chalcopyrite in the leach residues were separated by screening.
Since the pyrite particles were considerably larger than the chalcopyrite particles, they could be separated
easily using a No. 270 (53 m) mesh screen. Next, the copper concentrate was divided into two parts; one
part was leached in the absence of pyrite and the other part was leached in the presence of natural (nonenhanced) pyrite. The results are shown in Figure 4.
236
100%
Copper Extraction
80%
60%
40%
Ag/Py =100 ppm (Enhanced pyrite), C1

Ag/Py =100 ppm; After 10 hours: Non-enhanced pyrite, C2
Ag/Py =100 ppm; After 10 hours: No pyrite, C3
Ag/Py =100 ppm; After 5 hours: Non-enhanced pyrite, C4
Ag/Py =100 ppm; After 5 hours: No pyrite, C5
Ag/Py =100 ppm; After 1 hour: Non-enhanced pyrite, C6
Ag/Py =100 ppm; After 1 hour: No pyrite, C7
Ag/Py = 0 (Non-enhanced pyrite), C8
20%
0%
0
50
100
150
200
Time (h)
Figure 4 Chalcopyrite leaching in the presence of non-enhanced pyrite and the absence of pyrite upon
pyrite removal after 1, 5, and 10 h at an initial pyrite-to-chalcopyrite ratio of 2 and a potential set point of
450 mV and 80C
In the presence of natural pyrite (C8), complete copper extraction was achieved, although a long
retention time was required. Upon addition of silver-enhanced pyrite (C1), the rate of chalcopyrite leaching
increased and the required leach time decreased roughly by a factor of 8, from 200 to 27 hours.
Upon removing the silver-enhanced pyrite after 1 hour (C7) and 5 hours (C5), the rate of copper
extraction decreased significantly. These results indicate that the 10% loss of silver from silver-enhanced
pyrite does not occur immediately upon introducing the pyrite to the leach slurry. If the pyrite were to lose
that 10% silver at the beginning of the experiment, one would expect to observe similar kinetics in those
tests that were continued with no pyrite after 1 hour (C7), 5 hours (C5), and 10 hours (C3), because the
same amount of silver would have reacted with the chalcopyrite in each case, and therefore would have
catalyzed its oxidation at the same rate. However, Figure 4 clearly shows that the reaction was much faster
in the absence of pyrite when the pyrite was removed after 10 hours (C3). In this experiment, complete
copper extraction was obtained after 170 hours, whereas, in those experiments where pyrite was removed
after only 1 (C7) and 5 hours (C5), copper extraction proceeded extremely slowly.
When the silver-enhanced pyrite was removed after 10 hours, copper extraction continued rapidly
in the presence of non-enhanced pyrite (C2). However, rapid copper extraction was not observed in the
experiments where silver-enhanced pyrite was replaced with non-enhanced pyrite after 1 hour (C6) and 5
hours (C4). This observation is attributed to the formation of silver sulfide particles dispersed in the sulfur
layer. As mentioned above, it is hypothesized that the formation of silver sulfide increases the conductivity
of elemental sulfur, significantly. This layer may allow the transport of electrons from chalcopyrite either
directly to ferric ions or to pyrite. Therefore, under these conditions, even in the presence of non-enhanced
pyrite, the copper extraction proceeds rapidly. In the other two experiments, copper extractions of 12% and
28% were obtained after 1 hour (C6) and 5 hours (C4), respectively. Therefore, the thickness of the
conductive sulfur layer at that point was insufficient to ensure the transport of electrons to the end of the
process. Consequently, in these experiments, rapid leaching was not observed.
It is also important to note that, upon removing the silver-enhanced pyrite from the system and
substituting it with the natural pyrite (C2, C4, and C6), the leaching rates decreased immediately. This
abrupt decrease in the rates cannot be due to a change in the conductivity of the sulfur layer, since copper
extraction did not proceed very rapidly and the thickness of the sulfur layer did not vary significantly in the
next few hours after silver-enhanced removal. This observation is attributed rather to the catalytic
properties of pyrite. In order to evaluate the catalytic properties of pyrite, the rates of ferric reduction on
237
silver-enhanced pyrite and natural pyrite were measured and compared. The reduction of ferric ions was
studied at potentials lower than the rest potential of pyrite. The effect of the applied potential on the rate of
ferric reduction on natural (non-enhanced) and silver-enhanced pyrite is shown in Figure 5.
0.50
0.49
Potential (V) vs. Ag/AgCl
0.48
0.47
0.46
0.45
0.44
0.43
0.42
Silver-enhanced pyrite, 100 ppm
0.41
Natural (non-enhanced) pyrite
0.40
-5.5
-5
-4.5
-4
-3.5
-3
-2.5
-2
Log i (A/cm2)
Figure 5 Reduction of ferric on silver-enhanced pyrite and natural pyrite

Figure 5 shows the potentiodynamic curves at the scan rate of 1 mV s1 starting from the rest
potential of pyrite to 300 mV vs OCP. This figure clearly shows that the rate of ferric reduction on silverenhanced pyrite is faster than the rate on natural (non-enhanced) pyrite, by roughly a factor of 2.
The results shown above indicate the critical role of both silver and pyrite on the kinetics of
chalcopyrite leaching. In order to prove our hypothesis regarding the galvanic interaction between pyrite
and chalcopyrite, it was also important to measure the resistivity of the sulfur in both the presence and
absence of silver in the process.
To measure this resistivity, chalcopyrite was first leached completely in the presence of silverenhanced pyrite at a pyrite-to-chalcopyrite ratio of 2 and a silver-to-pyrite ratio of 100 ppm. Pyrite particles
in the range of 125-150 m and copper concentrate particles in the range of 30 to 53 m were used. After
complete copper extraction, pyrite and chalcopyrite residue (sulfur) were separated using a 53 m sieve. A
very small proportion of pyrite also passed through the 53 m sieve due to pyrite attrition during the
leaching process. Ultimately, the elemental sulfur and pyrite in the residue were separated using an
elutriation column. The sulfur residue was divided into two parts. Any silver sulfide formed during
leaching was leached from one part of this residue according to the procedure explained earlier. Finally,
1 g from each part of the sulfur residue was pressed into a pellet and the conductivity values of the two
pellets were measured according to the procedure described in our previous study (Nazari et al., 2012c).
The results are shown in Table 3.
Table 3 The resistivity values of sulfur residues in the presence and absence of silver sulfide
Sample ID
Sulfur with silver
Sulfur without silver
Resistivity (-cm)
1.06 0.10107
8.05 0.151010
Table 3 shows that the resistivity of the product sulfur without silver is about 3 orders of
magnitude higher than that of the sulfur with silver. This limits the electrical contact between pyrite and
unleached chalcopyrite. The galvanic interaction between the couple can be maintained by decreasing the
238
resistivity of the product layer. The results shown in Table 3 indicate that the resistivity of the sulfur layer
in the presence of minuscule amounts of silver is considerably lower.
The results shown above prove the hypothesis regarding the galvanic interaction between pyrite
and chalcopyrite, and the important role of both pyrite and silver in that interaction. The main role of silver
is to decrease the resistivity of the elemental sulfur layer and to enhance the catalytic properties of pyrite,
while the role of pyrite is to provide additional surface for ferric reduction. There are two critical factors to
ensure the galvanic interaction between two minerals. One is an electrical connection between the two
minerals, and the other is additional cathodic surface area. Under identical conditions, slower kinetics
observed during silver-catalyzed leaching compared to Galvanox leaching with silver-enhanced pyrite
can be attributed to the absence of a the cathodic pyrite surface in the former.
CONCLUSIONS
In this study, a model was proposed to explain the mechanism of silver-enhanced pyrite catalyzed
leaching of chalcopyrite in ferric sulfate media. The rapid rate of chalcopyrite leaching in the Galvanox
process has been attributed to the galvanic interaction between pyrite and chalcopyrite. Pyrite under the
conditions of the Galvanox process is inert and acts as a cathode. Pyrite thus facilitates the cathodic
reduction of ferric to ferrous. Acceleration of the reduction rate also increases the rate of oxidation as
charge neutrality must be maintained. In this study, it has been shown that in the process of silverenhanced pyrite catalyzed leaching, the catalytic properties of pyrite are enhanced in the presence of silver
and the rate of ferric reduction on silver-enhanced pyrite is considerably faster than this rate on natural
pyrite.
As chalcopyrite oxidation proceeds, sulfur layers of extremely high electrical resistivity form
around chalcopyrite particles. The formation of this layer limits the transport of electrons from chalcopyrite
to pyrite and inhibits the galvanic interaction between these two minerals. However, it has been shown that
in the presence of silver-enhanced pyrite, small amounts of silver leave the pyrite surface and react with the
sulfur product layer. Although the resulting silver level in the sulfur layer is very low, the resistivity of this
layer decreases by several orders of magnitude, thus facilitating electron transfer.
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Banerjee, P.C., Chakrabarti, B.K., Bhattacharyya, S., Das, A. 1990. Silver-catalyzed hydrometallurgical
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Hiroyoshi, N., Arai, M., Miki, H., Tsunekawa, M., Hirajima, T. 2002. A new reaction model for the
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Metallurgical Quarterly 8, 269282.
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Miller, J.D., McDonough, P.J., Portillo, H.Q. 1981. Electrochemistry in silver catalyzed ferric sulfate
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Hydrometallurgical Systems (Editor: Kuhn, M.C.), SME-AIME, New York, 327338.
Muoz, J.A., Dreisinger, D.B., Cooper, W.C., Young, S.K. 2008. Interaction of silver ions with sulphide
minerals with special emphasis on the chalcopyrite/pyrite galvanic couple. Canadian
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Nazari, G., Dixon, D.G., Dreisinger, D.B. 2011. Enhancing the kinetics of chalcopyrite leaching in the
Galvanox process. Hydrometallurgy 105, 251258.
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chalcopyrite: Comparative study between electrochemical and leaching responses. Journal of
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and microbial leaching solutions. PhD Thesis, The University of British Columbia, Vancouver,
BC, Canada.
241
REDUCTION KINETICS OF Fe(III) ON CHALCOPYRITE UP TO 110 C

*G.K. Yue1, E. Asselin1
1
Department of Materials Engineering, The University of British Columbia

309-6350 Stores Road
Vancouver, BC, Canada V6T 1Z4
(*Corresponding author: gkyue@interchange.ubc.ca)
ABSTRACT
In the present study, electrochemical measurements, especially cathodic potentiodynamic

polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the
kinetics of ferric reduction on chalcopyrite in aqueous Fe(II)-Fe(III)-H2SO4 solution at 90 C and 110 C.
Results from the calculation of speciation in the above solution reveal that, at both 90 C and 110 C, the
real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible
potential of the ferric/ferrous couple. Exchange current densities of the ferric/ferrous couple were obtained
and are on the order of 10-6-10-5A/cm2 at 90 C and 10-7-10-6A/cm2 at 110 C, respectively. The Tafel
slopes from the CPP method are higher than those from the CPC method at both 90 C and 110 C. The
transfer coefficients were about 0.36-0.59 at 90 C and 0.37-0.65 at 110 C. Based on the exchange current
densities obtained, the rate constant kc was calculated. It was found that kc at 90 C was slightly larger than
at 110 C, especially for the results obtained by the CPC method. The average rate constants are 862.17
cm/s for CPC and 65.30 cm/s for CPP at 90 C, and 477.69 cm/s for CPC and 63.53 cm/s for CPP at
110 C for nominal Fe3+/Fe2+ ratios ranging from 1:1 to 1000:1.

Niagara, ON, Canada
Edited by
242
INTRODUCTION
Chalcopyrite is one of the most abundant copper-bearing minerals, accounting for approximately
70% of the worlds known copper reserves (Wang, 2005). Most of the currently proposed leaching
processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Some of these
processes have been piloted in attempts to implement these technologies on an industrial scale, such as
Activox (U.S. 5,232,491, 1993), Nenatech (U.S. 5,993,635, 1999), Dynatec (U.S. 5,730,776, 1998),
AAC/UBC (U.S. 6,503,293, 2003), Total Pressure Oxidation (U.S. 5,698,170, 1997), CESL (U.S.
5,874,055, 1999) and Galvanox (U.S. 7,846,233, 2010).
To date, much effort has been devoted to understanding the kinetics and mechanisms of the
oxidative processes (Biegler & Horne, 1985; Crdoba, Muoz, Blzquez, Gonzlez, & Ballester, 2008,
2009; Ghahremaninezhad, Asselin, & Dixon, 2010; Hirato, Majima, & Awakura, 1987; Hiroyoshi,
Kuroiwa, Miki, Tsunekawa, & Hirajima, 2004; Warren, Wadsworth, & El-raghy, 1982) or the cathode
reduction reactions of chalcopyrite itself (Arce & Gonzlez, 2002; Biegler & Swift, 1976; Biegler, 1977;
Nava, Gonzlez, Leinen, & Ramos-Barrado, 2008), by chemical or electrochemical methods. However, as
the most important cathodic processes in chalcopyrite leaching systems, the cathodic reductions of ferric
ions or dissolved oxygen are worth measuring due to their effects on the overall leaching rate, as predicted
by mixed potential theory.
Some research has shown that the Fe3+/Fe2+ couple, indeed most redox couples, are much less
reversible on corroding or polarized chalcopyrite than on pyrite, platinum or freshly polished chalcopyrite
(Mcmillan, Mackinnon, & Dutrizac, 1982; Parker, Paul, & Power, 1981; Tshilombo, Petersen, & Dixon,
2002). Some investigators have assumed that it is the cathodic half-cell reaction (i.e. ferric reduction) that
limits the overall rate of leaching (Dixon, Mayne, & Baxter, 2008). It is generally accepted that the
reaction rate of the ferric/ferrous couple on chalcopyrite is much slower than that on platinum or pyrite, for
example (McMillan, Mackinnon, & Dutrizac, 1982; Parker, Paul, & Power, 1981). However, there is a lack
of published reports describing just how slow this reaction rate may be.
Our previous investigation (Yue & Asselin, 2012) studied the kinetics of ferric reduction on
chalcopyrite in in aqueous Fe(II)-Fe(III)-H2SO4 solution at 25 C and 70 C by cathodic potentiodynamic
polarization (CPC) and cyclic potentiodynamic polarization (CPP). Results from the calculation of
speciation in these solutions revealed that, at both 25 C and 70 C, the real Fe3+/Fe2+ ratio is much lower
than the nominal ratio, which leads to smaller values of the reversible potential for the ferric/ferrous couple
based on the Nernst equation. Exchange current densities of the ferric/ferrous couple with different
nominal Fe3+/Fe2+ ratios were obtained by extrapolating the cathodic linear Tafel line to the reversible
potential and are on the order of 10-7-10-6A/cm2 at 25 C and 10-6-10-5A/cm2 at 70 C, respectively. The
transfer coefficients were about 0.35-0.38 at 25 C and 0.35-0.45 at 70 C. Polarization plots obtained via.
CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 C and at 70 C. Based
on the obtained exchange current densities, the rate constant kc was calculated and is on the order of 10-1
cm/s at 25 C and 101 cm/s at 70 C.
The present work continues to explore the possibility of obtaining fundamental electrochemical
kinetic parameters for the important cathodic ferric reduction reaction on chalcopyrite in industrially
relevant leaching systems at temperatures from 90 C to 110 C. Exchange current densities, transfer
coefficients and rate constants, have been calculated to obtain detailed information about the
electrochemical processes involved.
EXPERIMENTAL
Electrode Preparation and Characterization
The chalcopyrite used in this investigation was obtained as massive mineral samples from the
Creighton Mine (Sudbury, Ontario). The quantitative phase analysis of the chalcopyrite ore was
243
determined using the Rietveld method and X-ray powder diffraction, and the result is shown in Table 1.
The material was of high quality, with a purity of 97.5% (mass percentage) and few impurities. Massive
electrodes were prepared by cutting the bulk chalcopyrite into approximately cubic shaped pieces with an
area of 1 cm2 exposed to the solution. The electrical contact between a copper wire and the sample was
made at the back of the sample, with silver conductive epoxy (MG Chemicals) for the experiments at 90 C
and electrically & thermally conductive adhesive (1700oF, AREMCO Products Inc) for the experiments at
110 C. The whole assembly was protected from the solution by mounting it in epoxy resin (cold cure),
leaving only one face of the electrode exposed to the solution. Before each test, working electrodes were
mechanically polished with no. 1200 grinding paper (silicon carbide, LECO) on a polishing wheel to begin
each experiment with a fresh surface. The surface was examined under an Optical Microscope (OM) before
each experiment to verify that no inclusion/significant cracks or voids existed.
Table 1 Results of quantitative phase analysis (wt.%)
Mineral
Ideal Formula
Sample Chalcopyrite
Chalcopyrite
CuFeS2
97.5
Pyrrhotite
Fe1-xS
1.7
Mackinawite ?
Fe9S8
0.8
Total
100.0
Electrolyte Preparation
Deionized water, sulfuric acid (H2SO4, 95.0-98.0%, Fisher Scientific Canada), Iron(III) sulfate
pentahydrate (Fe2(SO4)35H2O, 97%, Acros), Iron(II) sulfate heptahydrate (FeSO47H2O, 99+% for
analysis ACS, Acros) were used to prepare the desired electrolyte. Prior to each test, fresh solution was
prepared, with the concentration of H2SO4 and ferric ion being 30g/L and 10g/L, respectively. The ferrous
ion concentration was determined by the various nominal molar ratios of ferric to ferrous (1:1, 10:1, 100:1,
1000:1).
Electrochemical Measurements at 90 C
Electrochemical experiments were carried out using a standard three-electrode cell with a
thermostated water jacket, with graphite as a counter electrode (CE) and the prepared chalcopyrite
electrode as the working electrode (WE). A saturated Ag/AgCl electrode (saturated with potassium
chloride, Accumet* Glass Body, Fisher Scientific) was used as a reference electrode (RE). All potentials
have been converted from Ag/AgCl at 298 K to the saturated hydrogen electrode (SHE), i.e. ESHE (mV) =
EAg/AgCl + 197 mV. All further potentials in this study are quoted with respect to the SHE at 25 C unless
otherwise stated. The reference electrode was connected to a Luggin capillary to minimize IR drop. The
cell solution was slowly heated to the predetermined temperature by the circulating water from a ColeParmer Polystat Heated Circulating Bath with Analog Control, and kept at the constant temperature with an
accuracy 1 C.
Prior to use, the working electrode and counter electrode were immersed in ethanol for degreasing,
rinsed with deionized water, and finally dried with cool air. The electrode was immersed in the solution for
30 minutes to stabilize the potential before starting the measurements in order to ensure reproducibility.
All of the experiments were conducted under a predetermined experimental temperature, at 90 C.
The test solution was deaerated by sparging high-purity N2 prior to- and throughout the electrochemical
experiments at a constant flow rate to eliminate the effect of dissolved oxygen. The cell off-gas, after
244
passing through an Allihn condenser, was introduced into another container containing deionized water and
finally discharged to the fumehood. At first, the open circuit potentials (OCP) of the samples were recorded
for 30 min to yield a steady-state potential, and then potentiodynamic polarization curves were obtained.
Two types of experiments were performed: (1) cathodic potentiodynamic polarization curves (CPC) were
generated by changing the electrode potential automatically from OCP to -700 mV (vs. OCP) at a scan rate
of 0.5 mV/s; (2) cyclic potentiodynamic polarization (CPP) was started at 203 mV (vs. Ag/AgCl) by
scanning at a rate of 0.5 mV/s towards more positive potentials up to 653 mV (vs. Ag/AgCl), at which
value the potential scan was reversed and returned to where the polarization began.
The exchange current density, i0, is obtained from the curves using the intersection of the cathodic
linear extrapolation and the reversible potential of the ferric/ferrous couple.
Electrochemical measurements were performed using a Potentiostat/Galvanostat VersaSTAT 3F
Electrochemical System with an optional frequency response analyzer contained in a single unit, controlled
by the VersaStudio electrochemistry software package (Princeton Applied Research).
Electrochemical Measurements at 110 C
A 5100 low pressure reactor from Parr Instrument Company, with a 600 mL glass cylinder and
4848 reactor controller, was used for the electrochemical experiments at 110 C. A Pt-Nb electrode from
Cortest Inc was used as a counter electrode (CE) and the prepared chalcopyrite electrode as the working
electrode (WE). An external pressure balanced Ag/AgCl reference electrode with a double-porous junction
(filled with 0.1m/kg potassium chloride, Cortest Inc) was used and it was maintained at room temperature.
All potentials measured against Cortests external Ag/AgCl electrode filled with 0.1m/kg KCl have been
converted to the SHE, i.e. ESHE (mV, 110 C) = EAg/AgCl (observed potentials against the external Ag/AgCl
electrode) + 196 mV. The cooling loops and the magnetic drives were removed from the three port holes in
the head of the 5100 Reactor, in order to provide the space for the working electrode, counter electrode and
reference electrode which were installed to the head by Swagelok 316 stainless steel fittings.
Prior to use, the working electrode and counter electrode were immersed in ethanol for degreasing,
rinsed with deionized water, and finally dried with cool air. The electrode was immersed in the solution for
20 minutes to stabilize the potential before starting the measurements in order to ensure reproducibility. All
of the experiments were conducted under a predetermined experimental temperature, at 110 C. The test
solution was deaerated by sparging high-purity N2 prior to the electrochemical experiments at a constant
flow rate to eliminate the effect of dissolved oxygen. At first, the open circuit potentials (OCP) of the
samples were recorded for about 10-12 minutes to yield a steady-state potential, and then potentiodynamic
polarization curves were obtained. Two types of experiments were performed: (1) cathodic
potentiodynamic polarization curves (CPC) were made by changing the electrode potential automatically
from OCP to -700 mV (vs. OCP) at a scanning rate of 0.5 mV/s; (2) cyclic potentiodynamic polarization
(CPP) was started at about 204 mV (vs. the external Ag/AgCl electrode) by scanning at a rate of 0.5 mV/s
towards more positive potentials up to about 654 mV (vs. the external Ag/AgCl electrode), at which value
the potential scan was reversed and returned to where the polarization began.
Calculation of the Real Ferric/Ferrous Ratio in the Solution
To calculate the reversible potential of the ferric/ferrous couple, the concentrations of free ferric
and ferrous ions are required to use the Nernst equation. Over the last few decades, a lot of effort has been
made to predict the redox potential in aqueous Fe(II)-Fe(III)-H2SO4 solutions as a function of the initial
amounts of iron, acidity, and temperature (Casas, Crisstomo, & Cifuentes, 2005; Dry & Bryson, 1988;
Stipp, 1990). The most important species published in previous studies on the thermodynamics of this
system were taken into account to quantify the concentrations of five free ions and four complexes
involved as a function of temperature and the nominal molar ratio of ferric to ferrous. Fe(SO4)2- was
245
discarded in this study according to a report from the literature that at low pH values its concentration was
negligible (Dry & Bryson, 1988). This set was found to be the best to predict the experimental results.
Table 2 presents these species with their corresponding thermodynamic data, formation reactions and
equilibrium constants at various temperatures.
The thermodynamic data at 298 K (G0 and S0) for H+, Fe2+, Fe3+, SO42- and HSO4-, and the
equilibrium constants for HSO4- and the four iron complexes at 25 C and 35 C were taken from the
literature (Bard, Parsons, & Jordan, 1985; Cifuentes, Casas, & Simpson, 2006).
The G0 of the four iron complexes were calculated from the equilibrium constants at 25 C: first,
the G of the formation reaction was calculated using the equation G0 = -2.303RTLog Kf0; then, the G0
of the single iron complex can be estimated based on the calculated G0 of the formation reaction and the
known G0 for the remaining single species.
0
To calculate S0 of the four iron complexes, the enthalpy change H0 of the formation reactions
were calculated using the vant Hoff equation and the equilibrium constants at 25 C and 35 C. Then, the
entropy change S0 of the formation reactions were calculated according to the equation G0 = H0 -T S0.
Finally, the S0 for the single iron complex can be estimated based on the calculated entropy change S0 of
the formation reaction and the known S0 for the remaining single species.
Prior to calculating the speciation, to obtain the equilibrium constants for HSO4- and the four iron
complexes at 90 C and 110 C, models based on the Lewis formulation of the Criss-Cobble
correspondence principle (Lewis, 1970) were used to predict G0 of the main species in the solution. In
addition, because there is a lack of thermodynamic data at high temperatures in the literature for the neutral
species FeSO4, the average molal ionic heat capacity at high temperatures was estimated by using the
average heat capacity constants of simple cations and simple anions. It was found that this method gave
very reasonable equilibrium constant estimations. The calculated equilibrium constants at 90 C and
110 C are also listed in Table 2.
Table 2 Thermodynamic data and equilibrium (standard formation) constants for the main species
in aqueous Fe(II)-Fe(III)-H2SO4 solutions in the range of 25-110 C
Species
+
Log Kf0
Log Kf0
Log Kf0
Log Kf0
25 C
35 C
90 C
110 C
1.98
2.12
2.96
3.31
0.00
-744.63
20.10
-756.01
131.80
-91.20
-107.10
-841.99
134.19
Fe2+ + H+ + SO42- FeHSO4+
1.08
1.42
3.09
3.62
-848.67
3.26
Fe + SO4 FeSO4
2.25
2.33
2.80
2.98
-16.70
-280.30
-775.48
34.97
Fe3+ + H+ + SO42- FeHSO42+
2.48
2.90
4.89
5.50
-5.93
Fe + SO4 FeSO4
4.04
4.34
5.92
6.46
2+
FeHSO4
FeSO4
Fe
Species and Formation Reactions
0.00
HSO4
Fe
S0
(J/mol K)
2-
SO4
G0
(kJ/mol)
3+
FeHSO4
FeSO4
2+
-784.38
H+ + SO42- HSO4-
2+
3+
2-
2-
Five chemical equilibrium equations based on the above formation reactions, and additional four
component mass balance equations in terms of H+, Fe2+, Fe3+ and SO42-, were obtained and these nine nonlinear equations were solved using the Newton-Raphson technique in Matlab software.
Concentration of Species, mol/L
Concentration of Species, mol/L
246
(a)
0.1
H+
SO42HSO4-
0.01
Fe2+
FeHSO4+
FeSO40
3+
FeSO4
H+
SO42HSO4-
0.01
Fe2+
FeHSO4+
FeSO40
Fe3+
FeHSO42+
FeSO4+
1E-4
1E-4
1E-5
(b)
0.1
1E-3
Fe
FeHSO42+
1E-3
10
100
[Fe ]/[Fe2+]
1000
10000
1E-5
10
3+
100
[Fe3+]/[Fe2+]
1000
10000
Figure 1 Aqueous speciation for Fe(II)-Fe(III)-H2SO4 solutions at [H2SO4] = 30 g/L and [Fe3+]total = 10
g/L with different nominal molar ratios of ferric to ferrous: (a) at 90 C; (b) at 110 C
The results of the aqueous speciation for Fe(II)-Fe(III)-H2SO4 solutions with different nominal
Fe3+/Fe2+ ratios at 90 C and 110 C are presented in Figure 1. It should be observed that FeSO4+ is the
predominant species for Fe(III), and the concentration of free ferric ion is much lower. At both 90 C and
110 C, with the increase of nominal Fe3+/Fe2+ ratios from 1:1 to 1000:1, the concentration of free ferric
slightly increased, whereas the concentration of free ferrous decreased significantly. Under the same
nominal Fe3+/Fe2+ ratios, increasing the temperature from 90 C to 110 C resulted in a small increase of
free ferrous concentration and a decrease of free ferric concentration.
Table 3 lists the nominal and real Fe3+/Fe2+ ratio in aqueous Fe(II)-Fe(III)-H2SO4 solution. It can
be seen that at 90 C the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, and it is worth noting
that the situation is even worse at 110 C.
Table 3 Nominal and Real Fe3+/Fe2+ Ratio in aqueous Fe(II)-Fe(III)-H2SO4 solution
Fe3+/Fe2+ (Real) 90 C
Fe3+/Fe2+ (Real) 110 C
Fe3+/Fe2+
(Nominal)
Free Fe3+
Free Fe2+
Fe3+/Fe2+
Free Fe3+
Free Fe2+
Fe3+/Fe2+
1:1
6.22E-05
4.78E-02
1.30E-03
3.43E-05
4.96E-02
6.91E-04
10:1
9.91E-05
6.21E-03
0.02
6.23E-05
6.51E-03
0.01
100:1
1.04E-04
6.38E-04
0.16
6.64E-05
6.68E-04
0.10
1000:1
1.05E-04
6.39E-05
1.64
6.68E-05
6.70E-05
1.00
Cathodic Potentiodynamic Polarization Curves and Cyclic Potentiodynamic Polarization at 90 C

Figure 2 shows the CPC and corresponding OCP results at 90 C. It can be observed that the OCP
values are quite stable under each nominal Fe3+/Fe2+ ratio. The polarization plots for different nominal
Fe3+/Fe2+ ratios are similar, indicating identical processes in the systems. The reduction reaches a limiting
current density at approximately E = 250mV vs. SHE.
247
0.77
3+
0.75
0.7
0.6
E vs SHE (V)
OCP vs SHE (V)
0.8
2+
Fe /Fe =1:1
3+
2+
Fe /Fe =10:1
3+
2+
Fe /Fe =100:1
3+
2+
Fe /Fe =1000:1
0.76
0.74
0.73
0.72
0.71
0.5
0.4
Fe3+/Fe2+=1:1
Fe3+/Fe2+=10:1
Fe3+/Fe2+=100:1
Fe3+/Fe2+=1000:1
0.3
0.2
0.1
0.70
0.0
0.69
-0.1
-6
200 400 600 800 1000 1200 1400 1600 1800

Time (S)
-5
-4
-3
Log i (A/cm2)
-2
-1
0.76
0.9
0.75
0.8
0.74
0.73
0.72
Fe3+/Fe2+=1:1
3+
2+
Fe /Fe =10:1
Fe3+/Fe2+=100:1
Fe3+/Fe2+=1000:1
0.71
0.70
0.7
0.6
Fe3+/Fe2+=1:1
Fe3+/Fe2+=10:1
Fe3+/Fe2+=100:1
Fe3+/Fe2+=1000:1
0.5
0.4
0.69
0.68
E vs SHE (V)
OCP vs SHE (V)
Figure 2 Cathodic potentiodynamic polarization curves and corresponding OCP in deaerated aqueous
Fe(II)-Fe(III)-H2SO4 solution on chalcopyrite with different nominal molar ratios of ferric to ferrous at
90 C
200 400 600 800 10001200140016001800
Time (S)
0.3
-7
-6
-5
-4
Log i (A/cm2)
-3
-2
Figure 3 Cyclic potentiodynamic polarization and corresponding OCP in deaerated aqueous Fe(II)Fe(III)-H2SO4 solution on chalcopyrite with different nominal molar ratios of ferric to ferrous at 90 C
Figure 3 shows the CPP and corresponding OCP results at 90 C. Under each nominal Fe3+/Fe2+
ratio, the OCP varied in accordance with a similar trend, compared with that of the CPC result. The
polarization plots for different nominal Fe3+/Fe2+ ratios display similar behavior: there is no apparent
positive or negative hysteresis happening and the whole process is quasi-reversible. The forward anodic
potential sweep shows a small passivation region.
Addition of ferrous ion with the nominal Fe3+/Fe2+ ratio varying from 1000:1 to 10:1 has no effect
on the plots; but at a higher nominal Fe3+/Fe2+ ratio of 1:1, the curve shows a larger current, probably due
to the preferred oxidation reaction of ferrous ion on the chalcopyrite surface. The kinetic analysis of anode
processes is difficult because of the simultaneous occurrence of a number of reactions (anodic oxidation of
chalcopyrite itself and an additional competing anode oxidation reaction of ferrous to ferric) and is beyond
the scope of the present study.
It is clearly indicated in Figure 4 that the polarization plots obtained from the CPC and CPP
methods under different nominal Fe3+/Fe2+ ratios are in good agreement at 90 C, especially in the case of
100:1 and 1000:1 nominal Fe3+/Fe2+ ratios.
248
0.9
0.9
0.7
0.7
E vs SHE (V)
E vs SHE (V)
The standard potential for the Fe3+/Fe2+ couple (0.77V vs. SHE at 25 C) at 90 C was calculated
based on the thermodynamic data (G0) of the main species in the solution according to the Lewis
formulation of the Criss-Cobble correspondence principle. The value is 0.882 V vs. SHE at 90 C.
0.5
CPC Fe3+/Fe2+=1:1
CPP Fe3+/Fe2+=1:1
0.3
0.1
-6
-5
-4
-3
Log i (A/cm2)
-2
-0.1
-1
0.9
0.9
0.7
0.7
0.5
CPC Fe3+/Fe2+=100:1
CPP Fe3+/Fe2+=100:1
0.3
0.1
-0.1
-7
CPC Fe3+/Fe2+=10:1
CPP Fe3+/Fe2+=10:1
0.3
0.1
E vs SHE (V)
E vs SHE (V)
-0.1
0.5
-7
-6
-5
-4
-3
Log i (A/cm2)
-2
-1
-2
-1
0.5
CPC Fe3+/Fe2+=1000:1
CPP Fe3+/Fe2+=1000:1
0.3
0.1
-6
-5
-4
-3
Log i (A/cm2)
-2
-1
-0.1
-7
-6
-5
-4
-3
Log i (A/cm2)
Figure 4 Comparison of CPC and CPP results in deaerated aqueous Fe(II)-Fe(III)-H2SO4 solution on
chalcopyrite with different nominal molar ratios of ferric to ferrous at 90 C
Based on the obtained cathodic linear Tafel line and the reversible potential of the ferric/ferrous
couple, the transfer coefficients and exchange current densities were calculated for both CPC and CPP at
90 C. It is shown in Table 4 and Table 5 that OCP values are very stable and almost equal for both the
CPC and CPP methods under the same nominal Fe3+/Fe2+ ratio. OCP slightly shifted towards the positive
values when increasing nominal Fe3+/Fe2+ ratio. A slight increase in the cathodic Tafel slopes for the
reduction of ferric ions on the CuFeS2 surface by CPP was observed compared to those obtained by CPC,
and the slopes ranged between 0.123 and 0.159 V/decade for CPC and between 0.183 and 0.199 V/decade
for CPP. The measured Tafel slopes, according to 2.303RT/(F), yield values for in the range of 0.360.59.
Table 4 CPC results at 90 C
Fe3+/Fe2+
(Nominal)
Fe3+/Fe2+
(Real)
OCP
(mV)
Tafel Slope
(V/decade)
Transfer
Coefficient
ER (no speciation)
ER (speciation)
2
ER (V)
i0 (A/cm )
ER (V)
i0 (A/cm2)
1:1
1.30E-03
698.77
0.123
0.59
0.88
6.92E-07
0.67
3.37E-05
10:1
0.02
719.01
0.125
0.58
0.95
2.43E-07
0.75
1.01E-05
100:1
0.16
735.88
0.139
0.52
1.03
2.18E-07
0.82
6.09E-06
1000:1
1.64
750.60
0.159
0.45
1.10
1.75E-07
0.90
3.20E-06
249
Under the same nominal Fe3+/Fe2+ ratios, the calculated reversible potentials using the nominal
Fe3+/Fe2+ratio are higher than that using the real Fe3+/Fe2+ ratio, which leads to smaller values for the
exchange current densities in all of the cases for CPC and CPP. With the increase of nominal Fe3+/Fe2+
ratios from 1:1 to 1000:1, the exchange current densities declined from 3.37x10-5 A/cm2 to 3.20x10-6
A/cm2 for CPC and from 1.89x10-4 A/cm2 to 9.12x10-6 A/cm2 for CPP.
Table 5 CPP results at 90 C
Fe3+/Fe2+
(Nominal)
Fe3+/Fe2+
(Real)
OCP
(mV)
Tafel Slope
(V/decade)
Transfer
Coefficient
ER (no speciation)
ER (speciation)
2
ER (V)
i0 (A/cm )
ER (V)
i0 (A/cm2)
1:1
1.30E-03
691.10
0.190
0.38
0.88
1.52E-05
0.67
1.89E-04
10:1
0.02
723.92
0.183
0.39
0.95
5.21E-06
0.75
6.57E-05
100:1
0.16
733.74
0.188
0.38
1.03
1.23E-06
0.82
1.43E-05
1000:1
1.64
751.53
0.199
0.36
1.10
8.96E-07
0.90
9.12E-06
Cathodic Potentiodynamic Polarization Curves and Cyclic Potentiodynamic Polarization at 110 C

Figure 5 shows the CPC and corresponding OCP results at 110 C. It was shown that the OCP
values are relatively stable and no obvious deviation was found under each nominal Fe3+/Fe2+ ratio. The
polarization plots for different nominal Fe3+/Fe2+ ratios almost overlap with each other, implying identical
processes in the systems, despite the fact that the OCP values of 100:1 and 1000:1 nominal Fe3+/Fe2+ ratios
are a little larger than those of 10:1 and 1:1 nominal Fe3+/Fe2+ ratios. The trend is similar to that at 90 C.
The reduction reaches a limiting current density at approximately E = 150 mV vs. SHE.
0.60
0.7
0.59
0.6
0.5
0.57
Fe3+/Fe2+=1:1
Fe3+/Fe2+=10:1
Fe3+/Fe2+=100:1
Fe3+/Fe2+=1000:1
0.56
0.55
0.54
E vs SHE (V)
OCP vs SHE (V)
0.58
0.4
0.3
0.1
0.0
0.53
-0.1
0.52
-0.2
0.51
100 200 300 400 500 600 700 800

Time (S)
Fe3+/Fe2+=1:1
Fe3+/Fe2+=10:1
Fe3+/Fe2+=100:1
Fe3+/Fe2+=1000:1
0.2
-0.3
-5
-4
-3
Log i (A/cm2)
-2
Figure 5 Cathodic potentiodynamic polarization curves and corresponding OCP in deaerated aqueous
Fe(II)-Fe(III)-H2SO4 solution on chalcopyrite with different nominal molar ratios of ferric to ferrous at
110 C
Figure 6 shows the CPP and corresponding OCP results at 110 C. It appears that there is very
slight variation in the OCP values under each nominal Fe3+/Fe2+ ratio. A very similar tendency in the
polarization plots for different nominal Fe3+/Fe2+ ratios was observed: there is no apparent positive or
negative hysteresis existing and the entire process appears quasi-reversible. In general, the forward anodic
potential sweep shows a small passivation region which may result from the formation of passivation films,
and then a small linear transpassive Tafel region. It is worth noting that a small plateau region appears in
the reverse sweep. In addition, it may be mentioned that the polarization plots for the anodic forward and
reverse sweep with the nominal Fe3+/Fe2+ ratio of 10:1 almost overlap with each other.
250
0.9
0.62
0.60
0.7
0.58
3+
2+
Fe /Fe =1:1
Fe3+/Fe2+=10:1
Fe3+/Fe2+=100:1
Fe3+/Fe2+=1000:1
0.56
0.54
0.52
0.50
E vs SHE (V)
OCP vs SHE (V)
Fe3+/Fe2+=1:1
Fe3+/Fe2+=10:1
Fe3+/Fe2+=100:1
Fe3+/Fe2+=1000:1
0.8
0.6
0.5
0.4
0.3
0.2
100 200 300 400 500 600 700 800

Time (S)
-6
-5
-4
Log i (A/cm2)
-3
-2
Figure 6 Cyclic potentiodynamic polarization and corresponding OCP in deaerated aqueous Fe(II)Fe(III)-H2SO4 solution on chalcopyrite with different nominal molar ratios of ferric to ferrous at 110 C
Addition of ferrous ion with the nominal Fe3+/Fe2+ ratio varying from 1000:1 to 100:1 has no
apparent effect on the anodic plots, but for higher nominal Fe3+/Fe2+ ratio from 10:1 to 1:1 the curve shows
a larger current, probably due to the preferred oxidation reaction of ferrous ion on the chalcopyrite surface.
Obviously, it is suggested in Figure 7 that the polarization plots of CPC and CPP under different nominal
Fe3+/Fe2+ ratios are in reasonably good agreement at 110 C.
The standard potential for the Fe3+/Fe2+ couple (0.77V vs. SHE at 25 C) at 110 C was calculated
in a similar method to that used for 90 C. The value is 0.912 V vs. SHE at 110 C.
The transfer coefficients and exchange current densities were calculated for both CPC and CPP at
110 C. Table 6 and Table 7 show that OCP values are relatively stable and no obvious change was found
under each nominal Fe3+/Fe2+ ratio for CPC and CPP methods. For the CPC method, there is no significant
change in the cathode Tafel slopes for ferric reduction and the slopes varied between 0.117 and 0.129
V/decade. The measured Tafel slopes, according to 2.303RT/(F), give the values for in the range of
0.59-0.65. However, under the same nominal Fe3+/Fe2+ ratios, the Tafel slopes of CPP methods are higher
than that of CPC method, especially at the nominal Fe3+/Fe2+ ratio of 100:1. Consequently, this led to
smaller values for , in the range of 0.37-0.51. The higher Tafel slopes obtained from CPP at 110 C
suggest the surface layer formed in such a condition is different from that produced by the CPC method.
Further studies will be required to clarify the reasons for such a phenomenon.
Under the same nominal Fe3+/Fe2+ ratios, the calculated reversible potentials using the nominal
Fe /Fe ratio are also larger than those obtained using the real Fe3+/Fe2+ ratio, which results in smaller
values for the exchange current densities in all cases for CPC and CPP. This tendency is the same as that
observed at 90 C. With the increase of nominal Fe3+/Fe2+ ratios from 1:1 to 1000:1, the exchange current
densities declined from 6.47x10-6 A/cm2 to 3.04x10-8 A/cm2 for CPC and from 5.13x10-5 A/cm2 to
2.34x10-7 A/cm2 for CPP.
3+
2+
251
0.9
0.9
0.7
0.7
0.5
0.5
E vs SHE (V)
E vs SHE (V)
0.3
CPC Fe3+/Fe2+=1:1
CPP Fe3+/Fe2+=1:1
0.1
-5
-4
-3
Log i (A/cm2)
-2
-0.3
-1
1.0
0.7
0.8
0.5
0.6
E vs SHE (V)
E vs SHE (V)
-6
0.9
0.3
CPC Fe3+/Fe2+=100:1
CPP Fe3+/Fe2+=100:1
0.1
-6
-5
-4
-3
Log i (A/cm2)
-2
-1
-2
-1
0.4
0.2
CPC Fe3+/Fe2+=1000:1
CPP Fe3+/Fe2+=1000:1
0.0
-0.1
-0.3
CPC Fe3+/Fe2+=10:1
CPP Fe3+/Fe2+=10:1
0.1
-0.1
-0.1
-0.3
0.3
-0.2
-6
-5
-4
-3
Log i (A/cm2)
-2
-1
-6
-5
-4
-3
Log i (A/cm2)
Figure 7 Comparison of CPC and CPP results in deaerated aqueous Fe(II)-Fe(III)-H2SO4 solution on
chalcopyrite with different nominal molar ratios of ferric to ferrous at 110 C
Table 6 CPC results at 110 C
ER (no speciation)
ER (speciation)
Fe3+/Fe2+
(Nominal)
Fe3+/Fe2+
(Real)
OCP
(mV)
Tafel Slope
(V/decade)
Transfer
Coefficient
1:1
521.72
0.120
526.02
0.129
100:1
6.91E-04
0.01
0.10
583.06
0.119
0.64
1.06
3.29E-09
0.84
2.70E-07
1000:1
1.00
594.10
0.117
0.65
1.14
3.41E-10
0.91
3.04E-08
10:1
ER (V)
i0 (A/cm )
ER (V)
i0 (A/cm2)
0.64
0.91
6.35E-08
0.67
6.47E-06
0.59
0.99
4.99E-08
0.76
3.02E-06
Table 7 CPP results at 110 C

ER (no speciation)
ER (speciation)
Fe3+/Fe2+
(Nominal)
Fe3+/Fe2+
(Real)
OCP
(mV)
Tafel Slope
(V/decade)
Transfer
Coefficient
1:1
531.84
0.168
524.79
0.165
100:1
6.91E-04
0.01
0.10
606.68
0.207
0.37
1.06
3.50E-07
0.84
4.47E-06
1000:1
1.00
587.05
0.148
0.51
1.14
6.67E-09
0.91
2.34E-07
10:1
ER (V)
i0 (A/cm )
ER (V)
i0 (A/cm2)
0.45
0.91
1.89E-06
0.67
5.13E-05
0.46
0.99
2.12E-07
0.76
5.25E-06
252
Comparison of Exchange Current Densities Obtained at 90 C and 110 C

Figure 8 presents the obtained exchange current densities of the ferric/ferrous couple in deaerated
aqueous Fe(II)-Fe(III)H2SO4 solution on chalcopyrite with different nominal molar ratios of ferric to
ferrous at 90 C and at 110 C. It is clear that the calculated exchange current densities using the nominal
Fe3+/Fe2+ ratio (no speciation) are lower than those calculated using the real Fe3+/Fe2+ ratio (speciation) in
all of the cases for both the CPC and CPP method. Under the same nominal Fe3+/Fe2+ ratios, increasing the
temperature from 90 C to 110 C was observed to give rise to a surprising decrease of exchange current
density, independent of whether or not the speciation was taken into account. This result requires further
study for clarification but may be due to a fundamental difference in the surface of CuFeS2 related to an
increased rate of passivation at elevated temperature.
1E-3
1E-4
i0 (A/cm2)
1E-5
1E-6
1E-7
90 CPC no speciation
90 CPC speciation
90 CPP no speciation
90 CPP speciation
110 CPC no speciation
110 CPC speciation
110 CPP no speciation
110 CPP speciation
1E-8
1E-9
1E-10
10
100
[Fe3+]/[Fe2+]
1000
Figure 8 Comparison of the obtained exchange current densities of ferric/ferrous couple in deaerated
aqueous Fe(II)-Fe(III)-H2SO4 solution on chalcopyrite with different nominal molar ratios of ferric to
ferrous at 90 C and at 110 C
Comparison of Exchange Current Densities of Fe3+/Fe2+ Couple on Other Electrodes
The obtained exchange current densities for the Fe3+/Fe2+ couple on chalcopyrite were compared
with those obtained on other electrodes (Makrides, 1964a, 1964b; Stern, 1957). The reaction rate of the
Fe3+/Fe2+ couple is quite fast on the surface of oxide free metals such as platinum and was reported to have
an exchange current density of 1.5x10-2 A/cm2. On the contrary, a distinct decrease by several orders of
magnitude in the exchange current densities of the Fe3+/Fe2+ couple on Ni, Fe, Ti, Fe-Cr alloy and 304
stainless steel (with passive oxide films) was observed and the values are on the order of 10-5-10-8 A/cm2.
In the case of chalcopyrite, it was noted that the result was consistent with the exchange current densities
of the Fe3+/Fe2+ couple on the above-noted passive electrodes. The exchange current densities are
substantially less than that on platinum, on the order of 10-6-10-5 A/cm2 at 90 C and 10-7-10-6 A/cm2 at
110 C, due to the formation of a passive film.
Calculation of Rate Constants
Based on the obtained exchange current densities, the rate constants, kc, were calculated by
equation (1) (Paramguru & Ray, 1996):
=
(1)
253
where i0 is the exchange current density (A/cm2), Z is the number of electrons transferred in the
charge transfer reaction, F is Faradays constant (C/mol), kc is the rate constant (cm/s), is the bulk
concentration of ferric ion in the solution (mol/L), is the transfer coefficient, ER is the reversible potential
of the Fe3+/Fe2+ couple, R is the universal gas constant (J/molK) and T is the temperature (K).
The average rate constants are 862.17 cm/s for CPC and 65.30 cm/s for CPP at 90 C, and 477.69
cm/s for CPC and 63.53 cm/s for CPP at 110 C for nominal Fe3+/Fe2+ ratios ranging from 1:1 to 1000:1, as
shown in Table 8. It is evident that the values of the rate constants obtained by the CPC method are much
larger than those obtained by the CPP method at both 90 C and 110 C, and the rate constants obtained at
90 C are larger than those obtained at 110 C, especially for the results obtained by the CPC method. It is
necessary to study the reason for this discrepancy in future work.
Table 8 Calculation of rate constants at 90 C and at 110 C
kc (no speciation)
kc (speciation)
kc (no speciation)
kc (speciation)
CPC (cm/s)
CPC (cm/s)
CPP (cm/s)
CPP (cm/s)
90 C
0.3975
862.17
0.0309
65.30
110 C
0.1392
477.69
0.0164
63.53
Temperature
CONCLUSIONS
The aim of this study was to demonstrate the reduction kinetics of ferric ion on chalcopyrite in
aqueous Fe(II)-Fe(III)-H2SO4 solution at 90 C and 110 C. Results from the calculation of speciation in
this solution reveal that at 90 C the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, and it is
worth noting that situation is even worse at 110 C. Two types of experiments were carried out: cathodic
potentiodynamic polarization curves (CPC) and cyclic potentiodynamic polarization (CPP) technique. The
CPC polarization plots for different nominal Fe3+/Fe2+ ratio are similar, implying identical processes in the
systems. The CPP polarization plots for different nominal Fe3+/Fe2+ ratios display similar behavior. There
is no apparent positive or negative hysteresis happening and the entire process is quasi-reversible.
Exchange current densities of the ferric/ferrous couple in deaerated solution on chalcopyrite with different
nominal Fe3+/Fe2+ ratio were obtained and are on the order of 10-6-10-5A/cm2 at 90 C and 10-7-10-6A/cm2 at
110 C, respectively. The exchange current densities are substantially less than that on platinum due to the
formation of a passive film. Under the same nominal Fe3+/Fe2+ ratios, the Tafel slopes of CPP methods are
higher than those of CPC method at both 90 C and 110 C. Consequently, this led to smaller values for .
The transfer coefficients were about 0.36-0.59 at 90 C and 0.37-0.65 at 110 C. Based on the obtained
exchange current densities, the rate constant for ferric reduction on chalcopyrite, kc, was calculated and it
was found that the rate constants obtained at 90 C are larger than those obtained at 110 C, especially for
the results obtained by the CPC method.
ACKNOWLEDGEMENTS
The authors acknowledge the Earth and Ocean Science Department at the University of British
Columbia for providing the mineral samples. We also wish to thank Ms. E. Czech for her assistance in
obtaining the XRD data featured in this paper, and Mr. W. Wang for helping solve the non-linear equations
in the Matlab software. The authors acknowledge the financial support of the Natural Sciences and
Engineering Research Council of Canada (NSERC).
254
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257
HYDROTHERMAL PURIFICATION AND ENRICHMENT OF CHILEAN COPPER

CONCENTRATES. THE BEHAVIOR OF BORNITE, COVELLITE, PYRITE AND ENARGITE
*G. Fuentes1, J. Vials2
1
Department of Metallurgical Engineering

Universidad Catlica del Norte
Angamos 0610, Antofagasta, Chile
(*Corresponding author: gfuentes@ucn.c)l
2
Department of Materials Science and Metallurgical Engineering

Universidad de Barcelona
Marti I Franqus 1, E-08028, Barcelona, Espaa
ABSTRACT
The nature and basic kinetics of the hydrothermal reactions of bornite, covellite pyrite and
enargite with copper sulfate solutions were investigated, as a previous study on the behavior of the bulk
Chilean copper concentrates. The reaction of bornite produced digenite at 160 C and djurleite above this
temperature. Covellite was transformed to digenite at < 200 C and to chalcocite (Q and M) at > 200 C.
The pyrite reaction was significant at > 200 C and extensive at 240 C, enargite reacts only above 240C
and produces digenite. The hydrothermal treatment of Chilean Codelco-type copper concentrates with
hydrothermal reactions was similar to those obtained from pure mineral samples.

Niagara, ON, Canada
Edited by
258
INTRODUCTION
Studies on the hydrothermal enrichment of chalcopyrite concentrates were begun by MacGauley
and Roberts (1951), Roberts et al. (1953) and MacGauley and Schaufelberger (1956). In the 1970's these
processes were re-examined by McKay et al. (1972), and Johnson and Coltrinari (1976), but it not was
until the 1990s when the kinetics, mechanisms and full engineering aspects were studied by Barlett, (1992),
Jang and Wadsworth, (1994) and Peterson and Wadsworth (1994). The main objectives were to solve some
important problems in the copper pyrometallurgy: The increase of the smelting capacity, the reduction of
the iron slag and associated copper losses as well as the reduction of sulfur emissions. The present rise
in copper demand and price implies the production and subsequent treatment of very impure concentrates.
Thus, a significant increase of environmental problems can be expected in the copper pyrometallurgy. The
previous purification of concentrates can reduce the processing of wastes containing hazardous heavy
metals in the copper refineries and the hydrothermal treatment can be an alternative which combines both
enrichment and purification. On the other hand, Chuquicamata-type concentrates (Vials et al., 2004a)
contains digenite (Cu1.8S), pyrite (FeS2), chalcopyrite(CuFeS2), bornite (Cu5FeS4), covellite (CuS) and
sphalerite (ZnS) as the main mineral components, with minor amounts of enargite (Cu3AsS4), galena (PbS)
and molybdenite (MoS2).
The hydrothermal enrichment of chalcopyrite in the range 125 200 C occurs essentially as:
3CuFeS2 + 6 CuSO4 (aq) + 4H2O 5Cu1.8S + 3FeSO4 (aq) + 4H2SO4 (aq)
(1)
Peterson and Wadsworth (1994) reported that the kinetics were limited by mixed
diffusion/chemical control with zero order dependency of the [Cu2+] (aq). An electrochemical mechanism
was proposed which implied solid-state diffusion of copper ions through the sulfide lattices.
The hydrothermal treatment of Chilean Codelco-type copper concentrates with copper sulfate
solutions was investigated as a mean of removal of impurities and subsequent increase of the copper assay.
Examples of common impurities are zinc, which occurs as sphalerite and arsenic which occurs like
enargite. Currently, some Chilean copper concentrates contain 2-4% Zn and 0.5-1 % As.
EXPERIMENTAL
Materials
High purity mineral specimens were obtained: bornite crystals from Dzhezkazgan (Jezkazgan
Oblast, Kazakhstan), lamellar covellite from Butte (Montana, USA), pyrite crystals from Navajn (La
Rioja, Spain), enargite from Huencavlica, Per and concentrates Ch1 and Ch2 from the Chuquicamata
Mine, CODELCO NORTE, Division, Antofagasta region, Chile. The minerals specimens and concentrates
were characterized chemically and mineralogically, Fuentes, G., et al. (2009).
The chemical composition of mineral specimens was determined by electron microprobe
(EMPA). Mineralogical data were obtained by reflected-light microscopy, scanning electron microscopy
coupled by energy dispersive analysis (SEM/EDS) and X ray powder diffractometry (XRD). The samples
for autoclave experiments were obtained from the ground crystals by wet sieving. The bulk compositions
of the 25-40 and < 25 m fractions. Bornite was very pure, but the covellite bulk samples contained some
clay-like minerals, which were originally present between the crystal laths. This clay impurity was
specially accumulated in the finer fraction (< 25 m). The main impurities of the pyrite bulk samples were
chlorite and pyrophyllite which were present as sporadic inclusions in the pyrite crystals.
The chemical composition of concentrates was determined by wet analysis using inductively
coupled plasma spectroscopy (ICP OES) for the major elements, and plasma/mass spectroscopy (ICPMS) for the trace elements. Mineralogical data were obtained by X-ray powder diffractometry (XRD),
259
reflected- light microscopy and scanning electron microscopy (SEM) coupled by energy dispersive
spectroscopy (EDS). Five microscopic fields of 600x400 m, containing a total about 500 particles, were
examined for each concentrate in order to obtain a semiquantitative phase composition.
Autoclave Experiments
Experiments with concentrates and minerals specimens were performed in a PARR-4563 reactor.
The stirring speed was 800 min-1 in all experiments. After placing the sulfide sample and CuSO4 solution
in the autoclave, the air was eliminated using an argon current for 5 min. Then the system was raised to the
working temperature at the rate of ~5C/min, then maintained at this temperature for a fixed time, until it
was cooled to room temperature, again at the rate of ~5C/min. For the minerals specimens the reactions
were studied by treating 0.2g samples (25-40m) with 100cm3 of slightly acidified (H2SO4, pH 1.3-1.4)
copper sulfate solutions of known concentration. Under these conditions there was sufficient excess Cu2+ to
assume practically a constant copper concentration.
Stoichiometry experiments were performed with < 25m samples and a much lower excess of
Cu2+(aq)(0.8g sample in 80cm3 solution) to correlate the moles of Cu2+(aq) consumed with the moles of
Fe2+(aq) and SO42-(aq) generated. Solution composition was analyzed for Cu, Fe and S by ICP.
For the case of concentrates, the effects of temperature, contact time and Cu2+(aq) concentration
were studied in appropriate ranges according to the reactivity of the individual phases. The effect of
temperature was studied between 160-240C, by treating 0.85g of concentrate with 100cm3 of copper
sulfate solution of initially containing 8.5 g/L Cu2+, at an initial pH of 1.3, during 1 h. Under these
conditions, there was about the twice of initial Cu2+(aq) required to the complete conversion of all the sulfide
components. After the treatment, the pH, the solution volume and the residual copper concentration were
measured. Final pH all the experiments was in the range 0.9-1.1, as consequence of the stoichiometry of
the reactions. The effect of the contact time was studied in the same manner in the 0.25-2 h interval at
225C and 240C. The effect of copper concentration was studied in the range 1-8.5 g/L, also at 225C and
240C but by using only 0.2g concentrate in 100cm3 solution; this maintained a practically constant Cu2+(aq)
concentration, even in the experiments at low copper concentration. The removal of the different elements,
as well as the degree of copper incorporation into concentrate, was calculated using the solid compositions
and a mass balance. The elements studied included Cu, Fe, S, Zn, Tl, Bi, As, Mo, Hg, Te and Sb.
Table 1 - Composition of the original concentrates and those treated at different temperatures (Cu2+initial
8.5g/L, pHinitial1.3, 1h)
Cu (%)
S (%)
Fe(%)
Zn (%)
As (%)
Pb (%)
Mo (%)
Sb (%)
Bi (g/t)
Cd (g/t)
Te (g/t)
Tl (g/t)
Hg (g/t)
SiO2(%)
Original
Ch1
Ch3
33.5
31.8
33.4
31.8
21.6
18.3
2.10
3.07
0.48
0.79
0.090 0.091
0.016 0.055
0.012 0.042
69
110
104
110
4.7
10
0.4
1.1
21
6.9
5.4
8.0
Ch1
41.6
34.0
15.4
1.40
0.38
0.042
0.15
33
41
5.0
0.19
-
160C
Ch3
41.4
30.7
14.0
1.91
0.63
0.076
0.045
0.033
64
53
7.1
0.50
7.3
-
200C
Ch1
Ch3
49.9
51.1
31.8
27.6
11.3
12.1
0.69
1.16
0.36
0.58
0.026 0.036
0.13 0.041
0.035
13
27
22
36
2.6
5.8
0.13
0.20
15
4.5
-
225C
Ch1
Ch3
57.3
57.7
27.3
24.8
8.40
9.00
0.42
0.67
0.31
0.56
0.025 0.034
0.11 0.033
0.033
11
21
18
21
5.5
0.10
0.10
3.8
-
240C
Ch1
68.6
18.9
3.30
0.29
0.27
0.030
0.092
7
13
2.9
0.05
-
260

Bornite
Nature of the Reaction
Figure 1 shows the transformation of bornite into digenite and djulerite at 180C. The bornite
reaction occurs across a compact layer of copper sulfides retaining practically the size and shape of original
particles.
Figure 1 Transformation of bornite (bn) into digenite (dg) and djurleite (dj) at 180C (Cu2+ 5g/L). A: 2h.
(SEM/BSE). B: 4h. (optical micrograph)
Digenite was the only product detected at 100135 C. Under these conditions, digenite forms
very regular layers over the nuclei of the unreacted bornite. (Figure. 1A). This also permitted the
evaluation of the fraction of bornite reacted, by measuring the layer thickness. The formation of such
regular layers could be related to a PillingBetworth (Sohn and Wadsworth, 1979) ratio very close to 1 and
to the similar crystal structure.
Digenite at > 160C is partially transformed in a richer copper sulfide, djurleite (Cu1.94S) The
formation of djurleite implies nucleation at the aqueous solution-digenite interface and subsequent growth
of the djurleite across the previous formed digenite layer. The presence of djurleite was also reported by
Peterson and Wadsworth (1994) in the hydrothermal reaction of chalcopyrite.
From XRD results, the expected stoichiometry for the transformation of bornite into digenite and
djurleite can be written as:
Cu5FeS4 + 1.75Cu2+(aq) + H2O 3.75Cu 1.8S + Fe2++ 0.25SO42-(aq) + 2H+(aq)
(2)
Cu5FeS4 + 2.06Cu2+(aq) + 1.44H2O 3.64Cu1.94S + Fe2+(aq) + 0.36SO42-(aq) + 2.88H+
(3)
261
Kinetics and Temperature Effect

The fraction reacted determined from chemical analysis and from SEM measurements of the
product layer thickness, showed that bornite reacts with copper solutions at non-linear rates. This was
indicative of a kinetic control by solid layer diffusion.
The effect of copper concentration was negligible in the temperature range 120-135 C.
On the other hand, the temperature effect was studied for two hours in the range 110-180 C and
the fraction reacted at 180 C was closer to 0.95 and the Arrhenius plot of the product layer rate constants
at different temperatures gave a activation energy about 99 kJ/mol.
Covellite
The hydrothermal transformation of covellite was different to that observed for bornite. The
reaction occurs through irregular nucleation at certain points of the surface, also progressing irregularly
toward the interior of the particle (Figure 2).
Figure 2 Transformation of covellite (cv) to digenite (dg). (200C,Cu2+ 5g/L). A: 0.5 h. B: 1 h. C: 2 h.

(SEM/BSE)
262
In the range 160-190 C, digenite was the only reaction product. At 200 C and [Cu2+] (aq) < 5 g/L,
digenite still was the only product up to 2 h, but partially converted into a copper richer sulfide, in this case
chalcocite-Q (Cu1.96S), over long time periods (4 h) (Figure 3).
Figure 3 Optical micrograph (60 x 45m) showing intergrowth of digenite (dark grey) and chalcocite-Q
(light grey) from covellite reacted at 200C, 4 h, Cu2+ 5g/L
The effect of time was studied at 180-200C. In contrast with the transformation of bornite, the
hydrothermal reaction of covellite was of a non-parabolic type. This is related to the transformation of
covellite in a non-continuous layer; consequently, the data was treated with a kinetic model for a chemical
reaction control. In contrast with bornite, the effect of copper concentration , in the range 180-200 C,
shows the reaction rate of covellite increased with an increase in the copper concentration. The temperature
effect was studied at 160-220C for a fixed time of 2 hours. The results shows the hydrothermal conversion
of covellite was almost negligible at temperatures less 160C, but very fast at >190C. The Arrhenius plot
of the chemical rate constants gave a energy of activation about 110kJ/mol.
Pyrite
Figure 4 Transformation of pyrite (py) into digenite and chalcocite-Q (ch) at 240C, 2 h. ([Cu2+] 5g/L).
A: Spongy layer of reaction products (SEM/SE). B: Optical micrograph (60 x 45m) of a cross section the
same conditions
263
Pyrite can be transformed into copper rich sulfides (mainly digenite and chalcocite) but only at
significant rates at > 200C. An important difference with respect to the transformations of bornite,
chalcopyrite and covellite, was the high value (~1.6) of the Philling Betworth ratio of the pyrite reactions.
So the important increase in the volume if the particles causes that the product layer tends to break, mainly
in the points of maximum mechanical tension (corners).The results was the formation of a relatively
regular, but porous layer(Figure 4).
The effect of reaction time was studied at 225-240C. Non-parabolic reaction rates were observed.
This was not surprising since a porous layer is formed in the transformation of pyrite. The effect of the
copper concentration was studied at 225C and shows it has a significant influence on the rate of the
hydrothermal conversion of pyrite. The effect of temperature was studied in the range of 180-240C, and
the results showed one half conversion was obtained at 240C. The activation energy was about 108 kJ/mol.
Enargite
Sample 1: This was a very pure sample enargite (~96% enargite, ~4% tennantite), ground and
sieved to <15m. The aim of this experiment was to characterize the product of total conversion of the
enargite, as well as establishing the global stoichiometry of the reaction.
Study by Chemical Analysis
The composition of the sample 1 compared with the theoretical composition of enargite, it shows
in the Table 2. The data highlight the presence of small amounts of antimony replacing arsenic.
Table 2 Composition of sample and the theoretical enargite
Elements
Cu
As
Sb
S
Sample 1
44.7
16.0
1.8
31.9
Cu3AsS4
48.1
19.02
32.57
SEM/ EDS Mapping Study

The fine particles of enargite has converted completely in Cu2S. The coarse particles shows a
compact layer of Cu2S is observed very well by the technique of mapping (Figure 5). The outer layer is
enriched in copper and arsenic disappears.
A particle size of < 25 m, or better still, less than 15 m is required for enargite conversion. This
variable along with temperature appears to be the only possible for to act in the process. According to the
compact character of the layer, the mechanism involves diffusion of ions in solid state and therefore the
process must be of order 0 respects the Cu2+.
264
Figure 5 - Enargite particle attacked and mapped for S, Cu and As. Note the decrease of S, the increase in
Cu and As the disappearance of the outer layer
Theoretical Stoichiometry of the Hydrotermal Reaction of Enargite
According to the previous results, its consider that Cu2+ of the solution is reduced to Cu+ to form
Cu2S and the presence in the initial enargite is also as Cu2S because other species of copper is not detected
to complete conversion.
Oxidation of arsenic in enargite to As (III) or As (V) in aqueous phase does not provide enough
electrons for the reduction of Cu2+ necessary for transform the enargite to Cu2S and, therefore, it is
assumed that a part of the sulfur from enargite, is oxidized to SO4-. The two reactions for oxidation to As
(III) and As (V) can be written as:
Oxidation to As (III):
Cu3AsS4 + 3.6 Cu2+ + 5.8 H2O 3.3 Cu2S + AsO33- + 0.7 SO42- + 11.6H+
(4)
Oxidation to As (V)
Cu3AsS4 + 4 Cu2+ + 6 H2O 3.5 Cu2S + AsO43- + 0.5 SO42- + 12H+
(5)
Characterization of Concentrates
Chemical Composition
Table 1 presents the chemical composition of the concentrates showing the zinc and arsenic
contamination, and also by many deleterious elements such as Pb, As, Cd, Bi, Hg, Tl, and others. The main
difference between the two concentrates was the zinc content, being over 3% in the Ch3.
Mineralogic Composition
The XRD spectra of the concentrates showed a qualitatively similar mineralogy. The sulfide
minerals detected by XRD included chalcopyrite, digenite, pyrite, covellite, bornite, enargite and
sphalerite. Quartz was the principal nonmetallic component.
265
With regards to the copper sulfides, digenite was the main mineral in both samples, followed by
chalcopyrite, covellite and bornite. Sphalerite content was in the range of 35% and enargite between 1
2%. Other sulfide minerals such as galena and molybdenite were detected about 0.1% range. Pyrite was the
main iron carrier in both concentrates, especially in the Ch3 sample (35%). Digenite was observed as up to
150 m grains, free or forming intergrowth with all the copper species. Digenite was also commonly
associated with pyrite in the form of rims of digenite over pyrite grains, as consequence of natural
enrichment (cementation) processes. Chalcopyrite appeared usually as free grains up to 100 m, and rarely
as an intergrowth with covellite or bornite. Mixed chalcopyrite pyrite particles were not found. Covellite
occurred as up to 150 m grains, free or with the associations cited for digenite and chalcopyrite. However,
mixed covellitepyrite particles were not present. Bornite usually appeared as intergrowth with digenite,
chalcopyrite and covellite, as up to 50 m grains. Sphalerite was present as small free grains, usually
<25 m in size, or as mixed sphaleritedigenite particles. Enargite occurred as up to 100 m free grains.
Molybdenite and galena were observed only occasionally, so, their characteristics were not well known in
these concentrates.
Hydrotermal Treatment Temperature Effect
Removal of Impurities and Copper Enrichment
Previous results obtained on the hydrothermal reactions carried out on the individual mineral
species indicated that the temperature was the most significant effect in the transformation processes. This
effect was also clearly reflected in the treatment of the bulk concentrates. Table 1 shows the chemical
composition of the final products and Figures 6 and 7 present the degree of removal of the studied
impurities as a function of the temperature.
The behavior of both concentrates was very similar. The elements with more capacity of removal
by the hydrothermal treatment were Zn, Cd, Tl and Bi, which can be eliminated at around 80% if the
temperature is sufficiently high (225 C). The joint elimination of some of these elements (Cd, Tl)
supports the concept that they are associated to the sphalerite. Other elements such as Pb and Te were
extracted at intermediate ranges (4070%), whereas Mo, Hg, Sb and As showed moderate extraction levels
(2040%). Except for As, Te and Sb, the temperature has a marked effect on the elimination of almost all
the elements. Temperatures of 225 C are required for an effective elimination. The removal of S and Fe
increases with increased temperature, and the copper assay increases in the final concentrate. If the
transformation is carried out at 240 C, the residual quantities of Fe are minimal (~3%) and the product is
highly enriched in copper (~70%) and has low sulfur content (~20%) Table1.
Figure 6 - Concentrate Ch1. Temperature effect on the removal of impurities (Cu2+inicial 8.5 g/L, pHinitial 1.3,
1 h)
266
Figure 7 - Concentrate Ch3. Temperature effect on the removal of impurities (Cu2+inicial 8.5 g/L, pHinitial 1.3,
1h
CONCLUSIONS
(1) The reactivity of the different species during the hydrothermal transformation of Codelco Chileconcentrates was similar to the one observed when studying the individual mineral phases.
(2) The elements showing the highest capacity for elimination by hydrothermal transformation include: Zn,
Cd, Tl and Bi, which are eliminated at around 80% at 225 C. Other elements such as Pb and Te showed
intermediate removal of 4070% while the elimination of Mo, Hg, Sb and As was moderate (2040%).
(3) Temperature had the greatest effect on the elimination of impurities. Temperatures of 225 C were
required for their effective elimination.
(4) A concentrate with 33% Cu, 33% S, 22% Fe, 2% Zn, can be converted into a super concentrate
containing 70% Cu, 19% S, and 3% Fe, formed mainly by Cu2x S phases with residual amounts of 0.3%
Zn, 0.3% As, 0.03% Pb, 0.1% Mo, 7 ppm Bi, 13 ppm Cd, 2 ppm Te and 0.05 ppm Tl.
ACNOWLEDGEMENTS
The authors wish to thank the Universidad Catolica del Norte (Chile) for sponsoring and
University of Barcelona (Spain) for support in characterization studies.
The authors wish to thank the CICITEM, Center of Scientific and Technologic Research for
Mining (Chile), for auspices. Project R10C1004.
REFERENCES
Barlett, R.W.,1992. Upgrading copper concentrate by hydrothermal converting chalcopyrite to digenite.
Metallurgical Transactions. B, Process Metallurgy 33B, 241248.
Fuentes, G., Vials, J., Herreros, O., 2009. Hydrotermal purification and enrichment of Chilean copper
concentrates. Part 1: The behavior of bornite, covellite and pyrite. Hydrometallurgy 95, 104112.
doi:10.1016/j.hydromet.2008.05.005.
267
Peterson, R.D., Wadsworth, M.E., 1994. Solid, solution reactions in the hydrothermal enrichment of
chalcopyrite at elevated temperatures. In: Warren, G.W. (Ed.), Proc. of EPD Congress. TMS,
Warrendale, Pen, pp. 275291.
Jang,J.H., Wadsworth, M.E., 1994 Kinetics of hydrothermal enrichment of chalcopyrite ACS Symposium
Series 550, 45-58.
Johnson, P.K., Coltrinari, E.L., 1976. US patent 3957602
Mac Gauley P. J., and Roberts E.S., 1951. US patent 2568963
Mac Gauley P. J., and Schaufelberger F.A.,1956. US patent 2755172
Mac Kay,D.R., Swinkels, G.M., Szarnes, K.R., 1972. Ger patent 2207381
Sohn, H.Y., Wadsworth, M.E., 1979. Rate Processes of Extractive Metallurgy. Plenum Press, New York,
USA.
Vials, J., Fuentes, G., Hernndez, M.C., Herreros, O., 2004a. Hydrothermal removal of zinc and iron from
Chilean copper concentrates. In: Palfy, P., Solc, P.,Vircikova, E. (Eds.), Proc. of the VI
International Conference Metallurgy, Refractories and Environment. Technical University,
Kosice, Slovakia, pp. 255 260.
Vials, J., Fuentes, G., Hernndez, M.C., Herreros, O., 2004b. Transformation of sphalerite particles into
copper sulphide particles by hydrothermal treatment with Cu(II) ions. Hydrometallurgy 75, 177
187.
269
UNIFORM CORROSION OF TITANIUM UNDER MEDIUM TEMPERATURE

CHALCOPYRITE CONCENTRATE LEACHING CONDITIONS
*J. Liu, E. Asselin, A. Alfantazi
The University of British Columbia
6350 Stores Road
(*Corresponding author: arrowliu@interchange.ubc.ca)
ABSTRACT
The corrosion of commercially pure titanium (CP-Ti) was studied from room temperature up to
medium temperature (~160C) under conditions relevant to medium temperature chalcopyrite leaching
processes. The corrosion rates were measured by immersion and electrochemical tests in sulfuric acid. The
influences of chloride, cupric and ferric ions on the corrosion rate and behavior were also investigated.
Corrosion of the CP-Ti did not account for the total current density measured by linear polarization tests.
The corrosion rates of CP-Ti under medium temperature leaching conditions were surprisingly high. The
corrosion rate measured in ferric containing solution at 160C was approximately 20 mm/yr.

Niagara, ON, Canada
Edited by
270
INTRODUCTION
Titanium exhibits excellent corrosion resistance in many aggressive environments because of the
formation of a very chemically stable, highly adherent, and protective oxide film on its surface (Mitsuo et
al., 2002). Because titanium is the only metal available at a reasonable cost that resists the high temperature
corrosive slurries in many leaching processes, it is often chosen as autoclave liner material where it is
subjected to severe conditions of acidity, temperature and pressure (Grauman and Say, 2000).
A number of distinctly different hydrometallurgical processes for the pressure leaching of
chalcopyrite have been developed and patented by various companies and they can be classified into low,
medium and high temperature regimes (McDonald and Muir, 2007). For example, chalcopyrite concentrate
may be processed at medium temperatures (115-175C) and pressures of 800-2200 kPa (Dreisinger, D.,
2006; Sahu and Asselin, 2011). The lixiviant may contain 20 to 55 g/L sulfuric acid, 8 to 12 g/L chloride
ions, 10-25 g/L Cu2+ (Jones, 1995, 1997, 1999), and less than 1 g/L Fe3+ (Defreyne et al., 2005). The
amount of these additions is determined by the grade of the ores and details are shown in Table 1.
Table 1 Typical additives' concentration
Range(g/L)
Typical(g/L)
Cu2+
15-25 (high grade ores);
10-15 (low grade ores)
15
Cl11-14
12
H2SO4
30-55 (high grade ores);
20-30 (low grade ores)
30
Fe3+
<1.0
1.0
Titanium and its alloys are not completely immune to corrosion. Normally, the presence of
oxidizing species, Cu2+ and Fe3+, in the bulk solution ensures a passive rest potential for the titanium liner
of autoclaves (Vaughan and Alfantazi, 2006). Since sulfuric acid is a reducing acid, pockets of concentrated
sulfuric acid in the high-pressure environment (located underneath scale for example), which are directly in
contact with the titanium liner, may cause severe corrosion damage. There is a lack of publicly available
information as to the high temperature corrosion of Ti in these types of environments.
Indeed, many papers have been published in the field of titanium corrosion but there is less
information as it pertains to hydrometallurgical environments. Stern and Wissenberg (1959), Armstrong et
al. (1970) and Thomas and Nobe (1972) were some of the early researchers of the electrochemical behavior
of titanium. Armstrong et al. (1970) and Kelly (1976) studied the anodic dissolution of titanium in sulfuric
acid. Caprani and Frayret (1979) focused on the behavior of titanium in concentrated hydrochloric acid.
Grauman and Say (2000) later reviewed the application of titanium for hydrometallurgical extraction
equipment. More recently, Vaughan et al. (Vaughan and Alfantazi, 2006; Vaughan et al., 2010) studied the
corrosion of titanium and its alloys under hydrometallurgical conditions in the absence of metal cations.
In this study, the corrosion behavior of commercially pure titanium (ASTM Grade 2) was
investigated under chalcopyrite leaching conditions similar to those used in medium temperature copper
concentrate leaching. The corrosion rates of CP-Ti were measured by immersion tests and electrochemical
tests as a function of sulfuric acid concentration. The influence of different ions (Cl-, Cu2+ and Fe3+) was
also investigated. The approach taken here was to do polarization tests at different temperatures below
100C. After gaining an understanding of the corrosion mechanisms of CP-Ti, immersion tests were carried
out at 160C to simulate chalcopyrite concentrate leaching conditions and some tests were carried out at
160C in an autoclave for comparison.
271
EXPERIMENTAL
Materials and Solutions
The material investigated is commercially pure (CP) titanium (ASTM Grade 2) and its chemical
composition is listed in Table 2. There were five solutions used in this study. These have been listed in
Table 3 and will be referred to by their associated number throughout the remainder of this work. When
both Cl- and Cu2+ existed in the solution, these were put in solution in two ways at 12 g/L Cl- and 15 g/L
Cu2+ from either 19.77 g/L NaCl and 58.98 g/L CuSO4.5H2O, or 28.82 g/L CuCl2.2H2O and 16.73 g/L
CuSO4.5H2O.
Table 2 Chemical compositions of CP-Ti ASTM grade 2 (wt. %)
Al
Cr
Cu
Fe
Mg
Mn
Mo
Nb
0.005
0.001
Ni
0.005
0.001
0.001
0.14
0.008
0.001
0.001
0.001
0.001
OEQ
OT-CP
Pd
Ru
Si
Sn
Zr
0.004
0.137
0.224
0.046
0.01
0.01
0.003
0.005
0.003
0.001
Electrochemical Polarization Tests

Square CP-Ti samples (1.0cm1.0cm) were cut from Ti rod stock. Test procedures were with
reference to ASTM G5 (ASTM, 1999). The square CP-Ti samples were ground with1200 grit SiC. These
samples were then cleaned by rinsing with water, degreased with acetone, rinsed a second time, and
ultrasonically cleaned in distilled water for 3 minutes. After the solution was made, it was introduced into
the cell, heated to the desired temperature and de-aerated using argon sparging at a rate of 150 cm3/min for
at least 30 minutes prior to introducing the specimen. Argon sparging was maintained during the entire
experimental process. Open circuit potential (OCP) was first measured and then linear polarization (LPR)
or potentiostatic polarization was performed (Vaughan, 2003).
For each experiment, the electrode potential was allowed to stabilize at least one half hour until
the OCP was stable. All the LPR tests were performed at a scan rate of 0.167 mV/s from -20mV + OCP to
20mV + OCP. Tests below 100C were performed in a 1L jacketed cell, with a graphite rod as a counter
electrode and a Ag/AgCl reference electrode (saturated KCl solution) introduced to the cell through a salt
bridge/Luggin probe. The potentiostat used was a PAR model 273A. Tests at 160C were performed in a
2L autoclave and the potentiostat used was a VersaSTAT 4. The counter electrode was Pt wire. The
reference electrode is a UBC design and its potential is around 0 mv vs. Ag/AgCl (saturated KCl solution).
The potentiostatic polarization tests were performed according to the following procedure. The Ti working
electrode was immersed in 800ml of solution 2 and the desired potential was applied for 5 hours after OCP
reached stabilization. 200 ml of solution A or solution B were then injected into the cell in order to change
the composition of the original electrolyte to solution 5 or solution 3. The applied potential was kept
constant during the entire process and the current was registered for another 6 hours after the addition of
cupric or ferric (Ghahremaninezhad et al., 2012).
Table 3 Solution composition
NO.
Solution
1
2
3
4
5
5*
A
B
30g/L H2SO4
30g/L H2SO4 + 12g/L Cl- (NaCl)
30g/L H2SO4 + 12g/L Cl- (NaCl)+ 1.0g/L Fe3+(Fe2(SO4)3.5H2O)
30g/L H2SO4 + 12g/L Cl- (NaCl) + 15g/L Cu2+(CuSO4.5H2O)+ 1.0g/L Fe3+(Fe2(SO4)3.5H2O)
30g/L H2SO4 + 12g/L Cl- (NaCl)+ 15g/L Cu2+(CuSO4.5H2O)
30g/L H2SO4 + 12g/L Cl- + 15g/L Cu2+ (CuCl2.2H2O, CuSO4.5H2O)
30g/L H2SO4+12g/L Cl- (NaCl) +75g/L Cu2+(CuSO4.5H2O)
30g/L H2SO4+12g/L Cl- (NaCl) + 3.0g/L Fe3+(Fe2(SO4)3.5H2O)
272
Immersion Tests
Samples were weighed before and after immersion to various solutions and a precision scale
(0.0001g) was used. Samples were cut from the same Ti rod stock into 0.6 0.6 cm rectangles. Immersion
tests were carried out in small stainless steel pressure vessels coated with boron nitride to minimize vessel
corrosion during the test. Each vessel contained three samples embedded in a PTFE holder designed to
separate samples from each other and from the vessel walls, Figure 1. Since the temperature was 160C,
the vessels were clearly under pressure. The inner volume available in each vessel was around 7.0 ml and
the solution volume used was 3.58 ml. The blue (darker) region in Fig 1(c) represents the solution height in
the vessel. It was estimated that the solution level decreased by 0.1 mm under pressure. Thus all samples
were immersed in solution.
(a)
(b)
(c)
Figure 1 - Schematic of the container and sample holder

(a) The PTFE sample holder and samples; (b) The stainless steel pressure vessel coated with boron nitride;
(c) A sealed container with sample and solution (right hand side shaded area and left hand side shaded area,
respectively)
RESULTS
Linear Polarization Tests at 25, 55 and 85C
The LPR scan began at a cathodic potential (-20 mV + OCP) and increased to an anodic potential
(20 mV + OCP) at a scan rate of 0.167 mV/s. The results of LPR tests under different conditions are shown
in Table 4. For all five solutions, higher temperature decreased the polarization resistance of CP-Ti. For
solutions 1 and 2, OCP didnt change significantly with increasing temperature and remained relatively
stable at around -570 mV. For solutions 3, 4 and 5 (after the addition of Cu2+ or Fe3+), OCP increased with
increasing temperature. Since OCP and polarization resistance of CP-Ti in solution 5 and 5* are almost the
same, the following study focuses on solution 5. According to data listed in Table 4, an estimate of
corrosion current density and corrosion rate was calculated (Karimi, et al., 2011.), from:
i corr =
0.026
(1)
Rp
Corrosion Rate =
aicorr
nF
(2)
273
Where a is the atomic weight, is density and n is the number of equivalents exchanged. From the
Pourbaix diagram of titanium in water, n is +2 (Ti2+) in solution 1 and 2 while n is +4 (TiO2) in the other
solutions. The results are presented in Table 4. According to standards for relative corrosion resistance in
unit [mm/yr], Table 5 (Jones, 1996), solutions 1 and 2 resulted in unacceptably high corrosion rates when
temperature was higher than 55 oC. For the other solutions, the addition of corrosion-inhibiting oxidizing
metal cations (15g/L Cu2+or 1.0g/L Fe3+) reduced the solution corrosivity resulting in good to excellent
corrosion resistance.
Table 4 LPR testing results of CP-Ti at 25, 55, and 85 oC
T
(C)
25
55
85
25
55
85
25
55
85
solution
no.
OCP
(mV)
Rp
( )
-578
-572
-578
1262
166
68
i
(A
cm-2)
20.6
156.6
382.3
-560
-557
-587
301
351
519
1441
167
70
11187
4662
1934
18.04
155.6
368.7
2.3
5.6
13.4
Corrosion
Rate
(mm/yr)
0.358
2.723
6.649
0.314
2.708
6.413
0.020
0.049
0.117
solution
no.
OCP
(mV)
Rp
( )
i (A
cm-2)
305
363
525
9268
2487
1578
2.80
10.45
16.47
Corrosion
Rate
(mm/yr)
0.024
0.091
0.143
276
344
426
264
341
422
7913
1993
866
8124
2217
891
3.29
13.04
30.02
3.20
11.72
29.18
0.029
0.113
0.261
0.028
0.102
0.254
5*
Table 5 Standards for relative corrosion resistance in unit [mm/yr]

Relative corrosion
resistance
mm/yr
Outstanding
Excellent
Good
Fair
Poor
Unacceptable
<0.02
0.02-0.1
0.1-0.5
0.5-1
1-5
5+
Based on the significant change of OCP after the addition of ferric or cupric, a linear polarization
test of pure copper at 85C was carried out to ensure that results were not representative of a copper film
rather than the CP Ti surface. The results are shown in Table 6 where they are compared to the results for
CP-Ti at the same conditions. The polarization resistance of CP-Ti in solution 5 is much higher than that
for pure copper. Since the film formed on the surface of the copper electrode in solution 5 was copper, it
can be concluded that the layer formed on the surface of the CP-Ti electrode immersed in solution 5 was
not purely copper but a film likely composed of TiO2 and copper.
Table 6 LPR testing results of Copper and CP-Ti at 85C
Electrode materials
CP-Ti
Copper
Solution No.
2
5
5
OCP(mV)
-587.5
426.5
18.96
Rp( )
70.5
866
10.25
Potentiostatic Polarization Tests at 85C

Potentiostatic polarization tests were carried out under different applied potentials and in the
presence of ferric and cupric to differentiate between the total current (as measured) and the portion of the
current that may be due to ferric or cupric reduction. For each additive there was two applied potentials,
one was higher than the OCP and the other was lower. The OCP of CP-Ti in solution 5 and solution 3 are
0.42 mV and 0.52 mV, respectively. Table 7 shows the values of measured differences between the current
274
density of the potentiostatic experiments before and after addition of cupric or ferric to the original
electrolyte. i1 is the oxidation current density of CP-Ti and i (i = i2-i1) is the reduction current density of
Cu2+/Cu or Fe3+ /Fe2+. These are illustrated in Figure 2, which shows the current vs. time behavior of CP-Ti
after addition of cupric or ferric at different applied potentials. The last group of data in Table 7 is the
percentage of total measured current associated with CP-Ti corrosion in solution 5 and solution 3, i1/(|i| +
i1). According to Table 7 and Figure 2, when experiments were carried out in the cathodic region, the
absolute value of i was higher compared to the measured anodic current and this is due to a higher
cathodic overpotential on cupric (Figure 2a) and ferric (Figure 2b) reduction. These data indicate that the
corrosion current density obtained from LPR tests is not 100% from titanium corrosion. However, when
tests were carried out in the anodic region, near the OCP, the difference is not significant and the LPR
results are reasonable.
Immersion Tests at 160C
Corrosion rates obtained from the immersion tests are summarized in Table 8. These results
demonstrate that at 160C the corrosion rate of CP-Ti may be high and cannot be neglected. The corrosion
rates were calculated for the full 21 days of immersion. Assuming that localized corrosion is not present,
the average corrosion rate can be calculated by the following equation (Caprani and Frayret, 1979):
CorrosionRate = (K W)/(A T D)
(3)
Where K is a constant, for corrosion rate (mm/yr), K=8.763104; T is the time of exposure in
hours to the nearest 0.01 h; A = area in cm2; W is mass loss in g and D is density in g/cm3. For each
experiment (solution type) the larger the sample number, the deeper the sample was located in the
immersion test assembly. Even though the immersion tests were carried-out in a sealed environment,
oxygen was still present. According to Table 8, the corrosion rates of the upper samples were relatively
high. In some cases the samples gained mass throughout the test (negative corrosion rates) and an
explanation for this is likely because of the formation of a Ti oxide film.
After 21 days of immersion, the sample surface was roughened, (Figure 3). Although none of the
samples experienced a significant mass loss under these conditions, localized corrosion did occur.
According to Figure 3, the most severe corrosion happened on sample 4 immersed in solution 2 and this is
consistent with the LPR results. The surface color of sample 10 immersed in solution with cupric ions
indicates that there is copper formed on the surface. According to Table 4 and Table 8, corrosion rates of
CP-Ti at 160C (by immersion) are lower than electrochemically obtained corrosion rates at 85C. This
comparison shows that even though the temperature of the LPR tests is lower than in the immersion tests,
the corrosion rates obtained by LPR are significantly higher than the corrosion rates obtained for the
immersion tests. This may be because the solution volume-to-specimen area ratio of this study is around
0.033 mL/mm2. According to ASTM G31, the minimum solution volume-to-specimen area ratio is 0.20
mL/mm2. Generally, corrosion rates will increase with larger solution volume-to-specimen area ratio and
the volume of the test solution should be large enough to avoid any appreciable change in its corrosivity
during the test. Our experimental design did not anticipate such a significant effect from this ratio.
275
3.5x10-3
-2
Current density (A cm )
(a)
0.5 V vs. Ag/AgCl

0.4 V vs. Ag/AgCl
3.0x10-3
5.0x10-5
0.0
i
-5
-5.0x10
10000
20000
30000
40000
t (s)
8.0x10-4
(b)
0.6 V vs. Ag/AgCl

0.5 V vs. Ag/AgCl
-4
-2
Current density (A cm )
7.0x10
4.0x10-5
2.0x10-5
i
0.0
i
-2.0x10-5
0
10000
20000
30000
40000
t (s)
Figure 2 Current-time behavior of CP-Ti under different applied potential and in the presence of
different cations at 85C:
(a) Cu2+ and (b) Fe3+
Table 7 Potentiostatic polarization testing results of CP-Ti at 85C
Additive
Cu2+
Fe3+
Applied
Potential (V)
0.5
0.4
0.6
0.5
i1
(before, A cm-2)
8.17
10.22
9.06
10.62
i2
(after, A cm-2)
2.38
-60.50
0.09
-24.90
i
(A cm-2)
-5.79
-70.72
-8.99
-35.52
Percentage of current for

CP-Ti corrosion (%)
58.52
12.62
50.19
23.01
276
Table 8 Immersion testing results of CP-Ti at 160C

Solution NO.
Sample NO.
1
2
3
4
2
5
6
7
3
8
9
10
4
11
12
13
5
14
15
Note: - means mass gain.
1
Corrosion Rate
(mm/yr)
0.032
-0.064
0.000
0.032
0.043
0.032
-0.011
-0.032
-0.064
0.011
0.021
-0.043
0.021
-0.064
-0.021
Figure 3 Sample morphology of CP-Ti after 21 days of immersion in sulfuric acid with different
additions at 160C
277
Linear Polarization Tests at 160C

The LPR scan began when both temperature and OCP were stable at 160 5C. The results of
LPR tests in different solutions are presented in Table 9. The change in OCP for these three solutions is
consistent with the results obtained below 100 C. All polarization resistance values are very low and the
results in solution with 1.0g/L Fe3+ are extremely low (indicating high corrosion rates). During testing in
solutions with Cu2+, there were copper particles formed in the bottom of the autoclave. The working
electrode holder and reference electrode bridge in the autoclave were made of 316L stainless steel and were
slightly corroded after testing with solution 1 and 5. After testing in solution 4, with 1.0 g/L Fe3+, there was
severe pitting damage (Figure 4) which is unlike anything these authors have seen after immersion for less
than 4 hours at 100-160 C. The high CP-Ti corrosion rate obtained in solution 1, 4 and 5 is inconsistent
with the observations made at temperatures below 100C and further electrochemical work with this
system is underway.
Table 9 LPR testing results of CP-Ti at 160C
solution
no.
1
4
5
OCP
(mV)
214
348
332
Rp
()
74.7
10.0
77.0
i
(mA cm-2)
0.35
2.60
0.34
Corrosion Rate
(mm/yr)
3.04
22.61
2.96
Working electrode holder
Reference electrode bridge
Figure 4 Pitting damage on the 316L working electrode holder and reference electrode bridge in the
autoclave after 4 hours immersion at 160C in ferric containing solution
278
CONCLUSIONS
Based on electrochemical measurements, the corrosion rate of CP-Ti under medium temperature
chalcopyrite concentrate leaching conditions is high according to the standards for relative corrosion
resistance and deserves further study. The corrosion rates of CP-Ti were lower when metal cations (cupric
or ferric) were present in solution under 160C. Potentiostatic testing demonstrated that although cathodic
currents from ferric and cupric reduction interfered with the CP-Ti corrosion rate measurements, the error
was not significant. Corrosion rates obtained from the immersion tests at 160C followed the same trend
(as regards response to various solutions) as the data obtained electrochemically at temperatures below
100C. It is postulated that due to the very small solution volume-to-specimen area ratio used in this
study, the electrochemically obtained corrosion rates at 85C are significantly higher than the immersionmeasured corrosion rates at 160C. All polarization resistance results obtained in the autoclave were very
low resulting in high corrosion rates, especially in ferric-containing solution where a corrosion rate in
excess of 20 mm/yr was measured. There was severe pitting damage to any stainless steel exposed to this
ferric-containing solution.
ACKNOWLEDGEMENTS
The authors acknowledge the financial support of the Natural Sciences and Engineering Research
Council of Canada. J. Liu recognizes the China Scholarship Council for the Canada-China scholarship.
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and Corrosion Behavior of Titanium. Journal of The Electrochemical Society, 106, p. 759-764.
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Vaughan, J., 2003. Corrosion of titanium and its alloys at high temperatures and pressures. M.A.Sc, The
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281
ARSENIC STABILITY AND CHARACTERIZATION OF CESL PROCESS RESIDUES

*R. Bruce1, K. Mayhew1, G.P. Demopoulos2, A. Heidel3
1
Teck Resources Limited

12380 Horseshoe Way
Richmond, Canada V7A 4Z1
(*Corresponding author:robert.bruce@teck.com)
2
McGill University
Montreal, Canada H3A 2B2
3
Aurubis AG
Hovestrae 50
20539 Hamburg, Germany
ABSTRACT
Teck and Aurubis are working together to commercialize a technology for the processing of
copper arsenic sulphide concentrates that is economic and sustainable with regards to the environment and
community. The pressure hydrometallurgical approach is a desirable option as mineral extraction and
arsenic fixation can take place in a single autoclave vessel. A test work program was carried out where a
range of copper concentrates with varying arsenic grades was processed under CESL leach conditions.
This paper discusses the stability character (in terms of arsenic) of the resulting residues and their
mineralogy. The basic ferric arsenate sulphate phase (BFAS; otherwise known as type 2) was identified as
the main arsenic carrier. All CESL residues demonstrated high stability (<1 mg/L As) through a range of
aggressive (pH and ORP) environmental leach conditions.

Niagara, ON, Canada
Edited by
282
INTRODUCTION
Arsenic deportment and control in the copper industry needs an integrated approach involving
each stage of the value chain, i.e. exploration, mine operation, refining process and mine closure. Teck
Resources Limited (Teck), Canadas largest diversified mining company and Aurubis, Europes largest
copper producer, have formed a partnership to advance the application of CESL copper-gold technology
for the development of high arsenic bearing copper resources (Bruce et al., 2011).
Among the options for arsenic control in the metallurgical treatment of copper concentrates is the
precipitation of ferric arsenate, which is widely accepted as the most suitable method for stabilizing arsenic
(Ferron and Wang, 2003). The pressure hydrometallurgical approach to processing arsenic bearing copper
concentrates is a favorable option as mineral extraction and arsenic fixation can take place in a single
autoclave vessel. Under CESL pressure leaching conditions (150 C, 1380 kPa) high copper extraction and
arsenic (V) fixation is possible.
Within the pressure leach autoclave, arsenate and ferric iron react to form scorodite type phases.
The precipitate formed under CESL conditions is dependent on the Fe (III) /As (V) ratio and the tenor of
cations and anions, particularly excess sulphate (Gomez et al., 2011a). Previous studies on CESL residues
have found arsenic to be present as crystalline scorodite (FeAsO4.2H2O) (Bruce et al., 2011), basic ferric
arsenate sulphate (BFAS: Fe(AsO4)1x(SO4)x(OH)x(1x)H2O, where 0.3<x<0.7), and/or arsenate adsorbed
on to hematite (Gomez et al. 2011b). Although not a focus of previous work, scorodite was the
predominant precipitate formed when the concentrate Fe/As was <1.5 (Mayhew et al., 2010), and BFAS
was the predominant precipitate when the concentrate Fe/As was >10 (Gomez et al. 2011b).
The stability of crystalline scorodite and BFAS has been researched through a range of studies on
pure samples. Gomez et al. determined that both compounds exhibited negligible amounts of arsenic (<1
mg/L) in a TCLP-like 24 hour leachate. Longer-term testing implied that these compounds were quite
stable at a pH of 7, with BFAS being equally or slightly more stable than scorodite (Gomez et al., 2011a).
Characterization of arsenic precipitates in a dynamic copper leach plant is complex and requires
stability data to assist in identifying and characterizing such materials. Ultimately, study of environmental
and extrinsic factors that affect residue stability is required to ensure responsible mining, refining and
residue management practices. This paper discusses the stability character of CESL residues and their
mineralogy.
RESIDUE SAMPLE PRODUCTION
The residues to be analyzed for arsenic stability were produced at Tecks CESL facility in
Richmond, BC. The CESL facility employed a fully integrated pilot plant flowsheet to process copper
concentrate continuously to produce LME Grade A copper cathode and a washed residue stream for
testing. The residues discussed in this paper were produced in 2010 when several different copper arsenic
sulphide concentrates were processed to examine metals extraction, arsenic deportment to the final plant
residue, and final residue stability. The results of this work are summarized below and were published
(Bruce et al., 2011). The chemical and mineralogical analyses of the four concentrates processed during
the 2010 pilot plant campaign are presented in Table 1 and Table 2.
Table 1 Pilot plant concentrate elemental composition
Element (wt. %)
As
Cu
Fe
S
A
0.7
21.2
24.5
26.8
B
1.4
25.8
24.5
36.0
C
1.5
27.1
24.9
33.9
D
4.6
29.5
19.6
33.5
283
Table 2 Pilot plant concentrate mineralogy

Mineral (wt. %)
Chalcopyrite
Bornite
Luzonite/Enargite
Tennantite
Chalcocite / Covellite
Pyrite
Arsenopyrite
Gangue
Formula
CuFeS2
Cu5FeS4
Cu3AsS4
Cu12As4S13
Cu2S / CuS
FeS2
FeAsS
-
A
43
8
--3
9
2
23
B
22
6
5
1
18
38
-9
C
49
10
6
2
4
20
-9
D
38
7
20
2
5
18
-8
Concentrate A was processed to assess the health and safety controls in place at lower arsenic
tenors. Once the performance of these controls was confirmed, materials with a higher arsenic grade were
introduced to the plant. Test work on concentrate A is not discussed in this study.
The concentrates were introduced to the autoclave along with acidic feed liquor containing
chloride ions at a concentration of 12 g/L. Oxygen was sparged into the slurry and the resultant mixture
was processed at 150C and 1380 kPag for 90 minutes. The autoclave discharge slurry was sent to a
thickener for solid liquid separation. The residue proceeded to a counter current decantation circuit for
final washing while the copper rich PLS was processed in a solvent extraction circuit for copper recovery.
Following solvent extraction the raffinate was sent to an evaporator circuit to recover water for use as wash
solution throughout the process. A portion of the evaporator product was processed through a low (1.8 pH)
and high (8.5 pH) neutralization circuit for sulphate and impurity removal. Finally, the evaporator product
and neutralization product solutions were combined and recycled to the autoclave as feed liquor.
The residues produced in the copper pilot plant were subsequently processed through the CESL
gold pilot plant to assess the impact that alkaline processing (10.5 pH) might have on the stability of the
arsenic compounds. In the gold plant the residues were repulped with lime and processed through a
stainless steel pressure vessel at ambient temperature and a pressure of 2700 kPag. NaCN solution was
added to the pressure vessel and the residue was processed for 90 minutes prior to being discharged and
filtered. Their chemical compositions are given in Table 3.
Table 3 Chemical composition of copper and gold pilot plant residues
Element
(wt. %)
As
Cu
Fe
S (total)
S
Concentrate B
Cu Plant
Residue
1.8
1.2
29.7
26.2
16.9
Au Plant
Residue
2.0
1.0
28.1
26.4
17.7
Concentrate C
Cu Plant
Residue
2.0
1.0
34.2
27.0
23.3
Au Plant
Residue
1.7
0.8
27.4
25.3
17.7
Concentrate D
Cu Plant
Residue
6.1
1.3
25.7
27.7
23.4
Au Plant
Residue
5.7
1.7
27.6
25.9
21.5
In addition to these pilot plant residues, a flotation test was conducted on the concentrate C copper
plant residue to produce a concentrate and tailing sample. The purpose of this flotation test was to upgrade
the elemental sulphur content of the residue to examine the impact that this may have on the stability of the
arsenic phases contained. The chemical composition of these residues is presented in Table 4.
284
Table 4 Chemical composition of residues produced by flotation of concentrate C copper plant residue
Element (wt. %)
As
Cu
Fe
S (total)
S
Flotation Concentrate
0.99
1.93
17.2
72.9
66.0
Flotation Tailings
2.4
0.75
42.5
10.5
7.5
The 2010 pilot plant operations met metallurgical performance targets by achieving 97% copper
extraction for all concentrate samples and arsenic deportment of 99.5% to the final plant residues. Further
work however was required to assess the stability and suitability of residues for long term disposal. To
determine this, a comprehensive residue stability assessment program was developed.
STABILITY PROGRAM DESCRIPTION
McGill University was contacted to assist in generating a program. The stability program
comprises a detailed work plan that can be broken down into two main categories: residue characterization
and residue stability testing.
Residue Characterization
The characterization of the residue solids focused mainly on mineralogical analysis. The analyses
included X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersive X-ray
spectrometry (SEM-EDS, MLA), X-ray photoelectron spectroscopy (XPS), Micro-Raman analysis
(Raman), and Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR). All
residues produced were subjected to XRD and MLA analysis at Tecks Applied Research and Technology
center (ART) in Trail, BC. Following these analyses, selected residues were sent to McGill for XPS,
Raman, and ATR-FTIR analysis.
Residue Stability Testing
The stability of the residues produced in the copper and gold plants were tested using two
different methods. The first was the Toxicity Characteristic Leaching Procedure (TCLP, EPA Method
1311). This method involves gently agitating the solids in a pH adjusted solution for a period of 18-24
hours prior to analyzing the content of the filtered slurry. Maximum levels are set for the allowable
concentration of various elements in the filtrate. Arsenic was of the greatest interest for this study. The
TCLP analyses were conducted at the CESL research facility.
The second type of stability testing was conducted externally by Maxxam Analytics International
for a period of 8 weeks. The range of conditions tested for the various residues are presented in Table 5
with 98 tests being completed in total. The pH and Eh for all tests were either controlled to a set value or
adjusted at the beginning of the test and allowed to drift for the duration of the test. For the highest arsenic
content residues (concentrate D) additional tests were conducted at elevated temperatures (40C), while all
other tests were conducted at ambient temperature (21C).
285
Table 5 Test conditions for the first batch of residue samples

Variable
pH
Eh
Conc. B & C,
all residues
6, 7, 8 controlled
8 drifting
Conc. D,
all residues
5, 6, 7, 8, 9 controlled
7, 8, 9 drifting
50 mV, 300 mV,

Unadjusted
50 mV, 300 mV,

Unadjusted
These medium term stability tests involved placing 75 g of residue solids in 1.5 L of distilled
water and subjecting the mixture to mild agitation using a gyratory shaker at 100-110 rpm with a lateral
motion of 2 cm. The pH, conductivity, and potential of the tests were measured at scheduled times. This
was done daily for the first week, every two days until the end of the fourth week of testing and twice per
week thereafter. Upon measurement, if the pH or potential of a controlled test had deviated from the
target, an adjustment would be made using concentrated H2SO4 or 5% Ca(OH)2 slurry for pH and Na2SO3
or Na2S9H2O for Eh. At times tests that were below the potential target were allowed to agitate without
being capped in order to allow the potential to naturally increase through air entrainment. In all other
cases, the tests were purged with nitrogen for 1 minute prior to replacing the caps.
A 20 mL slurry sample was collected and filtered through a 0.2 m filter and submitted for ICPOES analysis. On days when sampling was scheduled to coincide with measurement of pH, conductivity
and potential, the sample for analysis was taken prior to measurement. The final sample was performed in
duplicate.
RESULTS
Residue Characterization
Characterization of residues produced from hydrometallurgical processes poses challenges as the
residues are generally finely intergrown with multiple compounds present in low concentrations when
compared to the bulk of the material. The CESL Process residue samples contained an abundance of
elemental sulphur and hematite when compared to the relatively low arsenic content. The XRD analysis
provided a quantitative assessment of the crystalline phases present but detected the presence of amorphous
materials. Insufficient crystalline arsenic phases were detected to host the required amount of arsenic
suggesting that a portion of the arsenic was present in an amorphous state.
The MLA analysis is able to provide better resolution than XRD and is not limited to identifying
only crystalline phases though it can be limited by fine grain sizes and intergrown species. The MLA
results were able to detect a Fe-SO4-As-hydrate species that contained the majority of the arsenic
contained in the residue samples. This Fe-SO4-As-hydrate phase appeared in the samples as a fine-grained
matrix of agglomerate material and also as disseminated free spheres. The MLA was able to detect the Asphases in the residues but without a positive identification of the mineral associations.
Based on the XRD and MLA results, further analysis was required to positively identify the
arsenic phases present in the CESL plant residues. Four samples were submitted to McGill which included
concentrate B, C, and D copper plant residues and concentrate D gold plant residue.
XPS investigates the surface chemistry of a substance, being able to determine elemental
composition of materials as well as providing chemical state and phase information. Two types of XPS
analysis were conducted. First, scans were conducted that focused on the As 3d orbital to determine the
oxidation state of the arsenic contained in the residue samples (+3 vs +5). These scans showed a good
correlation to the As 5+ curve as opposed to the As 3+ curve. This confirms that the arsenic contained
within these residues is present as some type of arsenate phase. Scans were also conducted on several
286
arsenate standards and the CESL residues show that the arsenic is in a chemical state that closely matches
with that found in sulphate
sulphate rich BFAS (Figure
(
).
1).
Figure 1 XPS As 3d spectra for 4 CESL residues and BFAS (sulphate rich)
he residue samples were then subject to vibrational analysis by Mirco
Mirco-Raman.
Raman. This method is
The
molecularly based and offers good sensitivity to ~ 1 wt%. Initial scans were run on the CESL residues
prior to sulphur removal with the result that only hematite and elemental sulph
sulphur
ur were identified. Even
after removal of the elemental sulphur no appreciable amount of arsenate phase was identified due to the
trong contribution of hematite.
strong
IR spectroscopy was chosen to further investigate arsenic speciation of the residue samples.
ATR-IR
The wavelength where arsenate, sulphate, and hydroxyl/water are detected differs from the wavelength
where iron oxides and sulphides are identified (Gomez
(Gomez et al., 2011
2011a).. This allows for an analysis of the
arsenate and sulphate environment
environment without interference from the abundant hematite and elemental sulphur
present in the solids. The scans conducted on the residue samples indicated that the materials fell into two
subsets with the concentrate
oncentrate B and concentrate
oncentrate C residues showing similar signatures
signatures, and likewise the
oncentrate D copper and gold plant residues exhibiting similarities. To understand the types of arsenic
concentrate
compounds present,
present the signatures for these two subsets of sample were compared against various arsenic
standards
standards including crystalline scorodite, BFAS (both arsenate rich and sulphate rich), as well as arsenic
bearing basic ferric sulphate and natrojarosite.
For the copper plant residues produced by processing concentrate B (Sample 1) and concentrate
oncentrate C
(Sample 2),
2) the signatures showed significant peaks in the sulphate region and a peak in the 1200 cm -1
indicative of the presence of jarosite in the sample (Figure
(
2).
This peak is less pronounced in the plot for the concentrate C residue indicating a lesser amount
of jarosite was present. Both signatures present multiple peaks in the arsenate region indicating that the
arsenic contained within the samples is not present as crystalline scorodite which presents a single peak.
Based on the signatures for the various arsenate standards this multiple banding for arsenate appears
similar to the arsenate region seen for sulphate rich BFAS. This would mean that the arsenic in these
samples is contained as BFAS or jarosite. Literature has shown that the ability of jarosi
jarosite
te to incorporate
arsenate into its structure is limited (Dutrizac
Dutrizac et al, 1987).
1987 . This would suggest that the majority of the
arsenic is contained as BFAS though there is a possibility that some arsenic may be adsorbed onto the
hematite present.
287
Figure 2 ATR-IR
IR plots for various arsenate standards, concentrate B copper plant residue (Sample 1), and
concentrate C copper plant residue (Sample 2)
The second subset of residues, concentrate D copper
opper plant residue
esidue (Sample 3) and concentrate D
p
esidue (Sample 4), are compared to arsenate containing BFS, BFAS (sulphate rich) and
gold plant
residue
natrojarosite in Figure 3.
Figure 3 ATR-IR
IR plots for various arsenate standards, concentrate D copper plant residue (Sample 3),
and concentrate D gold plant residue (Sample 4)
ue to the multiple bands detected in the arsenate environment and the lack of matching water
Due
hydroxyl bands,
bands the conclusion is drawn that the arsenate is not present as scorodite in these samples. One
item of interest is the presence of the jarosite sulphate band in the concentrate D copper plant
lant residue
esidue and
its absence in the concentrate D gold
old plant residue.
esidue. This can be attributed to the additional retention time
by processing the copper plant residue at an elevated pH in the gold process. There are definite similarities
in the character of the arsenic bands for both residue samples as well as the sulphate rregions
egions when
compared to BFAS.
BFAS. This would suggest that the arsenic present in these solid
solidss is contained in BFAS.
288
Residue Stability Testing

The TCLP testing was carried out by collecting residue samples from the pilot plant operations
and analyzing them several times a week. This resulted in the collection of 58 samples
samples, with tthe
he values for
arsenic in filtrate given in Figure 4.
Figure 4 Arsenic in filtrate for residue samples submitted for TCLP analysis
The TCLP results were positive with all residues produced in the copper and gold pilot plants
being well below the arsenic EPA limit of 5 mg/L and the British Columbia limit of 2.5 mg/L
mg/L.. The
majority of the samples were below the detection limit for arsen
arsenic by ICP-OES
OES of 0.1 mg/L (any samples
below the detection limit are shown as having 0.05
0.05 mg/L As in filtrate in Figure 4.
The highest arsenic value of 0.3 mg/L was obtained when analyzing residues produced from
processing concentrate D (~ 6% As). Processing
rocessing the material through the gold pilot plant did not
negatively impact the results of the TCLP analysis. These results compare well with TCLP results from
literature for scorodite and BFAS (Swash
(
and Monhemius, 1994
1994;; Gomez et al. 2011a
2011a).
ts from the medium term stability test work are extensive and include charts of arsenic
The results
solubility, pH, and potential for all 98 tests completed. Of these results
results, it is apparent that the residues
tested fell into two distinct categories: Low arsenic (~
( 2%) materials that exhibited little arsenic solubility
regardless of the conditions tested and high arsenic (~
( 6%) materials that showed variable arsenic solubility
and provided insight on the impact of the conditions tested on the stability of the arsenic bearing materials.
The low arsenic materials consisted of:
of: concentrate B copper and gold plant residues, concentrate
C copper and gold plant residues, and the residues produced during the flotation of conce
concentrate
ntrate C copper
plant residue. The results from the tests on these residues showed that after eight weeks of stability testing
testing,
the arsenic value in filtrate was less than the ICP-OES
ICP OES detection limit. This result held true for all
conditions tested. An ICP-MS
ICP MS scan was conducted on a selection of filt
filtrate
rate samples after 4 weeks of
testing to confirm the accuracy of the ICP-OES
ICP OES results.
results . The MS scan confirmed that there was arsenic
present in solution and that in all cases it was at concentrations below 0.1 mg
mg/L.
/L. As the arsenic in filtrate
values for all tests conducted for the low arsenic content samples presented the same low values after 8
weeks of testing they warrant no further discussion. However, the slurry potential of the tests conducted
on the flotation
flotation concentrate and tailings produced from concentrate C copper plant residue are of interest as
the elemental sulphur content in the residues varies by a factor of close to 10. This is worthy of
289
consideration as it is thought that the presence of elemental

elemen tal sulphur within the residue sample would lead
to reducing conditions which have been shown to result in solubility of various arsenic compounds
McCreadie et al, 2000).
2000 The slurry potentials for tests conducted on the flotation concentrate and tailings
(McCreadie
produced from concentrate C copper plant residue without adjustment of the test potential are shown in
Figure 5 and Figure 6.
Figure 5 Slurry potential for concentrate C

flotation concentrate test
Figure 6 Slurry potential for concentrate C

flotation tailings test
The slurry potentials shown in these charts indicate similar trends for both materials tested. For
tests where the pH was maintained at a set target the potential de
decreased
creased slightly throughout the test
reaching a final value of 150-200
150 200 mV after 8 weeks. For the tests where the pH was allowed to drift (pH 8,
Drifting),
Drifting) the slurry potential increased throughout the test with 8 week values being 300
300--350
350 mV. The
concentrate
concentrate C flotation concentrate sample did have the lower potential after 8 weeks when compared to
the tailings sample. Based
ased on the large difference in elemental sulphur content (66% in concentrate versus
7.5% in tailings) between the two samples,
samples if the presence of this compound created reducing condition
conditions,
the difference in test potentials measured should have been far more pronounced.
For the high arsenic materials (concentrate D copper plant residue and concentrate D gold plant
residue) measurable values
values for arsenic in filtrate were detected
detected. The
he results from these tests are more
informative than
tha those for the low arsenic materials. For
or these tests
tests, a broader range of pH was tested (pH
5 through pH 9) as well as one set of tests conducted at elevated temperature (40 C).
Figure 7 and Figure 8 present the arsenic in filtrate values for tests conducted on concentrate D
copper plant residue with constant pH as well as a drifting pH
pH, but with no adjustment of the slurry
potential.
potential
testing, the arsenic concentration in filtrate for all tests was low (< 0.3 mg/L)
After 8 weeks of testing,
with no test showing an increasing trend in the amount of arsenic present in solution. From Figure 7 it is
apparent that at a pH of 8 the amount of arsenic in filtrate
filtrate increased as compared to the lower pH tests.
This behavior was even more pronounced for the test conducted at a pH of 9 as would be expected based
on literature (Bluteau and Demopoulos, 2007).
2007). For all tests conducted at a pH of less than 8 the arsen
arsenic
ic in
filtrate after 8 weeks of testing was less than 0.1 mg/L. With both figures, it is apparent that an initial
amount of arsenic was detected after one day of testing. This can be partially attributed to entrained
arsenic from the residue sample. The immediate decrease noted after one week of testing is believed to be
through hematite adsorption of the arsenic.
Figure 8 shows that though the initial pHs of the tests were elevated (pH 8 9), the final arsenic
in filtrate did not match those of the tests
tests conducted at the matching controlled pH. This can be attributed
to the fact that for all drifting pH tests the slurry pH quickly decreased to the 44-55 range and remained there
for the duration of the test. This range of pH has been shown in literature (Bluteau and Demopoulos, 2007)
290
to be most favorable for arsenic stability for many arsenic bearing compounds. The same series of tests for
concentrate D gold plant residue are shown in Figure 9 and Figure 10.
Figure 7 Arsenic in filtrate for concentrate D Cu

Plant residue with constant pH and drifting Eh
Figure 8 Arsenic in filtrate for concentrate D Cu

Plant residue with drifting pH and Eh
Figure 9 Arsenic in filtrate for concentrate D gold

plant residue with constant pH and drifting Eh
Figure 10 Arsenic in filtrate for concentrate D

gold plant residue with drifting pH and Eh
The gold plant residues show low solubility of arsenic (0.1 0.2 mg/L) for the conditions tested.
Once again the tests conducted without pH control gave more favorable results when compared to the tests
where the slurry pH was controlled to achieve a specific
specific target. This can be attributed to the slurry pH
decreasing to a value of approximately 4.. This decrease in pH was more gradual for these tests which may
account for the brief increase in arsenic concentration followed by a gradual decrease. It is also worth
noting that the initial arsenic peak detected for the copper plant residues after one day of testing w
was not
apparent in these tests. This suggests that the soluble arsenic was washed from the residue within the
gold plant.
To compare to the results for the scenario where no adjustment was made to the slurry potential
potential,
two thresholds were considered: a slurry potential of less than 300 mV Eh and less than 50 mV Eh. For
these tests the slurry potential would only be adjusted should it exceed the target potential. The results of
tests conducted on concentrate D copper plant residue at both of these potential thresholds are shown in
Figure 11 and Figure 12.
The tests conducted at a potential of less than 300 mV produced results that were similar to those
conducted without any potential control. At the end of the eight week test cycle
cycle, a final arsenic in filtrate
value of less than 0.l mg/L was achieved. The tests conducted below an Eh of 50 mV provided very
different results. In these tests
tests the arsenic in filtrate began to increase after 2 weeks of testing and were
still increasing at the end of the 8 week test cycle. The results for tests conducted on the concentrat
concentratee D
gold plant residue showed similar behavior. This data suggests tha
that a modest decrease in slurry potential
291
should not be detrimental to the stability of the residues produced within the CESL autoclave but that a
strong reducing environment can result in increased arsenic solubility. This phenomenon has been shown
rature
re for various arsenate compounds.
compounds
in literatu

copper plant residue with Eh less than 300 mV

copper plant residue with Eh less than 50 mV
The final variable considered in this study was the impact of increased temperature on the stability
of the residues produced. The results for these tests are presented in Figure 13 and Figure 14. The arsenic
ltrate values for these tests were higher than those for tests conducted under the same conditions aat
in filtrate
ambient temperature,
temperature in agreement with previous observations (Bluteau
Bluteau and Demopoulos, 2007
2007), though
the arsenic in filtrate values were still less than 0.5 mg/L.

copper plant residue at 40C

gold plant residue at 40C
CONCLUSIONS AND FUTURE WORK

The test program conducted on the various arsenic bearing concentrates and the subsequent
residue stability testing of the materials produced was successful with all materials passing TCLP analysis
for arsenic as well as producing low concentrations of arsenic
arsenic in filtrate after leaching the samples for 8
weeks. The
he findings
findings from this work have helped to advance the collective efforts of the Teck
Teck-Aurubis
Aurubis
partnership for the future development of high arsenic bearing copper resources. The main conclusions th
that
at
can be drawn
drawn from this work are as follows:
The material produced when processing arsenic bearing material through an autoclave under
CESL conditions and 90 minutes retention time is thought to be Basic Ferric Arsenate Sulphate
2. This theory is supported by TCLP results which
(BFAS),, previously identified as Type 2.
match those for synthetic BFAS as well as XPS and ATR
ATR-IR
IR data that exhibit similarity to these
synthetic materials.
292
When tested under various pH and potential regimes, material containing 1-2.5% arsenic did not
present detectable levels of arsenic in filtrate after 8 weeks of leaching. This was achieved even
though the amount of elemental sulphur contained within the samples varied from 7.5-66%.
The materials that contained elevated (>6%) levels of arsenic performed well, producing less than
0.1 mg/L arsenic in filtrate after 8 weeks of testing under a variety of conditions. Tests conducted
at elevated (>7) pH and low (<50 mV) Eh produced the highest levels of arsenic in filtrate as
supported by existing literature. All leachates produced through the 8 week trial were far below
the EPA TCLP limit of 5 mg/L.
To continue this work, several items have been highlighted for further study. Firstly, explore the
impact of autoclave retention time on the character of the residue produced. At 90 minutes retention time,
the autoclave residue still contains amorphous material that may be eliminated at longer retention times.
Secondly, conduct testing on materials containing even higher amounts of arsenic to determine whether
there is a critical level of arsenic that, once exceeded, impacts the character of the residues produced.
Finally, advanced characterization methods such as the use of the synchrotron at the Canadian Light
Source have been suggested as a method to more quantitatively identify the arsenic phases present in the
CESL residue regardless of the complex environment.
The impact of the stability results contained in this paper will be explored further in future
projects, through integrating the leach results into an environmental assessment and permitting process
related to a mineral development project.
ACKNOWLEDGEMENTS
Thank-you to all Teck operations and maintenance staff who were integral in the production of the
residues studied in this paper. A special thanks to all Teck and Aurubis technical staff involved in the
analysis of this data as well as the residue characterization work at ART. The authors would also like to
thank the staff of McGill University, specifically Mario Gomez, and Maxxam Analytics International for
their fine work and guidance.
REFERENCES
Bluteau, M. and Demopoulos, G.P., 2007. The incogruent dissolution of scorodite Solubility, kinetics
and mechanism. Hydrometallurgy, Volume 87, p. 163-177.
Bruce, R., Heidel, A., Kadereit, H., Mayhew, K., Mean, R. and Wagner, O., 2011. Unlocking Value in
Copper Arsenic Sulphide Resources with the Cu-As CESL Technology, Hydrocopper 2011
Proceedings, Via del Mar, Chile.
Ferron, J. and Wang, Q., 2003. Striving for a Sustainable Mining Industry: Arsenic Control through an
Integrated Approach. SGS Lakefield Research Limited, Mining and the Environment Conference,
Sudbury.
Gomez, M. A., Becze, L., Celikin, M. and Demopoulos, G.P., 2011b. The effect of copper on the
precipitation of scorodite (FeAsO42H2O) under hydrothermal conditions: Evidence for a
hydrated copper containing ferric arsenate sulfate-short lived intermediate. Journal of Colloid and
Interface Science, Volume 360, Issue 2, p. 508518.
Gomez, M., Becze, L., Cutler, J. and Demopoulos, G.P., 2011a. Hydrothermal reaction chemistry and
characterization of ferric arsenate phases precipitated from Fe2(SO4)3-As2O5-H2SO4 solutions.
Hydrometallurgy 107, p. 74-90.
293
Schippers, A., & Jrgensen, B.B., (2001). Oxidation of pyrite and iron sulfide by manganese dioxide in
marine sediments. Geochimica et Cosmochimica Acta, 65, p. 915-922.
Sequeira, C.A.C., Santos, D.M.F., Chen, Y., & Anastassakis, G., (2008). Chemical metathesis of
chalcopyrite in acidic solutions. Hydrometallurgy, 92, p. 135-140.
Smith, F.G., &d Kidd, D.J., (1949). Hematite-goethite relations in neutral and alkaline solutions under
pressure. American Mineralogist, 34, p. 403-412.
Tenailleau, C., Pring, A., Etschmann, B., Brugger, J., Grguric, B., & Putnis, A., (2006). The transformation
of pentlandite to violarite under mild hydrothermal conditions. American Mineralogist, 91, p. 706709.
Tromans, D., (1998). Temperature and pressure dependent solubility of oxygen in water: a thermodynamic
analysis. Hydrometallurgy, 48, p. 327-342.
Warner, T.E., Rice, N.M., & Taylor, N., (1996). Thermodynamic stability of pentlandite and violarite and
new EH-pH diagrams for the iron-nickel sulphur aqueous system. Hydrometallurgy, 41, p.
107-118.
Watmuff, I.G., (1974). Supergene alternation of the Mt Windarra nickel sulphide ore deposit, Western
Australia. Mineralium Deposita, 9, p. 199-221.
Xia, F., Zhou, J., Pring, A., Ngothai, Y., & ONeill, B., (2007). The role of pyrrhotite (Fe7S8) and the
sample texture in the hydrothermal transformation of pentlandite ((Fe,Ni)9S8) to violarite
((Ni,Fe)3S4). Reaction Kinetics and Catalysis Letters, 92, p. 257-266.
Xia, F., Brugger, J., Chen, G., Ngothai, Y., ONeill, B., Putnis, A., & Pring, A., (2009). Mechanism and
kinetics of pseduomorphic mineral replacement reactions: A case study of the replacement of
pentlandite by violarite. Geochimica et Cosmochimica Acta, 73, p. 1945-1969.
295
CHALCOPYRITE: BIOLEACHING VERSUS PRESSURE HYDROMETALLURGY

F. Habashi
Laval University, Quebec City
(Fathi.Habashi@arul.ulaval.ca)
ABSTRACT
While bioleaching of pyrite concentrates has been successfully used in industry to liberate gold from
the sulphide matrix for subsequent cyanidation, the same technology cannot be recommended for leaching
chalcopyrite concentrates for copper recovery. It will be shown to be uneconomical and cannot compete with
pressure leaching technology. Data on the pilot plants that were constructed for this purpose and were shut
down will be given.

Niagara, ON, Canada
Edited by
296
INTRODUCTION
Bacterial leaching has been successfully applied for heap leaching of low-grade copper ores
(Habashi, 1978, 1999). One of the major operations is that at Bingham in Utah (Figure 1). The leach
solution collected at the bottom of the heap is extracted by organic solvents and the strip solution is
electrolyzed to get high purity copper. The process was extended to treat auriferous pyrite concentrates to
liberate gold and render it amenable to cyanidation by a process known as BIOX (Marsden & House, 2006;
Lunt & Briggs, 2005).
BIOX plants currently or recently in operation are the following:
Ashanti Goldfields Company, Ghana. Designed with an initial capacity of treating 720 tonnes of
concentrate per day, the Sansu plant has since been expanded and currently has four modules
processing 960 tonnes per day in all. It is by far the largest biooxidation plant in the world. The
capital cost of the plant totalled US $25 million (1994 terms) and the operating cost is currently US
$17/tonne milled.
Fairview, South Africa. The plant at the Fairview mine in Barberton, which was the initial pilot plant,
has been fully operational since 1986. It was originally designed to treat 10 tonnes/day of concentrate
but with the success of the project this has been increased to 55 tonnes per day. With the purchase of
Fairview by Avgolds Eastern Transvaal Consolidated, Avgold concluded a licensing agreement with
Gold Fields, formerly known as Gencor, entitling it to use the BIOX technology to treat its
concentrate.
Sa Bento, Brazil. A BIOX plant was recently in operation in Brazil at the Sa Bento Mine where a
pressure oxidation circuit is used to treat the refractory flotation concentrate. This plant has confirmed
the viability of combining bio-oxidation with pressure oxidation as a cost-effective method of
increasing capacity at an existing oxidation plant.
Wiluna, Australia. The plant at Wiluna Gold Mine, Western Australia, was commissioned in 1993.
Although originally designed to treat 115 tonnes per day of concentrate this has subsequently been
increased to 158.
Other plants at Tamboraque in Peru, Harbour Lights and at Youanami in Australia have been
commissioned recently.
Figure 1 - Bioleaching of low grade copper ore at Bingham in Utah

BIOLEACHING OF CHALCOPYRITE
In the past few years there has been interest to apply bacterial leaching to treat chalcopyrite
297
concentrates. For example, according to Paul Miller, Vice President Engineering of BacTech Mining
Corporation, a continuous small scale bioleach pilot plant was established to investigate the bioleaching of
chalcopyrite concentrates in 1998 by BacTech at Mt. Lyell in Tasmania (Miller, 2006). The plant was
integrated with downstream solvent extraction and electrowinning for copper recovery. Treating a few
kilograms a day of concentrate over a period of a year, the plant achieved 96% extraction of copper. It was
found further that the process could be applied successfully on concentrates containing arsenic.
According to the same source, the technology was extended and a demonstration scale plant was
constructed in 2001 by the joint technology partnership of BacTech and Mintek in conjunction with
Peoles in Monterrey in Mexico (Figure 2). The plant operated for a year with a capacity of 200 tpa
copper cathode production using commercial equipment, and demonstrated well the technical feasibility of
a totally integrated process with high levels of copper recovery from arsenic-containing concentrate blend.
On completion of the demonstration trial, a feasibility study was conducted for a commercial bioleaching
plant having an annual capacity of 25,000 tonnes of copper. However, due to the low price of copper at
that time BacTech did not go forward with the project to a commercial scale.
Figure 2 Pilot plant for bioleaching of chalcopyrite concentrates at Peoles in Monterrey (2001)
It is interesting that in 2002, Alliance Copper, which is a joint venture between BHP Billiton and
Codelco in Chile, also built a 20,000 tonnes/year demonstration plant near Chuquicamata (30 km from
Calama) in Chile for $50 million. The plant is composed of six large reactors, mechanically agitated, and
lined with acid-resisting brick. Since a thermophilic bacteria is used in the system it is possible to operate
at a temperature of about 90oC and this accelerates the reaction.
With the increase in copper prices in 2006 Paul Miller believed that the situation was then ready
to exploit this technology. In spite of this enthusiasm for bioleaching technology, one cannot recommend its
use for leaching chalcopyrite concentrates because it cannot be economical for the following reasons. The
leaching reaction for chalcopyrite is as follows:
CuFeS2 + 4O2 CuSO4 + FeSO4
From this it can be seen that a large amount of oxygen will be consumed, a large amount of lime will
be needed to precipitate ferrous sulfate, and there will be an excessive disposal and material handling problem
of ferrous hydroxide gypsum mixture:
298
FeSO4 + Ca(OH)2 + 2H2O Fe(OH)2 + CaSO4.2H2O

The reaction is slow; it is complete in 4 5 days when conducted and in addition, some bacterial
nutrients such as phosphate and ammonium ions must be supplied to the reaction mixture. In the recovery
step by electrolysis, acid will be generated and must be disposed of. Actually, all attempts to apply this
technology for chalcopyrite concentrates have failed.
PRESSURE LEACHING OF CHALCOPYRITE
When bioleaching technology is compared with pressure leaching, the reaction that takes place in
one autoclave at 150 oC and 1000 kPa oxygen partial pressure is as follows:
2CuFeS2 + 4H+ + 2O2 2Cu2+ + Fe2O3 + 4S + 2H2O
The advantages of this route are the following:
The reaction is fast, complete in 20 30 minutes

Oxygen consumption is 1 moles per mole chalcopyrite as compared to 4 moles in the case of
bioleaching, that is less than one third that required for bacterial leaching
One reactor is enough
Cu2+ is already separated from Fe2+ since Fe2O3 is precipitated during the reaction
All the sulfur in the concentrate can be obtained in the elemental form
When copper is recovered from solution by electrowinning, the acid generated at the anode is equal to
that required for leaching hence no acid disposal problem
There is no material handling and disposal problem involving lime addition
Any arsenic present in the concentrate will remain in the residue as ferric arsenate
Pressure leaching has been successful for treating pyrite and arsenopyrite concentrates to liberate the
gold in the matrix (Table 1). Figures 3 to 5 show typical autoclaves for treating concentrates while Figure 6
shows a schematic flowsheet for handling the concentrate. Figures 7 to 11 show details of the other
equipment in a pressure leaching plant.
Figure 3 - An autoclave for pressure leaching of pyrite concentrates
Figure 4 - View of a horizontal autoclave in operation
299
Figure 5 - A typical horizontal autoclave
Figure 6 - Typical flowsheet for pressure leaching of sulfide concentrates where an efficient
heat recovery system is in place
Figure 7 - A view of a high pressure piston pump
Figure 8 - Principle of a high pressure piston pump
300
Table 1 - Status of treatment of refractory gold ores by pressure hydrometallurgy

Start up
Plant Location
Owner
Feed
Medium
Capacity
t/d
Number of
autoclaves
ore
acid
2,700
concentrate
acid
240
1985
McLaughlin
USA
Homestake
USA
1986
San Bento
Brazil
Genmin
S. Africa
1988
Mercur, Utah
USA
American Barrick
Canada
ore
alkaline
680
1989
Getchell
USA
First Miss Gold
ore
acid
2,730
1990
Goldstrike
Nevada, USA
American Barrick
Canada
ore
acid
1,360
1991
Goldstrike
Nevada, USA
American Barrick
Canada
ore
acid
5,450
1991
Porgera, Papua
New Guinea
Placer Dome
Canada
concentrate
acid
1,350
1991
Campbell
Canada
Placer Dome
Canada
concentrate
acid
70
1992
Con
Lihir
Nerco Minerals
concentrate
---
90
1993
Goldstrike
USA
American Barrick
Canada
ore
acid
11,580
1994
Porgera, Papua
New Guinea
Placer Dome
Canada
concentrate
acid
2,700
1997
Lihir, Papua
New Guinea
Rio Tinto
---
---
---
1997
Dunedin, S.
Island, N.Z.
Macraes Mining
concentrate
acid
20,000
Figure 9 - Section of a flash tank
301
Figure 10 - Flash tanks in a plant
Figure 11 - Ore slurry pre-heater

CONCLUSIONS
Beside application in heap leaching of low grade copper ores, it is believed that bacterial leaching
can be applied only and effectively to liberate gold from auriferous pyrite concentrate but it cannot be
recommended for chalcopyrite concentrates.
REFERENCES
Habashi, F. (1978). Chalcopyrite Its Chemistry and Metallurgy, McGraw-Hill, New York, NY.
Reprinted by Mtallurgie Extractive Qubec, Qubec City, QC, Canada and distributed by Laval
University Bookstore, www.zone.ul.ca.
302
Habashi, F. (1999). A Textbook of Hydrometallurgy (2nd ed.), Mtallurgie Extractive Qubec, Qubec City,
QC, Canada. Distributed by Laval University Bookstore, www.zone.ul.ca.
Marsden, J.O., & House, C.I. (2006). The Chemistry of Gold Extraction (2nd ed., pp. 542-564). Society of
Mining, Metallurgy, and Exploration, Littleton, CO.
Lunt, D., & Briggs, N. (2005). Refractory Sulfide Ores - Case Studies. In M.D. Adams (Ed.), Advances in
Gold Ore Processing (pp. 920-936). Elsevier, Amsterdam.
Miller,
P.
(2006).
Bioleaching
of
http://www.bactech.com/s/Copper.asp.
Chalcopyrite
for
Copper
The
Future,
Zinc
305
LEACH RESIDUE FILTRATION AT THE HUDBAY

ZINC PRESSURE LEACH PLANT
S. Shairp
Hudbay
P.O. Box 1500
Flin Flon, Manitoba, Canada R8A 1N9
(susan.shairp@hudbayminerals.com)
ABSTRACT
After cooling and thickening, slurry from the second stage of the Hudbay zinc pressure leach
circuit is filtered and washed on a belt filter prior to disposal. At times, the belt filter can be a bottleneck to
the process. Preliminary studies show that filterability of the second-stage (HAL) autoclave leach residue
can be indicated by particle size distribution of the filter feed and filtered residue cake. In particular, the
Volume Weighted Mean Diameter, D[4,3], generated by a laser diffraction particle size analyzer from
samples of HAL Filter feed, shows residues that filter more poorly have a lower Volume Weighted Mean
Diameter than those that filter better.

Niagara, ON, Canada
Edited by
306
INTRODUCTION
Hudbay produces cast zinc metal from blends of zinc concentrates at its metallurgical complex in
Flin Flon, Manitoba, Canada, using Sherritts two-stage pressure leach process (Collins et al., 1994;
Collins et al., 1995; Barth et al., 1998; Shairp et al., 2006). Pressure leaching replaced the original roastleach-electrowinning process in 1993.
Filtration for the second-stage (HAL) leach residue originally consisted of two stages of vacuum
drum filtration with intermediate cake repulping stirred tanks. As part of Hudbays 777 Project, with a
designed increase in cast zinc production, a pre-feasibility study by SNC-Lavalin Inc. showed that losses of
soluble zinc in the zinc pressure leach residue could be reduced by installing more efficient filtering and
washing equipment. Based on laboratory performance, capital cost, installation ability, and potential
operating cost savings, a 70 m2 Filtres Phillipe belt filter was chosen for the HAL residue, and
commissioned in 2000/2001.
When the HAL belt filter is performing well, there is no pooling of water on the surface, moisture
content is relatively low, and subsequent analysis shows that water soluble zinc content is relatively low.
There have been occasions where the filter has performed poorly with respect to the aforementioned
parameters. Aside from the filter experiencing mechanical difficulties, there are several variables affecting
leach residue filtration:
Flocculant addition to the thickener and HAL filter feed line

Pulp density (%solids)
Particle size distribution of slurry solids
Slurry temperature
Filter speed
Filter vacuum
Wash water flows
Particle size distribution of HAL Thickener Underflow (HALTU) and HAL leach residue filter
cake (HALCK) was determined using laser diffraction at various times over the course of a few months,
including a time when the filter was performing poorly, to determine if particle size distributions
experienced in the plant indicate filterability of the HAL belt filter.
HUDBAY ZINC PLANT OPERATIONS
Pressure Leaching
Zinc concentrates typically contain sphalerite, ZnS, along with minor amounts of pyrite, FeS2, and
other sulphides, e.g., chalcopyrite, CuFeS2. At the Hudbay zinc plant, the zinc concentrate feed is
comprised of a blend of local and purchased concentrates. The blend is ground in a ball mill to achieve
>98% passing 325 mesh (45 m). The solids are thickened and pumped to a feed storage tank at
approximately 70 wt% solids, at a temperature of 45 to 48C.
The autoclaves operate at a temperature of 145-150C. Over 99% of the zinc is leached in the two
stages, leaving a residue from the second-stage leach (HAL) containing elemental sulphur, oxidic species
including jarosites and iron oxyhydroxides , gypsum/anhydrite, unreacted sulphides and gangue minerals.
Flashing and Conditioning from HAL Autoclave
HAL autoclave discharge is depressurized and cooled in two stages via one of two flashpots and a
flash tank. The flash tank pressure is monitored to keep the temperature above about 118C, above the
melting point of sulphur. The flash tank is equipped with a variable frequency drive. By adjusting the
agitator speed, the size of the molten sulphur droplets can be varied, which was important when the sulphur
307
separation circuit was on line. However, present practice is to maintain constant agitator speed. The size
of the sulphur droplets is also influenced by the composition of the leach residue and by the type and
addition rate of sulphur dispersants added to the autoclave (Chalkley et al., 1993).
The flashed slurry continues to an agitated conditioning tank in order that the sulphur may
transform to monoclinic crystal form.
The slurry is then forwarded to the HAL Thickener. The operator monitors the clarity of the
thickener overflow and adjusts flocculant addition to the HAL thickener feed line as required. The
operator also controls the thickener underflow discharge rate to maintain a pulp density of about 1.48 kg/L.
If the pulp density is too high, dilution water can be added to the HAL Belt filter feed box.
HAL Thickener underflow is pumped through a cooling tower, reducing the slurry temperature to
about 80C. The temperature of the residue is automatically controlled by the air flow rate through the
cooling tower. Too high a temperature would flood the vacuum system of the filter with steam.
Discharge from the cooling tower then flows into the filter feed tank. The slurry is pumped to the
HAL filter feed box, where it is mixed with flocculant, and dilution water, if necessary, then flows onto a
Filtres Phillipe 70 m2 horizontal belt filter. The residue undergoes three stages of countercurrent washing
as it is filtered. In the first and second stages the cake is washed with filtrate from the third stage of the
HAL filter. In the third stage, the cake is washed with evaporate from the zinc plants 4-stage evaporator.
PARTICLE SIZE TESTING
Samples were analyzed with a Malvern Instruments Mastersizer 2000 laser diffraction particle
size analyzer. All samples were analyzed within one day of the sample being taken. Sonication was turned
on for 2.0 minutes, which, in prior testwork, was found to be the minimum time required to produce stable
measurements.
Laser diffraction calculates the equivalent volume mean, D[4, 3] of the particle set, i.e., the central
point of frequency the volume distribution would rotate (Rawle, n.d.).
Water Soluble Zinc
Analyses of the filter cake samples are shown in Table 1. Samples were taken September 28,
2011 due to high moisture content in the filter cake: it is seen that this sample had a high water-soluble zinc
content. The subsequent samples were taken when the filter cake moisture content was, visually, as
expected.
Table 1 - Analysis of HAL filter cake (HALCK) samples
28-Sep-11
25-Oct-11
23-Nov-11
27-Jan-12
Zn
%
3.90
1.12
0.37
1.48
wsZn
%
3.71
0.90
<0.1
1.13
Fe
%
18.96
17.26
19.23
20.81
Cu
%
0.22
0.20
0.29
0.45
Pb
%
0.60
0.95
1.02
0.87
Ca
%
0.20
0.31
0.21
0.13
308
Flocculant addition to the HAL Thickener was consistent for all samples taken. The same
flocculant is also added to the feedbox of the HAL Filter. Flocculant dosage to the filter feedbox for the
samples taken varied, but did not correlate to the particle size distribution.
28-Sep-11
25-Oct-11
23-Nov-11
27-Jan-12
Volume (%)
5
4
3
2
1
79.4
104.7
60.3
45.7
34.7
26.3
20.0
15.1
11.5
8.7
6.6
5.0
3.8
2.9
2.2
1.7
1.3
1.0
0.7
0.6
0.4
0.3
Particle Size (um), not to scale
Figure 1 - HAL filter cake particle size distribution

There is a distinct difference in the shapes of the particle size distributions between the time of
poor filtration and those when the filter performed better. In the bimodal pattern, the coarser peak
represents the sulphur particles, which float naturally in the zinc sulphate solution, and can been seen in the
HAL Thickener Underflow. The finer peak represents the precipitates and gangue. The absence of one
peak in the September 28 sample may indicate that the sulphur micropellets were unusually fine or that the
sulphur micropellets had deposited as scale prior to the sample point. In the latter case, it would be
expected that assays would indicate iron enrichment; elemental sulphur analysis will be done to determine
if the sulphur has been depleted or not.
8
7
28-Sep-11 HALTU
Volume %
27-Jan-12 HALTU
5
4
3
2
1
182.0
138.0
104.7
79.4
60.3
45.7
34.7
26.3
20.0
15.1
11.5
8.7
6.6
5.0
3.8
2.9
2.2
1.7
1.3
1.0
0.7
0.6
0.4
0.3
Particle Size (um ), not to scale
Figure 2 - HAL thickener underflow particle size distribution

HAL Thickener Underflow samples show a similar distribution pattern, seen in Figure 2, though
some coarser particles were detected in the September 28 sample, particles 104-208 m totaled 0.12 vol%.
309
Comparison of particle size distribution in Figure 3 for the January 27, 2012 HALTU and
HALCK show that the distributions are similar:
6
27-Jan-12 HALCK
27-Jan-12 HALTU
Volume %
5
4
3
2
1
8.
7
11
.5
15
.1
20
.0
26
.3
34
.7
45
.7
60
.3
79
.4
10
4.
7
5.
0
6.
6
2.
9
3.
8
1.
7
2.
2
1.
0
1.
3
0.
6
0.
7
0.
3
0.
4
Particle Size (um ), not to scale
Figure 3 - HAL thickener underflow and HAL filter cake particle size distribution
In contrast, samples taken September 28, 2011 show relatively different distributions, shown in
Figure 4.
8
7
28-Sep-11 HALCK
Volume %
28-Sep-11 HALTU
5
4
3
2
1
158.5
104.7
69.2
45.7
30.2
20.0
13.2
8.7
5.8
3.8
2.5
1.7
1.1
0.7
0.5
0.3
Partice Size (um ), not to scale
Figure 4 - HAL thickener underflow and HAL filter cake distributions

Further investigation will need to be done to determine the cause of the difference. One possibility
is that particle dispersion was not complete with the amount of sonication time.
Slurry Temperature
Review of the filter feed temperature shows that for the September 28 sample, the filter feed
cooling tower temperature was the highest at 86.3C.
310
Table 2 - Filter feed cooling tower temperatures

Sample
Sept 28, 2011
Oct 25, 2011
Nov 23, 2011
Jan 27, 2012
Filter feed cooling

tower temperature, C
86.3
82.7
81.3
80.7
Basin and Nenashev (2000) showed that the transformation from monoclinic -sulphur to
orthorhombic -sulphur begins at about 95.4C and finishes at about 83C, though, in their work, one
sample did not complete transformation until 78.9C. It was noted that the purity of the samples played a
significant role.
In addition, monoclinic sulphur is sticky and known to contribute to scaling of process equipment
and blind filters, whereas orthorhombic sulphur is non-sticky (Fraser and McCombe, 2011).
If sulphur, which tends to have a coarser particle size distribution than the rest of the leach
residue, is depositing as scale, this would show an increase in fineness of the particle size distribution,
which may result in blinding of the filter cloth.
D[4,3] and Effect of Sample Preparation
D[4,3] is significantly lower with the September 28, 2011 sample than for the other samples. This
may be in part due to loss of sulphur micropellets as deposits on process equipment, which are coarser, and
may be sticky due to the temperature dependency of the crystal form.
During testing of the early samples, deposition of residue in tubing of the analyzer was visible
even after one measurement. Addition of sodium hexametaphosphate (HMP) to later samples prevented
buildup in the tubing. Comparison of the change showed that D[4,3] increases with addition of HMP, but
not enough to affect the results significantly.
Table 3 - D[4,3] with or without sodium hexametaphosphate (HMP)
HALCK Sample
D[4,3], m
No HMP
14.459
19.129
19.739
Sept 28, 2011

Oct 25, 2011
Nov 23, 2011
Jan 27, 2012
D[4,3], m
With HMP
20.502
21.771
wsZn
%
3.71
0.90
<0.1
1.13
HAL Thickener Underflow showed a similar significant difference, as seen in Table 4.

Table 4 - HALTU D[4,3]
HALTU Sample
Sept 28, 2011
Jan 27, 2012
D[4,3], m
No HMP
15.996
D[4,3], m
With HMP
20.208
311
Water soluble zinc did not necessarily correlate to D[4,3] which is not unexpected, as there are
other factors affecting filterability.
CONCLUSIONS AND RECOMMENDATIONS
While there are more easily identifiable indications of filtration behaviour of the HAL leach
residue on its dedicated belt filter, including cake moisture content, and monitoring of parameters affecting
filterability, preliminary studies show that laser diffraction analysis can give a singular parameter for
comparison of potential filterability. This may be in part due to fineness of sulphur micropellets or loss of
sulphur micropellets as deposits on process equipment, which would be determined by elemental sulphur
analyses of the samples.
ACKNOWLEDGEMENTS
Hudbay and Sherritt management are acknowledged for granting permission to publish this paper.
REFERENCES
Barth, T.R., Hair, A.T.C., & Meier, T.P. (1998). The operation of the HBM&S Zinc Pressure Leach Plant.
In J.E. Dutrizac, J.A. Gonzalez, G.L. Bolton & P. Hancock (Eds.), Zinc and Lead Processing (pp.
811-823), CIM, Montreal, Canada.
Basin, A.S., & Nenashev, B.G. (2000). Points of melting-crystallization and polymorphic transformations
of sulfur in density-temperature coordinates. High Temperatures High Pressures, Vol. 32, 461466.
Chalkley, M.E., Collins, M.J., & Ozberk, E. (1993). The behaviour of sulphur in the Sherritt Zinc Pressure
Leach Process. International Symposium - World Zinc 93 (pp. 325-331), Hobart, Australia.
Collins, M.J., McConaghy, E.J., Stauffer, R.F., Desroches, G.J., & Krysa, B.D. (1994). Starting up the
Sherritt Zinc Pressure Leach Process at Hudson Bay. Journal of Metals, Vol. 46, No. 4, 51-58.
Collins, M.J., Masters, I.M., Ozberk, E., Krysa, B.D., & Desroches, G.J. (1995). Operation of the Sherritt
Zinc Pressure Leach Process at the HBMS Refinery: the first fifteen months. In T. Azakami, N.
Masuko, J.E. Dutrizac & E. Ozberk (Eds.), Lead-Zinc 95 (pp. 680-696), MMIJ, Tokyo, Japan.
Fraser, K.S., & McCombe, W.E. (2011). Method for removing sulfur from a gas stream. United States
Patent Application Publication No. US 2011/0174155 A1.
Rawle, A. (n.d.). Basic principles of particle size analysis. Malvern Instruments Limited Technical Paper
MRK034.
Shairp, S., Barth, T.R., & Collins, M.J. (2006). Control of iron in the Hudson Bay Zinc Pressure Leach
Plant. In J.E. Dutrizac & P.A. Riveros (Eds.), Iron Control Technologies (pp. 171-187), CIM,
Montreal, Canada.
313
COPPER AND CADMIUM REMOVAL FROM ZINC SULPHATE SOLUTION

* S.M. Rebelo, R.G. Helberg
Hudbay
P.O. Box 1500
Flin Flon, Manitoba, R8A 1N9
(* Corresponding author: SRebelo@HudBayMinerals.com)
ABSTRACT
Copper and cadmium are removed from the zinc sulphate solution in primary purification by
cementation reaction followed by filtration. The solids are sent to the cake leach section where zinc and
cadmium are recovered from the copper rich slurry. The copper solids from cake leach are filtered, bagged
and sold. In order to achieve a lower cadmium copper cake, an altered process flow is suggested. It is
proposed the primary purification be split into two steps for individual removal of copper and cadmium.

Niagara, ON, Canada
Edited by
314
INTRODUCTION
Copper cake is a product of primary purification, also known as copper and cadmium removal.
Copper and cadmium are removed by cementation reaction in four stirred reaction tanks. The slurry is then
filtered through Shriver manual plate and frame presses with the solution advancing to the next stage of
purification, hot zinc purification (HZP). The solids from primary purification are further processed at the
cake leach section where zinc and cadmium are separated from the copper rich slurry. Cadmium and zinc
are dissolved in the cold cake leach tanks using spent electrolyte. Cadmium is recovered from this
cadmium rich solution by cadmium sponging, leaching and electro-winning circuits. The residue from this
cold leach step is further leached using spent electrolyte at a temperature of 85C. The copper rich solids
from hot cake leach are filtered on a drum filter and bagged in 1 ton bulk bags for shipping to buyers.
Current assays of copper cake are shown in Table 1.
product that is below 0.5% cadmium.
The goal is to produce a copper cake
Table 1 Copper cake assays

Element
Cu
Cd
Zn
Pb
Copper Cake (%)

70.0
5.4
4.2
4.5
In order to reduce the cadmium impurity in the copper cake, it is proposed that primary
purification be split into two steps, a copper removal and a cadmium removal section. Copper will be
cemented in the first step and the cadmium, together with the remaining copper, will be cemented in the
second step. The cadmium removal solids will be sent to cake leach where the remaining copper is
separated from the cadmium. The copper solids produced in the cake leach section will still have high
cadmium content, however the amount of this cake produced will be much less than the higher quality
copper cake produced in the copper removal section.
TEST WORK AND RESULTS
Test work involved copper removal step tests, cadmium removal step tests, and cadmium removal
solids leach tests. Most of the test work focused on the copper removal step tests to determine the optimal
conditions. The cadmium removal step tests and cadmium removal step solids leach tests were performed
to determine the down stream results.
Copper Removal Step Tests
The goal of the copper removal step tests is to cement copper out of a typically 145 g/L zinc
sulphate solution containing 850 mg/L copper and 850 mg/L cadmium, retaining a copper cake with
cadmium content less than 0.5%.
The conditions varied during testing were zinc dust addition, temperature, pH, and retention time.
The results and conditions of each of the copper removal tests are shown in Table 2.
315
Table 2 Copper removal step test results

Test
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
17
18
19
20
Zn dust
Zn/Cu
mol/mol
1.22
1.12
0.98
0.88
0.78
0.69
0.54
0.45
0.71
0.64
0.73
0.64
0.55
0.74
0.74
0.60
0.45
0.58
0.58
pH
Temp
o
4.23
4.25
4.60
4.60
4.78
4.78
4.53
4.53
4.66
4.66
4.70
2.00
4.56
4.23
4.23
4.66
4.50
C
70.0
65.0
69.0
67.0
76.0
71.0
73.0
78.0
75.6
70.0
72.7
81.0
74.7
65.4
65.5
65.6
71.7
48.0
85.2
Retention
Time
minutes
30
45
30
30
30
35
30
30
120
30
30
30
30
30
120
30
35
120
120
Solids
Cu
%
81.56
80.35
85.45
86.06
85.62
80.64
87.78
85.69
85.58
80.75
86.75
88.13
87.39
81.83
83.05
85.20
88.02
50.24
97.86
Solids
Cd
%
2.66
2.00
1.19
0.91
0.70
0.28
0.39
0.33
0.33
0.15
0.52
0.43
0.40
4.51
1.21
0.50
0.29
0.13
0.11
Solids
Zn
%
4.37
4.78
2.10
1.71
2.26
1.95
1.29
0.86
1.19
1.89
1.26
0.67
0.84
3.13
2.43
1.52
0.87
20.49
0.28
Solids
Pb
%
0.390
0.430
0.280
0.260
0.150
0.130
0.080
0.040
0.039
0.082
0.074
0.026
0.047
0.160
0.272
0.105
0.088
0.097
0.054
Cu
Recovery
%
99.12
99.12
97.46
97.46
93.68
66.23
70.10
61.72
81.23
50.92
85.98
87.58
81.45
36.46
73.82
94.58
78.08
71.24
65.75
Effects of Zinc Dust Dosage

The cementation reaction requires zinc dust addition to the primary purification tanks. The
majority of the copper removal step test work was performed to determine the ideal zinc dust dosage
required to cement as much as possible copper yet minimizing cadmium cementation.
Cd in Solids (%)
The test results show the cadmium content in the copper cake to be lower where zinc dust addition
dosages were lower. Figure 1 suggests that a stoichiometric zinc to copper ratio of 0.7 or less produces
solids with cadmium less than 0.5%.
2.8
2.6
2.4
2.2
2
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1.10
1.20
Zn/Cu (mol/mol)
Figure 1 - Zinc dust dosage versus cadmium in solids
1.30
316
The results further show, as seen in Figure 2, a lower copper recovery associated with zinc dust
additions of lower stoichiometric zinc to copper ratio. Considering the requirement of optimized copper
recovery yet limiting the cadmium content to 0.5% or lower, the ideal zinc to copper ratio zinc dust
addition is between 0.6 and 0.7 stoichiometric.
At zinc dust additions lower than 0.6 zinc to copper ratio, no significant further improvement is
seen in lowering cadmium levels in the copper cake yet a decline in copper recovery is seen. The copper
not recovered in this step is recovered at the cadmium removal step, but will be a lower quality copper
product.
120
Cu Recovery (%)
100
80
60
40
20
0
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1.10
1.20
1.30
Zn/Cu (mol/mol)
Figure 2 Zinc dust dosage versus copper recovery

The zinc and lead assay results for the copper removal test solids are shown in Figures 3 and 4.
Both zinc and lead content in the solids are lower at lower zinc dust dosage.
5.2
4.8
4.4
Zn in solids %
4
3.6
3.2
2.8
2.4
2
1.6
1.2
0.8
0.4
0
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1.10
Zn/Cu (mol/mol)
Figure 3 Zinc dust dosage versus zinc in solids
1.20
1.30
317
Pb in Solids (%)
0.48
0.44
0.4
0.36
0.32
0.28
0.24
0.2
0.16
0.12
0.08
0.04
0
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1.10
1.20
1.30
Zn/Cu (mol/mol)
Figure 4 Zinc dust dosage versus lead in solids
Effects of pH
A higher pH test with the addition of sodium hydroxide, and a lower pH test with the addition of
sulfuric acid were performed. Both the lower and higher pH tests produced solids high in cadmium and
zinc. For the lower pH test there was plating of copper on the equipment which is why the copper recovery
for this test is low. Altering the pH from the operating pH of 4.5 will not improve the quality of the
copper cake.
Effects of Temperature
For the three temperature tests the ideal pH and Zn dust dosage were used. These tests were
performed at the operating temperature of 65 oC, one test at a lower temperature of 48 oC, and the other test
at a higher temperature of 85 oC.
The lowest copper in the filtrate results from the temperature of 65 oC. Lower copper in the
filtrate indicates higher copper in the solids. The 65 oC test also cemented copper at a faster rate than both
the lower temperature and higher temperature tests; after 5 minutes the amount of copper remaining in the
filtrate was only 23% of the initial amount. The amount of copper remaining in the filtrate after five
minute intervals for the three temperature tests are shown in Figure 5.
The cadmium in solids assays for the three different temperature tests are shown in Table 3. In all
three cases, the required 0.5% or below cadmium in the solids was achieved. The lower copper in the
filtrate results, and thus suggested superior copper recovery, suggest that the temperature of 65 oC is the
ideal temperature. This overshadows the slight improvement in copper cake quality with regard to the
lower cadmium.
318
100
Cu remaining in the filtrate

(% of initial Cu)
90
80
Operating
Temp, 65
degrees
70
60
Lower
Temp, 48
degrees
50
40
30
Higher
Temp, 85
degrees
20
10
0
0:00
0:15
0:30
0:45
1:00
1:15
1:30
1:45
2:00
2:15
Time
Figure 5 Temperature versus copper in filtrate

Table 3 Effect of temperature on cadmium in the solids
Test Temperature
Operating Temperature, 65 oC
Lower Temperature, 48 oC
Higher Temperature, 85 oC
Cd in Solids (%)
0.21
0.13
0.11
Effects of Retention Time

There are five available primary purification tanks. The proposed new process splits the primary
purification into two separate sections; copper removal and cadmium removal steps. The first two primary
purification tanks are to be used for copper removal with the remaining three reaction tanks are to be used
for cadmium removal. The total available retention time for the copper removal step using two reaction
tanks is approximately 36 minutes and 18 minutes when one of the tanks is down for cleaning or repair.
Two retention time tests were performed for a total of 120 minutes at the ideal zinc dust dosage,
temperature, and pH. The filtrate copper assays for samples taken at different intervals throughout the test
for both tests are shown in Figure 6.
It was determined that the ideal retention time is between 30 and 40 minutes. At a retention time
between 30 and 40 minutes the copper in the filtrate is at the lowest resulting in the highest possible copper
in the solids. The cadmium in the filtrate remained relatively constant throughout the tests. However, for
both tests the cadmium in the filtrate was high after 30 minutes, indicating lower cadmium in the solids at
this retention time.
It can also be seen that after approximately 18 minutes, the retention time when only one tank is
available, the copper is low enough in the filtrate to produce a high quality copper cake. The two available
tanks for copper removal are thus sufficient to produce a high quality copper cake.
319
1100
1000
900
Cu (mg/L)
800
700
Test 9
Test 15
600
500
400
300
200
100
0
0:00 0:15 0:30 0:45 1:00 1:15 1:30 1:45 2:00 2:15
Time
Figure 6 Retention time versus copper in the filtrate for Tests 9 and 15
Ideal Conditions
The purpose of the copper removal step tests is to determine the ideal zinc dust dosage, pH,
temperature, and retention time that will produce a copper cake less than 0.5% in cadmium. A range of 0.6
0.7 zinc to copper, stoichiometric ratio produces a copper cake with the lowest amount of cadmium in the
solids.
The temperature range of between 65 and 70 oC combined with a pH of 4.5 are the conditions
seen in the current primary purification process. It is recommended that these remain the same for the new
process. The ideal retention time is between 30 and 40 minutes, which is also the available retention time
in the new design using two tanks for copper removal. These ideal conditions are tabulated in Table 4.
Table 4 Ideal conditions for the copper removal step tests
Condition
Zn/Cu ratio (mol/mol)
pH
Temperature (oC)
Retention Time (minutes)
Ideal Range
0.6 - 0.7
4.5
65 - 70
30 - 40
Cadmium Removal Step Tests
The goal of the cadmium removal step tests is to cement the cadmium and the remaining copper
from the copper removal step filtrate. After filtration the solution proceeds to hot zinc purification. The
solids are further processed at the cadmium removal solids leach step where cadmium, copper, and zinc are
separated.
In the plant, the new process will have three available reaction tanks for the cadmium removal
step; the available retention time is approximately 45 minutes. During the test work we determined the
ideal retention time for the cadmium removal step is approximately 20 minutes; the three available reaction
tanks are sufficient for cementing the cadmium and remaining copper. The filtrate assays for this test are
shown in Figure 7.
Analyses of the resulting solids from the cadmium removal step are shown in Table 5. The
resulting solids are higher in cadmium and lower in copper when compared to the current primary cake, a
320
Cu and Cd (mg/L)
typical assay also reported in Table 5. A similar or modified leach process to what is currently being used
to treat the primary cake will be utilized to leach this cadmium removal solids cake.
900
850
800
750
700
650
600
550
500
Cu
450
Cd
400
350
300
250
200
150
100
50
0
0:00 0:10 0:20 0:30 0:40 0:50 1:00 1:10 1:20 1:30 1:40 1:50 2:00
Time
Figure 7 Cadmium removal step test filtrate results

Table 5 Cadmium removal step test solid results compared to typical primary cake
Element
Cu
Zn
Cd
Pb
Cd Removal Step Test Solid Results (%)

14.39
33.21
22.74
0.79
Typical Primary Cake (%)

25.28
28.17
14.65
1.33
The filtrate from the cadmium removal step will feed the hot zinc purification process. The
cadmium removal step test filtrate is compared to the current hot zinc purification (HZP) feed assays in
Table 6. Test work resulted in a filtrate copper content of 3.3 mg/L which is higher than the typical assay
for copper in the HZP feed; however there have been times when the current process HZP feed copper
level is as high as 5 mg/L with no issue removing this copper in HZP.
Table 6 Cadmium removal step test filtrate results
Element
Cu
Co
Cd
Cd Removal Step Test Filtrate Results (mg/L)

3.3
23.9
9.36
HZP Feed (mg/L)

0.41
17
70
The test work proved this altered cadmium removal step to be a viable option, yielding a filtrate
that can be further processed in the next stage of purification (HZP).
Cadmium Removal Solids Leach Step Tests
The goal of the cadmium removal solids leach step tests is to leach the cadmium into solution for
recovery at the cadmium circuit, leaving a copper rich cake. This copper cake would then be bagged
separately from the copper removal step copper cake.
321
Several cadmium cake leach tests were done using cake obtained from primary purification during
a period around October 28th, 2011 in which the cake was low in copper. This cake resembled the cake
produced during the cadmium removal tests and was more readily available. The results and test conditions
of these leach tests are shown in Table 7.
Table 7 Cadmium removal solids leach step test conditions and results
Test
Time
Conditions
Acid Addition
(mL/g of cake)
Cd
%
22.74
Zn
%
22.16
Cu
%
14.04
Pb
%
0.82
1
2
3
4
5
6
1:30
5:45
5:00
1:30
5:00
1:30
2.34
2.35
2.35
2.35
4.06
4.06
21.30
1.33
18.40
22.40
16.20
18.30
30.8
0.79
3
3.72
3.28
11
15.2
77.9
54.1
47.8
53.4
42
2.39
6.02
3.02
2.73
3.07
2.45
4:15
2.35
1.42
1.14
80.30
3.84
4:15
2.35
15.46
3.45
54.17
2.91
9
10
4:00
4:45
Cold Leach
Cold Leach
Cold Leach
Cold Leach
Cold Leach
Cold Leach
Cold leach followed by hot
leach
Sulphuric acid used instead
of spent
Air sparging
More agitation
2.35
2.35
8.48
6.49
1.56
1.6
65.94
59.72
3.63
3.58
Initial
The first six tests were performed to determine the effects of acid dose and retention time. We ran
tests simultaneously under similar conditions with one test stopped after 1 hour and 30 minutes, while the
other test leached for 5 hours. It was determined that tests performed for 5 hours produce a copper cake
that is higher in copper and lower in cadmium than tests leached for 1:30. Tests performed with a higher
acid dose did not result in significantly higher copper or lower zinc than tests performed at the lower acid
dose; the cadmium is slightly lower in tests performed using the higher acid dose but not significantly.
The test with the highest copper in solids was test 7. This test was leached at room temperature,
or a cold leach, followed by a leach at 85 oC, a hot leach. This is similar conditions to the current cake
leach process. The resulting solids from the cold leach followed by hot leach were low in cadmium and
high in copper indicating that the cadmium removal step solids could be leached in the current cake leach
process and result in an acceptable cadmium removal step copper cake.
Other variables that were considered were sparging air into the leach, as well as more vigorous
agitation. These were included in tests 9 and 10. Both of these conditions, particularly air sparging,
improved the quality of the cadmium removal step copper cake and should be considered in improving the
current cake leach process.
Primary Cake Results in the Plant
The same primary cake that was used in the cadmium removal solids leach tests was also leached
in the cake leach section in the plant. When the copper in the copper removal feed was low the plant cake
leach section produced a copper cake lower in copper and higher in cadmium than typical copper cake
produced. A comparison of the assays of copper cake produced from the primary cake which is similar to
that of the cadmium removal step solids and typical copper cake assays is shown in Table 8.
If the cake leach section remained as it is, cold leach followed by a 85 oC hot leach, the resulting
secondary copper cake produced would be of lower quality copper cake than the current copper cake,
however it was proven in the test work that this copper cake can be improved by optimizing the cake leach
section.
322
Table 8 Copper cake produced in the plant when the copper in the copper removal feed was low
Element
Cu
Zn
Cd
Co
Pb
Copper cake produced when copper in copper

removal feed was low (%)
44.82
9.48
8.79
1.49
8.45
Typical copper cake assays

(%)
62.59
7.06
5.52
0.94
5.48
Mass Balance
The copper removal step test work in the ideal stoichiometric zinc to copper ratio range of 0.6 0.7 resulted in approximately 76% recovery of copper in the copper removal step copper cake. A total of
approximately 120 tons of copper is produced per month. Therefore, the resulting copper cakes produced
would be approximately 110 tons of copper removal step copper cake at 84 % copper and 65 tons of
cadmium removal step copper cake at 45% copper per month. Ideally after modifications to the cake leach
section the cadmium removal step copper cake would be higher than 45% copper.
PLANT CHANGES
The primary purification would be split into two separate sections; a copper removal section and a
cadmium removal section. Due to flow rates in the copper removal and cadmium removal sections new
filter presses for the copper removal are likely needed; the current Shriver plate and frame presses would
not work for both copper and cadmium removal presses. Due to the age of the Shriver plate and frame
presses, it is recommended that new filter presses be installed for both the copper removal and the
cadmium removal sections. With the separation of the two processes, new zinc dust feeders would be
required for the cadmium removal section as well as a new storage tank to hold the copper removal filtrate.
The economics of these changes is yet to be determined.
ALTERNATIVES
Separating the copper and cadmium removal into two separate sections is only one option for
improving the copper cake product. There are other options for the separate removal of cadmium and
copper which include recovering the copper directly from the low acid leach autoclave thickener overflow
stream by using direct electro-winning of copper by EMEW cells, or ion exchange followed by electrowinning of copper as copper cathode. Future test work involving these alternatives is to be completed.
CONCLUSIONS
To improve the quality of the copper cake and bring the cadmium below 0.5% the primary
purification should be split into two separate sections; a copper removal step and a cadmium removal step.
After several tests it was determined that the solids from the copper removal step result in
cadmium of less than 0.5%. The ideal conditions for the copper removal step are listed in Table 9.
The cadmium removal step following the copper removal will remove the cadmium as well as the
remaining copper from the solution through cementation by zinc dust addition. The filtrate from this step
proceeds to hot zinc purification for further processing. The solids resulting from the cadmium removal
step are shown in Table 10. These solids will need to be leached to separate the remaining copper and
cadmium in a process similar to the current cake leach process.
The current cake leach section, a cold leach followed by a hot leach, used to leach the cadmium
removal step solids will result in a lower copper content than the current copper cake, however
323
improvements such as sparging air can be made to the cake leach process to increase the copper content in
the solids and increase the cadmium in the filtrate. Using the new process there will be fewer copper solids
that are above 0.5% cadmium, as most of the copper will be removed in the copper removal step. The
cadmium rich filtrate is further processed at the cadmium section.
Table 9 Ideal conditions for the copper removal step tests
Condition
Zn/Cu ratio (mol/mol)
pH
Temperature (oC)
Retention Time (minutes)
Ideal range
0.6 - 0.7
4.5
65 - 70
30 - 40
Table 10 Cadmium removal step test solid results

Cu
%
14.39
Zn
%
33.21
As
%
0.03
Co
%
0.04
Cd
%
22.74
Pb
%
0.79
The test work shows that the primary purification can be separated successfully into separate
copper removal and cadmium removal sections, producing two separate copper cake products; a higher
quality copper cake as well as a copper cake similar to that currently produced. Approximately 110 tons or
75% of the total copper will be in the higher quality copper cake and 25% or 65 tons of the lower quality
copper cake will be produced.
Several changes to the plant will be necessary including the improvement and or replacement of
the Shriver primary presses, and also possible improvement to the cake leach section allowing for air
sparging into the leaching process.
Alternatives such as recovering the copper directly from the low acid leach autoclave overflow
should be investigated and considered.
ACKNOWLEDGEMENTS
The authors would l ike to thank the Hudbay Zinc Plant Technical Group and the Hudbay
Analytical Group.
Equipment Design
327
STRESS ANALYSIS OF BRICK LINED AUTOCLAVES

K. Brooks
KOCH KNIGHT LLC
5385 Orchard View Drive, S.E.
E. Canton, Ohio, USA
kevin.brooks@kochknight.com
ABSTRACT
Acid resistant brick lined autoclaves and related vessels are utilized in pressure oxidation for the
recovery of gold, copper, and other metals. The combination of the corrosion resistant membrane, acid
resistant brick, mortar and steel shell is a composite system that requires a sophisticated stress analysis. In
order to obtain meaningful results both the model and physical properties of the materials must be carefully
selected. Evaluation of the calculated results requires an understanding of both the failure mechanisms of
ceramics and experience with the performance of existing lining systems.

Niagara, ON, Canada
Edited by
328
INTRODUCTION
Acid brick lining systems are used in pressure oxidation autoclaves and related vessels to provide
thermal and mechanical protection for corrosion resistant membranes that are applied directly to the
interior of the vessel shell. The acid brick and mortar must be resistant to the process conditions and must
provide a mechanically reliable structure.
The construction of lined vessels incorporates a wide range of materials that can include the carbon
steel vessel, austenitic weld overlay, lead lining, organic membrane, ceramic brick, mortars and other alloy
components. The physical properties of the materials can vary by orders of magnitude and when combined
in the construction of the lined vessel create a complex composite structure. The materials may be bonded
together or act independently of each other. Stresses are induced into the lined vessel include pressure,
thermal expansion, chemical expansion and mechanical loads.
The complexity of these systems makes it is very difficult to account for all of the variables in the
structural analysis of lined vessels. Historically calculations were simplified and designers primarily relied
on experience with previous applications.
The greatly improved tools for Finite Element Analysis (FEA) available today allow for detailed
calculation of the stresses imposed on the vessel shell and lining. Koning & Lauzon (2004) presented a
paper on design fundamentals including a discussion on the application of FEA methods at Pressure
Hydrometallurgy 2004 in Banff. When a designer carefully constructs a model and selects the correct
materials properties for the calculations, meaningful and useful results can be achieved.
ACID BRICK VS. REFRACTORY
Although they are both ceramic materials, acid brick lining systems are different than refractory
linings in some aspects. The primary requirement for refractory systems is to provide thermal protection
and structures suitable for high temperatures (greater than 500 C). Acid brick linings operate in lower
temperature ranges and acidic solutions. These conditions require a different set of structural
considerations for the design of the acid brick lining. In addition to the thermal expansion, the acid brick
can also exhibit additional expansion due to the chemical interaction of the ceramic materials with the
process solution.
Although it might be anticipated that the stresses in acid brick systems would be lower than
refractory linings given the lower temperature, this is not the case. Due to the combination of a liquid tight
pressure vessel and an acid brick lining that must be free of any open paths to the underlying membrane
system, it is not possible to incorporate any expansion joints into the system. Therefore all thermal stresses
including the additional chemical expansion of the brick are accumulated in the structure.
FINITE ELEMENT ANALYSIS MODEL
The first step for the FEA is to select which sections of the vessel and lining are to be modeled.
Sections of the vessel should be selected for modeling that will provide the desired information without
creating a model that is too complex or overly simplified. Modeling of complete vessels often is not
practical and the desired information can be found by looking at specific areas of the vessel. Typical
sections for consideration are the shell, head, and individual nozzles. The shell and head section will
provide a good overall view of the basis lining construction. The highest stresses are found at the nozzles.
Localized brick lining failure of the brick compression rings surrounding the nozzles has occurred when
brick and mortar system was too brittle to allow for the higher stresses. It also may be desirable to consider
nozzle clusters to study the interaction of nozzles that are in close proximity to each other or other areas
with significant discontinuities in the lining. The shell and head areas can be considered on a 2D basis
while nozzles require 3D modeling. A knowledgeable FEA operator will need to select the nodes and
contact elements.
329
ure 1 Typical
cal model of autooclave section
Figu
ble consideratio
the mo
odel are itemsuttthat
can imposse stresses such
ch as the suppoort
Other possib
Figons
re 1for Typi
clave
es, exterior no
ozzle loading, internal
ures such as co
compartment w
walls and other
er similar item
ms.
saddles
i
structu
moreelesignificant
as ns
thefor
shell
ckness
reduce
ced
applicat
Thesee become
Other possible
possi
considerations
considerati
thethick
m
model
del areis items
that
impoppressure
e stresses
sucations. Another
supp er
hatfor
canlower
impose
rt
deration
is any
ctures
thatstruct
can liimit
influence
cempartment
heat flow frwalls
rom
consid
exterior
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saddl
n zzle
internal
such
as compartment
allsthe
and
oth .
ite s
,
loading,
nternal
structure
re or
These
Thes become more
mor significant as the shell thi
thickness
ness is reduced
redu d for lower pressure
ressure applications.
appli ions. noth
consideration
consi eration is any exterior structures
stru uresMATERIA
that can ALS
llimit
mit orPROPER
influence
influenRTIES
heat flow from
f om the
als properties required
for th
he
FEA
includdeTIES
density, ther
ermal expansiion, modulus oof
r MATERI
The material
MATERIALS
PROPE
LS
PROPERTIES
city, Poisons ration
r
ermal conductiv
vity. In order to evaluate thhe results, the al
allowable limiits
and ther
elastici
quired
for both
h compressive
tensile
esses.
limitsthermal
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be inco
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are req
an
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The materi
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e FEA
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e density,
thcanmal
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that
be
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inal
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n.
matrix
lasticity,
lasti ty, Poisons ration
ation and hermal
h mal conducti
ity. n order to evaluate the
t e results the allowable
lim ts
conductivity.
lowable limits
are required
re uired for bot
ses. The all
allowable
in rporated into
int a
both compressive andd tensile str
stresses.
wable limits can then be incorporated
es part
materials
such
h. as the carbonn steel shell aree readily availab
able within moost
The be
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for standard
matrix
matri that
used as
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fd nal
evaluatio
evaluation.
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operties for materials
m
that are
ar unique or pproprietary willl need to be pprovided by thhe
FEA programs.
p
or properti
h testing.
arematerials
must besuc
tak
aken
when
select
ecting
est
as sttandardized
suppliierThe
through
theseare
Car
for standard
standar
as the
carbon
carbo
steel shell
arprroperties
readily available
avail
le within mo
mtes
such
ods
may
not
always
al
provide
e
the
good
inf
ial
will
perfor
rm
as
part
of
formation
on
how
metho
materi
a
FEA programs.
Pr perties for materials
aterials that aree unique or proprietary
roprietary will
wi l need to be provided
rovided by the
t ea
rograms. Properties
osite.
compo
suppl
C e must be ttaken
en when selecting
sel ing these p operties as s andardized t t
er or throug testing. Care
methods
meth ds may not always
ways provide
provid the good in
information
ormation on how mater
material
perfo m as part of a
al will perform
d published for ceramic m
materials is bas
ased on sonic tes
est
For examplee most moduluss of elasticity data
comp site.
ods. As recom
mmended by Schacht
S
(1995
5), the preferred
metho
ed method forr developing tthe modulus oof
city
use forrmost
the brick
an
ndofmortar
is th
hrough
stress/s
/strain
testingmaterials
samples
at test
of
composite
elastici
Fortoexample
exampl
modulus
modulu
elasticity
data
ata published
for ceramic
aterials
is based
b e ed
on sonic
tthhet
pated
temperatures
developed
ed
stress /sstrain
curves fo
orf
anticip
off ),elasticity
valuues method
Modulus
meth
s recommended
reco g mended
byes.
Schacht
chacht
(199
(1995),
the preferr
preferred
fo from
he modulus
ds. operating
for
developing
the
of
and
mortar
com
mposites
provi
ides
a
better
ap
pproximation
o
of
how
these
m
materials
will
act
as
part
of
th
he
brick
a
elasticity
elasti ty to use for
fo the brick and
a d mortar is tthrough
rough stress/strain
stress train testing of composite
composit samples at the
t e
from
is as stress
a prelim
minary
screenin
lining system.
valuee .of the datas dev
The primary
anticipated
antici
operatin
temperatur
temperatures.
oeveloped
val sonic
velop
velopeds from
/ train curves
fngr
/strain
for
ated operating
elasticity
es demethods
of constr
of theeand
available
brick
composites
coerials
posites
provides
provruction.
des a better aapproximation
proximation off how these materials
aterials will act as part of the
t e
nd mortarmater
lining system.
primary valu of the
a ddeveloped
method is as a preli inary screeni g
eloped from sonic methods
OAD CASES
LO
mat ials of const uction.
consider a ran
ange of load cas
cases.
Once the model is created it
i is desirable
t AD
L to
nto account thee minimum and
an
ambbient temperatuures.
take in
an maximum anticipated
d take
an
heat gain
gto
is expected
should
Onceinto
the acco
moount
itt is solar
desirable
red.ge of load
del iswhether any
o consider
a range
es
take into
i to account th
ticipated ambient
am ient temperatures.
temperat res.
the minimum andd maximum anticipated
should
shoul take into account
acc unt whether anyy solar heat gain
ain is expected.
expect .
mal design muust

The therm
Also thee thermal desiggn
The ther
thermal
m st
al design must
Also the
th thermal desi n
330
The highest stress case may not be at the normal operating conditions. Due to the chemical
expansion of the brick the highest stress values are often found for either the shutdown ccase
ase or for
transitional cases during start-up.
start
This is a result of the expansion
exp ansion of the brick without any compensation
from the thermal expansion of the steel shell.
This is illustrated in the comparison of the compressive stresses in Figures 2 and 3.. Figure 2 shows
the calculated compressive stresses in a brick compression ring at the normal operating temperature and
pressure. Figure
Figu 3 is for the shutdown case at ambient temperature and pressure. The peak compressive
stress in Figure 2 for the normal
normal operating case is 36 MPa while the shutdown maximum compressive
stress in Figure 3 is 44 MPa.
Figure 2 Compressive stresss at normal operating conditions (MPa)
Figure 3 Higher compressive stress at shutdown condition (MPa)
331
Analysis should be performed for the normal operating condition, shutdown after full chemical
expansion of the brick, and a range of transitional points during start-up. Given a typical ramp up rate of
10 C per hour, the total start-up can take 20 hours plus any hold points. Two to three transitional points
should be analyzed for the start-up period.
APPLICATION OF THE FEA THERMAL ANALYSIS
The initial review of the FEA should include a validation step that compares the results with those
actually measured or observed in previous installations. Thermo graphic surveys are good tool to ensure
that the heat transfer film coefficients are reasonable. Figure 4 illustrates the detail information available
from a thermo graphic survey. The thermal surveys must include information on the exterior ambient
conditions and process temperature at the time of the survey to be useful.
Figure 4 Thermograph of autoclave agitator and adjacent nozzles

The thermal part of the FEA should be reviewed first. The allowable temperature for the membrane
is often below the operating temperature of the process. If the initial thermal analysis indicates that the
allowable temperature is exceeded, it will be necessary to consider either a thicker brick lining or possibly
and alternate membrane material. Lead, rubber and various other organic membranes are limited to
continuous maximum service temperatures in the range of 85-100 C. When it is not practical to provide a
lining that insulates the membrane to an acceptable temperature, more expensive weld overlays may
provide a solution. Weld overlays are most often used for nozzle liners where is difficult to compensate
for heat conducted from unlined blinds and pipe connections. Figure 5 provides a typical temperature
profile at an autoclave nozzle.
A common practice in autoclaves and other higher temperature applications is to utilize weld
overlays as part of the membrane system. This allows for the use of less expensive membranes in the
larger body of the vessel while providing a solution for the higher temperatures encountered in the nozzles.
The higher temperatures in the nozzles are due to agitator blinds, multi-nozzle blinds and piping
connections, which are not lined. The blinds and connections are exposed to the full process temperature
and allow the heat to be conducted down the nozzle neck. This limits the value of any insulating material
installed in the nozzle neck. The designer needs the FEA to aid in the selection of the location for the weld
overlay and membrane interface. This is also true of designs which utilize the combination of a lined
carbon steel section and an unlined alloy section.
332
ell and nozzle sect

ection at operat
ating conditionss (C)
Figure 5 Temperaturee profile of shel
Temperatur
sh l
s ion oper ing condition
CATION OF THE
T
FEA STR
RESS ANALY
YSIS
APPLIC
APPLICATION
APPLI ATION OF THE
HE FEA STRESS
ST ESS ANALYSIS
ANAL SIS
ep in the evaluuation is to creat
eate and review
ew a
After the therrmal requiremeents are satisfieed, the next step
thermal
the
requirements
requirem
are satisfi
satisfied,
d, the
nextallo
stowable.
in the The
eval al
cr
create
revi
ation is tolimit
andthe
review
x After
of thethe
highes
estmal
stress
values
es nts
calculated
ver
ersus
allowable
tsefor
vesssela
matrix
those
matrix
matri
the highest
highed tby
stress
values
valu cable
calculated
allowable.
lowable
limi
ves
el
wable.
allowable
the vessel
the applicab
pressurevvers
vs s those
ME
Sectionlimits
VIII,s for
Division
2 oor
vessel
shell are
arofestablished
su
such
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ASM
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establish
by the applicable
appliTh
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esselby the lisuch
AS
Vmiting
I, Division
e established
ch asare
in ASME
E Section
or
the
equivalent standards.
he le
posed
inings
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self VII,
lim
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imp
loads 2that
atr
other
standards.
im
imposed
l nings
are considered
conar
idered
self lim
li
loads th
osed by
linings
for equivalent
higher strress
limits. TThe
her
materials
are
established
ed iting
by testing
an
and
limits
fortheothe
allow the
T e stresses
allowable
allow
for higher
otcer
r materials
are
e established
establish
by testing
and
d
stress
limits
forforother
of the st
manufacturer.
m ess limits. The
ve
stress
ceramic
material
als
can be signnificantly
higher
experiience
The
The allowable
compressiv
er
experience
exper
anufacturer.
compressi
materials
materi
can1.25
be significantly
sig
ificantly
high
manufacturer.
hesmall
compressive
for ceramic
in un
niaxial
testing The
of
pieces
eces.e stress
The ultimat
ateamic
strength
cans be
mes
er
than indicated
i ence of the
higherhigher
under
tim
than
indicated
of small
pi
. The ultimate
ultim
strength
canSchacht
be 1.25(1995
ti 5).
ndicated
pieces.
es higher und
al
loading in
anduuniaxial
asiaxial
muchtesting
as 6 tiimes
loadinnge as
biaxial
higher
forr triaxial
noted by
biaxial
biaxi loading and as much as 6 t mes higher fo
for triaxial loading
loadi g as noted by Schacht (1995)
(199 )
ed by comparisson to previouus
As with thee thermal resullts, the stress analysis shoulld be validated
As with
the
th possible.
results,
resu results
stress
analysis should
shou
be validated
validat
by comparison
compari
on to previous
previo
when
p thermal The
expeerience
with evvidence
of stres
esss
with dprevious
installlations
rts, the may
corrrespond
installations
instal
whenonpossible.
ossible.
correspond
previous
experience
exp ing
rience
with
evidence
e s.idence
of str le,s
esultsatmay
respond
or failure
previous projjects
the co
po
ortions
indicati
relief ations
of with
the lining
stress
If availabl
high
relief
or failure
onements
previous
projects
pro vessel
the wil
pportions
of the bbest
indication
ng that the
stres
lining
indicating
. Ifis availab
measurem
on the
vects atshell
llrtions
provide
confirmati
moodel
valid. e,
stress//strain
stress/strain
stress strain measurements
measur ents on the vessel
essel shell wi
willl provide the best
est confirmation
confirmat on that the model
m del is valid.
o a direct comp
parison of the allowable
al
stres
ess limits, the FE
EA results musst be considered
ed
In addition to
to
tnderstanding
a direct comparison
comoffarison
of the allowable
lowable stress
strwhhich
s limits
the neces
F
FEA
muad
t be considered
consider
A resultsall
must
depth un
properties
are not
ecessarily
addressed
in thhe
the material
with an
a Ininaddition
with
in depth understanding
usuch
of
o the or
material
properties of
which
wm
ich are not necessarily
nsshrinkage
sarily all
dressedand
in the
thee
as the creep
cr
comprressibility
of addressed
m
mortars
membranes,
s derstanding
th
FEA.ann Properties
Properties
such
as difficul
the creep
or comp
compressibility
membranes,
embranes, shrinkage
hrinkage of mortars
ortars and t e
uch are
lteep
to allow
for in
iessibility
the FEAof
moodel.
brick/m
site
mortar
compos
brick/ ortar composite
difficu t to allow for in
n the FEA model.
m del.
ite are difficult
any mitigating iinformation, thhe designer ca
can
Once taking into account the allowable limits and an
Once
limits
and any
y mitigating
information,
nformation,
tlee stress
designer
can
n
mine
if taking
the construction
co into account
of the allowable
ust
be modified
ed
to eliminat
ate
unacceptablthe
values
es.
vessel mu
determ
determine
deter
if the construction
nstruction
the vesselvess
m
must
st shells,
be modified
modifi
to materials
eliminate
elimin seofunacceptable
unacceptab
e stress
values.
valu ng.
inesolutions
ble
sel
alter
ernate
constructioon,
and revisin
thicker orofreinforced
Possib
arre
Possi
a brick
or reinforced
rar.
einforced
ves
vessel
el shells,italternate
alt
nate materials
material
of construction,
constructi
n, or
andoptimized
revising
revisizedg
le solutions
e thicker
or mortar
nstances
is nnecessary
to deevelop
improve
ved
of theeare
the thiickness
In some
in
the
thickness
thials
of the
the the
brick
or mort
mortar.
In some
iinstances
ecessary to develop
d velop improved
impro d or optimized
optimi
ckness
stances it is necessary
to achieve
most
reliab
able. lining
cons
struction.
materi
materials
mater als to achieve
achiev the most reli
reliable
le lining con truction.
ONCLUSION
CO
C NCLUSION
A practice allow
ws for more rig
gorous analysis
is of lined vesssels. The FEA
A can be used tto
Current FEA
FEA
FEtheermal
practice
allo
s for design
more ri
rigorous
analysis
analys
of lined
vessels.
ves ar
els. The
FEA
cansubjected
be used to
ateCurrent
both the
and allows
struct
ctural
of
o orous
the lined
ves
essel.
Specific
ay be
to
areas
that FE
may
evaluat
evaluate
evalu
th or
rmal
and structural
stru
uralassessed
design and
off the
lined vessel.
v assel.
Specific
eas that ismay
mcoomplex
be subjected
too
e both the thermal
er temperatures
can be
an
modified
needed.
analysis
and muust
higher
stresses
Theeareas
higher
high temperatures or stresses can be assessed and
d modified as needed. Th
The analysis is complex
c mplex and must
m st
333
be validated by previous experience with similar applications. When the FEA results are used as a guide
the designer can avoid unanticipated failures and provide improved equipment reliability.
REFERENCES
Koning, A. & Lauzon, P. (2004). Design fundamentals for hydrometallurgy pressure vessel refractory. In
M.J. Collins & V.G. Papangelakis (Eds.), Pressure Hydrometallurgy 2004 (pp. 617-638).
Montreal, Quebec: Canadian Institute of Mining, Metallurgy and Petroleum.
Schacht, Charles (1995). Refractory Linings. New York. Marcel Dekker Inc.
335
EFFECT OF PRESSURE IN LEACHING OF LOW GRADE SULPHIDE ORE AT AMBIENT

TEMPERATURE DEVELOPMENT OF HYDROSTATIC PRESSURE REACTOR
*M.J. Latva-Kokko, T.J. Riihimki
Outotec (Finland) Oy
Kuparitie 10
Pori, Finland 28101
(*Corresponding author: marko.latva-kokko@outotec.com)
ABSTRACT
Oxidation autoclaves are normally operated at elevated temperature and pressure. The
improvement in kinetics is due to combined effect of temperature and partial pressure of oxygen. In this
paper exclusive effect of pressure has been studied with a low grade sulphide ore at below 100 C
temperature. These studies are related to development of a novel tower-like reactor that utilizes hydrostatic
pressure. Technology is designed to generate high amount of effective fluid volume for high solid content
slurries with lower energy consumption and improved kinetics compared to normal atmospheric operation.

Niagara, ON, Canada
Edited by
336
INTRODUCTION
Economical utilization of low-grade ores requires handling of enormous amount of material. This
sets new requirements for process equipment in terms of size and energy efficiency. For example on the
field of mineral processing this has lead to a six fold increase in the operating volume of mechanical
flotation cells over the past two decades. Ore beneficiation methods like flotation greatly reduce amount of
material that needs to be further processed in smelters or hydrometallurgical refineries. However with
some ore types, such as nickel laterites and refractory gold ores, traditional concentration technologies
cannot be utilized. Thus direct leaching of ground ore could be an attractive option. In many cases normal
atmospheric tank leaching has traditionally been a non-feasible option mainly due to high capital and
operational expenses induced by large amount of stirred reactors required. Main restriction for increasing
reactor size to beyond 500 m3 has been mechanical load and power requirements set by mixing in cases
when high dispersion efficiency of gas is required.
THEORETICAL BACKGROUND
In hydrometallurgical industry autoclaves are typically operated at elevated temperature and
pressure. In many cases increase in operating temperature is the desired phenomena and improvements in
kinetics are strongly related to that. Thus increase in pressure might be induced solely by water vapor
pressure. However when gaseous feed is present, pressure itself has a strong effect on leaching kinetics for
various reasons and its role should not be neglected.
Pressure increases leaching kinetics in applications utilizing gas, like oxidative leaching, through
at least three different mechanisms. Firstly pressure increases solubility of oxygen in water. As seen in
Figure 1, according to Tromans (1998), the effect of pressure to solubility of oxygen is in fact higher than
the effect of temperature at a range that pressure leaching processes are typically operated. Increased
solubility of oxygen increases driving force of leaching reactions.
Figure 1 Effect of temperature and pressure on the molal solubility of oxygen in water (Tromans, 1998)
Secondly if temperature is kept constant increase in pressure increases oxygen content inside
dispersed gas bubbles. This is due to the fact that in steady state gaseous phase is saturated with water
vapor. Computational oxygen content inside pressurized vessel that is fed with pure oxygen is shown in
Table 1 below. Oxygen content of reactive gas has a significant effect on leaching kinetics. For example
Cheng and Lawson (1991) reported 40% increase in copper extraction level after one hour when air was
changed to pure oxygen while leaching of chalcocite in sulphate-chloride solution at 85 C temperature.
Later on Harvey and Yen (1998) has proven that oxygen content in the bubbling has a significant role in
leaching rate of zinc and copper concentrates at elevated temperature and pressure. Tests were made at
210 C temperature and 689 kPa over pressure with oxygen concentrations from 65% to 100%.
337
Table 1 Oxygen content of gaseous phase inside pressure vessel fed with pure oxygen at steady state
Pressure (barg)
Oxygen content
1
2
5
10
20
50 %
66 %
83 %
91 %
95 %
Third effect that pressure has to dispersed gas is decrease in bubble size. Luo et al. (1999) found
that inside slurry bubble column bubble size distribution at elevated pressure was significantly smaller than
at ambient pressure. This is partly induced by compression of gas, but Luo et al. pointed out that as
pressure increases, gas inertia increases and surface tension decreases. Therefore the maximum stable
bubble size decreases. Decrease in bubble size distribution increases area for mass transfer between gas
and solution leading in most cases to improved leaching kinetics.
EXPERIMENTAL ARRANGEMENTS
In order to study the exclusive effect of pressure to leaching of a low grade sulphide ore three
batch leaching tests were conducted. Feed material was finely ground multimetal sulphide ore with 91%
below 45 m and D50 around 20 m. Chemical composition of feed material is shown in Table 2.
Table 2 Chemical composition of low grade sulphide ore used in tests
Element
Content
Ni
Fe
Co
Cu
Zn
S
0.35%
11.6%
0.02%
0.27%
1.04%
9.0%
Atmospheric batch leaching test was made in open reactor made of titanium. Fluid volume of the
reactor was 5 L. Reactor was equipped with a mixer having two impellers rotating at speed of 1000 rpm.
Oxygen was fed below the lower impeller with flow rate of 250 mL/min. Pressure leaching tests were
made in one gallon titanium autoclave with fluid volume of 2.7 L. Autoclave was equipped with a mixer
having two impellers rotating at speed of 1000 rpm. Pressure was set and controlled by oxygen feed below
the impeller. Studied over pressures were 3 and 9 bars.
All leaching tests were made with solids concentration of 450 g/L in sulphuric acid solution with
pH of 3.0. Reaction temperature was 90 C and duration of each test 24 hours. During the tests pH and
temperature were followed and samples were taken at 4 to 8 hours intervals in order to find out the
differences in leaching rate.
Extraction curves of nickel, zinc and cobalt are shown in Figure 2. Leaching behavior of these
elements seems to be very similar and clearly dependent on the pressure. Results were very systematic;
extraction of nickel and zinc improved from 46% to 92% and extraction of cobalt from 28% to 78% when
pressure was increased to nine bars. Behavior of iron and copper was different. Iron leached from the ore at
338
the early stage of the batch tests. Leached iron then oxidized and precipitated most probably as goethite as
the batch test continued. Thus in the end iron was mainly in the solids with roughly 0.5% extraction level.
Copper seemed to experience same kind of precipitation behavior during these tests and its extraction level
at the end was at significantly lower level compared to Ni, Zn and Co. Copper precipitation was probably
due to considerably high pH level at the end of the test.
100
90
80
Ni extraction (%)
70
60
50
9 bar
40
3 bar
atm
30
20
10
0
0
12
16
20
24
Time (hours)
100
90
Zn extraction (%)
80
70
60
50
9 bar
40
3 bar
atm
30
20
10
0
0
12
16
20
24
Time (hours)
100
90
Co extraction (%)
80
70
60
50
9 bar
40
3 bar
atm
30
20
10
0
0
12
16
20
24
Time (hours)
Figure 2 Extraction curves of Ni, Zn and Co during batch leaching tests made at different pressures
339
HYDROSTATIC PRESSURE REACTOR

Based on theoretical aspects and test results presented in previous chapters it is clear that increase
in pressure is highly beneficial for oxidative leaching. Based on these findings Outotec has developed a
novel type of reactor that utilizes hydrostatic pressure. This tower-like structure is designed to generate
high amount of effective fluid volume for high solid content slurries with lower energy consumption and
improved kinetics compared to normal atmospheric operation. Even though there can be considerably high
pressure (up to 10 bars) at the bottom of the reactor it is classified as an atmospheric reactor.
Design and Mode of Operation
A schematic drawing of the hydrostatic pressure reactor is shown in Figure 3. Reactor
construction can be divided in three sections. At the bottom of the reactor there is a cylindrical tank that
gives high amount of pressure leaching zone for improved leaching kinetics. Bottom tank also allows
settled solids to be suspended during start-up or in occasional shutdowns. For this purpose tank can be
equipped with additional mixers. Volume of the bottom tank is roughly half of the total effective volume.
Extending from the bottom tank there is a tower-like midsection that consists of inner and outer
tube. Slurry flows downward in the inner tube and upward in the outer tube. Desired hydrostatic pressure is
generated by height of the midsection. Gas is dispersed in to downward flowing slurry in order to
maximize efficiency of gas utilization. Top part of the reactor is designed for smooth circulation of slurry
and removal of excess gas bubbles. Downward pumping impeller is located so that it can be easily
accessed from above for maintenance.
In traditional stirred tank reactors mechanical energy is used to mix the entire content of the tank.
Hydrostatic pressure reactor developed by Outotec operates in a different manner. Here slurry is circulated
inside the reactor. Slurry flow is generated with a downdraft mixer located at top of the inner tube. Mixer
acts like a pump and puts the slurry in motion with 1 m/s flow rate through inner tube. Reactor dimensions
are designed so that upward slurry flow through outer tube is also close to 1 m/s to avoid settling of the
solids.
Power required to keep the slurry in motion inside the tower-like reactor is far less than power
that would be required for mixing the entire content of total fluid volume. Average energy consumption
would be below 0.1 kW/m3 compared to 1 kW/m3 that is typical for traditional stirred reactor when high
dispersion efficiency of gas is required. This enables construction of much larger reactor units ranging
from 1000 m3 up to 5000 m3. Energy efficiency of the hydrostatic pressure reactor is optimized by detailed
design. Down draft mixer is located so that it pumps slurry that contains minimum amount of dispersed
gas. Transferring mechanical energy to this kind of slurry is much more efficient than to slurry containing
high amount of gas. In gas dispersion zone inside the inner tube gas bubbles tend to flow downward at
slower rate than the slurry itself. This makes gas bubbles oscillate in the flow and thus less energy is
required for gas-liquid mass transfer.
Suitable Applications
Hydrostatic pressure reactor developed by Outotec should be seen as an option for both heap and
atmospheric tank leaching. It is especially designed for applications requiring high amount of effective
reactor capacity. Utilization of hydrostatic pressure improves kinetic behavior for processes limited by
mass transfer between gas and liquid. Due to enormous unit size and tower like structure hydrostatic
pressure reactor will have some limitations for arranging gas feed and heat transfer. This means that the
most suitable applications might be leaching of low-grade sulphide ores and concentrates. On the other
hand this kind of device could be also used for precipitation purposes like iron removal.
Based on results obtained from batch leaching tests a small comparison between heap leach,
atmospheric tank leaching and hydrostatic pressure leaching was made. All values presented in Table 3 are
340
only indicative. It can be seen that use of hydrostatic pressure reactors would decrease the plant footprint
and energy consumption remarkable. These figures show that this kind of novel reactor concept can make a
crucial difference in feasibility estimation of a low grade ore body.
Figure 3 Schematic drawing of hydrostatic pressure reactor developed by Outotec (Hultholm et al. 2009)
Table 3 Comparison of different leaching options for low-grade sulphide ore when target is to
produce 100 000 tpa of zinc
Heap leach
Retention time
Unit size
Amount of reactors
Footprint
Energy consumption of mixing
Atmospheric tank
leach
Hydrostatic
pressure reactor
48 h
350 m3
330
21 120 m2
923 077 MWh /a
24 h
4000 m3
14
3 584 m2
46 154 MWh /a
150 days
250 m x 8 m
length 1.9 km
480 000 m2
However it should be kept in mind that hydrostatic pressure reactor is not an autoclave.
Temperature inside the reactor must be kept at ambient level, below 100 C. Reactor concept also limits
maximum pressure that can be obtained to level of 10 bars. Thus hydrostatic pressure reactor is not suitable
for applications where use of high temperatures or pressures is required.
CONCLUSIONS
Economical utilization of low-grade ores requires handling of enormous amount of material. In
many cases normal atmospheric tank leaching has traditionally been non-feasible option mainly due to high
capital and operational expenses involved with large amount of stirred reactors. Outotec has developed a
novel type of reactor that utilizes hydrostatic pressure. Tower-like structure of the reactor is designed to
generate high amount of effective fluid volume for high solid content slurries with lower energy
341
consumption and improved kinetics compared to normal atmospheric operation. Thus construction of very
large reactor units ranging up to 5000 m3 is feasible.
Pressure increases leaching kinetics in applications utilizing gas, like oxidative leaching, through
three different mechanisms. Pressure increases solubility of oxygen in solution and oxygen content inside
the gas bubbles. On the other hand bubble size distribution of dispersed gas is decreased with increased
pressure. Due to these phenomenons pressure was shown to have a remarkable effect in leaching behavior
of low grade sulphide ore. In the future this kind of novel reactor concept can make it possible to utilize
low grade ore bodies that have been considered non feasible with current technologies.
REFERENCES
Cheng, C.Y. and Lawson, F., 1991. The kinetics of leaching chalcocite in acidic oxygenated sulphatechloride solutions. Hydrometallurgy Vol 27 (3), 249-268.
Harvey, T.J. and Yen, W.T., 1998. The influence of chalcopyrite, galena and pyrite on the selective
extraction of zinc from base metal sulphide concentrates. Minerals Engineering Vol. 11 (1), 1-21.
Hultholm, S-E., Lilja, L., Nyman, B., Pekkala, P., Ruonala, M., Tiihonen, J., and Vaarno, J., 2010. An
open pressurised agitated reactor and a method for mixing gas and slurry with each other.
International Patent, No. 2010/061054A1, June 3 2010.
Luo, X., Lee, D.J., Lau, R., Yang, G., and Fan, L-S., 1999. Maximum stable bubble size and gas holdup in
high-pressure slurry bubble columns. AIChe Journal Vol 45 (4), 665-680.
Tromans, D., 1998. Temperature and pressure dependent solubility of oxygen in water: a thermodynamical
analysis. Hydrometallurgy Vol 48 (3), 327-342.
343
DIRECT CONTACT HEAT TRANSFER BETWEEN STEAM AND AQUEOUS SLURRIES

D.T. White
Principal Consultant - Metallurgy
Snowden Mining Industry Consultants Pty Ltd
87 Colin Street
West Perth 6005
WA, Australia
(david.t.white.mmt@gmail.com)
ABSTRACT
Metallurgical extraction processes often call for the heating of aqueous slurries. Indirect heat
exchangers are generally not feasible for service with high yield stress slurries because of low heat transfer
rates. It is more appropriate to heat the slurry by direct contact, typically with steam as the heating
medium. Although having a long and successful history, direct-contact heat transfer to aqueous slurries
has been used without the support of pilot plant research. This paper provides results of the needed
research, the work being done at a scale large enough to enable direct scale up to commercial operations. A
pilot plant heater was constructed and tested to develop an understanding of the slurry heating process and
to ensure that commercial scale heaters were appropriately sized.

Niagara, ON, Canada
Edited by
344
INTRODUCTION
Pressure Leaching Operations
Pressure leaching operations are often used to oxidise sulphide gold ores, or for extraction of
nickel and cobalt from laterite ores with sulphuric acid. Where there is sufficient sulphur available, the
exothermic pressure oxidation reactions can be self sustaining at temperatures as high as 225 oC, without
having to preheat the feed slurry. At lower sulphur levels, slurry preheating is required. This is typically
achieved by utilising the flash steam released from the slurry letdown stages and contacting this directly
with cold incoming slurry ahead of the autoclave. The vessels where this slurry-steam contact is made are
known as heaters or condensers, with the number of pre-heat stages varying, depending on how much heat
is evolved in the oxidation reaction (Mason, 1990).
In nickel laterite pressure acid leaching processes, which operate between 245 and 270 oC, the
only significant exothermic reactions are those associated with dilution of sulphuric acid in the leach. As a
consequence, slurry preheating with flash steam is always used commercially. In practice the number of
flash steam preheating stages required varies from 1 to 3, driven by a number of factors, including other
uses for flash steam and the upper temperature limit at which preheated slurry can be pumped. A diagram
of a typical pressure acid leach train is shown in Figure 1.
For pressure acid leaching operations and at low sulphur levels in pressure oxidation, boiler
generated direct steam addition to the autoclave is required to sustain the reaction temperature. For this
reason it is imperative that the flash steam slurry heat transfer is efficient and the slurry temperature
approaches that of the flash steam closely.

Figure 1 Schematic of a typical pressure acid leaching autoclave train
345
Role of the Slurry Heaters

Heaters are counter-current flow devices, in which flash steam is introduced at the bottom of a
column against a falling stream of slurry, which is pumped into the top of the column. Heat and mass
transfer occur simultaneously as the steam is condensed by the cooler slurry.
Pressure from the autoclave discharge slurry is released through ceramic choke valves into a
series of brick lined flash vessels. Each flash vessel is usually associated with a particular heater. The
temperature profile along the heater train results in a corresponding pressure profile, and pumps are located
after each heater to direct the slurry to the next heater stage and finally to the autoclave vessel.
Centrifugal pumps are used to transfer slurry from one heater to the next, while the autoclave is
fed by one or more positive displacement pumps operating in parallel. The positive displacement pumps
are fitted with water cooled drop-legs to separate the sensitive polymer diaphragm from the hot slurry.
The drop-legs maintain an oscillating column of cooled slurry, which transmits the pumping impulse to the
hot autoclave feed slurry. While the drop-legs protect the pump diaphragm from heat degradation, the
pump check valves are exposed to the full slurry temperature from the final heater. Degradation of the
check valves places a ceiling on the temperatures the pump can handle, and thus on the final heater
discharge temperature. Typically, this is in the range 160oC to 200oC, and represents the autoclave slurry
feed temperature. After dilution of sulphuric acid, or other exothermic reactions, the remainder of the heat
necessary to bring the slurry to operating temperature is provided by high pressure steam injection.
A major issue to consider in the heating process is efficiency of heat transfer. If flash steam
bypasses the slurry stream, this energy is lost to atmosphere. If, as a consequence, the autoclave slurry
feed temperature is less than its design target, the energy shortfall has to be met by additional high-pressure
steam, with an obvious impact on the plant energy balance and operating costs. Failure to operate the
autoclave at design temperature can affect the process by increasing the acid consumption, reducing the
leach kinetics or leach efficiency, or adversely affecting the settling characteristics of the leach residue.
Historical Background
Direct Contact Condensers have been in use since the dawn of the Industrial Revolution, some
300 years ago (BCLM, 2012; Csele, 2008). These evolved to the high capacity barometric condensers in
modern industrial use. Interestingly, although a number of design configurations have been utilized, little
information exists on heat transfer rates and even standards for barometric condensers (HEI, 1995) have no
information on sizing for thermal performance. Where heat transfer rates have been determined (How,
1956), it is by rating the performance of operating equipment, where nozzle placement and size appear to
be the main drivers of equipment size.
In the laterite nickel industry, direct contact heaters were installed on the Tailings Stills at Nicaro,
Cuba in 1944 (Boldt & Queneau, 1967). Beaverlodge Uranium, Canada, which commenced operations in
1954, included pressure leaching with vacuum flashing and direct contact splash heaters (Mancantelli &
Woodward, 1955). The first Pressure Acid Leach operation, at Moa Bay Cuba, commissioned in 1959,
uses direct contact heaters with a packing, fabricated of expanded metal lath to cope with the, extremely
high effective viscosity (Carlson & Simons, 1961).
Gold pressure oxidation operations in North America have made extensive use of splash heaters
utilising flash steam for pre-heating incoming slurry. There have been at least 16 leach trains in 6
operations built since 1985, with each train containing 2 or 3 heaters (Mason & Gulyas, 1999).
In the late 1990s, three nickel laterite pressure acid leaching plants commenced operation in
Western Australia. These utilised the basic design principles developed for the North American pressure
oxidation operations. Between 2 and 4 stages of direct contact slurry heating were installed. Heater sizes
varied significantly between these operations, despite throughputs being similar, with heater diameters
346
varying by a factor of more than two. The number of trays also varied, as did tray spacing. In one
operation a number of trays fell out without loss of performance. In another they were all removed and
performance apparently improved. Further investigation revealed that similar size disparities exist between
gold pressure oxidation operations.
For the handling of slurries and fouling liquids for direct-contact heat transfer, baffle tray columns
are often specified. These include splash trays or disk and doughnut arrangements to redistribute the slurry
and improve the heat transfer (Houghland, Lemieux, & Schreiner, 1954; Fair, 1993). More complex
packing or bubble cap contacting methods are generally avoided in slurry service because of the risk of
blockage and scaling. Figure 2 shows the types of baffle arrangements often used (Houghland, Lemieux,
& Schreiner, 1954), with the general characteristics of baffle tray columns having been described by Fair
(1993).
Figure 2 Types of baffle arrangements

Fractionation Research, Inc. (FRI) conducted a number of studies of baffle tray performance in a
1.2 m column including among other results volumetric rates of heat transfer for helium and nitrogen
contacting several oils (Ognisty & Kao, 1988). The results were later correlated by Fair (1990). FRI also
reported results of heating absorption oil by superheated steam (Barben, Yanagi, & Stupin, 1961). Several
observations were made:
The volumetric heat transfer rate increased with gas rate, with a direct proportionality. Doubling
the gas rate at constant liquid rate doubled the rate of heat transfer.
347
At constant gas flow rate, the heat transfer rate increased with increasing liquid rate.
When tray spacing was cut in half (600 mm to 300 mm.), for the same flow rates, the volumetric
heat transfer coefficient increased significantly, in the range of 35 to 70%. Doubling the gas
velocity through the curtain area appeared to create more dispersion volume and interfacial area.
Later work by FRI, dealing with distillation in baffle tray columns, generally corroborated the
above, utilizing the heat transfer/mass transfer analogy (Fair, 2003). Banik, Majunder, & Sarkar (1992)
measured the heat transfer performance of several fractionating devices (excluding baffle trays) for
condensing steam heating water in the presence of significant amounts of non-condensables (air). Transfer
rates were high, but were reduced by the presence of the non-condensables. FRI reported the results of
work for condensing heat transfer by liquid sprays into a condensing vapour in the cyclohexane/n-heptane
system (Kunesh, 1993). Heat transfer rates were again high, at around 100 kW/m3-K.
Context of the Current Study
In the aftermath of the construction of the nickel laterite pressure acid leaching plants at Cawse,
Bulong and Murrin Murrin, in Western Australia in the late 1990s, it became apparent that instantaneous
leaching capacity would typically be volumetrically constrained.
Provided enough acid and steam could be added to the Autoclave, capacity would be constrained
by the capacity of pumps, slurry heaters, and flash vessels, rather than a significant drop off in nickel
extraction with decreased leach residence time.
One method of increasing throughput without increasing volumetric flow is to maximise the
solids content of the slurry entering the Autoclave. This also reduces steam and acid consumption.
A number of techniques had been contemplated previously, including heating up to 100 oC and rethickening (Simons, 1957), and maximising slurry densities to a practical handling limit, by thickening. A
number of new projects also became interested in maximising the solids content of pressure acid leach
slurries, to reduce capital costs of leaching trains.
At around the same time the Australian Alumina industry was implementing paste thickening of
red mud digestion (leach) residue, to improve operational efficiency. This included improved recovery of
alumina hydrate and caustic soda, and dewatering of final tailings before storage (Doucet & Paradis, 2010).
The paste thickener technology was based on developments carried out by Alcan from the mid-1970s.
It was determined that a reasonable practical (or design) slurry rheological handling limit for
centrifugal pumping was a yield stress of around 100 Pa. This was supported by rheological testwork
(McCrabb, Chin, & Miller, 2004).
Test work showed that flow of 100 Pa yield stress slurries down baffle trays inclined at 30 was
steady and sustainable. This work also demonstrated rapid break-up of the slurry curtain under the
influence of a moderate gas flow, as shown in Figure 3 (White & Miller, 2005).
However, it was apparent that there was no data in the published literature to support direct
contact slurry heating of such high viscosity slurries. This paper provides results of the needed research,
with the work being done at a scale large enough to enable direct scale up to commercial operations.
348
Figure 3 - Flow testing, (a) without gas flow, (b) with gas flow
PILOT PLANT
It was decided to build and operate a pilot plant baffle tray heater column, to determine the direct
contact heat transfer properties of high viscosity slurries.
Design
On the basis of literature studies, it was decided that the heat transfer zone in the column would,
in all respects except for the diameter, be the same size as anticipated for a commercial unit. The baffles
were 50% cut, on a 30 slope from the horizontal. Base case tray spacing was 600 mm (24 inch), with an
alternative of 300 mm (12 inch), if heat transfer was troublesome. A steam spreader was also included in
the design, to allow direct steam injection into the slurry. A 450 mm (18 inch) diameter column was
chosen for two reasons:
There was limited steam and slurry available to do testing (so the smaller the size the better).
There was experience with performance comparisons between different sized columns in heat and
mass transfer service which correlated well. In particular, the 18-inch column at the University of
Texas at Austin, the 48-inch column at Fractionation Research, in Oklahoma, and many
commercial columns have been compared.
Configuration
The heater column consisted of sections of 300 and 600 mm high flanged pipe, bolted together,
with trays sandwiched between the flanges at either 300 or 600 mm spacing, to make up the heat transfer
zone. In addition, there were head, sparger and sump sections. Either six, 600 mm spaced, or seven,
300 mm spaced, trays were used to maintain correct piping and instrumentation alignment. Steam was
supplied from a diesel-fired package boiler with a nominal capacity of 500 kg/h of saturated steam. A
general arrangement of the column is shown in Figure 4.
349
Figure 4 - General arrangement of pilot plant heater vessel

Thickened slurry was held in a storage tank and pumped into the column using a peristaltic pump.
This slurry was produced by a combination of a centrifuge and thickener, to enable reuse after being
diluted during each series of heating tests.
Flowmeters on the steam, slurry and vent lines enabled the flows into and out of the heater to be
monitored. Temperature profiles were obtained with resistance temperature devices; these included
streams in and out of the heater, as well as those positioned in the slurry stream falling from each baffle
tray to the next. Pressure was measured at points along the heater. Flow and temperature data were
collected using a multi-channel data-logger and recorded on line.
Slurry Properties
The slurry used in the test work was a typical limonitic (geothitic) nickel laterite slurry. A
summary of properties is shown in Table 1.
350
Table 1 - Slurry properties

Property
Solids Density
Slurry Density
% Solids
Solids Volume Fraction
Particle Size: 100% passing
Particle Size: 50% passing
Heat Capacity
Thermal Conductivity
Value
2900 - 3100
1450 1550
45 - 51
23 26
75
10
2.5 2.7
0.6 0.68
Units
kg/m3
kg/m3
% w/w
%
m
m
kJ/kg-K
W/m-K (est)
The slurry was thickened before each set of tests to achieve a nominal yield stress of 100 Pa.
Yield stress variation with slurry solids content is illustrated in Figure 5. The variation in percent solids
was produced by filtering, then diluting the slurry.
600
Test 12
Test 33
Test 41
Test 47
Trendline (All Values)
Vane Yield Stress, Pa
500
400
y = 0.01e0.19x
300
200
100
0
40
42
44
46
48
50
52
54
56
58
60
Solids, % w/w
Figure 5 - Vane yield stress dilution profile for selected slurry heater feed samples
The slurry tested was time-independent. On thickening, some structure developed, owing to the
use of polymer flocculants. For practical purposes, this breaks down during pumping. Rheograms, or
shear stress vs shear rate curves, for selected test samples are shown in Figure 6. The shear rates of
relevance are typically < 200 s-1, which coincide with velocities in commercial pipe flow. A good
rheological description is the Hershel-Bulkley, yield stress power law model:
Shear Stress = Yield Stress + K (Shear Rate)n
351
400
350
Shear Stress, Pa
300
250
200
150
100
Tests 9 & 12
Test 32
Tests 41 & 42
50
Test 19
Test 37
Tests 45 & 47
0
0
20
40
60
80
100
120
140
160
180
200
Shear Rate, 1/s
Figure 6 - Rheograms for selected slurry heater feed samples

Operation
The heater was operated at atmospheric pressure. This simulates the low pressure slurry heater in
a commercial plant, which receives undiluted or worst case rheology slurry, with a target yield stress of
100 Pa. Maximum slurry temperature was therefore limited to around 100 C, depending on liquor salt
content, and column base pressure. Heating was investigated over a range of slurry and steam flows. The
nominal test conditions are shown in Table 2. A number of additional tests were undertaken:
Water was substituted for slurry;

Higher flow rates of 6.3 t/h for slurry and up to 530 kg/h for steam;
Sub-stoichiometric steam flows;
Air addition to the steam inlet line;
Repeats of some tests.
Three heater design configurations were used for each of the tests:
1.
2.
3.
600 mm tray spacing with a steam sparger, immersed in the slurry;

600 mm tray spacing, with simple steam pipe distributor located in the vapour space;
300 mm tray spacing, with simple steam pipe distributor located in the vapour space.
A full set of tests on one heater configuration was performed in a few hours. Test runs were
carried out over six campaign days. After heating and dilution, slurry was centrifuged and thickened to reestablish rheological properties. Slurry rheology and solids content were measured before each campaign.
Predictive mass and energy balances were carried out before each test. These included allowances
for variations in slurry solids content, which ranged from 45 to 50 wt% solids. Flowmeters and
temperature instruments were calibrated and cross checked in the following manner:
352
Flowmeters: Separate mass measurements on tanks, cross checking against other flowmeters,
physical observation and energy balance closure.
Temperature device placement: Observation of system dynamics when flow conditions were
changed and observation of sub-stoichiometric operation.
Table 2 - Slurry heater pilot plant nominated test conditions
Test Type
1a
1b
1c
2a
2b
3a
3b
3c
Slurry Mass Flowrate, t/h

2.43
2.43
2.43
3.65
3.65
1.83
1.83
1.83
Steam Mass Flowrate, t/h

0.21
0.31
0.42
0.31
0.42
0.16
0.21
0.42
Comments
Stoichiometric
Steam to Vent
Steam to Vent
High Flow, Stoichiometric
High flow, Steam to Vent
Low Loading, Stoichiometric
Low Loading, Steam to Vent
Low Loading, Steam to vent
Observations
Slurry heating was found to be very rapid, as was the response of the heater to changes in slurry or
steam flow rates. The temperature profiles from the various test conditions are shown in Figures Figure 7
to Figure 12, with the associated experimental conditions shown in Table 3. These can be summarised as
follows:
Slurry attained a temperature approach of 5 oC or less ( slurry temperature of 95 C or higher) in

the top two or three trays of the heater, during venting (excess steam) tests, regardless of slurry
flow rate and heater configuration used. Figure 7 shows this effect at a slurry flow 3.9 t/h. Note
that there were 6 trays for the 600 mm configuration.
At higher slurry flow rates, there was no degradation in performance (Figure 8).
A difference in temperature profile between excess and stoichiometric steam flow is noticeable
(Figure 8).
There was no temperature profile difference between viscous slurry and water (Figure 9).
Where sub-stoichiometric steam flows were used, steam became the limiting reagent, so heating
occurred in the lower trays. Slurry discharge temperature was at, or very close to, the calculated
estimate. Figure 10 shows this effect.
The effect of air addition was interesting. Provided there was enough vent flow for the steam-air
mixture temperature to be greater than 95 C, heating remained rapid and occurred in the top two
trays of the column. However, at low vent flows, the vent temperature decreased to 80C
(indicating a 50/50 volume air-steam mixture) and the slurry heating profile spread out. The
discharge slurry temperature was still close to the calculated estimate (Figure 11).
The heater was very responsive to changes in slurry and steam flow rate, with the effect of
changes apparent within 60 seconds. This is consistent with calculated slurry and steam residence
times. Figure 12 shows the vent steam flow rate and tray six (top tray) temperature response to
the introduction of slurry. Once the slurry reached the top of the column (represented by a fivesecond delay), both vent steam flow and top tray temperature fell rapidly.
353
Table 3 - Experimental conditions for tests referred to in Figures Figure 7 to Figure 11

Test
No.
Fluid
Steam
Inlet
%
solids
Spreader
Spreader
Spreader
Spreader
Pipe
Pipe
Pipe
Pipe
Pipe
Pipe
Pipe
Pipe
Pipe
Tray
Spacing,
mm
600
600
600
600
600
600
600
300
300
300
300
300
300
7
9
12.1
12.2
19
22
28
32
33.1
33.2
33.3
36
37
Water
Slurry
Slurry
Slurry
Slurry
Slurry
Water
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
41
Slurry
Pipe
42
Slurry
45
47
0
45.4
45.1
45.1
50.2
50.4
0
52.2
51.1
51.1
51.1
54.9
54.2
Yield
stress,
Pa
N/A
51.2
45.3
45.3
83.4
84
N/A
81-103
81-103
81-103
81-103
81-103
82.4
Slurry
flow,
kg/h
1426
3521
2441
2457
3907
2470
2613
3944
3794
3764
3768
1895
3582
300
52.3
58.1
4032
Pipe
300
52.4
67.5
4010
Slurry
Pipe
300
51.4
122.7
6295
Slurry
Pipe
300
51.5
114
6111
Steam Vent Comments

flow, Flow,
kg/h
kg/H
206
7
Stoichiometric
423
55
Steam to Vent
247
36
Steam to Vent
216
13
Steam to Vent
382
38
Steam to Vent
319
11
Steam to Vent
461
16.1 Steam to Vent
408
58
Steam to Vent
311
7
Stoichiometric
280
5
Stoichiometric
307
6
Stoichiometric
202
9
Steam to Vent
196
Sub-stoichiometric
Steam to Vent (+10
407
53
m3/H air)
Stoichiometric
336
15
(+10 m3/H air)
486
78
Steam to Vent
Steam to Vent (+
511
30
air)
100
90
Temperature, oC
80
70
60
50
Test 9, Spreader, 600mm Tray Spacing
40
Test 19, Pipe, 600mm Tray Spacing
30
Test 32, Pipe, 300mm Tray Spacing

20
Feed
Tray 7
Tray 6
Tray 5
Tray 4
Tray 3
Tray 2
Tray 1
Product
Figure 7 - Temperature profile examples for each heater configuration, with excess steam addition
354
100
Temperature, oC
90
80
70
Test 36, 1.9 t/H, Excess Steam

Test 45, 6.3 t/H, Stoichiometric
60
50
Feed
Tray 7
Tray 6
Tray 5
Tray 4
Tray 3
Tray 2
Tray 1
Product
Figure 8 - Temperature profiles at differing slurry flow rates
100
Temperature, oC
90
80
70
Test 12, Slurry
Test 7, Water
Test 22, Slurry
Test 28, Water
60
50
Feed
Tray 6
Tray 5
Tray 4
Tray 3
Tray 2
Figure 9 - Temperature profiles for slurry and water
Tray 1
Product
355
100
90
Temperature, oC
80
70
60
50
40
Test 32, Excess Steam

Test 33, Stoichiometric
30
Test 37, Sub-Stoichiometric

20
Feed
Tray 7
Tray 6
Tray 5
Tray 4
Tray 3
Tray 2
Tray 1
Product
Figure 10 - Effect of sub-stoichiometric steam flow
100
Temperature, oC
90
80
70
Test 32, Excess Steam

Test 33, Stoichiometric
Test 41, Excess Steam + Air
Test 42, Stoichiometric Steam + Air
60
50
Feed
Tray 7
Tray 6
Tray 5
Tray 4
Tray 3
Tray 2
Figure 11 - Effect of non-condensable gas in steam
Tray 1
Product
356
300
102
250
100
200
98
150
96
100
94
50
92
Temperature, oC
Vent Steam Flow, m3/H
Vent Steam Flow

Tray 6 Temperature
90
0
10
20
30
40
50
60
70
Time from Start of Slurry Flow, seconds
80
90
Figure 12 - Heater thermal response to commencement of slurry flow

DATA ANALYSIS
Test data were plotted and scrutinized to find steady-state operating periods useful for analysis.
Of the 48 tests performed (37 slurry, 11 water), 45 provided data suitable for manipulation. Multiple data
sets were obtained from 15 tests. Excess steam was used in 30 tests. Air was introduced with steam in five
tests. Analysis for each test consisted of:
Summarizing the steady-state data;

Identifying the trays over which heating took place;
Determining the heat transferred, log-mean temperature difference, and volume of column
utilised;
Calculating the volumetric heat transfer rate;
Calculating the volumetric heat transfer coefficient.
Table 4 gives a summary of the data analysis for the tests referred to in Figures 7 to Figure 11.
Heat Transfer Rate

Heat transfer rates were lower than that calculated by How (1956) for a barometric condenser, but
similar to that of Kunesh (1993) for sprays. The How analysis gave a rate of 3100 kW/m3, and Kunesh
1570 kW/m3, with the pilot plant ranging from 400 to 2200 kW/m3.
Heat Transfer Coefficients
Volumetric heat transfer coefficient values ranged from 20 to 90 kW/m3-K. These are the same
order of magnitude as those given for spray condensation of 93 to 135 kW/m3-K (Kunesh, 1993). The
number of trays required for heat transfer stayed the same, regardless of slurry flow, confirming both the
heat transfer rate and heat transfer coefficient increase with increasing flowrate. This is consistent with
357
experience in other heat and mass transfer applications, where column height or number of trays required
does not change significantly over a wide operating range.
The volumetric heat transfer coefficient (Ua), has been represented as a function of the gas and
liquid mass velocities, using the empirical equation (Fair, 1961A; 1972; 1990):
Ua = C1 G m L n
It was felt that it would be helpful to determine if such relationships held, to give confidence in
scaling-up outside of the tested mass flow rates. The primary focus was on excess steam or venting tests,
as these most closely matched the steam to slurry ratios expected in a commercial plant. A plot of Ua vs L
shows a definite upward trend with increasing flow, as shown in Figure 13. A reasonable correlation was
obtained, based on Fairs empirical equation:
Ua = 16.83 G0.37 L0.63
(kW/m3-K)
(R2 = 0.64)
It was also possible to correlate Ua with the simplified expression:

Ua = 10.54 L0.82
(kW/m3-K)
(R2 = 0.58)
A similar upward trend exists for the stoichiometric tests, as shown in Figure 14, but the
correlation is weaker:
Ua = 7.14 G0.13 L1.06
(kW/m3-K)
(R2 = 0.35)
Ua = 5.44 L1.14
(kW/m3-K)
(R2 = 0.32)
or:
Ua, Volumetric Heat Transfer Coefficient, kW/m3-K
100
90
Ua = 16.8 G0.37 L0.63 kW/m3-K

R = 0.64
80
70
60
Ua = 10.54 L0.82 kW/m3-K
50
R = 0.58
40
Spreader, 600 mm
30
Spreader, 600 mm
20
Pipe, 600 mm
Pipe, 300 mm
10
Pipe, 300 mm
0
0
6
8
10
L, Slurry Specific Flow, kg/s-m2
12
14
16
Figure 13 - Volumetric heat transfer coefficient plotted against slurry specific flow rate, for venting tests
Ua, Volumetric Heat Transfer Coefficient, kW/m3-K
358
100
Ua = 5.44 L1.14 kW/m3-K
R = 0.32
90
80
Ua = 10.54 L0.82 kW/m3-K
70
60
50
40
30
All Data
20
10
Tray by Tray
Analysis
0
0
L, Slurry Specific
10
12
14
16
Flow, kg/s-m2
Figure 14 - Volumetric heat transfer coefficient plotted against slurry specific flow rate, for stoichiometric
tests, with the correlation line compared to that of the venting tests
Heat Transfer Mechanism
Further analysis indicated that for the volumetric heat transfer coefficients calculated to be
plausible, a large slurry surface area was required, such that there must be significant droplet formation in
the shower zone between trays. This is consistent with Figure 3. Observations made during heater
reconfiguration, revealed slurry spatter on the column walls. It seems clear that the shower contacting zone
is neither liquid nor gas-continuous in the usual sense. The gas, however, causes some atomization of
liquid, which enhances interfacial area. Filming of the operation of the Baffle Tray column at
Fractionation Research (Sakata, 1980) also shows the degree of turbulence in this type of device.
Fluid
Water
Slurry
Slurry
Slurry
Slurry
Slurry
Water
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
Test
No.
7
9
12.1
12.2
19
22
28
32
33.1
33.2
33.3
36
37
41
42
45
47
Ua,
Tray
Tm,
Slurry
Steam
Analysis Over:
Heat Transfer
o
3
C
kW/m
-K
Spacing,
%
Inlet Specific Inlet Outlet Inlet Inlet Vent Vent Trays Volume, Total, Volumetric,
3
3
mm
solids flow, Heat, Temp, Temp, flow, Temp, flow, Temp,
kW
kW/m
m
o
o
o
0
C
C
C
C
kg/H kJ/kg-K
kg/H
kg/H
600
0
1426
4.2
21
96
206
101
7
101
2
0.19
124
666
28
24
600
45.4 3521
2.7
22
97
423
101
55
101
2
0.19
199
1070
27
40
600
45.1 2441
2.7
22
96
247
101
36
101
2
0.19
139
746
26
28
600
45.1 2457
2.7
22
95
216
101
13
101
2
0.19
138
742
28
27
600
50.2 3907
2.6
26
100
382
101
38
101
3
0.28
207
742
17
44
600
50.4 2470
2.6
25
97
319
102
11
101
2
0.19
127
683
27
26
600
0
2613
4.2
20
100
461
101
16.1
101
2
0.19
242
1300
18
72
300
52.2 3944
2.5
28
99
408
101
58
101
3
0.14
199
1422
20
72
300
51.1 3794
2.6
26
99
311
101
7
96
6
0.28
195
700
21
34
300
51.1 3764
2.6
26
98
280
101
5
91
6
0.28
194
695
20
35
300
51.1 3768
2.6
26
98
307
101
6
91
6
0.28
194
697
20
34
300
54.9 1895
2.4
26
99
202
102
9
100
3
0.14
93
664
22
31
300
54.2 3582
2.5
46
78
196
103
82
1
0.05
79
1696
30
56
300
52.3 4032
2.5
30
96
407
101
53
101
3
0.14
187
1342
23
59
300
52.4 4010
2.5
27
87
336
101
15
79
3
0.14
169
1210
29
42
300
51.4 6295
2.5
25
95
486
101
78
90
4
0.19
313
1681
25
67
300
51.5 6111
2.5
25
97
511
101
30
101
3
0.14
313
2242
24
93
Table 4 - Data analysis for tests referred to in Figures Figure 7 to Figure 11
359
360
SCALEUP TO INDUSTRIAL SLURRY HEATERS

In general the aim of scale-up to an industrial design is to minimise the size of the industrial unit,
without compromising performance at design flow rates. For the heaters, this consists of three major
components:
1.
2.
Diameter to avoid flooding, excessive pressure drop and entrainment carryover of slurry.
Heat transfer volume (number of trays / height) to ensure adequate heat transfer from steam to
slurry.
Sump residence time to provide adequate slurry residence time for control of multi-stage
pumping trains.
3.
For the purpose of determining an energy balance over the heater and the whole leach train, a
slurry-steam temperature approach must be chosen. Typically this is 5 oC in slurry service, although values
as low as 2 oC have been used.
Diameter
Flooding testwork was carried out on baffle tray devices by FRI in the early 1960s (Barben,
Yanagi, & Stupin, 1961), for a variety of hydrocarbons at different pressures. Lemieux (1983) presented
capacity data from air water tests. Fair (1993) consolidated and presented these results in the same
format as his earlier correlation for sieve tray capacity (Fair, 1961B). A re-plot of the above data is
presented in Figure 15, for use in heater diameter determination. For condensing service the correlation is
somewhat conservative, especially at high liquid flow rates. Less conservative estimates are now available
(Kister & Olssen, 2011).
Capacity Parameter, C sb, flood , m/s
0.50
y = 0.244e-1.180x
FRI: Hydrocarbons
Lemieux: Air - Water
0.05
0.01
0.10
Flow Parameter, L'/G'( G/L)0.5
Figure 15 - Window area flood capacity chart for baffle trays at 600 mm spacing
1.00
361
To calculate the required diameter, the following steps are taken:

1.
Calculate the Flow Parameter, FP:

FP =
L .

G
The slurry and steam flow rate chosen are the worst case (highest) for flooding calculations.
2.
Determine Csb, flood, the capacity parameter, from Figure 15 above, or use the relationship:
Csb, flood = 0.244 exp [-1.18 FP]
3.
4.
C, = U
Determine Uflood, the gas flooding velocity based on the heater window or open area (typically
50% of total cross-sectional area for baffle trays).
U
= C,
Determine the design velocity, Udesign, typically 70% of Uflood.

Udesign = 0.7 Uflood
Udesign can be between 60% and 80% of the flooding velocity, depending on the degree of
conservatism required, and the potential for future plant de-bottlenecking.
The above flooding calculations are conservative for condensing heaters where a significant
amount of steam condenses and exit velocities are low.
5.
Window Area, Aw is then determined:

A =
G
U
For a 50% baffle tray, total area AT = 2AW and the column diameter, DT is:
DT
(8Aw/)0.5
For the above calculation to be valid, baffle tray spacing must be sufficient so that it does not limit
vapour cross flow. For 50% cut baffle trays, cross flow becomes limiting when the spacing is less than
20% of the column diameter, so for a 600 mm spacing the column diameter can be up to 3.0 m.
Heat Transfer Volume Required
This issue can be looked at in a number of different ways, depending on the sophistication the
designer believes is warranted and how aggressive or conservative the design needs to be. The pilot plant
tests demonstrated the robustness of the baffle-tray heater for direct contact heating of viscous aqueous
slurries using steam.
362
Scale-up could therefore be made on the basis that heating took place over one to three trays in the
pilot plant. If excess steam with low levels of non-condensable gases were used, an aggressive design
would require only 2 trays. The reality of pressure leaching plants means that flash steam containing noncondensable gases is likely from time-to-time, its availability may be variable and slurry distribution is
often a practical compromise.
In this situation, the pilot plant has demonstrated that 6 trays are adequate in all circumstances to
maximise slurry heating, and achieve close slurry - steam approach temperatures. While this approach
may seem overly simplistic, leading to an overly conservative design, it should be recognised that the
vessel diameter, sump volume, phase disengagement height, and height allowances for steam and slurry
inlets in combination, tend to be more dominant factors in the overall vessel size and cost.
The 50% cut baffle is physically robust, and easy to construct, so is generally recommended for
this duty. As discussed previously, a variety of other tray types can also be used (Houghland, Lemieux, &
Schreiner, 1954; Fair, 1993; Lemieux, 1983).
The 30o tray slope used for the pilot plant is adequate for any slurry, and can be reduced to 15o or
less for low yield stress (< 20 Pa) slurries. Horizontal trays can be used for dilute slurries and liquids.
Sump Residence Time
It is necessary to have sufficient sump residence time for plant process control. A typical heating
train in a pressure leaching facility consists of two or three heaters in series, each fed with variable speed
centrifugal pumps, followed by two positive displacement autoclave feed pumps, operating in parallel.
Start up of this combination under operating conditions requires several minutes, even when the procedure
is automated.
For stability of this procedure, and in normal operation, a nominal three-minute residence time
(full to empty), based on design flow rates is recommended. Shorter residence times tend to lead to low
and high level trips when process control upsets occur, while longer residence times cannot generally be
justified due to increased equipment costs.
CONCLUDING REMARKS
It has been demonstrated that direct-contact heating of extreme rheology aqueous slurries using
steam requires no special design considerations in excess of those already applied in commercial designs.
A simplified expression might be: If it can be pumped, it can be heated.
Steam flow rate has little influence on heater performance. The slurry will absorb all of the
energy available. To again use a simple concept: Hot steam will find cold slurry.
Non-condensable gases can have a significant effect on heater performance at low specific steam
flow rates, spreading the slurry temperature gradient out over the length of the heater. Nevertheless, the
pilot plant demonstrated the slurry will absorb all of the energy thermodynamically available.
The sloped, 50% cut baffle tray column has confirmed itself as a robust device in this duty. As
few as 2 trays can be considered for pure steam service, but a 6 tray heater will handle a full range of
anticipated conditions.
A short time after this work was completed, an existing commercial operation experienced slurry
heater flooding due to a combination of high throughput and scale formation on the trays. Analysis of the
operating data confirmed that the column was operating well into the flooding range, as defined by Figure
15, confirming this correlation is somewhat conservative in a condensing system. To reduce scaling, the
363
number of trays was reduced from 10 to 5. Heat transfer performance remained consistently good, further
validating the pilot plant work.
ACKNOWLEDGEMENTS
Two people require special mention:
Mike Miller as close collaborator and enthusiastic supporter on this subject and co-author on a
previous paper we wrote on the subject (White & Miller, 2005).
Professor James R. Fair (1920 2010), who, as can be seen from the text and references was a
pioneer and long term collaborator in the area of mass transfer and distillation, with emphasis on baffle tray
columns.
NOMENCLATURE
AT
Column (or tower) total cross sectional area, m2
Aw
Window cross sectional area, m2
C1, K, m, n
Constants, the values of which depend on the system being considered
Csb, flood
Capacity parameter at flood, based on superficial area, m/s.
DT
Column diameter, m
FP
Flow parameter,
Gas (steam) mass velocity entering the heater, kg/s-m2
Gas (steam) mass flow entering the heater, kg/s
Liquid (or slurry) mass velocity exiting the base of the heater, kg/s-m2
Liquid (or slurry) mass flow exiting the base of the heater, kg/s
Gas (steam) density, kg/m3
Liquor (or slurry) density, kg/m3
Tm
Log mean temperature difference, oC
Ua
Volumetric overall heat transfer coefficient, kW/m3-K
Udesign
Design gas velocity on the heater window or open area, m/s
Uflood,
Gas flooding velocity based on the heater window or open area, m/s
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367
REFRACTORY LINING DESIGN FOR PRESSURE OXIDATION AUTOCLAVES

I. Donohue, E. Barrette, M. Pearson
Hatch
Sheridan Science and Technology Park
2800 Speakman Drive
Mississauga, ON, CAN, L5K 2R7
ABSTRACT
This paper presents the technique and benefits of the finite element approach for designing the
refractory lining in pressure oxidation autoclaves. One-dimensional equations are used to develop an initial
refractory design. ANSYS Parametric Design Language (APDL) scripts are then used to build and analyse
a more accurate three-dimensional finite element model to verify the refractory thickness, determine weld
overlay requirements, and assess mechanical stability. The APDL scripts provide a cost effective means to
quickly evaluate various boundary conditions and multiple designs to determine the optimal lining
configuration and nozzle layout.

Niagara, ON, Canada
Edited by
368
INTRODUCTION
New ore processing facilities demand increased capacity, requiring hydrometallurgy processes
that have larger reactor vessels operating at higher pressure and temperature. Many pressure
hydrometallurgy operations require vessels with an impermeable membrane and one or more courses of
refractory or ceramic brick. The membrane provides corrosion protection for the vessel shell and the brick
provides thermal protection for the membrane. Designing a refractory lining with an economic service life
as a thermal barrier requires the refractory to be erosion resistant, chemically compatible with the process
fluid, and mechanically stable. A fundamental understanding of the factors affecting the lining system is
essential as designs move further away from the industrys experience base.
During basic engineering the refractory lining design is developed using one dimensional
cylindrical conduction equations for heat transfer and classical hoop stress-strain relationships for
determining mechanical stability. The results of the thermal calculations specify the refractory thickness
that should prevent the membrane temperature from exceeding the design limit. Mechanical stability of the
lining is determined by examining the sensitivity of lining stability with respect to various parameters.
There are three criteria that must be satisfied to conclude mechanical lining stability:
1.
2.
3.
The process or face course refractory remains in compression for all operating conditions.
Stresses must not exceed the materials crushing failure strength.
The refractory lining must remain in contact with the shell membrane (i.e. no gaps).
Using a one dimensional model is sufficient for conceptual design and lining definition during the
basic engineering phase of a project. However, during detailed engineering three dimensional finite
element models (FEM) should be examined to mitigate the assumptions associated with the one
dimensional analyses. Typically 80% of a finite element analysis (FEA) budget is allocated for model and
mesh generation. It is possible to reduce the budget allocated for FEM development if the analysis is
conducted in ANSYS using the ANSYS Parametric Design Language (APDL). Using APDL, it is possible
to write scripts that will create and analyse a model based on design parameters and boundary conditions
that are defined by the analyst. The scripts allow the computer to complete the most time consuming part
of the FEA (i.e. model and mesh generation), which reduces the duration of the analysis and required
number of man-hours. Another APDL advantage is the ability to easily and rapidly make design changes
based on the thermal and stability analysis results.
There are various factors affecting the refractory lining that must be considered when using FEA
for a thermal or stability analysis. The factors include shell deflection, modeling assumptions, material
assumptions, chemical swell, porosity, and boundary conditions. Each factor must be accounted for to
produce useful results.
Thermal analysis boundary conditions are applied to simulate operating conditions. The results
are analysed to verify that the temperature of the membrane does not exceed the design temperature. Areas
around the nozzles typically exceed the design temperature so the membrane in these areas is replaced with
weld overlay, which is more temperature resistant and more expensive. The amount of overlay required for
each nozzle can be determined from the thermal finite element analysis results.
Mechanical stability boundary conditions are applied in various combinations to generate the
largest gap, tensile stress and compressive stress in the lining. The results are assessed considering the
stability criteria utilized in the one dimensional analysis. It is important to note that the mechanical stability
analysis is qualitative in nature and requires experience to effectively interpret the results.
The purpose of this paper is to illustrate the potential cost savings that are possible if APDL is
used to conduct FEA and present the factors that affect the thermal and mechanical stability analyses for a
refractory lined autoclave.
369
FINITE ELEMENT MODEL DEVELOPMENT

Various CAD software packages are available that can be used to create a three dimensional solid
model suitable for FEA. The model must be segmented or simplified so that the desired mesh can be
applied to different regions considering the various element attributes. Autoclave models tend to be quite
large, so it is best to minimize the number of nodes by generating a hexahedral or hex-dominant mesh and
avoid tetrahedral elements. The ANSYS FEA software package contains three programs that can be used to
generate a mesh for thermal and structural analyses; ANSYS ICEM, ANSYS Workbench, and ANSYS
Classic. The program selected to create the mesh can have a significant impact on the analysis budget due
to the complexity of the autoclave geometry.
Mesh Generation
An ICEM mesh is generated using the blocking method, which requires creating blocks that
capture all features (ex. cover, nozzle, support, gasket, seal ring, etc.) of the autoclave geometry. Blocking
in ICEM is easier if the model has been sliced considering how each feature will be captured by a block.
Blocking time can be reduced by dividing the autoclave into different components taking advantage of
repetition because the mesh for these components can be copied when the mesh is assembled. Depending
on the vessel, it may be possible to block mesh a single head, half the vessel body, a single support, and
each unique nozzle. The block method generates a 100% hexahedral mesh for each block and projects the
mesh onto the geometry according to the block to geometry associations.
Recent advancements in the Workbench mesh routine and availability of additional mesh
constraints have made it possible to generate a continuous mesh, with the desired element quality, in the
autoclave shell and nozzles. Preparing an autoclave for Workbench requires strategically slicing the model
so that mesh constraints can be applied that will guide the ANSYS meshing algorithm. With the correct
combination of slicing and mesh constraints it is possible to achieve a 100% hexahedral mesh in the
nozzles and hex-dominant mesh elsewhere. Obtaining the desired autoclave mesh in Workbench is less
time consuming than using ICEM.
Geometry can be imported or created in Classic, however, for a one-off analysis it would be more
efficient to use Workbench because the Classic interface is not as user-friendly. Classic is well suited for
repeated analyses of autoclaves because the vessel geometries tend to have similar features that can be
created parametrically using APDL. Model parameters and APDL commands are written in macro files,
and when the master file is called in Classic the autoclave model and mesh are generated. APDL
commands are written in such a way that building the model and applying mesh constraints results in a
100% hexahedral mesh in the nozzles and hex-dominant mesh elsewhere.
Analysis Setup
The parametric APDL scripts are programmed to prepare and analyze the model once the mesh is
generated. Conducting an analysis in Workbench requires manually preparing the model by applying
material properties, contacts and boundary conditions. An ICEM mesh must be imported into either
Workbench or Classic to complete an analysis. Importing an ICEM mesh into Classic facilitates the use of
APDL scripts to prepare and analyze the model; provided that groups of elements volumes or surfaces
were named in ICEM.
Design Changes
Design changes are easily implemented when using the APDL scripts by simply modifying the
model parameters and running the scripts to regenerate an updated model. Design changes in ICEM and
Workbench can be more problematic. ICEM blocks are associated to the underlying geometry (i.e. points,
curves, and surfaces). Mesh constraints, contacts, material properties, and boundary conditions applied in
Workbench are also associated to the geometry. Therefore, design changes that affect geometry numbering
370
will be time consuming because a large number of manual operations might be required to check and fix
the associations. Parametric relationships can be implemented in ICEM and Workbench; however, due to
the relationship between mesh or analysis constraints and the geometry these programs are limited to
dimensional changes only.
Analysis Budget
It is the number of nozzles on the autoclave that has the greatest impact on the amount of time
required to model and mesh the vessel. Consider the autoclave in Figure 1 which has twenty-nine nozzles,
three supports, and three courses of refractory. Out of the twenty-nine nozzles there are thirteen unique
nozzle designs. The estimated time required to generate the finite element model using each of the three
previously discussed methods (ICEM, Workbench, and APDL) is presented in Table 1. Note that this
estimate is for illustration only and is subject to change depending on the autoclave design and analyst
experience. The time required to solve the model, review results and generate a report is very similar for all
three methods and is not discussed.
Figure 1 Autoclave model geometry created using APDL

Table 1 Man-hours to create autoclave FEM
ANSYS
Model
Mesh
Assembly
Setup
Total
ICEM
Workbench
APDL
40
40
n/a
120
40
n/a
24
n/a
n/a
16
20
24
200
100
24
ICEM and Workbench both require a significant number of man-hours for model and mesh
creation. The ICEM method requires additional man-hours to assemble the meshed components. Analysis
setup for an ICEM model requires creating a script whereas the Workbench analysis setup is done
manually through the graphical user interface.
Model creation, mesh generation, and analysis setup are all tasks that are completed by the
computer by running the APDL scripts. The scripts are complex and take a significant amount of time to
write. The time to write the scripts is not included in the hours estimate because the script development has
already been completed in advance of the project assignment. The man-hours estimate is the time required
for the analyst to input the parameters into the scripts and modify the scripts if necessary. Provided that
scripts have been developed, the use of APDL can significantly reduce the man-hours required to complete
an analysis. Currently, scripts have been developed that can be used to complete a thermal analysis. These
scripts are in the process of being modified to accommodate structural analyses.
371
THERMAL ANALYSIS
One-dimensional heat transfer calculations are used to determine the refractory thickness that
should prevent the membrane from exceeding the design temperature. The through thickness thermal
gradient is calculated for the shell, heads, and each unique nozzle. Refractory thickness is modified for the
different regions until the membrane temperature is less than the design temperature, which is notably
lower than the material service limit. This provides a design margin for the one-dimensional analysis
method.
The temperature dependency of the formulas for ambient natural convection and radiation
requires using an iterative method to calculate the thermal gradient. Natural convection formulas for
different geometric orientations are considered to examine the effect of autoclave component orientation
on membrane temperature. In practice the nozzles and a region of the shell around each nozzle are typically
too hot for the membrane so weld overlay is applied as an acceptable alternative, but is more expensive.
The amount of overlay that should be applied around each nozzle is estimated based on past experience
and what is practical for the nozzle layout. The resultant refractory thickness and estimated weld overlay is
sufficient for basic engineering definition.
During detailed engineering the one-dimensional assumptions should be mitigated by conducting
a more accurate three-dimensional thermal analysis. The finite element model is initially created using the
one-dimensional results for refractory thickness and a few other modeling and material assumptions. Once
the autoclave geometry is adequately represented, boundary conditions are applied to the model to simulate
operating conditions. The results of the three-dimensional analyses are used to verify that the membrane
temperature is less than the design temperature and refine the estimate for weld overlay. Depending on the
results the model is modified and reanalyzed.
Modeling and Material Assumptions
When creating the autoclave model it is crucial to account for the nozzle closure details because a
significant amount of heat is conducted through the cover and flange connection increasing the temperature
of the nozzle and shell. Modeling the closure details requires some assumptions to make the geometry
suitable for meshing. The conductivities of the closure materials are adjusted based on past experience to
achieve accurate temperatures in the nozzle region.
Ceramic paper is installed between the refractory and membrane. Compared to the refractory it
has a relatively low thermal conductivity and can have a significant impact on the results depending on
how the paper is incorporated into the model. When considering the paper it is important to remember that
moisture will diffuse through the porous refractory during operation and be absorbed by the paper. It is
unknown whether the paper will completely dissolve over time or remain intact in an unknown state. The
conductivity is greatly affected by moisture content, so it is conservatively assumed that the paper has a
relatively high conductivity, or alternatively the paper is not included in the model.
Modeling each individual brick surrounded with mortar is not practical from a modeling and
meshing perspective, so each course of brick and mortar is assumed to be a homogeneous composite
material with properties that are a combination of the brick and mortar material properties. When
determining the composite conductivity it is important to consider that the refractory datasheet value does
not account for moisture absorbed by the porous refractory during operation. It is also worth noting that the
reported conductivity is based on a statistical analysis of test data. There is variation in the data because the
conductivity varies between test samples and there is error associated with the conductivity test. Typically
a temperature sensitivity analysis is conducted examining the range of conductivity values for the brick and
mortar.
372
Boundary Conditions
Thermal boundary conditions are applied to both the interior and exterior surfaces of the model to
simulate operating conditions. Process and ambient temperatures are applied to the vessel according to the
design operating conditions. An equivalent convection coefficient of 500 W/m2K is applied to the interior
of the autoclave which accounts for convection and radiation heat transfer. The magnitude of the
convection coefficient has been determined during previous computational fluid dynamic studies and
ranges from 300 500 W/m2K for fluid convection at the wall, to 1500 2000 W/m2K for condensation
of water vapour.
The convection coefficient applied to the autoclave exterior approximates natural convection for
air against a cylindrical surface and has a magnitude of 5 7 W/m2K. Radiant thermal energy for the
exterior surface of the model is included in the analysis by using an equivalent radiation coefficient,
radiation to ambient, or radiosity. The ANSYS radiosity algorithm predicts thermal energy loss and
thermal energy exchange between surfaces in view of each other as a result of gray diffuse radiation.
Radiation heat exchange and radiosity are temperature dependent and require multiple iterations to
converge to a solution, which can be time consuming for larger models. The correct emissivity must be
applied to the exterior of the model because emissivity will have a significant effect on the resultant
temperature. It is advantageous to use an equivalent convection plus radiation coefficient of 10 14
W/m2K for multiple analyses, then consider a verification run using natural convection with radiation or
radiosity as a final analysis.
The magnitude of the ambient natural convection and radiation equivalent convection are
determined based on the results of the one dimensional analysis. This assumes that the temperature
dependency of convection and radiation is negligible, which is valid because the temperature variation on
the exterior of the model is typically not significant. Using an equivalent ambient convection ignores the
effect of radiosity which can cause a notable increase in temperature. This is mitigated by setting the
allowable design temperature for the membrane to account for the radiant heat exchange.
The membrane temperature is sensitive to the ambient conditions. An assessment of the air
circulation and ambient temperature in close proximity to the vessel should be conducted to determine if
the local ambient air conditions are adversely different than the boundary conditions considered in the
analysis.
Thermal FEA Results New Design
When designing a new refractory lining, thermal FEA results are examined to determine if the
refractory lining provides sufficient thermal protection for the membrane. This is accomplished by
examining the results to determine if any area of the membrane exceeds the design temperature. If the
membrane temperature is excessive then the refractory thickness is increased. An alternative is replacing
the areas of the membrane that exceed the design temperature with weld overlay. This may prove to be
more cost effective than increasing the refractory thickness, especially if the hot spot is localised around a
nozzle shell junction.
Typical membrane thermal profiles are presented in Figure 2, which illustrates the effect of using
an equivalent natural convection plus radiation coefficient versus natural convection with radiosity. As
expected the temperatures for the results that consider radiosity are noticeably hotter and are more
accurate. Using radiosity and conducting a more accurate analysis it is possible to increase the design
temperature for the membrane. The location of the design temperature isotherm dictates the
membrane/overly boundary as illustrated in Figure 3 using temperatures of 90oC and 100oC. The required
amount of weld overlay is determined based on the location of the design temperature isotherm. It is up to
the analyst to decide upon a suitable design temperature considering the analysis assumptions. The design
temperature limit may be critical if the boundary conditions are modified or vary significantly from those
analyzed.
373
Temperature (oC)
Ambient Boundary Conditions [T= 25oC, h=12 W/m2K]
Ambient Boundary Conditions [T= 25oC, h=5 W/m2K, Radiosity (e=0.9)]

Figure 2 Membrane thermal analysis results
Temperature (oC)
Ambient
Boundary Conditions [T= 25oC, h=12 W/m2K]
Ambient Boundary Conditions [T= 25oC, h=5 W/m2K, Radiosity (e=0.9)]

Figure 3 Membrane/overlay interface temperature
Thermal FEA Results Existing Vessel
Thermal analysis is useful when making design changes to an existing vessel. For example, an
increase in vessel oxidation or leaching capacity may require increasing the operating temperature.
However, increasing the process temperature will require increasing the diameter of the weld overlay
around the nozzles to prevent overheating of the membrane. Since the autoclave is already in service, a
more cost effective alternative is adding Pertetrafluoroethylene (PTFE) polymer sleeves in the nozzles.
The amount of PTFE required for a given nozzle can be determined by conducting a series of
thermal analyses with increasing PTFE thickness. For this type of analysis it is important to know the
existing amount of overlay around each nozzle. For this example, the vapour zone nozzles have a ring of
weld overlay with an outer diameter that is 300 mm larger than the nozzle opening. Therefore, the location
of the design temperature isotherm must be measured for each nozzle to verify that the isotherm occurs
within the overlay and not the membrane.
374
The location of the design temperature isotherm measured from the nozzle inner diameter for each
nozzle is presented in Figure 4. Looking at the results of for the existing configuration only nozzles B, C, I,
and M1 require additional PTFE in the nozzles. Increasing the PTFE thickness for these nozzles decreases
the region of the membrane that exceeds the design temperature. Sufficiently increasing the PTFE
thickness for each of the nozzles results in an isotherm that falls within the existing overlay limits.
Note that weld overlay was not used around liquid zone nozzles H, M2, and M3. The liquid zone
nozzles are typically sanded-out in operation which insulates the nozzle. Therefore, results for these
nozzles are of little concern because excessive temperature for these nozzles are not observed in practice.
However, if the sanded-out condition does not occur then the membrane in these areas may be
compromised.
PTFE
Existing
Case 1
Case 2
Case 3
Case 4
A
25
25
25
25
25
B
25
38
50
63
75
C
25
38
50
63
75
D
25
25
25
25
25
Nozzle PTFE Thickness, mm

E
F
G
H
25
25
25
none
25
25
25
none
25
25
25
none
25
25
25
none
25
25
25
none
Figure 4 Membrane/overlay interface location
I
25
38
50
63
75
M1
25
38
50
63
75
M2/M3
none
none
none
none
none
375
MECHANICAL STABILITY ANALYSIS

Mechanical stability of an autoclave refractory lining is initially examined using the one
dimensional stress model presented in Design fundamentals for hydrometallurgy pressure vessel
refractory linings by A. Koning and P. Lauzon (Proceedings of the Conference of Metallurgists Pressure
Hydrometallurgy, CIM 2004). The one dimensional model provides an effective means to assess
mechanical stability and examine the sensitivity of lining stability with respect to various parameters;
operating conditions, material properties, chemical swell, design parameters, and installation factors. The
criteria for assessing stability using the one dimensional method are as follows:
The process or face course refractory must remain in compression for all operating conditions.
Stresses must not exceed the materials compressive failure strength.
The refractory lining must remain in contact with the shell membrane for all operating conditions.
The complicated autoclave geometry requires a more detailed assessment of mechanical stability
using finite element analysis. The first step in obtaining lining stability is minimizing the deflection of the
shell because excessive deformation can lead to brick failure. Once the shell has been adequately stiffened,
the refractory lining can be incorporated into the model. This requires modeling and material assumptions
because it is not practical to model each individual brick. An important factor to consider when modeling
the refractory lining is accounting for chemical swell. Once the refractory has been adequately represented
in the model, boundary conditions can be applied in various combinations so that the largest gap, tensile
stress, and compressive stress are generated in the lining. The results of each load case are assessed
considering the same stability criteria utilized in the one dimensional analysis. It is important to note that
the mechanical stability analysis is qualitative in nature and requires experience to effectively interpret the
results.
Shell Deflection
Dimensional tolerances for brick lined vessels are specified in DIN 28060 which is useful for
determining allowable tolerances in the fabricated vessel. However, this standard does not consider the
distortions resulting from the applied loads and the affect on the refractory lining. The rules in the ASME
Boiler and Pressure Vessel Code Section VIII, Div. 1, are used to determine the required thickness and
dimensional tolerances for the design of welded steel pressure vessels. Though the code establishes
sufficient shell thickness to ensure safe operation for the specified design conditions without failure, it does
not provide design requirements for a refractory lining. Thermal expansion, pressure, gravity, and external
loads act to deform the vessel. The shell of the vessel can deform elastically without causing much
concern, however, the refractory lining is very rigid and responds poorly to deformation. Excessive
deformation of the shell can increase the bending stresses in the lining and possibly lead to lining failure.
Since the brick lining has a very low resistance to induced bending stresses, additional analyses are
required to determine the required shell thickness to minimize deformation. Deflection analyses are
conducted on a model of the vessel without the internal refractory lining considering operational loads. The
vessel designer or engineer must determine a deflection criterion that cost effectively minimizes shell
deformation to reduce the loading on the refractory lining.
Modeling and Material Assumptions
During the development of the refractory lined autoclave model, it is assumed that the membrane
is fully bonded to the shell and the pair move independently of the refractory lining. This allows gaps to be
generated between the refractory lining and membrane. Typically the refractory lining includes a layer of 2
4 mm thick ceramic fibre paper which is installed between the membrane and refractory.
The ceramic paper creates a slip plane between the refractory membrane interfaces and provides
room for refractory expansion. During operation moisture will diffuse through the porous refractory and be
absorbed by the paper, however, it is unknown whether the paper will completely dissolve over time or
remain intact in an unknown state. Since model convergence is difficult to achieve if a physical gap is
376
created around the refractory (statically indeterminate solution) the paper is included in the model with a
relatively low Youngs Modulus to cushion the expansion of the refractory. This provides the required
expansion allowance so that the observed stress in the lining is not excessive.
Modeling each individual brick and the surrounding mortar in the autoclave lining is not practical
from a modeling and meshing perspective, so an acceptable approximation is representing the refractory as
a composite. It is assumed that the composite is a homogeneous material with properties (density, thermal
expansion coefficient, Youngs modulus, Poissons ratio) that are a combination of the brick and mortar
material properties. Depending on the brick or mortar being used in a particular region it possible to apply
different composite refractory properties throughout the model (i.e. compartment walls, baffles,
compression rings, vapor zone, liquid zone, nozzles, face course, backup course, etc.). Assuming that brick
and mortar thicknesses are constant in a particular region, it is possible to develop these composite material
properties using a volume fraction approach.
Generally it is assumed that the composite refractory properties do not vary significantly over the
temperature range from ambient to operation. This assumption poses a problem when incorporating
Litharge (i.e. lead based) mortar into an analysis because this mortar is known to soften significantly at
elevated temperatures. Through past experience the softening of the mortar has been found to significantly
reduce lining stresses, resulting in a mechanically stable lining. The difficulty in determining the composite
Youngs Modulus is further complicated by the fact that the modulus for brick and mortar is not typically
measured at elevated temperatures. To account for the softening of the mortar, a reasonable approximation
is to reduce the composite modulus, calculated using elastic moduli of both brick and mortar materials
measured at room temperature, by roughly one order of magnitude based on empirical observations of
existing lining systems.
Irreversible Chemical Swell
Almost all fireclay brick used in refractory linings experience irreversible chemical expansion
when exposed to an aqueous solution due to hydration of the alumina and silica matrix. Chemical
expansion data is obtained through laboratory tests that involve immersing a single brick in an aqueous
solution with a known acid concentration. The expansion takes months to occur and the amount of
expansion is dependent on temperature, pressure, and acid concentration.
In practice, chemical expansion is limited to a few inches behind the hot face of the process or
face course of refractory. A reduced level of chemical expansion must be applied to the finite element
model composite refractory because, unlike the laboratory tests, only the process face is directly exposed to
the aqueous solution. Since refractory is porous, some of the aqueous solution will diffuse through to the
intermediate and back courses of refractory. The intermediate and back courses are significantly cooler
than the hot face, so each layer of refractory will not experience the same amount of chemical expansion.
Chemical expansion in the finite element model is simulated using a modified temperature dependant
thermal expansion coefficient that accounts for both thermal expansion and irreversible chemical swell.
Boundary Conditions
The applied boundary conditions include temperature, operating pressure, hydrostatic pressure,
nozzle loads, and gravity. Temperature loads are obtained from the results of the thermal analysis. The
refractory lining is porous, so pressure is applied to the membrane. When applying hydrostatic pressure the
conservative approach is to assume that the vessel is full of slurry. Depending on the results of the
deflection analysis, it may be possible to ignore the nozzle loads if the results show that the shell and
nozzles are stiff enough to carry the nozzle loads and prevent any significant load transmission to the
refractory. Boundary conditions are applied in various combinations to generate the largest gap, tensile
stress, and compressive stress in the lining. Typically this is achieved considering two load cases:
Minimum operating pressure and minimum ambient temperature.

Maximum operating pressure and maximum ambient temperature.
377
Stability Assessment
Mechanical stability analyses produce qualitative results because of the underlying assumptions
required to create the model. Stability of the refractory is analysed considering a minimum of two different
load cases so that the largest gap, tensile stress, and compressive stress are observed. The overall stability
of the lining is determined by examining the size of the gap and stresses generated in the model.
Mechanical stability is achieved if the refractory is in compression, stresses do not exceed failure
limits, and a gap is not created between the refractory and membrane. The tensile strength of the composite
refractory is in the order of 6 MPa. The shear strength of the composite refractory is assumed to be the
same order of magnitude as tensile strength. A typical compressive strength for the composite refractory is
in the order of 100 MPa. The compressive strength is adjusted depending on the material test results for the
refractory used in the lining.
It is reasonable to expect that the mortar in the back course of a refractory lining will crack
because of the low tensile strength of the mortar. However, since all thermal cycling occurs at the hot face,
it is not expected that cracking of the backup course mortar will have any long term consequences.
Therefore, analysis of principal stresses is typically focused on examining the stresses generated in the face
course of the composite refractory.
A plot of the gap that can be generated between the refractory and membrane is shown in Figure
5. The open gap occurred because chemical swell was not included in the analysis. Including chemical
swell would have eliminated the gap, resulting in no visible contours for a plot of gap size. The gap size
will also be affected by the application of the maximum or minimum pressures and temperatures.
Gap Size (m)
Figure 5 Gap Size between the membrane and refractory when chemical swell is ignored
Figure 6 shows the compressive stress for two different refractory lining configurations. The
lining in the first model (Case 1) consists of fireclay brick throughout the vessel, Litharge (i.e. lead-based)
mortar in the vapour zone face course and potassium silicate mortar throughout the remainder of the vessel.
The second model (Case 2) was analysed consider a stiffer phenolic resin-based mortar in the vapour zone
face course compression rings and in the face course of the vapour zone nozzles. From examination of the
stress plots it can be concluded that the stiffer mortar in the nozzles and compression ring has reduced the
compressive stress around the nozzle opening. A comparison of the first and third principal stresses is
required for the liquid zone and vapour zone face course of refractory to determine if the lining is in a state
of compression. Stresses through the entire vessel must also be examined to verify that the material
strength has not been exceeded. Sensitivity of the stress results with respect to material properties may also
be required to determine the overall mechanical stability of the lining.
378
Maximum Compressive Stress (Pa)

Lining
Face Course Composite Cold Face
Face Course Composite Hot Face
Case 1
Case 2
Figure 6 Maximum compressive stress in the vapour zone face course of refractory
CONCLUSION
Thermal and mechanical stability analyses for autoclave refractory linings can be completed using
a finite element model created in either ANSYS ICEM or ANSYS Workbench. However, a much more
efficient alternative is using APDL scripts. Scripts have been developed and used to conduct several
thermal finite element analyses. The successful use of the scripts has motivated the modification of the
scripts for mechanical stability analysis. This is currently a work in progress.
Refractory lining design is improved by conducting thermal and mechanical stability analyses
using three dimensional finite element analyses. Thermal analyses are used to optimize refractory
thickness and determine the required amount of weld overlay. Mechanical stability analyses provide a
method to qualitatively assess the lining to improve the economic service life of the design. However, it is
important to recall that obtaining useful results requires carefully considering the various factors that affect
the refractory lining; shell deflection, modeling assumptions, material assumptions, chemical swell,
porosity, and boundary conditions.
379
ADVANCED CONTROL OF PRESSURE HYDROMETALLURGICAL PLANTS

R.K. Jonas
Honeywell Process Solutions
1860 W. Rose Garden Ln., #K20
Phoenix, AZ 85027-2708
(bob.jonas@honeywell.com)
ABSTRACT
Pressure leaching and pressure oxidation in autoclaves are important alternatives in the extractive
processing of gold, copper and nickel ores. The application of advanced control to pressure leach and
pressure oxidation autoclaves could achieve significant benefits as has been shown in alumina pressure
leaching. This paper compares and contrasts alumina digestion autoclaves to other mining autoclaves with
respect to advanced controls. The application of advanced control in alumina with over 30 units controlled
worldwide, and its benefits will be reviewed. The design and potential benefits from advanced control for
pressure oxidation and leaching will be presented.

Niagara, ON, Canada
Edited by
380
INTRODUCTION
It is this authors position and the purpose of this paper to propose that advanced control could be
effectively applied to autoclaves in the nickel, gold, and copper mining processes. This is based on the
proven effectiveness
effectiveness of advanced control on autoclaves used in the alumina industry for pressure leaching
of bauxite ores. Incremental, but significant increases in production could be realized by applying
advanced control to autoclaves, as evidenced by the alumina industr
industry,
y, and this not being implemented in
other autoclaves in the mining industry.
industry
In addition, today the mining industry is being challenged to improve their production methods. In
some markets like nickel, there is pressure to improve productivity and reduc
reducee the cash cost per ton. While
in other markets like copper and gold, demand is vigorous with favourable pricing, and there are
advantages to increase production and productivity given limited plant capacity. Advanced control has
proven its
it capability to improve
mprove mineral processing operations through increases in throughput
throughput, recovery,
as well as reducing variability. In todays mines, autoclaves are being used to a much larger sc
scale
ale and with
much larger importance, thus it would be beneficial to improve operational performance through the use of
advanced control.
ccordingly, it is
is the author supposition that an opportunity exists in the mining industry to use a
Accordingly,
proven advanced control technology to improve the operations and financial performance of mines using
autoclaves.
autoclaves
METHOD
To further the discussion that advanced control can be applied to autoclaves in various mineral
processes, it will be shown that autoclaves in alumina and those used in nickel, gold, and copper have
similar process and control
control issues. The first part of the discussion will compare and contrast the autoclave
processes. The second part will discuss the control strategies
strategies and issues pertinent to improving control.
There a number of features in common with autoclaves used in tthe
he mining industry for pressure
hydrometallurgical extraction. The ones discussed herein are Pressure Acid Leaching (PAL) and Pressure
Oxidation (POX) and Alumina Pressure Leaching (APL) that have very similar processes as seen in
Figure 1 and as discussed in the next sections.
`
Figure 1 Autoclave process used in pressure hydrometallurgical extraction
381
Pressure Oxidation and Pressure Acid Leach Autoclaves

Pressure Acid Leach Autoclaves
The High Pressure Acid Leach (PAL or HPAL) processes include preheaters, an autoclave, and
flash tanks. The PAL process is most often used for processing nickel lateritic ores. The most common
PAL autoclave design consists of a single titanium clad steel cylindrical vessel, and typically the long
dimension is horizontal, enabling the vessel to be compartmented and stirred. The feed to the PAL process
is a milled ore slurry of 1-3% grade of Ni that is heated in 1-3 direct flash preheaters. The feed is
continuous to the autoclave which flows sequentially thru the compartmented vessel, providing the needed
retention time that range from 75-100 minutes. Sulphuric acid is added directly to the autoclave, usually in
the 1st stage, but can also be injected in the 2nd and 3rd stages. The acid/ore ratio and the autoclave
temperature are the important variables to manipulate to achieve the optimal leaching rates. The
temperature of the reaction varies from 230 to 260C and is controlled by the manipulation of fresh steam
to the last heater. The reaction occurs at pressures from 4000 to 4500 kPa. The leached slurry flows from
the autoclaves to a series of 2-4 flash tanks to reduce their pressure to atmospheric conditions for further
processing and the resulting flash steam is used in the preheaters (Mayze, 1999).
Pressure Oxidation Autoclaves
The Pressure Oxidation (POX) process differs in principle as its objective is to not leach metals
into solution like PAL and APL, but to convert sulphides to oxides for further hydrometallurgical
treatment, e.g., cyanidation. The POX process is used to treat copper, gold, and several other types of
sulphide ores. Nonetheless, the process is similar to the others discussed, using preheaters, an autoclave,
and flash tanks. The autoclaves are typically brick and lead lined horizontal vessels, and compartmented
for the staged addition of oxygen. Acid is not usually added, as sulphuric acid is generated from the
oxidation of sulphur bearing ores. The reaction temperatures are in the range of 110 to 230C, pressures
range from 1000 to 3500 kPa, and the residence time varies from 60 to 120 minutes. The oxidation
reaction is exothermic, and with the use of flash steam for preheating, there is little need for additional
heating under operating conditions. In fact, in some cases the autoclave is water cooled (Dreisinger, 2006;
Jeffrey et al., 2009).
There are about 10 sites that have installed large scale PAL autoclaves and approximately 10 large
scale sites using the POX process. Most of these operations have started up in the last 15 years (Feldheiser,
2007). Figure 2 shows the large scale of these newer autoclaves.
Figure 2 Autoclave for PAL (image courtesy of Wikipedia)
382
Alumina Digestion Autoclaves

Autoclaves are used for the leaching of aluminum minerals from bauxite ores, and are an integral
part of the Bayer hydrometallurgical process for production of alumina (Al2O3). This process is typically
called alumina digestion, but for notational purposes it will be referred to as the Alumina Pressure
Leaching process (APL). The Bayer process with APL has enabled commercial scale production of
alumina for a century. The industry average age of these plants is approaching 40 years, and the oldest
plants in use today has been in production since 1941 (Intl. Aluminium Inst., 2008).
The APL process includes preheaters, autoclaves, and flash tanks. The most common
configurations consist of one or two steel cylindrical autoclaves in series, and both horizontal and vertical
autoclaves are common. The feed to the digestion process is a milled ore slurry of 25-40% alumina grade.
In most cases only the alkali liquor is heated by indirect flash heat exchangers (preheaters) prior to entering
the autoclave, but in some designs both the bauxite slurry and sodium caustic liquor are heated together in
the preheater. In all cases of heating, the final temperature is controlled by the addition of fresh steam to
the last preheater stage. The feed is continuous to the autoclaves, and designed for a retention time of
approximately 20 minutes, and it should be noted that compartmented vessels are not used. The ratio of ore
to caustic feed is tightly maintained along with reaction temperature, as these are the essential variables
manipulated to achieving optimal leaching rates. A temperature around 140 or 240C is optimal, depending
on type of mineralized alumina in the bauxite. The pressure of the reaction is not crucial and the typical
autoclave pressure runs about 3500 kPa. The pregnant liquor and barren solids flow unobstructed as a
combined stream to a series of 3 - 4 flash tanks that reduce their pressure to atmospheric levels at
temperatures near to 100C. Slurry from the flash tanks is pumped to atmospheric thickeners to separate
pregnant liquor from the gangue solids.
In total there are over 50 medium to large alumina refineries worldwide using the common APL
process described above. The author has estimated that there approximately 100 autoclave process trains at
these sites. In Figure 3, a photo can be seen of an alumina autoclave (vertical configuration). In addition, a
comparison of the key processes characteristics of these three different types of autoclaves can be found in
Table 1.
Figure 3 Autoclave used for alumina digestion (image courtesy of Usiminas Mecanicas)
Table 1 Comparison of autoclave processes
Process
Autoclaves
Flash Tanks
Heaters (flash)
Temperature
Pressure
Retention time
PAL
Horz. or Vert.
2-4
Direct
230-260C
4.0-4.5 MPa
75-100 min.
POX
Horz.
1-3
Direct
110-230C
1.0-3.5 MPa
60-120 min.
APL
Horz. or Vert.
1-4
Indirect
140-240C
~3.5 MPa
20-30 min.
383
DISCUSSION OF CONTROL STRATEGIES FOR AUTOCLAVES IN MINING

Advanced Control of Alumina Pressure Leaching
The advanced control of APL process using Multivariable Predictive Control (MPC) is well
accepted in the alumina industry. This advanced control technology has been applied to alumina autoclaves
since 1996 (Mason, 1998). It is estimated that worldwide over 30 autoclave unit trains are MPC controlled
(Jonas & Craw, 2011), each train being defined as single production line consisting of heaters, autoclave
and flash tanks. Thus it can be conclude that 30% of 100 medium-to-large APL autoclaves are controlled
by MPC. For purposes of this discussion it will be useful to understand some important control issues for
the APL process, and then discuss how MPC technology addresses these key issues.
In alumina digestion, the key parameters that effect recovery efficiency and production are
(Freeman, 1998; Jonas, 2004):
A/TC ratio.
This is the ratio of alumina (A) to total caustic (TC) in solution after digestion; in essence it is the
amount of alumina hydrate that has gone into the caustic liquor solution. There is an optimal
value of A/TC ratio for getting the highest recovery, but not so high as to be supersaturated and to
cause unwanted precipitation prior to the controlled precipitation of the alumina in the
precipitation tanks. The A/TC ratio is most easily regulated by adjusting feed flows of caustic
solution and ore slurry.
Temperature.
The reaction rate for alumina dissolution is closely related to autoclave temperature, and typically
there will be an optimum temperature associated the bauxites ore type that is used at the plant. The
temperature is regulated by the addition of fresh steam to the last heater feeding the autoclave.
Other plant constraints.
For each alumina autoclave process there will be a number of variables that can be measured and
need to be included as part of a control strategy for the plant; these are in addition to the afore
mentioned variables for temperature and A/TC ratio. It is important the MPC monitors and
controls other key plant variables so that the changes made by MPC to control A/TC ratio,
temperature and feed flows are well coordinated and that the operator does not have to turn-off
MPC to manage these other variables. For convenience, these are referred to as constraint
variables. In fact, MPC technology does not treat these constraints differently; it is merely a
convenient way to discuss the control problems that tend to not to be directly attributed to the key
controls for quality. Most often the constraints are closely related to process equipment limits
being reached at high feed flows, and thus can regulated by the MPC by adjusting the feed flows.
Some examples include; high flash tank levels, high heater pressures, high slurry pump load, low
autoclave retention time, etc.
MPC Technology Applied to Alumina Pressure Leaching

MPC is a standard off-the-shelf technology that has been in wide-spread use since the late 1990s,
with thousands in use for industrial plants and over 200 used in mining. The advantage of MPC is having a
more exact knowledge of the process dynamics and interaction. This additional knowledge is manifested in
the form of a matrix of singular models, these singular models mathematically describe the singular result
of manipulating one plant control (e.g. slurry flow) and its effect to one measurement (e.g., vessel
pressure). These singular models are measured from the operating plant data. An example is shown in
Figure 4; explicitly the Slurry flow is changed and the resulting changes to vessel pressure are measured
(left image), then this is converted to a singular model with a graphical representation (center image), and
then this single model is added to a matrix of other singular models (right image). These models are
measured and put in place at time of commissioning.
384
Figure 4 Example of how models are built for use by MPC

The MPC uses the model matrix to predict control behaviour in order to achieve better control
through coordinated and proactive control actions. Feedback of real
real-time
time plant measurements form an
important role in MPC as well, to correct predictive response for real world reactions, and thus keeping the
plant running well. In plants like alumina digestion with slow pro
process
cess responses and large number of
interactions (mostly between the flows and constraints), the plant can be run better with MPC as
multivariable predictions allow the control to react faster and smarter than with feedback only, and thus
provide a responsive
responsive and stable control of the plant. With normal plant controls, and most other advanced
control strategies, little or no predictive control is used and the controls rely primarily on feedback control.
Typically the MPC technology is implemented with lit
little
tle or no programming. The system is
loaded with the models that were measured at the site, and then configured for the desired operating ranges
and optimization priorities. The Honeywell MPC comes with standard operator interface that is often used
in mining,
mining, which is shown in Figure 5, but custom schematics are used as well.
Figure 5 Standard operator interface of MPC, used for alumina pressure leaching
Advanced Control Strategies for PAL
The PAL process, as it is used in nickel and cobalt mining, has many similarities to APL process
used in alumina as described above. From a process control perspective, they share common aspects as
well. In PAL, the key parameters that effect recovery efficiency in the overall process are:
Free acid (alternatively

(alternatively pH)
The control of free-acid
free acid in the leached solution is important for achieving the optimal leaching
recoveries and acid efficiencies. This residual free acid can vary due to differing constituent is in
the ore body. Free acid concentration has shown
sh own to be more accurate and reliable than pH for
strong acids that have metal constituents (Schwabe,
(
1960; Chen, 1998). Most often the free acid
385
content of the leached slurry is determined from a batch sample and processed in the lab. Free acid
is most easily regulated by adjusting acid or feed flow to autoclave, or alternatively via an acid to
ore ratio controller. Some autoclaves may have multiple acid injection points into autoclave
compartments, in which case individual acid/ore ratios could be used for each compartment that is
trimmed from single free acid measurement. Furthermore, at least one site has installed automated
sampling method suitable for pH instrumentation, electrodeless pH measurement is also showing
promise (Saini, 2009). It is worth noting that in alumina APL electrodeless conductivity is a key
measurement for inferring A/TC ratio and is common in most of the applications of MPC
technology.
Temperature
The kinetic efficiencies for PAL are closely related to temperature (Rubisov et al., 2000) and
typically there will be an optimum temperature vs. energy point associated the ore body.
Temperature is typically regulated by the addition of fresh steam to the last heater stage or in some
cases by the direct injection into autoclave compartments.
Other, such as plant constraints.
The author presumes, that like alumina APL, for each PAL process there will be a number of
variables that can be measured and used as part of a control strategy for the plant. As stated earlier
in the APL discussion, it is convenient to characterize these as constraint or limit variables of the
plant to stay within the operational limits. These could be high flash tank levels, high heater/vessel
pressures, high slurry pump load, low retention time, and even up/downstream equipment (tank
levels, etc.).
The application of MPC for the PAL process should perform well, given the long time delay in
the PAL process (retention time) that is more than double that seen in APL. According to the authors
experience, time delays much longer than 10-15 minutes are a challenge to control from either manual or
automated means. However, the predictive capability of MPC could be limited by the infrequent analyzing
the leached solution free acid concentration, a key quality parameter to be used by MPC. One option for
consideration that could improve the situation, is if the leached solution free acid could be inferred from
conductivity and other measurement, similar to the practice for A/TC ratio in the alumina industry. Also,
an analysis of the variability in ore slurry (solids, particle size) and of the acid concentration may support
an implementation of an effective feedforward control strategy in the MPC that would compensate for
these feed variations and thus reduce the importance of good feedback control using free acid
measurement.
MPC Strategies for POX
The POX process as it is used in mining for gold, copper, and other metals has some similarities
to APL process used in alumina as described in prior sections. From a process control perspective, these
autoclaves share common aspects as well, but the POX process should realize far greater improvement
from the use of MPC. This is because POX has more complexities due to multiple injection points of
reagent (oxygen) and having the need for heating or cooling the autoclave compartments on an individual
basis. In POX, the key parameters that effect good process control are:
Oxygen partial pressure

An important control aspect of POX autoclaves is the control of oxygen partial pressure, also
known as overpressure (Vizsolyi et al., 1967). This is maintained by the manipulation of oxygen
flow (or alternatively, a total oxygen to ore ratio). In addition, a suitable ratio or temperature
scheme is needed to split the oxygen to the individual autoclave compartments.
Temperature
A critical control requirement for POX autoclaves is the control of temperature. POX temperature
control is complex due to the exothermic heat profile that changes across the autoclave
compartments. Often the first compartment requires heat and later compartments require cooling
of the exothermic reaction (Dunn, 2009). In many cases, the first few compartments will have
their own measurements and control means (generally, those compartments that receive oxygen).
386
Thus the temperature control across the autoclave would be complex and interactive, affected by
ore flow, individual compartment oxygen flows, and compartment cooling or heating means. This
type of complexity is well managed by MPC control.
Plant constraints
The POX plant will have its unique individual constraints to depending on the plant design and
condition as noted in PAL and APL discussion. In addition the POX could also have constraints
related to the individual compartment oxygen and temperature measurements.
In summary, POX process is well suited for MPC, it is a process that very interactive and one that
could be sufficiently instrumented (O2 flows, temperatures, oxygen overpressure). Given the longer
retention times of POX vs. APL, a MPC with its predictive control should improve performance more than
we have seen in the alumina industry. Comparisons of the key control issues for mining autoclaves are
shown in the Table 2.
Table 2 Summary of MPC strategies and advantages for autoclaves in mining
Key Objectives
Solvent Reaction
Temperature of
Reaction
Constraints,
other variables
(varies per plant)
APL
A/TC ratio inferred from
conductivity sensor is
key measurement
PAL
Free Acid concentration
is key measurement
(lab, which limits MPC)
Primarily controlled by
Ore and Caustic Liquor
flows (ratio)
20-30min reaction time,
control well by MPC
Measured at last heater
Acid & Ore flows
(ratio), multiple
injection points
reaction time > than
APL, control better by
MPC
Measured at last heater
Controlled by steam
Controlled by steam
Vessel pressures
(variable scaling, effect
max flow)
Flash Tank Levels
Similar to APL, but less

scaling effects
POX
Oxygen Overpressure is
key measurement,
multiple compartments
and measurable exotherm.
Oxygen and Ore flows,
multiple injection points
reaction time > than APL
& multiple injections &
temperature indications,
MPC control much better
Measured in multiple
compartments
Easy with MPC by steam,
water, 02 manipulation
Similar to PAL
Limits per compartment
(temperature, O2-ore
ratio)
Multiple limits favor
better control by MPC
RESULTS OF MPC FOR MINING AUTOCLAVES

Results for Alumina Pressure Leaching MPC
For 16 years, MPC has proven its capability to improve the control of mining autoclaves. Today
over 30 alumina autoclave unit processes are delivering tangible business value to the operators. The
success of MPC is because of its capability to manage the autoclave processes that are difficult to control
due to slow and highly interactive dynamics (Fiske, 2005). MPC technology improves the stability of these
difficult to control plants in a way that allows the MPC to increase throughput or achieve higher recoveries,
as well as achieve this in a robust fashion that insures good control 24/7 (Jonas & Craw, 2011). This is
certainly the case in alumina digestion where our MPC has been applied on numerous APL autoclaves, and
well as evidence by repeat users of MPC that have multiple autoclaves at single sites and for owners with
multiple sites in same region (Oliveira et al., 2009).
387
The two main benefits areas from the use of MPC in APL autoclaves are:
1)
2)
Increasing recovery or yield and/or

Increasing production via throughput (feed) increases.
In the case of alumina and the business drivers for MPC, typically only one of these benefits areas
is the focus of autoclave application based on the on current market conditions. In general, when market
demands are strong, the focus for setting up the MPC is to increase production, and thus recovery is a
lesser focus and simply maintaining the historical recoveries is sufficient. However, the current trends in
alumina is to use the MPC to reduce variability and then target improving recover/yield so as to reduce
costs (as well as improving intermediate product quality that has stabilizing effect on the overall process).
In either case, the MPC structure is identical, but more care might be given to the accuracy and
repeatability of certain models and measurements in order to insure delivery the targeted benefits.
For example in APL, when targeting improving recovery efficiencies, care would be taken to
insure the model of liquor flow changes to A/TC ratio are accurate and perform well. The result is the
MPC is empowered do its best to regulate A/TC by better disturbance rejection while at the same time
making the type of control actions that promote further A/TC stability (coordinated control actions and
slower optimization control actions). The superior capability of MPC to reduce A/TC variability allows
the MPCs built-in optimizer to increase the average A/TC ratio for improved extraction efficiencies while
also avoiding high A/TC excursions, thus realizing higher recoveries without creating the problem of
unwanted auto-precipitation downstream that are associated with high excursions in A/TC ratio.
This same capability of MPC technology for improved control and stability can be used to achieve
higher throughputs by managing the multiple and concurrent equipment and quality constraints associated
with high feed flows. With conventional controls and expert systems, when multiple and concurrent
constraints are present, the controls tend to be ill-coordinated and often this results in control induced
cycling. For example, the feed slurry flow control may switch back and forth being constrained by high
flash tank level or high slurry pump motor-load, resulting in swinging feed flows. With MPC the
coordination between constraints is smooth and little or no cycling occurs, which allows running to higher
feed averages. The typical results realized by users of MPC for alumina autoclaves are shown below:
Table 3 Benefits achieved in APL autoclaves
Benefit type
Increased recovery
(extraction efficiency)
Increased throughput
Amount
1.0 to 1.85%
( Oliveira et al., 2009; Freeman, 1998)
~1%
(Lawrence & Jonas 2005; Jonas 2004)
Expectations of MPC for PAL and POX Autoclaves

To the best knowledge of the author, no true MPC technology has been applied to autoclaves used
for PAL or POX. One practitioner has applied a non-MPC advanced control with the limited scope of only
controlling pH control of a POX autoclave, and has reported a 0.5% extraction efficiency increase (Khan et
al., 2009). In addition, if one can conclude from the prior discussions that these autoclave processes and
control strategies are similar, then this would strongly suggest that MPC control for PAL and POX can
improve control and deliver significant benefits. Methods exist in the industry to study the suitability and
calculate the benefits using MPC (Haskins, 1995; Jonas, 2008), using a process data driven method and
effective site audits. It is recommended this be done as a next step.
It is the opinion of the author that, in absence of the above recommended studies, the potential
benefit increase for PAL and POX should be similar to that for the APL process (of 1-2% increase), for the
following reasons:
388
Improve effectiveness of control by use of predictive MPC

The comparison of the larger process delays in PAX and POX to those in the APL processes
suggests that MPC could achieve even greater control improvements over any existing
conventional or expert rules controls that by their nature have limited predictive capability. The
greater variability of conventional control arising from either the
need for tuning in non predictive controls, that for the sake of stability, are slower than dominate
process time constants, and thus unmeasured disturbances are poorly rejected and setpoints are not
well maintained.
overactive tuning used to slow control associated from the long process dynamics (prior
discussion point), that results in periodic cycles originating from control overactive tuning.
Improved effectiveness of control by use of multivariable MPC
The large number of interactions associated with controlling some of the individual POX
compartments, as well as need for constraint riding for both PAL and POX processes, indicates a
process that would be much better be managed by MPC. In fact, the greater complexity of the
POX autoclave in comparison to the APL autoclave would suggest that MPC for POX would have
even better results than those seen in APL.
MPC may not improve control because of the use of slow lab data
The APL application uses real-time conventional process measurement as well as real-time
inferential data (which are derived from real-time conventional instruments that feature periodic
adjustments coming from infrequent lab updates). The result is that the APL application realizes
improvements from nearly 100% real-time feedback data. The PAL and POX applications may
suffer from not having the same use of real-time measurements; hence control improvements
would likely be less (to an extent unknown without auditing each site). The improvements from
APL are not derived from using better real-time feedback, as the benefit improvements presented
previously for APL were compared to non-MPC applications with same instruments and same or
similar inferential sensors for feedback. Also, as noted in the prior section, there may be
opportunities to use other real-time measurements for MPC feedforward control (feed slurry
density, acid concentration) to mitigate the lack of real-time feedback. These MPC methods are
not reflected in the improvements cited for APL (as good feedback measurements diminished the
need for these feedforward mechanisms), and thus we can infer that the MPC feedforward control
for PAL and POX can have a meaningful effect on MPC improvements.
CONCLUSION
Multivariable predictive control has been effective in controlling many large and complex
hydrometallurgical complexes, including a large share of the worlds alumina autoclave processes. Some
of these MPC applications have been in place for 16 years, and a good number of more than 30
applications approaching 8 years being in service. They have delivered well over 1% improvements in
extraction efficiencies, and when production is needed, approximately 1% in throughput increases.
The re-emergence of autoclaves in mining, that are larger in scale and more complex, underlines
the importance of these operations and leads one to wonder if the operators of autoclaves could also benefit
from the use of robust MPC technology. Certainly, PAL and POX autoclaves have challenges that need to
be addressed for the successful and sustained application of MPC. I believe this a challenge that can be
met with sound engineering and technologies, that can be done now and with few risks and a small
investment.
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THE FLASH RECYCLE SYSTEM FOR THE COOLING OF AUTOCLAVES

PROCESS DESIGN AND OPERATION
*F. Crundwell1, N. Steenekamp2
1
CM Solutions
Office Suite 119, Killarney Mall, 60 Riviera Road, Johannesburg
(*Corresponding author: frank.crundwell@cm-solutions.co.za)
2
Lonmin Platinum, South Africa
ABSTRACT
The leaching of sulphide minerals generates a significant amount of energy. There are three
systems that might be used to remove this energy. These are: cooling coils, quench water, and flash recycle.
Flash recycle is the recycling of slurry from the autoclave to the feed tank. Heat is removed in this
arrangement when the slurry at elevated temperature and pressure is flashed to atmosphere, releasing steam.
The slurry is returned to the autoclave at lower temperature, resulting in cooling. The cooling is directly
proportional to the steam released from the recycled slurry. Design equations and results for the flash
recycle system are presented. A fourth proposal for removing heat is to recycle slurry from the back of the
autoclave. These four alternatives not only remove the heat, but also have an effect on the leaching
efficiency. Amongst the four alternatives, design calculations indicate that the flash recycle option is the
optimal solution in terms of leaching efficiency and heat removal, and recycling product from the back of
the autoclave is the worst. In spite of its efficiency in terms of heat removal and leaching, the
implementation of the flash recycle system is limited to a few operations in the platinum industry.

Niagara, ON, Canada
Edited by
392
INTRODUCTION
In considering ways to improve leaching operations, focus is placed on the chemistry, on the
kinetics, the agitation and perhaps even on the gas mass transfer conditions. Attention is less frequently
placed on the removal of energy from these reactors and how this might limit performance.
The pressure leaching of sulphides releases a significant amount of heat. For example, the reaction
for the leaching of chalcocite, Cu2S, given by
Cu 2 S(s) + 2.5 O 2 (aq) + H 2 SO 4 (aq) 2 CuSO 4 (aq) + H 2 O(aq)
(1)
has a heat of reaction of 6 MJ/kg Cu2S. Viewed another way, this heat of reaction is about 29 MJ/kg of the
sulphur contained in the chalcocite, which is the heat of combustion of coal. This means that the amount of
heat generated in the leaching of sulphides is similar to burning a mass of coal that is equivalent to the
mass of sulphur contained in the minerals. All of this heat needs to be removed from the autoclave.
There are three basic systems for the removal of heat from an autoclave: (i) quenching with cold
fluid; (ii) cooling with coils; and (iii) flash recycling. Of these, the flash recycle has received very little
attention even though it is effective and relatively easy to implement. This paper describes the flash recycle
system, presents the process design equations for the flash recycle, and discusses the operation of flash
systems (Crundwell, 2010; Steenekamp & Dunn, 1999).
The flash recycle system discussed here is not the same as the flash-splash system employed in the
laterite industries. In those applications, the flash-splash system is used to recover energy from the back
end of the autoclave. The purpose of the flash recycle is the opposite, to remove energy. In the splash-flash
arrangement, steam is recycled from the back end to heat the feed. In the flash recycle, slurry is recycled
and flashed to remove heat.
PROCESS DESCRIPTION
The flash recycle system is shown schematically in Figure 1. Slurry is fed from the feed tank to
the first compartment of the autoclave. The autoclave operates at elevated temperature and pressure. The
slurry flows through the autoclave compartments, and discharges under pressure to the pressure letdown
vessel.
water vapour
flash recycle
control valve
leach slurry
feed tank
autoclave
Figure 1 Schematic diagram of the flash recycle system. Hot slurry is recycled from the autoclave to the
feed tank, resulting in steam release from the feed tank
393
Part of the slurry in the first compartment autoclave is returned to the feed tank. The flow rate of
the recycle stream is controlled by a valve. Because the feed tank operates at atmospheric pressure, the
recycled slurry boils, which simultaneously releases water vapor and lowers the temperature to that of the
atmospheric boiling point. Thus, the temperature of the feed slurry is limited to the boiling point. Cooling
in the autoclave is a direct result of the difference in the temperatures of the recycle and the feed streams.
The amount of cooling is directly proportional to the amount of water vapor released from the
slurry recycle stream in the feed tank. Increasing the recycle flow cools the autoclave; decreasing the flow
increases the autoclave temperature.
PROCESS DESIGN
The amount of slurry that is recycled and water that is flashed is required for the process design.
Apart from providing the design equations, the analysis is illuminating because it shows exactly what the
mechanisms of cooling are at the feed (or flash) tank and at the autoclave compartment.
Required Autoclave Feed Rate

The purpose of this section is to demonstrate the calculation of the recycle rate that is required to cool the
autoclave. This is determined by performing a mass and energy balance on the system.
Consider the flow sheet of the system that is shown schematically in Figure 2. Assume that the autoclave is
a multi-compartment horizontal vessel. The feed slurry and the flash recycle stream are mixed in the feed
tank. The feed slurry is heated by the hot recycle, and the temperature increases to the boiling point. The
contents of the feed tank are pumped into the first compartment of the autoclave. Part of the contents of the
first compartment are drawn back to the feed tank under the pressure of the autoclave. The rest of the
contents overflow the compartment weir into the second compartment.
The energy balance on the first compartment of the autoclave is given by:
(2)
q 3 = q 2 + H r rate
where q is the rate of energy flow in J/h, Hr is the heat of reaction in J/mol, and rate is the rate of reaction
in mol/hr. The subscripts refer to the stream numbers shown in Figure 2.
Equation (2) has neglected minor contributions, such as the energy carried in the gas flows to the
compartment.
61
41
21
31
51
Figure 2 - A schematic diagram of the flash recycle system on the first compartment of an autoclave
394
Equation (2) can be expanded as follows:

m 3C P 3 (T3 T0 ) = m 2C P 2 (T2 T0 ) + H r rate
(3)
where m is the mass flow of the stream, CP is the average heat capacity of the stream, and T is the
temperature. The reference temperature, T0, is taken as 25C.
In order to simplify the analysis, it is assumed that m2 m3 and Cp = Cp2 Cp3. Applying these
assumptions, we get that Equation (30 can be written as:
m 2C P (T3 T2 ) = H r rate
(4)
The left-hand side of Equation (4) represents the heat removed while right-hand side represents the heat
generated by reaction.
Equation (4) demonstrates how cooling is effected in the compartment. Since T2 < T3, Equation
(4) indicates that the heat generated can only be removed by dilution. In other words, the flash recycle
cools the autoclave compartment by increasing the amount of cooler fluid that enters it.
Solving Equation (4) for the mass of material entering the first compartment, we get:
m2 =
H r rate
C P (T3 T2 )
(5)
Equation (5) specifies the mass of slurry in the recycle stream. If the autoclave compartment is operating at
T3 and the atmospheric boiling point is T2, then the flash recycle rate is m2 in order to remove an amount of
energy equivalent to H r rate J/h.
Amount of Water Flashed

The overall energy balance around the feed tank and the first compartment of autoclave is given
by the following expression:
q 6 = q 1 q 5 + H r rate
(6)
The energy in stream 6 is the sensible heat up to the boiling point and the heat of evaporation at
the boiling point. Thus, the energy balance can be written as follows:
m 6C p (Tb T0 ) + m 6 = m1C p (T1 T0 ) m 5C p (T5 T0 ) + H r rate
(7)
where is the latent heat of vaporization of water.

The overall mass balance is given by the expression:
m5 = m1 m 6
(8)
Substitution of the mass balance into the energy balance yields the expression:
m 6C p (Tb T0 ) + m6 = m1Cp (T1 T0 ) (m1 m6 )Cp (T5 T0 ) + H r rate
(9)
395
The rearrangement of this equation yields the expression for the amount of steam generated in the
flash recycle system:
m6 =
H r rate m1C p (T5 T1 )
(10)
+ Cp (Tb T5 )
The calculation of the amount of water evaporated is sensitive to the amount of leaching achieved
and the amount and temperature of the feed flows. This is because the numerator in Equation (10) is the
difference between two large numbers. As a result, a small change to either of these values has a large
effect on the calculated amount of water flashed.
Required Flash Recycle Rate

The required flash recycle rate can be calculated from the mass balance around the feed tank,
given as Equation (11):
(11)
m 4 = m 2 m1 + m 6
Numerical Example
To calculate the volumetric flow rate of feed to the autoclave, we need to calculate the heat
generated. Assume that the autoclave operates at 140C and that the reactions that might possibly occur in
the autoclave are those given in Table 1. Also shown in Table 1 are the conversions for each of these
reactions, and their corresponding heats of reaction.
Table 1 - The reactions in the autoclave and their heats of reaction
Reaction
1
2
3
Conversion
Cu 2S + 0.5 O 2 + H 2SO 4 CuS + CuSO 4 + H 2 O

CuS + 2 O 2 CuSO4
CuNi 2S 4 + 7.5 O 2 + H 2 O CuSO 4 + 2 NiSO 4 + H 2SO 4
Heat of reaction
at 140C, kJ/mol
163
800
3089
1.00
0.71
0.89
The calculation of the total energy generated is shown in Table 2.

Table 2 - Calculation of the energy generated by reaction
Component
Cu2S
CuS
CuNi2S4
Mass flow
in feed
t/hr
2.000
0.000
0.6
Molar mass Molar flow Heat of reaction

kmol/kg
159
0
310
kmol/s
0.003494
0.003494
0.000538
kJ/mol
163
800
3090
Reaction
Energy
Conversion Generated
MW
1
0.57
0.71
1.98
0.89
1.48
Total
4.03
Thus, the volumetric flowrate of the feed to the first compartment of the autoclave is calculated as
follows:
m2 =
4.03
= 86.4 t/h
4.2(140 100)
The heat capacity of water is 4.2 kJ/kg.
(12)
396
Note that the mass calculated in Equation (12) is the mass of water in the slurry. This is justified
by the observation that the dissolved components do not contribute much to the heat capacity, and the
concentration of solids in the slurry is low.
Assuming that the feed is at a temperature of 55C and consists of 28.2 t/h of slurry, of which 2.6
t/h is solids, and 21.5 t/h is water, the amount of water vapor generated is calculated from Equation (10):
m6 =
4.03(1000) 21.5 / 3.6(4.2)(140 55)

= 3.26 t/h
2265 + 4.2(100 140)
(13)
The final quantity to calculate is the flash recycle rate, which is given by Equation (4):
m 4 = m 2 m1 + m 6 = 86.4 21.5 + 3.26 = 68.2 t/h
(14)
Note that all of these flows calculated refer only to the mass flow of water in the system.
Comparison with Simulation

It might be argued that any one of the assumptions that led to the design equations is invalid. In
addition, it can also be argued the calculations are sensitive to the values used. Consequently, it is useful to
obtain another independent verification. Therefore, in order to confirm that these assumptions are valid, the
autoclave and the flash recycle were modelled using Cycad Process software (www.cycadprocess.com).
The methods used in these simulations have been described in previous publications (Crundwell, 1994,
1995, 2001, 2005; Crundwell and Bryson, 1992). The results from the calculations using this modelling
package are shown in Table 3. These results indicate that there is good correspondence between the manual
calculation and the simulation.
Table 3 - Comparison of the flash recycle parameters
Parameter
Flow rate of water in the feed to the
autoclave
Amount of water vapour flashed from
feed tank for each autoclave
Flow rate of water in the recycle
stream from the autoclave
Manual
calculation
86.4 t/h
Cycad Process
simulation
89.7 t/h
3.26 t/hr
3.52 t/h
68.2 t/h
71.7 t/h
Two Limiting Cases

The pressure is flashed to atmospheric pressure in the flow-control valve on the recycle stream.
The derivation of the design equations in this section has assumed that the steam generated in the pressure
letdown does not simply disengage and exit through the feed tank vent without heating the contents of the
feed tank to their boiling point.
An alternative case might be to assume that full disengagement occurs, so that all the steam
generated simply exits without heating the slurry in the feed tank. This would result in the temperature of
the feed tank being somewhat lower than the boiling point of the solution. This alternative assumption has
proved to be incorrect in practice the solution is close to boiling point because disengagement does not
occur in an idealized manner. One consequence of a feed tank point that is close to boiling is that there
might be excessive wear of the autoclave feed pump.
397
EFFECT OF FLASH RECYCLE ON LEACHING PERFORMANCE

The removal of heat is such a challenge in autothermal leaching that it limits the productivity of
these reactors. Cooling might be effected by cooling coils, the addition of cold solution (quench cooling) or
the use of air rather than oxygen as the oxidant. There is little volume for cooling coils in each
compartment; as a result, the amount of cooling that can be affected is about 1.0 to 1.5 MW.
Since it is much easier to remove heat by flash recycle than cooling coils, it is advantageous to
flash recycle from as much of the autoclave as possible. As a result, some of the compartments may be
combined into one larger compartment. However, this has a disadvantage, in that the optimum
configuration for leaching is a series of tanks, which means that the more compartments the better the
leaching conversion. Thus there is an interesting trade-off between the size of the first compartment and
the subsequent compartments.
Interesting as this optimization study might be, some engineers have a raised a more basic
question: they assert that the increased flow through the first compartment due to the recycle stream
reduces the residence time and hence reduces the leaching conversion. This question is analyzed by
considering a component mass balance for a simple recycle stream around the first compartment of the
autoclave. The schematic flow sheet is shown in Figure 2.
The component balance around the mixing point is given by:
Q1C1 + Q 4C 4 = Q 2C 2
(15)
where Q is the volumetric flowrate and C is the concentration of a component.

The component balance around the material leaving the compartment is given by:
Q 3C 3 = Q 4 C 4 + Q 5 C 5
(16)
The mass balance across the compartment is given by:

Q 2C 2 = Q3C3 + rate V
(17)
where rate is the rate of reaction of the component and V is the volume of the compartment. These
equations can be combined to give the following expression:
Q1C1 = Q5C5 + rate V
If we made the assumption that Q1 Q5, we can rewrite this expression as:
V
C1 = C 5 + rate
= C 5 + rate
Q5
(18)
(19)
where is the residence time. This is the same as the expression that would be written if there were no
recycle. The residence time is not V/Q2 but V/Q5.
The result given in Equation (19) clearly demonstrates that the flash recycle from the autoclave
does not alter the residence time and does not affect the leaching conversion. This is confirmed by
operating practice at Lonmin Platinums base metal refinery.
INDUSTRIAL IMPLEMENTATION OF FLASH RECYCLE SYSTEMS

Impala Platinum invented and implemented the flash recycle in the late 1980s. This first
implementation was closely followed by Lonmin Platinum in the early 1990s. Recently, Anglo American
398
Platinum have implemented flash recycle. All of these applications are to the copper pressure leaching
stage of their base metals refineries.
The equipment is uncomplicated: material is removed from the autoclave through a dip pipe and
flows to the feed tank under pressure. The flow is controlled by an angle valve, which also allows for the
pressure letdown.
CONTROL
The temperature control of the autoclave is through two PID control loops, shown in Figure 3.
The rate of the feed to the autoclave is adjusted so that the level in the feed tank is maintained at a set point.
The flow rate in the flash recycle stream is adjusted to maintain the temperature in the autoclave. Cyclical
behaviour is frequently observed because of the dynamics of the system. Model-based multivariable
control, illustrated in Figure 4, has been shown to eliminate this cyclical behaviour. The feed tank level and
autoclave temperature are controlled by one multi-variable controller instead of two independent PID
control loops.
temperature
set-point
PID
Controller
level
set-point
Feed
Slurry
TI
LI
PID
Contoller
Figure 3 Control loops for the flash recycle
Multi-Variable
Controller
TI
LI
Feed Slurry
Figure 4 Multivariable control of the temperature in the autoclave
399
COMPARISON WITH OTHER HEAT REMOVAL SYSTEMS

The flash recycle is compared here with cooling coils, quench cooling, and recycling from the
back of the autoclave. The comparison is made on the basis of a three-compartment autoclave, in which the
first compartment is twice the size of the each of the other two. The four systems have been modelled for
this comparison. Shrinking particle kinetics with population balances are used to describe the leaching
reactions. Mass transfer kinetics are used to describe the transfer of oxygen from the gas phase to the
solution.
It is assumed for the purposes of this comparison that all the heat can be removed by these four
systems.
The conversion for each of these four systems is shown in Figure 5. It is at first glance surprising
that the flash recycle system has a higher conversion than that achieved with cooling coils. However, the
residence time in the last two compartments is slightly higher because water has been removed as a result
of flashing. For the same reason, quench cooling has a lower conversion than both the flash recycle and
cooling coils, that is, additional water lowers the residence time.
Back flash refers to the proposal that the part of the slurry from the back of the autoclave be
recycled to the front of the autoclave. While recycling around a single CSTR has the same as residence
time as the tank itself, recycling around a series of CSTRs, like an autoclave, does affect the residence time.
As shown in Figure 5, recycling slurry from the back of the autoclave has the worst performance because it
reduces the residence time.
Figure 5 The conversion at each compartment in a three-compartment autoclave

The productivity of the autoclave, in tons of material leached per unit volume per unit time, is
shown in Figure 5. The productivity of the flash recycle is highest, because more sulfides are leached,
generating more energy, for the same size of autoclave. It is worth noting that retrofitting a flash recycle
system to an autoclave that is limited by heat removed will produce a much greater increase in productivity
than that shown in Figure 6. The reason for this is that the implementation of a flash recycle system allows
other limiting factors to be removed. For example, the change to flash recycle may be accompanied by a
change from air to oxygen. As a result, the rate of reaction can be significantly improved at the same time.
400
.
Figure 6 The productivity of the autoclave with different methods of cooling
CONCLUSIONS
Flash recycle has been implemented at three base metals refineries in South Africa. The leaching
of copper sulphides releases significant amounts of heat, which can be effectively removed using flash
recycle. The process design equations and the control strategy for flash recycle have been presented here.
Four options for the removal of heat were studied to determine their leaching efficiency and their
effectiveness of heat removal. Design calculations and simulations were performed to determine the
leaching efficiency and autoclave productivity for each of these options. Based on these calculations, flash
recycle is the best overall option.
REFERENCES
Crundwell, F.K. (1994). Micro-mixing in continuous particulate reactors. Chem. Eng. Sci. 49, 3887-3896.
Crundwell, F.K. (1995). Mathematical modelling of leaching reactors. Hydrometallurgy, 39, 321-335.
Crundwell, F.K. (2001). Modeling, Simulation and Optimization of Bacterial Leaching Reactors.
Bioengineering and Biotechnology 71, 255-265.
Crundwell, F.K. (2005). The Leaching Number: its definition and use in determining the performance of
leaching reactors and autoclaves. Minerals Engineering 18,13151324.
Crundwell, F.K. (2010). Optimization of Exothermic Pressure Leaching System, ALTA 2010 Nickel and
Cobalt Pressure Leaching and Hydrometallurgy Forum, ALTA Metallurgical Services.
Crundwell, F.K., & Bryson, A.W. (1992). The modelling of particulate leaching reactors the population
balance approach. Hydrometallurgy 29, 275-299.
Steenekamp, N. & Dunn, G.M. (1999). Operations of and improvements to the Lonrho Platinum Base
Metal Refinery, EPD Congress 1999, pp. 356390 TMS.
401
SPECIAL DESIGN CONSIDERATIONS FOR

PRESSURE HYDROMETALLURGY PILOT PLANTS
P. Martin
Senior Project Manager and Engineer, Zeton Inc.
740 Oval Court
Burlington, Ontario, Canada L7L 6A9
(pmartin@zeton.com)
ABSTRACT
Pilot plants for pressure hydrometallurgy represent special design and project execution
challenges. Over the past twenty years, Zeton has designed and fabricated a variety of world-class pressure
hydrometallurgical pilot-plant facilities, and this paper discusses design considerations and strategies
related to such projects. Project execution methods are also discussed, and guidance is given for the
selection of materials of construction and for the selection of appropriate pressure and temperature design
points for pressure hydrometallurgical pilot equipment. The paper concludes with a discussion of the need
for process similarity with future commercial operations and the realities of pilot-scale equipment.

Niagara, ON, Canada
Edited by
402
INTRODUCTION
The process technology developer or owner and the designer/fabricator of a new pilot-plant
facility are faced with some difficult technical choices even after the decision to build a dedicated plant has
been taken. A pilot-plant project is usually on the critical path of a large commercial project involving
investments many multiples greater than the capital cost of the pilot plant. Schedule savings in the design,
manufacture, and commissioning of the pilot plant or in a rapid completion of the experimental program
can be disproportionately beneficial to the overall development project. However, inappropriate shortcuts
resulting in major oversights can be disproportionately problematic.
A number of considerations and suggestions for both the project execution approach and the
process engineering design of pressure hydrometallurgical pilot-plant facilities are presented as a guide for
potential owners and operators of new pilot-plant equipment and facilities.
THE UNIQUENESS OF THE PILOT SCALE
A pilot plant is a processing system that operates at a scale intermediate between the laboratory
and the commercial scale. In the hydrometallurgy field, pressure oxidation and leaching laboratory
experimentation is often done batchwise, whereas pilot plants generally operate in the same mode as
commercial operations as continuous processes (often with one or more recycle streams). However, the
tendency to view the pilot plant as merely the commercial plant in miniature can lead to some incorrect
design assumptions. A full-scale commercial plants goal is to generate tonnes per hour of product of
suitable quality, whereas the pilot plants goal is to generate process knowledge and understanding in the
form of both experimental data and operational observations and to do so in an economical and timely
fashion. This is a key difference, one that makes the pilot scale a unique undertaking, and one that must be
kept clearly in focus during all parts of the design process.
Pilot plants for hydrometallurgical process development are often complicated by an issue not
encountered to the same extent in plants for the energy and chemicals sectors: the source of feedstock (i.e.,
the mine and concentrator, if required) may not be constructed until long after the pilot campaign is
completed. In these cases, samples of the ore body will have to be collected by drilling (sometimes at great
cost) and beneficiated or otherwise processed in small batches to obtain a representative feedstock sample.
The cost of a campaigns worth of feedstock for the pilot plant can be a significant fraction of the total cost
of the pilot program, and the smallest feasible pilot plant throughput that will give valid data is therefore
desirable.
It is helpful to compare and contrast the pilot and commercial scales in terms of objectives and
design factors arising from these objectives, as detailed in Table 1.
A pilot plant will have different design data sources, objectives, scales, lifespan, operational
conditions, and product than a commercial operation and should have a separate, distinct design and
project execution approach.
PROJECT EXECUTION STRATEGIES FOR PILOT PLANTS
The development timescale for the design, fabrication, and commissioning of a new pilot plant is
characteristically much shorter than that for the commercial facility, and the commercial pressure to meet
these tight schedules can be enormous. However, the technical and financial risk of carrying out an
inadequate pilot program or skipping the pilot step entirely is also quite clear.
One of the issues that is unique to the pilot-plant scale is that although the individual pieces of
equipment are smaller than those of the commercial plant by orders of magnitude, the overall level of
complexity of a pilot project as measured by the number of pieces of equipment that must be designed,
procured, installed, plumbed and wired, tested, etc. is not reduced to the same extent. Further, custom-
403
engineered equipment such as pre-heaters and autoclave and flash vessels in exotic materials are often
needed. Accelerated project schedules and the project execution strategies needed to meet these schedules
are therefore critical to the overall project success.
Table 1 Comparison of commercial and pilot scale operations
Factor
Key Objectives
Commercial Scale
Continuous generation of on-spec
product(s)
Pilot Scale
Process knowledge and

understanding
Operational observations
Scale-up data
Scale
Tonnes per hour
Kilograms per hour
Operation
Continuous, maximizing up-time
Continuous campaigns lasting up to

several weeks
Design Life
Tens of years
Between one and ten years
Maintenance
During operation, as much as

possible
Between campaigns
Operational Mode
Steady state
Chasing steady state
Data Acquisition and

Control
As needed to maintain steady state
To obtain steady state and the

necessary process data for scale-up
Operating Temperature
and Pressure
Commercially optimal conditions
Beyond commercially optimal

conditions (to establish optimum)
Design Points
Single
Multiple
Flowsheets
Single, fixed
Frequently multiple, variable
Source of Design Data
Pilot plant
Laboratory data and simulations,

experience
Capital Project
Timescale
Several years
One year
Need for Operational

Flexibility
Modest
Considerable
We have found that an integrated design/build approach offers advantages over the conventional
strategy of detailed design followed by fabrication by a contractor. Because the engineers who carry out
the design directly supervise the fabrication, large numbers of detailed drawings and specifications are
rendered unnecessary. The approach is also more flexible to change, permitting the design of long-lead
items to be frozen earlier in the schedule with less fear of schedule impact. The design/build approach
tends to reduce the project schedule and minimize engineering costs, but it can only be implemented with
confidence in operations where direct supervision is feasible.
Figure 1 compares a typical high-level conventional engineering, procurement, and construction
management (EPCM) project schedule and a fast-track design/build project schedule. Both examples
assume preliminary design is complete.
404
Figure 1 Comparison of EPCM/fabrication (top) and design/build (bottom) project duration in months
Skid-Mounted Modular Construction
Our approach to the design of pilot plants is predicated on the use of individual horizontal- or
vertically-oriented modular steel frameworks or skids that are sized to both fit the facility and to
maximize the efficient use of common, rapid modes of shipment to destination. Skid-based modular
factory construction reduces cost and schedule in several key ways:
It permits fabrication in an efficient factory environment rather than on a construction jobsite, and
productivity and accuracy of fabrication are thus increased.
Schedule savings are realized through simultaneous execution. For instance, the plant fabrication
can occur at the same time as the construction or modification of the facility to house the plant
without interruption or delay.
Factory testing reduces commissioning time considerably, as problems can be diagnosed and
rectified more quickly in the factory than on the plant site.
Skid-based modular factory construction is familiar to the mining industry, which frequently uses
this method for equipment that must be shipped to remote mine sites. Modular construction is particularly
well suited to pilot plants due to the scale and size of the individual pieces of equipment. Frequently,
entire pressure hydrometallurgical pilot facilities can be fit onto two or three modules (Figure 2a).
Modules can also be sized to permit physical re-configuration of a flexible pilot plant space, permitting the
testing of multiple flowsheets without the need to remove and re-install individual pieces of equipment
(Figure 2b).
For larger, semi-works and demonstration-scale plants, the selection of module sizes is an
exercise in balancing the desire to keep the number of skids as small as possible to minimize reassembly
labour on site and the cost and complexity of shipment. This modularization exercise must take place
before the sizes of all equipment are frozen and possibly even before a throughput capacity is determined.
Seemingly minor differences in the size of individual pieces of equipment can make successful
modularization possible without affecting the function of the plant in a detrimental way. As an example, a
recent Zeton basic design study for a multi-skid demonstration project allowed us to reduce the cost of
shipment from over 7.5% for the clients original module concept to under 2.5% of module capital cost.
We did so by optimizing the layout around module sizes that were transportable using readily available
road transport equipment under normal road permits, altering the dimensions of certain pieces of
equipment to fit these module dimensions without affecting their process function. More important than
405
these cost savings, a schedule savings of over two months (from 14 to 12 months from start to delivery on
site) was realized solely as a result of an optimized layout.
Figure 2a Large skid modules
Figure 2b Small skid modules
Strategies to Control Quality

Caution should be used in the application of corporate engineering standards for components,
materials, and methods of construction to pilot-plant projects. The application of inappropriate standards
or the misapplication of standards can result in unnecessary cost and schedule delays without improving
product quality in a meaningful way. In fact, the inappropriate use of commercial plant specifications may
limit the options available to the plant designer to the point where key pilot-plant project goals may be
compromised (Dukhedin-Lalla, 2003).
Here are some examples of practices and substitutions that can save unnecessary costs and delays
in a pilot-plant project:
Avoid painting carbon steel pipe. If exterior corrosion is an issue, consider using non-metallics,
galvanized steel, or schedule 10 stainless steel with 150# fittings for nonhazardous utility services.
Painting is expensive and disruptive to the production of small plants, and the labour savings from
eliminating it will almost certainly pay for the additional cost of stainless steel pipe and fittings
Use tubing and compression fittings up to inch OD instead of welded pipe. The labour savings
can be dramatic, particularly if you have to make changes later.
If you expect to tear down and reconfigure your plant frequently, consider using removable
insulating jackets rather than rigid insulation.
Do not be afraid of threaded pipe. With good sealant systems and proper installation practice,
threaded pipe can be leak-tight and reliable below 2 inch NPS. Fabrication costs are lower and
reconfiguration is much easier than with welded pipe systems.
Several items related to materials specification can be eliminated to reduce cost and improve
schedule with little impact on the overall quality of the installed product (Table 2). As an example of these
alternative methods, one might choose to not give the designer/fabricator a list of approved valve
manufacturers and models but merely the basic design requirements (design point, acceptable type,
materials, oxygen cleaning, etc.) and allow the designer/fabricator to shop the marketplace for the correct,
scale-appropriate product.
406
Table 2 Alternative methods for project and materials quality control

Common Practice
Total positive materials identification
Alternative Practice
Mill certificates and inward or in-process materials
quality control procedures
Approved manufacturer lists for pipe and

fittings
If required, approved and disapproved country of

origin lists
Full-scale plant valve and instrument

specifications
Outcome-oriented specification with a suggested

vendors list if necessary
Full-scale plant pipe, vessel, and electrical

specifications
Focus on codes and standards (ASME, AWS, NEC,

etc.)
DESIGN STRATEGY FOR PILOT PLANTS

Design Inputs: Lab Data and Simulations
The right way to do an equipment design project is to start with a fully developed process flow
diagram with a complete mass and energy balance evaluated at the desired operating point. Unfortunately,
one of the purposes of most pilot-plant projects is to provide that very data for the potential full-scale
facility. With pilot plants, uncertainty and multiple potential operating cases are the rule rather than the
exception. Operation outside the optimum conditions is necessary to establish where the optimum
conditions lie.
Lab data and simulations are important sources of information to size vessels, pumps, and
instruments. It is far easier, quicker, and more cost effective to use simulations to evaluate the basic
feasibility of various process options for a new process than it is to do so by means of pilot-scale
experimentation. Simulations and designed lab experiments can help avert major pitfalls; however, batch
lab data and simulations cannot substitute for continuous pilot-plant data. If you wait for the flowsheet and
the mass and energy balances to be nailed down completely before beginning the design exercise for the
pilot plant, you will never get started.
We advocate the practice of bench scale engineering in process development (Szabo, 2004). In
this practice, process chemists and metallurgists work together with the process and design engineers as
early in the development process as possible. Hands-on multidisciplinary teamwork and interaction of this
sort generates broader process knowledge, yielding more complete and accurate information for the design
of a successful pilot plant.
Rather than establishing a single design point based on a simulation, we have found that it is
better to use the simulation data to parameterize your design and establish an operating range for each
piece of equipment. The process design of the pilot plant can then be carried out over the full parametric
range to ensure that the plant has the turndown you need to handle a wide range of operational cases. To
get the desired rangeability, you may need to select a more flexible device or multiple pieces of equipment
or instruments or you may even need to design different process approaches. It is always better to go into
the design exercise with this in mind rather than to attempt to retrofit the required rangeability later.
Sometimes it is simply necessary to re-evaluate the operating range requirements in terms of available
instrumentation and set more realistic expectations.
407
Choosing the Design Point for Pilot Plant Equipment

For an established process, choosing the temperature and pressure ratings of equipment is a
relatively straightforward exercise. However, choosing the maximum operating pressure and temperature
combination for the major pieces of equipment in a pilot plant can be more challenging. In fact, choosing
the correct combinations is one of the key decision processes in any pilot plant project, meriting significant
analysis and thought. Choosing a design point that is too low can render the plant useless, while choosing
a point that is inappropriately high can increase the cost and delivery schedule of the plant by a significant
fraction. An inappropriately high point may also hamper operation of the plant by unnecessarily limiting
the types of closures, equipment, valves, and instrumentation that can be used, resulting in increased
downtime or a reduction in the ability of the plant to deliver the desired measurements, products, and data
in a timely fashion. Even in a pilot plant, it may not be in the best interest of the project as a whole merely
to guess high.
The need to correctly determine these combinations means that a breakpoint analysis for the
proposed materials of construction should be carried out as one of the preliminary design exercises. By
identifying natural limits for pressure and temperature arising from the required materials of construction,
natural breakpoints for the design and pressure and temperature combinations for various pieces of
equipment can be determined. Figures 3 and 4 demonstrate some of the natural breakpoints applicable to
process equipment. Crossing a natural breakpoint can come with a significant cost, schedule, or operability
penalty and should not be done lightly.
450
grafoil, IGC in SS
315
PEEK, Kalrez, Ti, HT oils

232
PTFE (entrapped)
175
viton
150
ETFE
135
PVDF, FRP
100
PP, boiling mode HX
80
untreated CW
60
PVC, SCC in 316SS

cooling w ater
30
carbon steel
-20
liquid N2
-400
-200
-177
200
400
600
Temperature (degrees C)
Figure 3 Natural limits for temperature (Martin & Dietrich, 2003)

Note that the maximum operating pressure and temperature are distinct from the maximum
allowable working pressure and temperature of vessels, valves, or equipment. The former is determined by
process considerations, while the latter is calculated based on actual wall thicknesses, flange ratings, and
gasket or seal performance. Depending on the type and specification of relief devices used for
overpressure protection and the desired reliability of operation, the maximum feasible continuous operating
pressure for a system may be between 70% and 90% of the maximum allowable working pressure of the
pressure-limiting device(s) protected by the relief valve(s) or rupture disk(s).
408
10000
pressure (psig)
150#
1000
300#
600#
100
1500#
10
Limit for non-ASME
tankage
1
-200
200
400
600
temperature ( degrees C)
Figure 4 Natural limits for pressure (ANSI 316SS Flange Classes)

(Perry & Green, 1984, p. 75)
Selection of Materials of Construction
If you are in new process territory and corrosion service is an issue, you cannot trust the charts or
the experts. From our hard experience, we recommend accelerated corrosion testing done at the lab scale
prior to making final materials selections. If possible, select a material completely immune to the type of
corrosion you may face. Note also that the experience in your laboratory batch reactor may not accurately
simulate the conditions experienced in all parts of a continuous pilot plant over the long term.
Keep in mind that the available selection of metallic materials for a pilot plant is more limited
than for a commercial system. A special alloy that you may be thinking about for the commercial plant is
probably not available in less than full mill runs of pipe or fittings, especially at the smaller sizes. Fittings
or even pipe may have to be fabricated from bar stock. This is particularly true of highly corrosion
resistant materials such as the titanium-palladium alloys and tantalum. Whereas intermediate alloys such
as duplex and super-duplex or 6% molybdenum stainless steels may offer significant cost advantages at the
commercial scale when compared with highly resistant materials such as titanium or high nickel alloys,
these intermediate alloys offer only marginally greater fabrication costs at the pilot scale. Any of these
materials are significantly more expensive and less readily available than the common grades of stainless
steel at the pilot scale. In our experience, the relative cost factors found in commercial plant fabrication
(and found in the cost comparison tables presented by vendors of alloys and pipe and fittings) dramatically
underestimate the installed cost differences actually observed in pilot-plant fabrication. Figure 5 compares
the historical industry-accepted commercial scale ratios of the cost of piping systems (Perry & Green,
1984, p. 106) versus those encountered in a recent pilot-plant design study (Sue-Kam-Ling, 2008).
Clearly, the comparative cost between various candidate materials of construction is scale-dependent and
varies with time as alloy constituent prices fluctuate.
If a knowledge of the service life of materials of construction are key to the success of the pilot
program, we recommend constructing the plant from the commercially-standard alloy that best suits the
corrosion service requirements for the durability period of the plant, and the use of corrosion coupons
and/or electrically insulated test spools for materials testing.
Methods of corrosion protection such as acid brick lining, titanium cladding, electrochemical
protection, and lined pipe are also scale-sensitive methods, infeasible below a certain physical size for
409
practical reasons. The use of solid resistant materials or alternative lining methods and materials must be
pursued for pilot projects below a certain size out of physical necessity.
Figure 5 Comparison of total procurement and fabrication cost for various piping
materials of construction (Sue-Kam-Ling, 2008)
Special Considerations for Titanium

Titanium and its alloys are extensively used in pressure hydrometallurgical pilot plants. Among
its various other properties, titanium in direct pressure-bearing service has a safe allowable stress that is
strongly de-rated with increasing temperature to the code limit of 315 oC. Figure 6 shows the strong
temperature dependence of safe allowable stress (S) for commercially pure titanium. The saturation
pressure for steam (P) is plotted alongside for comparison purposes. These factors combine such that
modest changes in operation temperature can have significant effects on required wall thickness
(proportional to the ratio P/S). The effect is most pronounced for pilot plants, where the use of titanium as
a lining may be physically infeasible due to the small size of the vessels in question.
There is a strong tendency for equipment manufacturers to attempt to use the beta grades of
titanium that are commonly used in the aircraft industry, as these grades are stronger, especially at
temperature. However, the corrosion resistance of these grades, particularly Ti-Al46V (grade 5), is greatly
inferior to that of commercially pure titanium in many hydrometallurgical services. Vendors of equipment
(pumps, valves, etc.) may be unaware of the differences and may specify and/or use these grades
unknowingly. Caution must be used to ensure that all wetted materials from all sources are fabricated from
the correct grades of material.
410
Pressure, or Stress (psi)
1800
1600
1400
Titanium safe
allowable stress (psi)
/10
1200
1000
Steam saturation
pressure (psia)
800
600
400
200
0
0
100
200
300
400
Temperature (degrees C)
Figure 6 Safe allowable stress for titanium and steam saturation pressure vs.
temperature (Perry & Green, 1984, p. 106)
Simplify
Unnecessary complexity leads to unnecessary cost and delay. This money may be better spent on
additional training for operators or more campaigns.
Consider carefully the life cycle and operating mode of your pilot plant. Will it be essential or
even permissible to continue operating while you repair or replace key pieces of instrumentation or
equipment, or will a shutdown be inevitable? If the latter is true, block and bleed valves on instruments,
double-block valves, and bypasses around control valves and the like may merely add unnecessary cost and
complexity to the system without adding significant safety or value. Costs of installation and testing,
procurement, and engineering specification and selection of labour rise in nearly direct proportion to the
number of tagged items on a plants P&ID drawings. Elimination of unnecessary components can result in
significant reductions in the cost and delivery lead time for a plant.
Quite simply, focus on what you need to pilot, and do not pilot the rest. If it adds complexity
without improving the plants ability to give you the data or product you need, eliminate it. The simple
measures listed below can dramatically reduce the cost of the post-autoclave processing sections of the
plant:
Where height permits, use gravity overflow instead of pumps.
Standardize on a few tank sizes with variable overflow level.
Eliminate level controls in favour of air-tolerant pumps.
Use a single variable speed motor to drive multiple agitator shafts.
Process and Reaction Engineering Factors

A good pilot-plant design must balance the need for physical and equipment similarity to the
commercial process with the other goals of the pilot-plant program. Taking, for example, the ratio of the
pilot feed rate to the commercial feed rate as a measure of process scale, it is clear that some design factors
411
change with scale while others do not, and this can fundamentally affect the function of pilot equipment.
Similarly, whereas residence time and ore/concentrate feed particle size are kept constant with scale, the
volume and linear dimensions of reactor vessels, the area of settlers and heat exchangers, and the sizes of
piping/tubing and throttling valve orifices decrease with decreasing scale. When the variables and the
constants collide, severe processing problems, such as plugging, inadequate gas contact time, or excessive
heat loss, can result. At a certain minimum scale, geometric scale down of the commercial unit operation
or equipment becomes fundamentally infeasible and alternative approaches must be used. Often these
approaches involve switching some unit operations, such as feeding and flash letdown from continuous to
semi-batch. Careful and creative equipment design is necessary to ensure that the equipment will continue
to work reliably for the duration of a campaign while maintaining sufficient process similarity to give
reliable pilot-scale experimental data and observations.
concentration of feed component

exiting last tank (as fraction of inlet
concentration), unitless
Another key factor is the period of time necessary to achieve steady state operation. Postautoclave hydrometallurgical systems are characterized by large numbers of tanks in series, some of them
mixed and some (e.g., thickeners and clarifiers) deliberately unmixed. Care must be used in determining
the length of campaign necessary to achieve true steady state operation in all important parameters. As
Figure 7 shows, multiple, equal-sized, mixed tanks in series closely approach plug flow behavior, requiring
a cumulative flow equal to a smaller fraction of the total residence time for all tanks to achieve a steady
state in the discharge from the last tank. In other words, whereas a single, stirred tank takes a cumulative
flow equal to 3 times the volume of the tank for the outlet to reach 95% of a new steady feed concentration,
a flow of only 1.6 times the volume of a ten-tank system will reach the same 95% exit concentration from
the last tank. Unfortunately, the presence of thickeners and settlers greatly complicates this simple
analysis. Countercurrent decantation systems are particularly problematic in terms of requiring long
campaign cycles to achieve true steady state operation. The inclusion of intermediate storage tanks at
various points in the process to reduce the impact of process interruptions is, therefore, a prudent step to
avoid the risk of a lost campaign due to equipment outages (particularly immediately after the autoclave
flash tank). Of course, the practical need for these storage tanks must be balanced against concerns of
solution composition change through ageing.
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Tank 1
Tank 2
Tank 3
Tank 4
Tank 5
Tank 6
Tank 7
Tank 8
0
10
15
20
cumulative flow through tanks (as a fraction

of the volume of one tank), unitless
Tank 9
Tank 10
Figure 7 Response of a cascade of equal-sized, stirred tanks in series to a step change in feed
concentration
412
CONCLUSIONS
A pressure hydrometallurgical pilot-plant project has a different design data source and different
objectives, scale, lifespan, operational conditions, and product than a commercial plant project for the same
technology and therefore should be given a separate, distinct design and project execution approach. The
small size, significant complexity, and tight schedule of pressure hydrometallurgical pilot-plant projects
make them ideally suited to a modular, skid-based design/build approach.
Some design factors change with scale while others do not. Accordingly, some unit operations of
the commercial plant, plus some methods of fabrication and materials of construction may be limited to
minimum physical size or throughput scale and require alternative approaches to be successful at the pilot
scale.
Design for operational flexibility and rangeability is key to pilot-plant success. Multiple operating
points and parametric design established through the use of lab experiments and simulations are the rule
rather than the exception. Natural break points for temperature and pressure arising from materials
selection should be taken into consideration for design, and these breakpoints should not be crossed
without due consideration. Particular care must be given toward the selection of operating temperatures for
titanium equipment, as minor changes in temperature can have significant impact on required titanium wall
thickness.
ACKNOWLEDGEMENTS
The author would like to acknowledge the contributions of the late Debbie Marshall of
Falconbridge, numerous staff at SGS Lakefield worldwide, and Norm Connor, Tom Farr, Andrew Luong,
and Avinash Singhal of (Vale) Inco who have provided insight and guidance to the author and his
colleagues at Zeton in the hydrometallurgical pilot-plant field.
REFERENCES
Dukhedin-Lalla, L. (2003). Pros and cons of applying plant specifications to pilot plants. In D. Edwards
and C. Tiech (Eds.), Pilot plants in process development topical conference proceedings (pp. 213
221). San Francisco, CA: American Institute of Chemical Engineers.
Martin, P.F., & Dietrich, M.J. (2003). Tips and tricks for fast track pilot plant projects. In D. Edwards and
C. Tiech (Eds.), Pilot plants in process development topical conference proceedings (pp. 287
295). San Francisco, CA: American Institute of Chemical Engineers.
Perry, R.H., & Green, D.W. (Eds.). (1984). Perrys chemical engineers handbook (6th ed.). New York,
NY: McGraw-Hill.
Sue-Kam-Ling, M. (2008). Cost comparison of pilot-scale tubing and piping systems based on materials of
construction. (unpublished confidential work term report). University of Waterloo, Waterloo, ON.
Szabo, P. (2004). Between lab and pilot plant. In Process development symposium proceedings. Chicago,
IL: American Institute of Chemical Engineers.
413
APPLICATION OF TUBE DIGESTION TECHNOLOGY

TO THE NON FERROUS METALS INDUSTRY
J.A. Gorst, *B. Haneman, W. Slabbert
Hatch and Associates
61 Petrie Terrace
Brisbane, Australia
(*Corresponding author: bhaneman@hatch.com.au)
ABSTRACT
The Bayer process involves the digestion of bauxite in caustic liquors at high temperature and
pressure. Typically the digestion section of the plant involves the heating of liquors up to the digestion
temperature followed by flashing of the digestion product to atmospheric pressure with the flashed steam
used to pre-heat the incoming cold slurry. Despite the heat recovery, the digestion process is a high
consumer of energy. The application of tube digestion technology in such plants has resulted in significant
improvements in refinery energy efficiency with associated benefits of process simplification and refinery
flow sheet capital cost reduction. This paper reviews the potential application of this technology to other
metals within the non-ferrous industry.

Niagara, ON, Canada
Edited by
414
THE BAYER PROCESS

A typical Bayer flow sheet is shown in Figure 1. The raw feed material bauxite (containing
aluminium hydroxide as gibbsite Al(OH)3 and boehmite AlO(OH)) is digested in caustic liquors (caustic
soda is the solvent) at high temperature and pressure. This process extracts the alumina and silica and any
carbon present on the ore. The slurry is then flashed down to atmospheric condition allowing for heat
recovery from the flashed vapour and producing slurry supersaturated in alumina.
Figure 1 Typical Bayer flow-sheet

Following the digestion process the mud is removed via thickening and then pressure filtration to
remove fine particulate and produce a clarified liquor with dissolved alumina in solution. The resulting
pregnant liquor is then cooled allowing the alumina in solution to precipitate as aluminium trihydrate
Al(OH)3. The precipitated hydrate is then filtered and washed and classified into fine and coarse fractions.
The fine material is returned to the precipitation process as seed while the coarse fraction is calcined at
high temperature to produce alumina. The filtrate from the filtration process (spent liquor) is then heated
by the incoming pregnant liquor before being fed to an evaporation process which produced the strong
caustic liquor required in the digestion process. Finally, the mud from the thickening process is washed to
recover caustic and then fed to tailings ponds. The washer overflow is then mixed with the digester product
to increase super-saturation.
THE DIGESTION PROCESS
The objective of the digestion process is to heat the slurry to the required digestion temperature
and maintain this for the required residence time to extract the alumina contained in the bauxite. The
desired temperature depends on the composition of the bauxite ore.
Gibbsite can be extracted at relatively low temperatures (145C and 7 atm.) while boehmite needs
to be extracted at relatively high temperatures ( > 250C, 50 atm.). Ores with boehmite content greater
than 5% typically need extraction via the high temperature processing route.
415
Figure 2 Typical digestion flowsheet

A schematic of the digestion process is shown in Figure 2. This depicts a low temperature process
with three stages of recuperative heating and the use of digestion vessels (vertical autoclaves) to provide
residence time. A high temperature process typically utilises eight to twelve stages. Bayer digestion
processes are referred to as either dual stream or single stream depending on whether slurry or liquor is
fed to the recuperative heaters. For a dual stream process, caustic liquor is fed to shell and tube heaters
where it is heated by the recovered flash steam. After recuperative heating, the liquor is heated to above
the digestion temperature by live steam. The heated liquor is then mixed with bauxite slurry and fed into
the digesters where some steam injection is required to maintain the desired digestion temperature due to
the large endothermic nature of the leach reaction. Following the digesters the slurry is flashed down to
atmospheric conditions in a series of flash vessels, with the flashed steam providing the heating in the
recuperative heating section.
The single stream process is similar to the dual stream process except that the liquor and bauxite
slurry are mixed prior to being fed to the recuperative section. For high temperature refineries, the single
stream Tube Digestion flow sheet (Deboer et al.,2005) is preferred. This flowsheet utilises jacketed pipe
heaters (in lieu of shell and tube heaters) to heat the slurry stream to the target digestion temperature and
holding tubes are used to provide the requisite reaction residence time in lieu of autoclaves or digester
vessels. Alumina refineries employing this flow sheet technology benefit in three key aspects:
Pressure Leach Conditions of the Reactor Design
Reaction conditions are optimised to allow the selection of pipe reactors which provide plug flow
reaction conditions. In this way, the requirement for using multiple CSTRs in series to achieve the
required extraction efficiency is avoided and the residence time required for the reaction is reduced,
typically to one third of that required for the traditional digester. The reaction temperatures are further
optimised (increased) to take advantage of the faster reaction kinetics at elevated temperatures. As the
thickness of the reactor (pressure vessel) increases linearly with its diameter, constraining the pipe reactor
diameter to not more than 600 mm allows standard piping runs of commercially available piping schedules
(25mm thickness or less) to be substituted for the autoclaves. This further reduces the cost and complexity
associated with autoclave agitators, gland seals, pressure relief systems, access platforms and associated
blowdown piping.
416
Energy Efficiency for the Pressure Leach Process Facility

The intrinsic energy efficiency of the Tube Digestion flowsheet stems from the use of multiple
pressure let down stages (typically 8-12) and the use of indirect slurry heaters. In this configuration, the
energy liberated from the flash cooling stages is matched to the 'heat sink' in the cold slurry stream. The
flowsheet utilises positive displacement feed pumps at the commencement of the heating circuit only
(Figure 3). As such, slurry at approximately 80-90C is exposed to the pump wet end. This hydraulic
arrangement is made possible by the use of indirect steam recuperative jacketed pipe heaters. The use of
these slurry indirect jacketed pipe heaters is made economic given that carbon steel is the preferred
material for leaching in caustic soda. The selection of the jacketed pipe heater (JPH) over a shell and tube
type heater is a life cycle cost analysis driven by mechanical reliability considerations, as the jacketed pipe
heater is more resilient to the erosion mechanisms present with slurry flow. The upfront cost penalty to
using the JPH (relative to the shell and tube heater) is an approximate 2-2.5 fold increase in carbon steel
weight per unit of installed heat transfer area.
Resulting from the thermal match in heat source and heat sink, no additional steam from the
digestion unit needs to be sent to other plant areas to improve the energy profile. A target overall refinery
energy consumption (for all processing areas) of approximately 8.5 GJ/MT alumina may be expected. This
represents a 20-23% reduction in energy consumption relative to a high temperature dual stream circuit
incorporating direct steam injection.
Figure 3 Tube digestion flowsheet

Capital cost Reduction for All Refinery Processing Facilities
Single stream digestion with indirect heating and wet-oxidation technology also eliminates plant
liquor circuit dilution and the need for separate liquor circuit organics removal facilities. This reduces
additional liquor circuit evaporative requirements (typically to one third), low pressure steam demand,
capital cost for the evaporation and organics control plant and steam load on the boiler plant.
In maximising digestion temperature, the bauxite charge ratio is also optimised. As a result, digestion flow
productivity is maximised (alumina production per unit plant flow) reducing the refinery circulating flow
throughout the downstream process areas. For a high temperature refinery employing the Tube Digestion
flowsheet, a 10-15% reduction in refinery capital cost is not uncommon when compared to a dual stream
flowsheet with direct steam injection.
417
APPLICATION TO NON FERROUS REFINING

Refractory gold and Nickel flow sheets have been examined to ascertain their suitability to the
adoption of Tube Digestion technology. Each potential application has been assessed in relation to the
three salient benefits listed above i.e. the leach equipment used, the energy use for the pressure leach
facility and the overall capital cost for the refinery.
REFRACTORY GOLD
Process Description and Flowchart
Whereas free-milling gold is easily extracted via cyanide leaching, refractory gold requires a pretreatment step to liberate the gold from the host matrix. Once liberated the gold is extracted by cyanide
leaching. At least three pre-treatment methods are used: roasting, pressure oxidation and bioleaching, of
which pressure oxidation is the most prevalent, as measured by the number of commercial installations.
Pressure oxidation involves the oxidation of a sulphide ores or concentrates with oxygen under conditions
of high pressure and high temperature, and is currently performed commercially in pressure autoclaves.
Pressure oxidation is used commercially with either acidic conditions (~pH1.5), or mildly alkaline
conditions (~pH8) (Thomas et al 2000).
The first gold autoclaves operated at about 170C but over the last thirty years the design
temperature has gradually been increased up to 230C to optimise reaction conditions for the mineralogy of
the ore body. With this increase in temperature has come faster reaction kinetics thereby optimising
autoclave capital intensity, i.e. shorter reaction times.
Feed pre-heating with flash steam from the pressure letdown stages is commonly employed in
gold pressure oxidation plants that treat whole ore, i.e. a feed with low calorific value. On the other hand,
plants that treat sulphide concentrates, i.e. a feed with high calorific value, commonly use cooling inside
the autoclave, followed by a single flash stage. Figure 4 shows a typical pressure oxidation autoclave
arrangement with three heat recovery and pre-heat stages.Heat recovery is achieved by direct heating of
the feed slurry with the flash steam from the pressure letdown stages. The recuperative temperature is
limited to approximately 190C by the pump limitations at the hot end. Sparging with live high pressure
steam is typically used to raise the slurry temperature to the required operating temperature. Gold
autoclaves typically have four to six agitated compartments, with an overall hydraulic retention time of
between 20 minutes and two hours, depending on the operating temperature and the nature of the feed
material (Mason et al 1999).
For the acidic pressure oxidation circuits (~pH1.5) the combination of slurry abrasion, low pH,
high temperature, and high pressure restrict the selection of autoclave materials normally to titanium-clad
carbon steel, or more commonly, acid-resistant brick-lined carbon steel(Clary R. et al 2004).
Application of the Tube Digestion Flowsheet to Acidic Pressure Oxidation Circuits
For the alumina flowsheet, increasing the caustic leach temperature provides benefits in both
reducing the residence time to achieve a targeted extraction efficiency and also a higher caustic liquor
productivity, i.e. alumina production per tonne of caustic liquor used in the feed stream of the digestion
facility. As many bauxite reserves contain between 25% - 50% of extractable alumina, the feed stream
composition of base metal to solvent is set by a stoichiometric limit, not a hydraulic constraint. Increased
reaction temperature therefore allows a higher feed ratio of bauxite to the caustic liquor (to within a
targeted margin of equilibrium concentrations).
418
For refractory gold ores treated in an acidic pressure oxidation circuit, the feed stream ore
concentration is set by the constraints of a pumpable mixture of the ground ore, by the ability to mix the
slurry inside the autoclave and disperse oxygen and the ability to control temperature inside the autoclave
based on the sulphur content of the feed. Increased reaction temperature therefore is of limited benefit for
reducing the autoclave size. The reaction kinetics for the sulphide oxidation do however accelerate at
elevated temperature and reduced reactor residence time will result.
Molten salt heating for bauxite ores (Lalla et al.,2006) has been used to maintain heat transfer of
the plug flow pipe reactors under scaling conditions and may provide a viable alternative to direct steam
sparge of the gold autoclave. Shell side temperatures of up to 400C can be maintained with molten salt.
Subject to a reasonable reduction in reaction residence time at elevated temperature, the substitution of the
titanium clad carbon steel autoclave with a titanium tube reactor should be viable. Titanium-niobium alloys
(or equivalent) for the oxygen sparge nozzles would be required per present autoclave practices.
Figure 4 Generic gold pressure leach flowsheet with three stages of heat recovery
Energy Efficiency for the Pressure Leach Process Facility and Refinery
As outlined above, the energy recovery capacity of the Tube Digestion flowsheet is an economic
assessment over the life of the refinery, based on the use of carbon steel as the ideal material of choice for
the caustic leach circuit. Multiple pressure let down and heater stages improve the overall energy recovery
of the circuit. The digestion circuit process parameters provide the energy and capital cost trade off as
indicated in Figure 5.
The equivalent application for the refractory gold flow sheet would require significant cost in
titanium materials for the jacketed pipe heater tube and shell material. With a metal cost in the vicinity of
15 times that for carbon steel, the optimal energy recovery is more likely represented by a region bounding
the inflexion point of the steam consumption curve, i.e. 3-5 stages. Furthermore, the use of the direct
contact heater resolves the issue of potential shell side contamination that would otherwise exist in the shell
and tube or jacketed pipe heater. As a result of the materials required for corrosion resistance, the energy
map of the tube digestion flowsheet cannot be readily translated to the refractory gold pressure oxidation
flowsheet.
419
Bayer Circuit - Flash Stage Optimisation

20,000
450.0
19,000
400.0
18,000
350.0
HP Steam
17,000
250.0
15,000
200.0
14,000
HP Steam (T/h)
HX Area (m2)
300.0
16,000
150.0
13,000
12,000
100.0
HX Area
50.0
11,000
0.0
10,000
2 stage
4 stage
6 stage
8 stage
10 stage
12 stage
14 stage
Figure 5 Bayer digestion flowsheet - heater area vs steam consumption

Capital cost reduction for all refinery processing facilities
Unlike the Bayer flowsheet for alumina processing where the solution discharging from the
pressure leach facility contains the valuable dissolved metal, the valuable product discharging from the
refractory gold pressure leach facility is the solids stream (containing the gold solids particles). The
autoclave discharge is first directed to neutralisation tanks (for pH adjustment) prior to further processing.
The discharge from the neutralisation facility is further thickened with the underflow pulp directed to
carbon in leach tanks.
As it is thickener underflow that is further processed (not thickener overflow per the alumina
process), the elimination of direct steam injection in the pressure leach circuit does not reduce the CIL tank
sizes and the similar capital cost savings in eliminating the direct steam injection are therefore not
applicable.
Application of the Tube Digestion Flowsheet to Alkaline Pressure Oxidation Circuits
Alkaline pressure oxidation circuits dont have the same onerous materials of construction
requirement, and therefore make this process a potentially suitable candidate for tube digestion technology.
The autoclaves can potentially be substituted for tube digestion reactors. The potential advantages of
substituting autoclaves with tube reactors include:
Simpler pumping arrangement due to lower slurry pumping temperature,
Increase in the recuperative temperature due to removal of pumping limitations,
Improved thermal efficiency with the increase in recuperative temperature,
Potential reduction in reaction time due to increased extraction temperature,
Lower capital costs of pipes versus autoclaves,
Simpler equipment configuration (no agitator seal water and backup seal water systems),
Shorter residence time due to the tube digesters plug flow characteristics, and
The residue of the alkaline pretreatment is primarily iron oxide and does not require washing or pH
neutralisation before cyanidation.
420
NICKEL LATERITES
Process Description and Flowchart
Nickel is currently extracted from laterite ores using either an acidic high pressure leach process,
or an alkaline leach at elevated temperature such as at Queensland Nickel. The alkaline leach (Caron)
process is an energy intensive combination of pyrometallurgy and hydrometallurgy and is no longer
considered viable for a green-field project (Dalvi et al 2004). A simplified flow-sheet of the high pressure
acid leach (HPAL) process is shown in Figure 6. After crushing and screening, the laterite ore is mixed
with sulphuric acid and fed to the pressure acid leaching process as a slurry. Here it is heated to typically
200 C before being fed to the autoclaves.
The slurry in the autoclaves proceeds through a series of stirred compartments while steam and
oxygen are added to achieve the desired leaching temperature and residence time. On exiting the autoclave,
the slurry is flashed down to atmospheric pressure. After cooling the solution is neutralised with limestone
and the solids separated in a counter-current decantation circuit. Nickel is then extracted from the resulting
overflow in a downstream purification and metals refining plant (Mayze 1998).
The pressure leach part of the process follows the same type of flow-sheet used in gold and shown
in Figure 4. The pre-heating of the slurry is achieved via direct contact with flash steam in splash towers.
Typically three stages of flash steam recovery area used. As with gold, recuperative temperatures are
generally restricted to 190 C by the inter-stage pumping requirements.
Application of the Tube Digestion Flowsheet to the Nickel Laterites
The recent trend for HPAL processes is to seek higher temperatures and lower reaction times.
This leads to lower capital costs via smaller autoclaves at the expense of higher energy costs and dilution
via an increase in steam injection. As for the refractory gold ore, the use of a tube reactor (with plug flow)
can reduce the residence time required for the reaction relative to the multi-CSTR chamber present in the
autoclave. This has the potential for capital cost reductions by substituting piping for autoclaves and
simplifying the equipment configuration (no agitator seal water and backup seal water systems).
Energy Efficiency for the Pressure Leach Process Facility and Refinery
As with the gold pressure oxidation process discussed earlier, the use of direct contact splash
towers for heat recovery imposes limits on the heat recovery achievable in the HPAL process. The
maximum recuperative temperature is constrained to approximately 190-200C due to the requirements for
inter stage pumping. With an indirect pre-heat section, the pumping is provided at the feed to the first
heating stage thereby removing the recuperative temperature limit. This has a direct impact on energy
efficiency and leads to the following advantages described in the previous section. However, the leach
conditions, temperatures and chloride concentrations are such that exotic materials of construction are
required (typically titanium clad carbon steel). As such, while improved heat recovery is possible, the
energy efficiencies achieved in the Bayer process are not as readily transferable for nickel laterite
processing.
Capital Cost Reduction for All Refinery Processing Facilities
As distinct from the gold pressure oxidation process, the intention in HPAL is the recovery of the
acidic liquor at the end of the leach process rather than the solids. Therefore an elimination of steam
injection will lead to a reduction in the liquor circuit volumetric flow. As a result downstream equipment
sizes are able to be reduced.
421
Figure 6 - HPAL process

CASE STUDY - REPLACEMENT OF AUTOCLAVE WITH TUBE REACTOR
A feasibility level case study has been performed examining the opportunity for a tube reactor to
replace the high temperature autoclave for three selected flow sheets. All flow sheets and autoclave sizings
have used actual industrial applications as reference data. The three flow sheets selected for analysis have
been a gold acid leach, a gold ore alkaline leach and HPAL nickel laterite.
The materials of construction for the gold acid leach autoclave were a lead and refractory brick
lined carbon steel with titanium coated internals. For the tubular reactor SAF2205 was used. For the gold
alkaline leach, a brick lined (for erosion) carbon steel was used for the autoclave whilst a standard carbon
steel A106GrB pipe material was selected for the tubular reactor. For the HPAL nickel laterite autoclave, a
titanium clad steel was selected whilst titanium piping was used for the tubular reactor.
Table 1 below summarises the salient process parameters used for the cost estimate comparison,
whilst Table 2 summarises the results of the autoclave and tubular reactor sizing and estimated direct
installed costs in US$(2012).
For both the gold acid and alkaline leach flow sheets, the tubular reactor kinetics were limited by
the oxygen mass transfer kinetics, not the sulphur oxidation kinetics. As such, for the tubular reactor, no
additional benefit could be obtained by increased reaction temperature. Plug flow reactor kinetics provided
an estimated 21.2% reduction in reactor residence time relative to the autoclave reactor. Slurry flow
through the tubular reactor was assumed to be non-settling with static inline mixers (using the feed pump
power) used to increase oxygen transfer rates. Nevertheless, significant piping runs of SAF2205 (2,800 m,
Table 2) and carbon steel (4,200 m, Table 2) were required to maintain the residence time for these flow
sheets. As for Bayer circuit tubular reactor installations, runs of flanged 70-75m long piping would be
incorporated into a series of pre-fabricated modular pipe racks.
422
Table 1- Autoclave vs tubular reactor process design parameters

Process / Technology
Temp
(C)
Residence
Time (mins)
Oxygen Feed
(m3/h)
Slurry Feed
(m3/h)
Gold - Acid Leach

Autoclave
Tubular Reactor
225C
225C
59.0
46.5
293.0
293.0
174.2
174.2
Gold - Alkaline Leach

Autoclave
Tubular Reactor
225C
225C
90.0
70.9
188.3
188.3
113.0
113.0
HPAL Nickel Laterite

Autoclave
Tubular Reactor
250C
290C
50.0
17.4
0.0
0.0
337.0
337.0
Table 2 - Autoclave vs tubular reactor cost estimate

Process / Technology
Diameter
Length
(m)
Material Of Construction
Cost
(US$M)
Gold - Acid Leach

Autoclave
Tubular Reactor
4.3 m
DN400/DN300
18.5
2,800
Mild Steel, lead & brick lining

SAF 2205
35.2
40.7
Gold - Alkaline Leach

Autoclave
Tubular Reactor
4.3 m
DN300/DN250
18.5
4,200
Mild Steel, brick lining

Carbon Steel A106BGrB
30.7
21.7
HPAL Nickel Laterite

Autoclave
Tubular Reactor
4.3 m
DN350
25.8
1,040
Mild Steel titanium clad

Titanium
40.4
46.6
For the nickel laterite flow sheet, the tubular reactor kinetics were not limited by oxygen mass
transfer kinetics. As such, for the tubular reactor, additional benefit could be obtained by increased reaction
temperature. The combination of plug flow reactor kinetics and increased reaction temperature was
estimated to provide a 65% reduction in reactor residence time relative to the autoclave reactor. As above
for the gold acid and alkaline leach, slurry flow through the tubular reactor was assumed to be non-settling.
Approximately 1,040 m of titanium piping was required to maintain the residence time for this flow sheet.
As a result of the large investment in special piping materials, the acid leach conditions for the
tubular reactors represented an approximate 15% increase in capital cost relative to the autoclave
installation. In addition, for both the acid and alkaline gold leach flow sheets, fluid mechanics involving
oxygen transfer in piping is a key design consideration for the successful operation of the system proposed.
Nevertheless, although only a feasibility level of process design and capital estimate data has been
assessed, these cost differentials are thought to be competitive and do not factor into account the on-going
operational and maintenance related cost savings that could accrue relative to the inherent costs associated
with the more classical autoclave installation. For the gold alkaline leach, the tubular reactor was estimated
to provide a 29% reduction in installed cost relative to the autoclave and despite the piping quantities
involved, is seen as viable alternative.
423
CONCLUSION
This paper has described how significant reductions in Bayer refinery energy and capital cost have
been achieved with the incorporation of tubular digestion technology in the pressure leach area of the
refinery. These attributes have been examined for gold and base metals in the non ferrous industry in an
attempt to identify where similar reductions in energy and cost may translate to other industries. Early
indications are that the gold and nickel processing flow sheets may all benefit from selected application of
this technology.
In addition to capital cost reductions, the tube digester employs the principles of process
simplification eliminating the requirements for the autoclave agitators seals, auxiliary cooling water supply
systems and their maintenance, pressure relief systems and associated effluent containment and blowdown
equipment and the ongoing regulatory inspection and testing requirements associated with the pressure
vessel.
REFERENCES
Clary, R. Gulyas, J., Cheung, P., 2004. Design and materials selection of autoclaves and auxiliary
equipment. Pressure Hydrometallurgy, CIM Met Soc.
Deboer, D.J., Edwards, M and McIntosh, P., 2005. Design, Startup and Operational Aspects of the new
process at Comalco Alumina Refinery, 7th Internation Alumina Quality Workshop, 5 p. 32-36.
Dalvi, A.D., Bacon, W.G. and Osborne, R.C., 2004. The past and future of nickel latertites, PDAC 2004
International Convention, p 1-27.
Lalla, A., Arpe, R., 2006. 30 years of experience with tube digestion, Conference Of Metallurgists, 9 p.
105-113.
Mason, P.G., Gulyas, J.W., 1999. Pressure Hydrometallurgy : No longer regarded with trepidation for the
treatment of gold and base metal ores and concentrates. EPD Congress 1999, The Minerals,
Metals & Materials Society, 1999.
Mayze, R. 1998. An Engineering Comparison of the Three Treatment Flowsheets in WA Nickel Laterite
Projects, ALTA 1998 Nickel/Cobalt Pressure Leaching & Hydrometallurgy Forum.
Thomas, K.G., Williams, R.A., 2000. Alkaline and acid autoclaves at Barrick Gold, A review, EDP
congress, The Minerals, Metals & Materials Society.
Platinum Group Metals
427
DEVELOPMENT OF THE TWIN METALS MINNESOTA FLOWSHEET INCORPORATING

THE PLATSOL PROCESS
J.A. Brown1, *C.A. Fleming1, G. Barr2
1
SGS Canada Inc.
185 Concession Street
Lakefield ON, Canada K0L 2H0
(*Corresponding author: chris.fleming@sgs.com)
2
Twin Metals Minnesota
380 Saint Peter Street Suite 705
Saint Paul MN,USA 55102
ABSTRACT
The Polymetallic Twin Metals Project deposits in Northern Minnesota are being developed by
Twin Metals Minnesota. Amongst the flowsheet alternatives being examined at a pre-feasibility study level
is one involving flotation of a bulk concentrate followed by high temperature autoclaving of the
concentrate using the PlatsolTM Process to solubilize all the valuable metals in the concentrate (Cu, Ni, Pt,
Pd and Au). Autoclave operating conditions have been established in which recoveries of all the pay metals
are in the 92 to 99% range, and the autoclave residence time has been reduced to an hour. The stability of
the precious metals in solution after autoclaving has been assessed, as well as the impact of internally
recycling process liquors to the feed to the autoclave.

Niagara, ON, Canada
Edited by
428
INTRODUCTION
Platinum group metals (PGMs; platinum, palladium, rhodium, ruthenium, iridium and osmium)
are traditionally recovered from their ores by production of a high-grade concentrate by flotation and/or
gravity concentration followed by smelting of the concentrate. Concentrates are smelted to remove nonsulphide minerals and converted to remove iron and sulphur. The resulting high PGM grade matte is
processed hydrometallurgically to leach the base metals, leaving a residue with a very high grade (20-40%)
PGM concentrate for final refining to individual PGMs. Due to the complexity of this process and its high
capital cost, this process can only be applied economically to high grade PGM ores. Lower grade PGM
concentrates might be accepted as copper and nickel concentrates but may not yield attractive payment
terms for the PGMs. The mineralized Duluth Gabbro region of Minnesota hosts several low grade base
and PGM deposits and Twin Metals Minnesota is working to develop the Twin Metals Project deposits.
Earlier studies at both pre-feasibility and feasibility level, by other mining companies, have failed to yield
an economically viable project based on the traditional process. It is possible to produce a saleable copper
concentrate from these ores, but economic recovery of nickel and PGMs into saleable concentrates proved
elusive.
In the late 1990s and early 2000s the Platsol process was developed at SGS in Lakefield,
Ontario (at the time Lakefield Research Limited) for the NorthMet deposit (also within the Duluth Gabbro)
owned by PolyMet Mining. The process developed was a high temperature chloride-assisted pressure
oxidation process capable of dissolving simultaneously the base metals (Cu, Ni, Co, Zn), gold and the
PGMs.
This paper discusses recent testwork involving the Platsol process for the development of a
flowsheet for Twin Metals Minnesota. Test data presented primarily focuses on PGM extraction under
various operating conditions.
TWIN METALS MINNESOTA
Twin Metals Project Deposits Geology & Mineralogy
Regional Geology
The Cu-Ni-PGM mineralization of the Twin Metals Project deposits is hosted by the maficultramafic Precambrian Duluth Complex. The Duluth Complex is related to the Midcontinent Rift System
and is cogenetic with the Keweenawan volcanics. The Complex extends from the Ontario border in the
north to the city of Duluth in the south. It consists of 12 sub-intrusions, one of which, the South Kawishiwi
Intrusion (SKI), is the host rock for the three deposits. The footwall contact is sharp against the Middle
Precambrian Virginia, Rove and Biwabik Formations, the Neoarchean rocks of the Vermilion greenstone
belt and the Early Cambrian Giants Range Batholith and is gradational with the overlying North Shore
Volcanics.
The lithologies in the SKI include anorthosite, troctolite, gabbro, granodiorite and
granite/granophyre. The rocks have been differentiated into an early Anorthositic Series in the upper part
of the Complex and a later Troctolitic Series in the lower two thirds. Field relations indicate that the
Anorthositic Series is older than the Troctolitic Series, but age dating indicates that two are close in age.
The Felsic Series cuts both the anorthosites and troctolites.
Mineralization
The Cu-Ni mineralization occurs as low-grade, disseminated sulfides in the basal zone of the SKI
and as massive sulfide mineralization at the basal contact of the SKI. Chalcopyrite is the predominant
copper mineral with lesser cubanite. Bornite neodigenite, covellite, chalcocite, tenorite, cuprite and native
copper are also present. Pentlandite is the main nickel sulfides; nickel also occurs in pyrrhotite and in
silicate minerals such as olivine. Platinum, palladium, gold and cobalt are also present in low
concentrations.
429
Concentrate Mineralogy
The sulphide mineralogy of the Twin Metals Project bulk concentrates is made of chalcopyrite,
cubanite, pentlandite and pyrrohotite. Gangue constituents make up ~50-60% of the concentrate mass and
primarily consist of feldspar, olivine, pyroxene and mica/clays with minor amounts of iron oxides.
Chalcopyrite accounts for roughly two thirds of the copper, with cubanite accounting for the
remaining third. Pentlandite carries most of the nickel with minor amounts (~2%) associated with silicates
and oxides. The dominant PGM minerals in the concentrates are michenerite, sperrylite, paolovite,
stibiopalladnite, kotulskite, froodite and minor amounts of PGM-Sn and Ni alloys. The PGMs are
generally very fine grained and <10 m in size.
THE PLATSOL PROCESS
Platsol is a single step, high temperature pressure leaching process. It was developed in 1998
for PolyMets NorthMet Project at SGS Lakefield. The key feature of the Platsol process is that it is a
chloride-assisted total oxidation process. The base metals sulphides are completely oxidized with oxygen
to soluble metal sulphates, iron hydrolysis products and sulphuric acid while gold, platinum and palladium
are dissolved and stabilized as chloro-complexes by the presence of chloride in solution. The addition of a
small amount of chloride ions to the solution at high autoclave temperature (> 200OC) represents an
incremental change in autoclave chemistry that effectively allows recovery of all the metals of value in a
single processing step.
The chemical reactions occurring in the autoclave are shown below. The dissolution of Au, Pd, Pt
is favoured at high oxidation potential, acidity and temperature. (Note that the mineralogy of the PGMs
may be very complex, but for simplicity only the metallic species are considered.)
Chalcopyrite Oxidation/Iron Hydrolysis
CuFeS2+17/4O2+H2O = CuSO4+1/2Fe2O3+H2SO4
(1)
Pyrite Oxidation
FeS2+15/4O2+2H2O = 1/2Fe2O3 + 2H2SO4
(2)
Pyrrhotite Oxidation
FeS+9/4O2+H2O = 1/2Fe2O3 + H2SO4
(3)
Nickel Sulphide Oxidation

NiS+2O2 = NiSO4
(4)
ZnS+2O2 = ZnSO4
(5)
CoS+2O2 = CoSO4
(6)
Zinc Sulphide Oxidation
Cobalt Sulphide Oxidation
Gold Oxidation/Chlorocomplex Formation

Au+1/4O2+1/2 H2SO4+4NaCl = Na3AuCl4+1/2Na2SO4+1/2H2O
Platinum Oxidation/Chlorocomplex Formation
(7)
430
Pt+O2+2 H2SO4+6NaCl = Na2PtCl6+2Na2SO4+2H2O
(8)
Palladium Oxidation/Chlorocomplex Formation

Pd+1/2O2+H2SO4+4NaCl = Na2PdCl4+Na2SO4+H2O
(9)
A process flow diagram for the Platsol process is shown in Figure 1. Feed concentrate would
likely be thickened and filtered to control the water balance and then repulped in recycled copper SX
raffinate and chloride laden process water. The autoclave discharge would either be directly filtered or
thickened and filtered. The washed autoclave residue would go to the hydrometallurgical tailings facility.
Platsol pregnant leach solution (PLS) would advance to PGM recovery after ferric iron is reduced by
addition of sulphur dioxide. PGMs are recovered from solution by precipitation on copper sulphide (CuS),
which is generated by treating a slip stream of copper solvent extraction (CuSX) feed with sodium
hydrogen sulphide. The PGM-bearing CuS concentrate is then thickened and filtered and the PLS, now
free of PGMs, advances to partial neutralization where excess acid is neutralized by addition of ground
limestone. Copper is extracted from the PLS with an oxime solvent extractant in three stages. Loaded
organic is scrubbed and then stripped and copper is recovered from the electrolyte by electrolysis. The
raffinate from CuSX is split and a portion is recycled to the autoclave feed to build up the concentration of
nickel, and as a source of acid (if needed). The balance advances to secondary neutralization where iron
and aluminium are removed by neutralization to pH 4 to 5 with ground limestone, and the purified liquor
advances to nickel and cobalt recovery by mixed-hydroxide precipitation. The intermediate Ni/Co
hydroxide product would then be further refined by TMM to final products.
BATCH AUTOCLAVE TESTWORK
A number of flotation concentrates were prepared from Twin Metals Project drill core by
crushing, milling and batch flotation in 2 kg or 10 kg float cells at the SGS laboratory in Lakefield with the
purpose of assessing the response of Twin Metals Project ore to the patented Platsol Process. The test
work was generally carried out on rougher concentrates in which base and precious metal recovery was
maximized in concentrates with 5 to 10% mass pull. The concentrates were tested in nearly one hundred (at
the time of writing) Platsol tests, which were designed to optimize the autoclave operating conditions for
maximum precious metal recovery, to assess the impact of internal recycling of process liquors to the
autoclave feed, and to evaluate the impact of ore and concentrate variability in the Twin Metals Project
deposit to the Platsol Process.
Procedures
All Platsol tests were carried out in standard 2 L Parr titanium autoclaves. Generally, for each
test, a given amount of concentrate (with known moisture content) was slurried with the required amount
of de-ionized water. For tests conducted on reground concentrate, the feed was first ground in a laboratory
pebble mill for a predetermined time to achieve a target particle size. Reagents (H2SO4 and chloride salts)
were then added according to the prescribed dosages. The vessel was then sealed and heated to the desired
temperature before 700 kPa oxygen overpressure was applied. A bleed of vent gas was continually
withdrawn from the autoclave through a water chilled condenser to ensure an oxidative environment and to
assist oxygen transfer. Agitation was supplied by dual axial/radial pitched blade turbine impellers and a
magnetic drive at ~720 RPM. At the conclusion of the test the autoclave was cooled fairly quickly to less
than 100C with an indirect cooling coil before the vessel was opened. The hot slurry was then filtered and
samples of the filtrate and the washed residue were submitted for analysis. A portion of the filtrate was
stabilized with an equal volume of aqua regia and this sample was analyzed for Au, Pt and Pd.
The sulphide oxidation reaction is exothermic and the sulphide grade of the concentrate feeding
the pressure oxidation (POX) process determines the pulp density of the feed to the autoclave. In this way,
the exothermic sulphide oxidation reaction generates the heat needed to maintain the autoclave at the
desired operating temperature, without the need for supplemental heating or cooling (autothermal
431
operation). When the source of sulphide ions is pyrite, the equation for calculating the optimum pulp
density for autothermal operation has been determined by Conway and Gale (1990) as:
Pulp density (w/w%) = 100 / (0.3[%S2-] + 0.825)
(10)
Although there is insignificant pyrite in the Twin Metals Project concentrates, this equation
proved to be a useful guide for determining the required pulp density for the Twin Metals Project Platsol
tests.
CONCENTRATE
PRESSURE
LEACHING
O2
L/S
TAILINGS
O/F
SO2
PGM RECOVERY
CuS
PGM
CONCENTRATE
L/S
O/F
CaCO3
H2S
NEUTRALISATION
1
S
CuS production on
CuSX feed bleed
O/F
L
L/S
O/F
S
CuSX
WASH
CuSX EXTR
CuSX
STRIP
CuEW
Cu Cathode
S
Fe/Al removal
CaCO3
L/S
Ni/Co PRODUCT
L
NaOH
MIXED
HYDROXIDE PPT
THICKEN
FILTRATION
REPULP
FILTER
MgO
L
Ni/Co CLEAN-UP
L/S
Mg REMOVAL
L/S
Ca(OH)2
Ca(OH)2
Figure 1 Platsol process flowsheet
Process Water
432
Twin Metals Project Feed Concentrates to Platsol Process

Most of the Platsol tests were conducted on two flotation concentrates, identified as MC-1 and
MC-3. A third concentrate, MC-2 was used for a smaller series of tests and several individual variability
samples were also tested. Chemical analysis of the three MC concentrates is listed in Table 1.The particle
size distributions for the as received flotation concentrates most used in the Platsol tests (MC-1 and MC3) are shown in Figure 2, as measured by Malvern laser particle size analyzer.
Table 1 Twin Metals Project concentrate chemical analysis
Element / Sample ID
Au g/t
Pt g/t
Pd g/t
Rh g/t
Ag g/t
S= %
S%
SO4 %
S %
Cu %
Ni %
Co %
Zn %
Fe %
Mg %
Mn %
Al %
Ca %
Si %
Na %
C(t) %
C(g) %
TOC leco %
CO3 %
Cl g/t
MC-1
1.48
3.20
6.21
0.24
30.9
16.0
16.4
MC-2
1.14
2.44
5.45
9.73
2.44
0.069
0.025
23.5
2.92
0.036
4.80
3.91
10.8
7.12
1.78
0.054
0.026
19.2
3.59
0.08
6.35
4.25
10.4
10.8
1.15
0.1
0.06
0.05
121
MC-3
1.87
4.13
7.63
0.31
35.6
14.6
15.4
0.1
<0.05
10.0
2.53
0.086
0.051
24.1
4.51
0.078
4.08
2.69
10.3
0.52
0.12
0.07
<0.05
<0.05
210
433
100
Vol. % Passing
MC-1
80
MC-3
60
40
20
0
0.1
10
Size (m)
100
1000
Figure 2 Particle size distribution of Twin Metals Project concentrates

Oxidation and Base Metal Extraction
Dissolution of base metals (Cu, Ni in particular but also Co and Zn) was generally insensitive to
the pressure oxidation conditions applied , with high extractions of ~99% or better for Cu and Ni in nearly
all tests conducted. Sulphide sulphur in the feed concentrates was efficiently oxidized to sulphate, with
residual sulphide in the residue of <0.2% on average for >98% sulphide oxidation. Final free acidity of the
POX PLS ranged from ~20 to 50 g/L with 20 g/L thought to be the practical minimum for effective PGM
dissolution.
Although copper and nickel extractions of 99% or better were routinely achieved, even at the
coarser feed sizes, there was some evidence that extractions of both Cu and Ni were slightly lower at the
finest re-grind particle sizes of 10 and 20 m feed sizes. This counter-intuitive result was believed to be
due to low residual acidity in these tests, which in turn resulted from increased liberation of acidconsuming gangue minerals at the finer grind sizes. In particular, magnesium in solution increased sharply
at the finer grind sizes.
Nickel extraction was lower in tests where a synthetic Cu SX raffinate was used as feed liquor to
the autoclave. This was also an unexpected result and testwork is ongoing in attempt to achieve higher Ni
extraction when recycling Cu SX raffinate to the autoclave. The main metal ion constituents of the CuSX
raffinate are nickel and magnesium ions, and Table 2 lists conditions and Ni extraction results for a series
of tests conducted on the MC-3 concentrate involving a synthetic Cu SX raffinate and various
concentrations of magnesium. The raffinate solution contained ~0.5 g/L Cu, 0.5 g/L Al, 1.2 g/L Na and the
indicated concentrations of Ni and Mg. In all but the first test listed, chloride was added as magnesium
chloride (and as calcium chloride in the first test listed). The data show that nickel recovery decreased
from ~99% to as low as ~88% and was generally in the low 90s%. Increasing the acid added to the POX
feed from 49 to 185 kg/t (which increased the final free acid concentration of the autoclave discharge
liquor from ~25-30 g/L to ~50 g/L) did not improve the nickel extraction significantly, nor did increasing
the retention time in the autoclave from one hour to 2 hours. Nickel extraction did not appear to be
affected by the Mg concentration, at least over the range tested (0 20 g/L in the feed liquor, resulting in 8
28 g/L Mg in the PLS), but nickel extraction improved when lower Ni tenor recycle solutions were used.
This indicates that the decrease in nickel extraction efficiency was due to a nickel solubility limitation.
The residual unleached nickel does not appear to be unreacted sulphides because residual sulphide levels
were low. Rather the Ni is presumably co-precipitating with hematite and other hydrolysis reaction
products when the concentration of nickel in solution exceeds a certain value.
The value of nickel is very important to the overall economic viability of the Twin Metals Project,
and a loss of 5 to 10% Ni recovery could not be tolerated. The trend indicated in Table 2 may well be
overcome with further optimization testwork, but if not, only a limited amount of CuSX raffinate would be
434
recycled to the autoclave feed; thus maintaining high Ni extraction. In this event, most of the make up
water will be final tailings solution after nickel precipitation and solution neutralization with lime, in which
case the recycle chloride will be mostly in the form of calcium chloride, and recoveries similar to those
achieved in the first test in Table 2 should be achievable.
Table 2 Test conditions and Ni extraction data with synthetic Cu SX raffinate recycle
Ni
POX Feed, g/L

Mg
0
3.25
6.5
13
13
13
13
13
13
13
13
13
0
20
20
0
20
20
20
8.5
18.5
3.5
18.5
3.5
Cl
Acid, kg/t
H2SO4
Temp.,
C
Residence
Time, h
15
15
15
10
15
15
15
10
10
10
10
10
49
49
49
49
49
185
49
49
49
49
49
49
240
240
240
240
240
240
240
240
230
230
240
240
1
1
1
1
2
1
1
1
1
1
1
1
Ni
Extraction,
%
98.9
97.8
96.2
93.3
93.3
92.7
92.6
91.9
91.9
91.2
90.8
88.5
PGM Extraction
Effect of Particle Size, Residence Time & Temperature
The effects of grind size, temperature and residence time on PGM extraction during standard
Platsol tests with the MC-1 concentrate are shown in Figure 3 and 4. Extraction generally increases with
increasing residence time up to 2 hours and there is evidence that some regrinding is beneficial. And
extractions were higher at higher temperature in most cases.
The reason for the decrease in Au and Pt extractions in the later stages of very long leach tests
(from 2 to 4 hours) is not known for certain, but could be due to a change in the solution chemistry, such
as a decrease in the acid or ferric concentrations in solution after prolonged time in the autoclave.
Alternatively, Au and Pt might co-precipitate with something else that is unstable in solution, such as
silicon or aluminum. For example, the results suggest that the gangue becomes more reactive at finer grind
sizes, and this could result in more silica and aluminium dissolving, which could subsequently reprecipitate if these metal ions hydrolyze or became super-saturated in solution. This precipitation could be
taking Au and Pt down with it.
The effects of grind size, temperature and residence time on the extraction of PGMs from the MC3 concentrate are shown in Figures 5 and 6. Once again, PGM extraction was generally more favourable
with a regrind, although further work is needed to optimize the re-grind particle size for the feed to the
autoclave. Some re-grinding will almost certainly be beneficial, but there seems little justification for
grinding as fine as a P80 of 10 m. In fact, over grinding beyond the optimum will lead to difficulties in
solid liquid separation as well as higher acid consumption due to gangue reactivity and possibly to
instability of the PGM chloro complexes in solution. The optimal concentrate feed size is probably in the
P80 range of 40-80 m.
The rate of PGM dissolution was fast at 240C and the extraction efficiencies of Au, Pt, and Pd
were highest after only 60 minutes in the autoclave and then declined with longer residence time (Figure
6).
20
40
60
80
100
20
40
60
80
2
3
POX Time, h
20 m grind
100 m grind
20
40
2
3
POX Time, h
10 m grind
40 m grind
no grind
20 m grind
100 m grind
20
40
60
2
3
POX Time, h
20
40
2
3
POX Time, h
230C
240C
220C
20
40
60
80
100
2
3
POX Time, h
230C
240C
Figure 4 Effect of temperature and residence time on PGM extraction from MC-1 concentrate (unground, 6 g/L Cl as NaCl)
220C
230C
240C
60
80
100
20 m grind
100 m grind
220C
2
3
POX Time, h
10 m grind
40 m grind
no grind
Figure 3 Effect of grind size and residence time on PGM extraction from MC-1 concentrate at 230C (6 g/L Cl as NaCl)
10 m grind
40 m grind
no grind
80
80
60
100
100
Pt Extraction, %
Pt Extraction, %
Au Extraction, %
Au Extraction, %
Pd Extraction, %
Pd Extraction, %
100
435
436
100
Extraction, %
80
60
40
Au
Pt
Pd
20
0
0
20
40
60
Feed Size, P80 m
80
100
Figure 5 Effect of grind size on PGM extraction fromMC-3 concentrate at 240C, 2 h residence time, 12
g/L Cl as CaCl2
PGM Extraction, %
100
90
80
Au
Pt
Pd
70
60
Au 230C
Pt 230 C
Pd 230C
50
0.5
1.5
POX Time, h
Figure 6 Effect of residence time on PGM extraction from MC-3 concentrate, 240C & 230C (2 h), 12
g/L Cl as CaCl2
Effect of Pulp Density
Figure 7 shows the effect of pulp density of the slurry feeding the autoclave on base and precious
metal extraction from the MC-2 concentrate. Normal pressure oxidation practice is to feed the autoclave at
a pulp density of 50% or more, which is much higher than that required for autothermal operation, and then
add cooling water downstream in the autoclave to maintain the target temperature and pulp density. The
pulp density in the first one or two compartments can therefore be significantly higher than the last few
compartments. The results in Figure 7 show that when treating Twin Metals Project concentrates at a pulp
density of anything more than about 40%, this practice could lead to slow oxidation kinetics and
consequently poor heat generation in the first compartment. The trends seen in Figure 7 could be due to
one or more of three interrelated causes:
Some of the Twin Metals Project rougher concentrates tested became very viscous at solids
densities > 30%, which would have slowed the rate of oxygen mass transfer in the autoclave, and
therefore slowed the rate of sulphide oxidation.
Residual acidity in the autoclave discharge decreased with increasing pulp density, which
suggested that acid consumption by gangue constituents increased more than acid generation via
437
sulphide oxidation. The Platsol process requires residual free acidity of > 20 g/L, and it dropped
well below this figure in the tests conducted at high pulp density.
Chloride concentration was always based on the concentration of NaCl in solution, therefore the
available chloride per unit mass of solids decreased at higher solids density, lowering the driving
force for PGM solubilization, and decreasing the stability of the PGM chloro complexes in
solution.
100
80
80
60
60
Extraction, %
100
40
Au
Pd
S" Oxid'n
20
40
Pt
Cu
20
Sulphide Oxidation, %
The negative effect on PGM recovery of operating at higher pulp densities could be overcome by
(i) adding more acid to the feed to ensure that the residual acidity target of >20 g/L is always met, (ii)
increasing the chloride concentration in proportion to the solids content of the autoclave and (iii) operating
the autoclave at higher temperatures of 230 to 240C to lower pulp viscosity. Higher temperature could
however have the opposite of the desired effect as it could lead to increased gangue leaching, particularly
Mg, which would tend to lower the effective free acidity.
0
0
10
20
30
40
Pulp Density, w/w%
50
Figure 7 Effect of pulp density on PGM, Cu extraction & sulphide oxidation of MC-2 concentrate (25
m P80, 230C, 2 h retention time, 6.1 g/L Cl as NaCl, 35 kg/t H2SO4)
Effect of Chloride Source & Concentration
Chloride strength was shown in the test work to be a critical parameter for determining PGM
extraction. PGM extraction efficiency improved progressively as the chloride concentration was increased
from 0.6 g/L to >10 g/L. This is shown in Figure 8 and Figure 9 for MC-1 and MC-3 concentrate,
respectively. The chloride source was sodium chloride in the tests shown in Figure 8, whereas the chloride
was added as calcium chloride in Figure 9. In both cases the PGM extraction increases with increasing Cl
concentration.
Sodium chloride was used as the source of chloride in all the tests on MC-1 concentrate, as this
had been the standard bench testing protocol for the Platsol Process at SGS (Lakefield). However, there
are potential issues with the use of sodium salts, such as the build up of sodium sulphate in a closed water
system. In addition, sodium ions promote the formation of sodium jarosite and alunite in the leach residue,
and the formation of these precipitates could in turn impact precious metal recovery negatively, as well as
the solid/liquid separation and geotechnical/environmental characteristics of the leach residue. As the
amount of sodium chloride in the autoclave was increased, the amount of aluminum in solution decreased,
and the differential between Na added as NaCl and Na remaining in the PLS increased (as shown in Figure
10), implying that sodium and aluminium were precipitating out of solution in the autoclave. This is
consistent with sodium and aluminium precipitating out as sodium alunite.
Most of the chloride needed for the Platsol process recycles internally to the autoclave feed
from two aqueous streams within the overall flowsheet. One source is the copper solvent extraction
438
raffinate, where the chloride will be mainly in the form of magnesium chloride. This source will be used if
acid is needed to pre-treat the autoclave feed, as the SX raffinate is expected to contain20-40 g/L acid. In
addition, recycling copper SX raffinate to the autoclave feed will build the concentrations of nickel and
cobalt, which will in turn lower capital costs in the downstream Ni/Co recovery plant. However, the
amount of copper SX raffinate that can be used will be limited by the tolerance of the Platsol process to a
build up of magnesium and nickel in solution. Test work indicates that the process is tolerant at magnesium
concentrations of up to at least 20 g/L, although the tolerance for nickel build up is lower.
The other source of internal chloride recycle will be process water. In the overall flowsheet, the
final tailings water after nickel recovery is treated with lime to precipitate Mg and Mn as their hydroxides.
This converts the chloride ion from the magnesium salt to the calcium salt. This process water will be
recycled internally as coolant to the autoclave and as wash water in the various solid/liquid separation
steps. Therefore, once the tolerance limit for raffinate recycle has been reached, the remaining water
recycled to the autoclave feed will be process water, in which the chloride will be in the form of calcium
chloride.
PGM Extraction (%)
100
80
~35 m P80
60
40
Au
Pt
Pd
no regrind
20
0
0
8
Cl Conc. (g/L)
12
16
Figure 8 Effect of chloride concentration, added as NaCl, on PGM extraction from MC-1 concentrate at
230C, 2 h residence time
PGM Extraction (%)
100
95
90
85
80
75
70
65
60
Au
Pt
Pd
Cl Conc. (g/L)
12
16
Figure 9 Effect of chloride concentration, added as CaCl2, on PGM extraction from reground MC-3
concentrate with P80 of 41 m, 240C, 2 h residence time (1.5h for the 12.5 g/L Cl test)
439
80
70
60
50
40
30
20
10
0
600
500
%Na Precipitated
Al in PLS
400
300
200
100
mg/L Al in PLS
%Na Precipitated
0
0
12
16
Cl Conc. (g/L)
Figure 10 Effect of Cl concentration on Na removal and Al dissolution
Variability
Several concentrate samples were prepared to test the response of mineralogical variability across
the Twin Metals Project deposit to the PlatsolTM Process. The composition of the nine concentrates tested
to date is shown in Table 3, along with the acid balance and PLS compositions from comparative Platsol
tests and the metal extraction efficiencies. The sulphide sulphur content of the various concentrates ranged
from 10.4 to 18.5%, while copper and nickel grades varied from 6.8 to 11.6% and 1.7 to 3.0% respectively.
Magnesium was the main reactive gangue component of all the concentrates and its grade varied from 2.4
to 4.5%, with higher sulphide grades generally corresponding to lower Mg levels in the samples.
All of the sulphide in the feed concentrates was converted to sulphate in the PlatsolTM Process. In
addition, acid was added to the feed for each test to precondition the pulp to pH 1.8 prior to pressure
oxidation, and that acid is also listed in Table 3. After autoclaving, the sulphate was distributed between
metal sulphate compounds in solution (mainly Cu, Ni and Mg), free sulphuric acid in solution and
insoluble metal sulphate compounds in the residue (gypsum, alunite, jarosite and basic iron sulphate). The
relative amounts of sulphate associated with metals in solution (after discounting the sulphate equivalent
chloride), and in the solid residues is also listed. It can be seen that between ~10 and 30% of the total
sulphate in the autoclave discharge (generated plus added) reported to the residue when the chloride was
provided as NaCl. The deportment of sulphate to the solids was generally slightly higher when calcium
chloride was used and considerably lower when magnesium chloride was used. It is also important to note
that magnesium in solution consumes about 4 kg of acid for every kilogram of magnesium dissolved and
that the acid consumed by Mg and other gangue constituents was for some samples almost as much as that
required to sustain the Cu+Ni in solution. In those tests the final free acidity was lower than the target of
>20 g/L for the Platsol process and leach extractions suffered. Copper and nickel extractions were less
than 99% and PGM extractions were also generally lower. It should be noted that PGM extractions of
>90% were achieved with the MC-1 and MC-3 composites under modified conditions (higher temperature
and chloride concentration, with little impact on the acid balance) but for direct comparison purposes, only
tests performed at 230C, 16-23% solids, 6.1 g/L Cl as NaCl, 700 kPa oxygen overpressure and 2 hour
residence time are listed.
440
Bulk
Conc
1+5
1.47
3.24
7.92
12.2
6.82
1.72
17.4
3.50
1.43
Bulk
Conc
2+6
1.4
3.45
6.62
12.9
8.43
1.84
20.1
4.46
1.26
Bulk
Conc
3+7
1.06
3.31
7.57
14.9
8.83
2.44
20.7
2.48
1.32
Bulk
Conc
4+8
1.33
3.32
7.32
13.4
8.83
2.12
18.4
2.95
1.22
Bulk
Conc
1-8
1.26
3.08
6.87
12.8
8.79
2.14
19.8
3.15
1.17
307
446
550
353
370
405
375
377
23
35
49
19
33
35
30
32
32
167
43
116
235
36
53
98
72
74
197
142
187
242
154
169
205
183
181
44
88
90
37
95
91
31
46
61
84
59
111
62
73
65
127
109
85
g/L in PLS
Cu
Ni
Mg
H2SO4
22900
5640
3730
38
19000
4310
7210
11
23100
5320
6840
28
23500
6020
2520
45
24100
5720
8930
11
25300
5070
8050
15
25400
6650
3970
24
24800
5930
4970
19
20200
4700
4850
16
Cu
Ni
Mg
Au
Pt
Pd
99
99
57
74
89
92
97
97
72
80
82
63
99
99
73
67
81
83
99
99
53
96
93
92
97
97
78
81
75
70
98
98
61
82
82
79
98
98
71
93
79
77
98
98
70
89
68
72
99
99
68
93
79
79
Acid Balance, kg/t
Head Analysis
1.87
4.13
7.63
14.6
10.0
2.53
24.1
4.51
1.17
Comb
Cln
Conc
1.71
2.93
6.87
18.5
11.6
2.97
26.1
2.40
1.27
Extraction, %
Table 3 Twin Metals Project concentrates and blends; acid balance and metal leach efficiencies
Sample ID
MC-1
MC-2
MC-3
Au g/t
Pt g/t
Pd g/t
S= %
Cu %
Ni %
Fe %
Mg %
S2- / Cu+Ni
1.48
3.2
6.21
16.0
9.73
2.44
23.5
2.92
1.31
1.14
2.44
5.45
10.4
7.12
1.78
19.2
3.59
1.17
Generated by
S2- Oxid'n
479
H2SO4 Added
Free H2SO4
SO4 with
Cu+Ni
SO4 with Mg,
Al etc.
SO4 in POX
Residue
PGM Stability
During the testwork it was observed that, under certain conditions, a portion of the dissolved
PGMs, particularly Au, was reprecipitating to the residue before being recovered from solution. In a series
of 14 tests on the MC-3 concentrate, the Au tenor dropped over a two hour period by 20% on average
(whether the static pulp was naturally allowed to cool or was mixed in a heated water bath at 80C) and
gold losses ranged from ~40% down to <10% depending on the conditions. Some reprecipitation of Pt and
Pd was also observed under certain conditions, but on average was very low at ~2% each and very near the
analytical precision for these elements in solution. Higher chloride concentrations improved the stability
of gold in solution but did not eliminate the reprecipitation issue completely.
441
Even though the Platsol slurry was well oxidized under most of the conditions tested, there was
usually a low concentration of ferrous iron in the PLS; ranging from <5 mg/L to as high as 180 mg/L, and
it was noted that the Au tenor of the Platsol PLS showed a broad correlation to the ferrous iron levels
(Figure 11). It was also noted that the ferrous levels generally increased during the aging period after POX
and so in a few tests small amounts of hydrogen peroxide were added immediately after pressure oxidation
to oxidize the ferrous to ferric. In those cases the Au in solution was stabilized. More detailed testwork in
this area is ongoing at the time of writing.
mg/L Fe(II)
200
150
100
50
0
0.00
0.10
0.20
0.30
mg/L Au
0.40
0.50
Figure 11 Ferrous iron relationship with Au in solution

CONCLUSIONS
An extensive Platsol bench test program has been conducted at SGS in Lakefield to study and
optimize the autoclave conditions for effective extraction of base and precious metals from Twin Metals
Project concentrates. Copper and nickel extractions were generally about 99% under most conditions
tested. PGM extractions varied somewhat depending on the autoclave conditions but extractions of 95%
for Au and Pt and 90% for Pd have routinely been achieved with higher chloride concentrations (~15 g/L),
higher temperature (240C) and shorter retention time (1 h). These conditions are more aggressive than
those that were developed for the NorthMet Project (5-10 g/L Cl, 225C and 2 h residence time). Some
obstacles were identified during the testwork; primarily (i) a drop in Ni extraction when recycling CuSX
raffinate and (ii) PGM stability in solution post-POX. Both of these issues are part of ongoing testwork,
with further testwork planned at both bench and pilot level in the coming months.
ACKNOWLEDGEMENTS
The authors wish to thank their respective companies, Twin Metals Minnesota and SGS for use of
the data published in this paper and resources required to complete it. We also wish to acknowledge the
independent consulting metallurgists working on the project for their analysis and input in the testwork, in
particular Dr. Roman Berezowsky and Dr. Jim King. Valuable contributions were also made by Mr.
Holger Bannach, Dr. John Marsden, Dr. Derek Kerfoot and Dr. Grenvil Dunn.
REFERENCES
Conway, M.H. and Gale, D.C., 1990. Sulphurs impact on the size of pressure oxidation autoclaves.
Journal of Metals, 42(9), 19-22.
Ferron, C.J., Fleming, C.A., Dreisinger, D.B., & OKane, P.T. 2002. Pilot plant demonstration of the
platsol process for the treatment of the northmet copper-nickel PGM deposit. Mining
Engineering. 54(12), 33-39.
442
Ferron, C.J., Fleming, C.A., Dreisinger, D.B., & OKane, P.T. 2001. Platsol treatment of the NorthMet
copper-nickel - PGM bulk concentrate - pilot plant results. Alta Conference.
Ferron, C.J., Fleming, C.A., OKane, P.T., & Dreisinger, D.B. 2001. Application of the Platsol Process
for the simultaneous dissolution of copper, nickel, gold and PGMs from sulphide concentrates and
autocatalysts. Precious Metals, 25, 129-157.
443
THE CHEMISTRY AND MINERALOGY OF A NICKEL COPPER MATTE LEACH

*G.C. Summerton1, D.C. Craig1, P. Dinham1, N. McCulloch2, S. Dowling2
1
Anglo Americans Technical Solutions Research

8 Schonland Street, Crown Mines, 2025, South Africa
(*Corresponding author: grant.summerton@angloamerican.com)
2
Anglo American Platinum Limited

Rustenburg Base Metal Refiners
Farm 202JQ, Old Main Road, Rustenburg, South Africa
ABSTRACT
Development of a process for the treatment of a nickel copper matte rich in the minerals
heazlewoodite, chalcocite and bornite has demonstrated significant base metal recoveries and metal
separation efficiencies. The determination of chemical and mineralogical changes occurring in the
individual leaching stages in laboratory experiments has enabled a better understanding of the complex
leaching chemistry. The chemistry and mineralogy of the piloting and laboratory processes are discussed.

Niagara, ON, Canada
Edited by
444
INTRODUCTION
The nickel-copper sulfide ores of the South African Bushveld Complex are among the most
important Platinum Group Metal (PGM) bearing ores, and contain the worlds largest reserves of platinum.
The treatment used in the recovery of PGMs from these ores includes three types of processes, namely ore
concentration using physical techniques such as flotation and gravity separation, concentration by
pyrometallurgical means, hydrometallurgical extraction of the base metals followed by the PGMs.
Following milling of the ore, flotation involves the separation of high value minerals from gangue by
taking advantage of the differences in their hydrophobicity. These differences are generally maximized
through the use of a surfactant or wetting agent. Concentrates are then thermally treated and melted which
brings about physical and chemical changes that enable the recovery of base metals and PGMs. The main
aim of the smelting and converting process is to separate and eliminate the valuable metals from the bulk
of the unwanted gangue and essentially all of the iron and to concentrate the metal values into a high grade
converter matte. The matte can be further enriched by magnetic separation, producing a PGM-rich
magnetic fraction and a base metal-rich non-magnetic fraction. The magnetic fraction is treated by
hydrometallurgical processes to produce a PGM concentrate which is further refined to separate and purify
the individual metals. The non-magnetic fraction is treated to produce marketable metal values such as
nickel, copper, cobalt and to a lesser extent PGMs. The principal objective of any hydrometallurgical
extractive process is to leach the desired elements selectively into an aqueous phase so as to separate them
from the bulk of the material. (Crundwell, Moats, Ramachandran, Robinson and Davenport, 2011;
Hundermark, Mncwango, de Villiers and Nelson, 2011).
We present here an economical laboratory process which requires little acid make-up for the
leaching of a nickel copper matte and specifically the nickel and copper rich mineral phases heazlewoodite,
chalcocite and bornite to near completion. Although the process presented here includes a new polishing
leach stage, it is generally based on a modified and now extended Sherrit Gordon process developed for
Anglo Americans platinum business in 2006, (Bryson, Hofirek, Collins, Stiksma and Berezowsky, 2008).
The basis of this work is ongoing research in order to better understand and optimise the leach
characteristics of varying feed mineralogies. The process can generally be divided into four leaching stages
which may be extended to a fifth should a further enriched PGM concentrate be desired. The stages operate
in the sequence: copper removal; nickel atmospheric leach; nickel non-oxidising pressure leach; copper
pressure leach; and copper polishing leach. The generalised process is depicted in Figure 1.
The primary objective of copper removal is to hydrolyse copper and iron and in so doing generate
a clean nickel solution (<10 mg/L copper and iron). The fresh matte is used to remove soluble copper and
iron from the incoming lixiviant, under atmospheric oxidising conditions. Iron and copper are precipitated
from solution as their hydroxide and basic sulfates by hydrolysis, thereby generating a solution relatively
free of copper and iron. The acid generated by the oxidative hydrolytic reactions is consumed by the
dissolution of up to 15% of nickel from the nickel copper matte. The initial starting pH will be between 2.5
and 3, with a terminal pH of around 6.
The nickel atmospheric leach stage utilises liquor from the nickel non-oxidising leach which is
loaded with sulfuric acid and copper. This is contacted with the residue from copper removal in what is
effectively a two stage atmospheric leach which is initially non-oxidising and then oxidising. The primary
objective of the nickel atmospheric leach is, in addition to the extraction of nickel and iron, and the
consumption of acid generated in the nickel non-oxidising leach, to effect the net precipitation of soluble
and acid soluble copper, as copper sulfides, retain iron in solution as ferrous, and produce a product liquor
containing about 10 g/L copper and 15 g/L sulfuric acid. Leached nickel can be recovered by
electrowinning.
445
Nickel
Electrowinning
Nickel
Copper
Matte
Copper Removal
PGM
Concentrate
Nickel Atmospheric
Leach
Nickel Non-Oxidising
Leach
Copper Polishing
Leach
Copper Pressure
Leach
Solid Flow
Copper
Electrowinning
Liquid Flow
Figure 1 A simplified overview of the process

The primary objective of the nickel non-oxidising leach is to produce solids with sufficient sulfide
sulfur to meet the requirements of the copper pressure leach, with effective utilization of copper sulfate
while providing a residue with a Cu:Ni ratio of approximately 8:1. Additional nickel and iron is dissolved
by metathesis reactions with copper sulfate at an elevated temperature, under non-oxidising conditions.
The non-oxidising leach is capable of complete extraction of nickel although this is undesirable as it would
result in the formation of excessive amounts of acid which could not be accommodated by the nickel
atmospheric leach. Furthermore, the formation of a nickel non-oxidising leach residue which is nickel
deficient would require the addition of acid to the copper pressure leach in order to get adequate
dissolution of copper.
The primary objective of the copper pressure leach is to leach all remaining nickel and copper
minerals to completion. The acid required by the leach is provided in part by the acid producing oxidative
dissolution of the remaining nickel containing minerals. Leached copper can be recovered by
electrowinning as well as directed to the nickel non-oxidising leach where a higher copper concentration is
required for metathesis reactions.
A copper polishing leach can be employed to further leach any copper remaining in the copper
pressure leach residue. The objective of the polishing leach is to significantly reduce the mass of the
residue produced in the copper pressure leach and is so doing produce a PGM-rich concentrate which can
be processed further.
EXPERIMENTAL
Tables 1 and 2 provide a general elemental and mineralogical composition of the nickel copper
matte feed to the process.
All pressure oxidation experiments were carried out in an 8 L Pressure Product Industries
autoclave LC type reactor. Agitation was provided by a Dyna/Mag (MM-T60) mixer driving a single 3pitched blade impeller agitator. Heating was provided by a mantle belt around the exterior of the reactor
chamber whilst cooling was provided by a cooling coil located centrally within the reactor volume. The
agitation speed was monitored by a DynaMag MAXjr Tach1 tachometer and the temperature controlled by
a LFE electronic process controller. The temperature was monitored by an internal thermocouple probe to
446
an accuracy of 3C and maintained at the desired set points by external heating and by passing cooling oil
through the internal cooling coil. Cooling oil was cooled to a set point of -20C by a Labcon low
temperature water bath and was regulated by a solenoid valve. In order to simulate oxidising or nonoxidising conditions either oxygen or nitrogen was introduced into the autoclave near the base of the
reactor and below the impeller through a dip tube. The gas input rate to the autoclave was measured at
regular intervals by monitoring the reactor off gas flow. Gas pressure was monitored and maintained by a
Dynisco 1390 digital pressure gauge. A sample tube fitted to the reactor drew approximately 40 mL
samples during runs at regular intervals. The lixiviant was prepared such that a final volume in the reactor
after all additions would be 6000 mL. The elemental composition and acid content of the lixiviants used is
detailed in Table 3. The experimental conditions used are listed in Table 4.
Table 1 Typical elemental composition of the nickel copper matte
Ni
(wt%)
Cu
(wt%)
Fe
(wt%)
S(total)
(wt%)
41
32
23
Table 2 Typical mineralogical composition of the nickel copper matte
Heazlewoodite
(wt%)
Chalcocite
(wt%)
Bornite
(wt%)
Other#
(wt%)
54
17
20
Includes minerals such as godlevskite and pentlandite
Magnesium (as magnesium sulfate) was added as an inert tracer element and used to correct for
any evaporative concentration effects. The required solid charge was added to provide a solid:liquid ratio
of 1:6, the reactor sealed and the agitator set to 2000 rpm and heated to the required temperature and
pressure (if not atmospheric).
After reaching the desired leaching conditions, sulfuric acid was introduced into the vessel by
injection under pressure using a sample burette. The gas sparge was started and set at the required flow
rate. Samples were drawn regularly and suction filtered hot using a 45 m membrane filter. After
measuring its volume the filtrate was set aside for solution analysis. The remaining solid was washed with
approximately 50 mL water at about 80 C and dried for further chemical or mineralogical analysis.
Table 3 Elemental composition and acid content of the lixiviants used
Leach
Cu
(g/L)
Copper
5
Removal
Nickel
20
Atmospheric
Nickel Non65
Oxidising
Copper
20
Pressure
Copper
12
Polishing
#
Adjusted to exact requirement
Ni
(g/L)
Fe
(g/L)
Initial Acid*
(g/L)
Liquor Origin
98
pH 2.7
Fresh
80
44
50
15
15
40
Fresh
15
50
Fresh
Nickel NonOxidising#
Copper
Pressure#
* Added at full pressure and temperature
447
Table 4 Experimental conditions used for the different leaching stages

Leach
Copper
Removal
Nickel
Atmospheric
Nickel NonOxidising
Copper
Pressure
Copper
Polishing
Temperature
(C)
Pressure
(kPa)
Gas
Sparge Rate
(L/min)
Reaction Time
(min)
80
atmospheric
O2
240
90
atmospheric
N2, air
1, 2
180, 60
155
688
N2
240 - 300
145
688
O2
240 - 300
155
988
O2
300+

Copper Removal
The copper removal leach produces a nickel sulfate solution which is relatively free of copper and
iron. Nickel copper matte is contacted with the feed liquor under oxidising atmospheric conditions. Nickel
is solubilised by the oxidative dissolution of heazlewoodite.
Ni3S2 + 0.5O2 + H2SO4 2NiS + NiSO4 + H2O
(1)
Acid consumed during this process results in an increase in the pH of the solution and provides
the driving force for the oxidative and hydrolytic precipitation of copper and iron. The oxidative and
hydrolytic reactions for iron and the hydrolytic reaction for copper are given as follows.
2FeSO4 + H2O + 0.5O2 2Fe(OH)SO4
(2)
2Fe(OH)SO4 + 4H2O 2Fe(OH)3 + 2H2SO4
(3)
2FeSO4 + 5H2O + 0.5O2 2Fe(OH)3 + 2H2SO4
(4)
3CuSO4 + 4H2O CuSO42Cu(OH)2 + 2H2SO4
(5)
Figure 2 depicts trends over the four hour leach period. Iron is readily precipitated to <10 mg/L
within the first 30 minutes and to <5 mg/L after the first hour. The pH increased from 2.7 to 5.9 by that
time essentially all the copper had been precipitated. The overall nickel extraction, based on solids analysis
was determined to be 19%.
448
114
112
110
108
106
104
102
100
98
96
7
6
5
4
3
2
1
0
0
50
100
150
Ni Concentration (g/L)
Cu and Fe Concentration (g/L) and pH
200
Time (minutes)
Cu
Fe
pH
Ni
Figure 2 Copper, iron, pH and nickel profiles for the copper removal solutions
Nickel Atmospheric Leach
The nickel atmospheric leach is conducted under atmospheric conditions and is sequentially
staged as non-oxidising and mildly oxidising. The overall objective of the leach, in addition to the further
extraction of nickel and iron, is to consume acid with the net precipitation of copper as copper sulfide. The
copper removal solids are reacted with acidic copper-rich product liquor produced in the nickel nonoxidising leach. Initially, the basic copper sulfates and ferric hydroxides are readily re-dissolved by the
acidic feed solution.
NiSO42Ni(OH)2 + 2H2SO4 3NiSO4 + 4H2O
(6)
CuSO42Cu(OH)2 + 2H2SO4 3CuSO4 + 4H2O
(7)
2Fe(OH)3 + 3H2SO4 Fe2(SO4)3 + 6H2O
(8)
Re-dissolved ferric is subsequently reduced in the oxidative leaching of heazlewoodite.

Ni3S2 + Fe2(SO4)3 2NiS + NiSO4 + 2FeSO4
(9)
In the first stage of the nickel atmospheric leach, in the absence of air, the leaching of nickel and
iron is predominantly by 1:1 exchange or metathesis reaction with soluble copper. Copper derived from the
re-dissolution of basic copper sulfate and copper present in the nickel non-oxidising leach solution
participates in the further leaching of heazlewoodite by metathesis, producing predominantly chalcocite
and millerite. Millerite and troilite are also expected to react by metathesis exchange with soluble copper.
Ni3S2 + 2CuSO4 Cu2S + NiS + 2NiSO4
(10)
NiS + CuSO4 CuS + NiSO4
(11)
FeS + CuSO4 CuS + FeSO4
(12)
449
In the oxidising portion of the process, the leaching is oxidative in nature and results in the
consumption of the acid generated by reactions in the nickel non-oxidising leach. Acid control during the
leach is critical to ensure that there is sufficient acid remaining after the initial re-dissolution of basic
copper sulfate and ferric hydroxide, to not starve the acid-demanding oxidative dissolution of nickel in the
second stage of the leach.
Ni3S2 + H2SO4 + 0.5O2 2NiS + NiSO4 + H2O
(13)
4NiS + H2SO4 + 0.5O2 Ni3S4 + NiSO4 + H2O
(14)
FeS + H2SO4 + 0.5O2 FeSO4 + S0 + H2O
(15)
The sequential non-oxidising and oxidising conditions result in the conversion of heazlewoodite
to millerite and then polydimite. Conditions are mildly oxidising so as to minimize the oxidation of copper
sulfides to diginite and anilite. Following depletion of heazlewoodite and millerite, or in parallel with the
leaching of millerite, some of the more reactive copper sulfides may also react, to produce diginite and
anilite, (Hofirek and Kerfoot, 1992; Hofirek and Nofal, 1995).
5Cu2S + H2SO4 + 0.5O2 Cu9S5 + CuSO4 + H2O
(16)
4Cu2S + H2SO4 + 0.5O2 Cu7S4 + CuSO4 + H2O
(17)
4Cu9S5 + H2SO4 + 0.5O2 5Cu7S4 + CuSO4 + H2O
(18)
110
100
90
80
70
60
50
40
30
20
10
20
18
16
14
12
10
8
6
4
2
0
0
50
100
150
Ni and H2SO4 Concentration (g/L)
Cu and Fe Concentration (g/L)
Figure 3 shows soluble metal and acid trends over the four hour leach period. Noticeable is the
continued dissolution of nickel and iron over both the non-oxidising and oxidising stages of the leach. Acid
consumption occurs during the dissolution of iron hydroxide and basic copper sulfate early in the leach as
well as during the oxidative leach. Also noticeable is the depletion of copper from solution during the nonoxidising portion of the leach.
200
Time (minutes)
Cu
Fe
Ni
Acid
Figure 3 - Copper, iron, nickel and acid profiles for nickel atmospheric leach solutions
450
Nickel Non-oxidising Leach

The non-oxidising pressure leach takes place at an elevated temperature and pressure under a nonoxidising nitrogen atmosphere. The objective of the leach is to further leach nickel and iron and to produce
a solid residue with sufficient sulfide sulfur to meet the leach requirement of the subsequent copper
pressure leach. Additionally sufficient acid must be produced in order to meet that required by the nickel
atmospheric leach.
Initially reactions involve a 1:1 exchange of nickel and iron with soluble copper resulting in the
dissolution of nickel and copper and the precipitation of copper as cupric sulfide. Reaction of the cupric
ions so produced results in the oxidation of sulfide sulfur to sulfate, generation of acid, and the
precipitation of copper as cuprous sulfide. As a consequence, as the non-oxidative leach proceeds, so the
Cu:Ni ratio progressively increases. Aggressive non-oxidising conditions such as high temperatures or
excessive residence times can result in the leaching of nickel to completion. This would lead to the
formation of excessive amounts of acid and the precipitation of large amounts of copper. It has been
determined that the leaching of nickel and precipitation of copper to achieve a Cu:Ni ratio of between 6:1
and 8:1 will ensure that the amount of acid produced in the non-oxidising leach can readily be
accommodated in the nickel atmospheric leach. Furthermore, the formation of non-oxidising leach residues
with a Cu:Ni ratio greater than 8:1 would require the addition of make-up acid to the copper pressure leach
as there would be little or no benefit of acid produced by the oxidative leaching of fletcherite and
polydimite.
Non Acid Producing Metathesis Reactions
Residue from the nickel atmospheric leach generally contains heazlewoodite, polydimite and
millerite. The direct 1:1 exchange reactions of heazlewoodite, polydimite and millerite are show.
Ni3S2 + 2CuSO4 Cu2S + NiS + 2NiSO4
(19)
NiS + CuSO4 CuS + NiSO4
(20)
FeS + CuSO4 CuS + FeSO4
(21)
As evidenced from our mineralogy studies, the major form of iron in the nickel atmospheric leach
residue is bornite. The dissolution of iron from bornite by metathesis with soluble copper is shown.
Cu5FeS4 + CuSO4 2Cu2S + 2CuS + FeSO4
(22)
The formation of fletcherite from polydimite is known. (Bryson, et al., 2008; Hofirek, et al.,
1992). It has also been postulated that fletcherite can be formed by metathesis with soluble copper, with the
dissolution of nickel and precipitation of copper in a 1:1 ratio, without the oxidation of sulfide sulfur.
Ni3S4 + CuSO4 CuNi2S4 + NiSO4
(23)
5NiS + 3CuSO4 Cu2S + CuNi2S4 + 3NiSO4
(24)
Acid Producing Metathesis Reactions

In the metathesis of soluble copper with heazlewoodite, millerite and polydimite, the copper can
also react as an oxidant of the sulfide sulfur, with the reduction of the cupric copper to cuprous. It has been
shown that millerite is most reactive whereas polydimite is least reactive.
5Ni3S2 + 18CuSO4 + 4H2O 9Cu2S + 15NiSO4 + 4H2SO4
(25)
451
6NiS + 9CuSO4 + 4H2O Cu9S5 + 6NiSO4 + 4H2SO4
(26)
8Ni3S4 + 45CuSO4 + 28H2O 5Cu9S5 + 24NiSO4 + 28H2SO4
(27)
The further reaction of fletcherite, with copper sulfate is given.

8CuNi2S4 + 37CuSO4 + 28H2O 5Cu9S5 + 16NiSO4 + 28H2SO4
(28)
Depending on the availability and reactivity of the remaining copper sulfides, copper sulfate may
react as an oxidant with copper sulfides such as covellite and anilite to produce diginite or chalcocite and
acid.
6CuS + 3CuSO4 + 4H2O Cu9S5 + 4H2SO4
(29)
5Cu7S4 + 3CuSO4 + 4H2O 19Cu2S + 4H2SO4
(30)
6Cu7S4 + 3CuSO4 + 4H2O 18Cu2S + Cu9S5 + 4H2SO4
(31)
Figure 4 shows the cementation of copper and further leaching of nickel and iron as well as a
steady increase in the available acid due to the acid producing metathesis reaction of soluble copper with
nickel and copper sulfides.
Copper Pressure Leach
The copper pressure leach takes place at elevated temperature and pressure under an oxidising
atmosphere. The objective of the leach is to extract the remaining nickel and copper from the non-oxidising
leach residue and to oxidize the sulfide sulfur to predominantly sulfate. The major sulfide minerals in the
copper pressure leach feed includes diginite, anilite, polydimite and/or fletcherite as well as residual
bornite.
80
Concentration (g/L)
70
60
50
40
30
20
10
0
0
50
100
150
200
Time (minutes)
Cu
Fe
Ni
Acid
Figure 4 - Copper, iron, nickel and acid profiles for nickel non-oxidising leach solutions
452
The initial stages of the oxidising leach involve the reaction of cuprous copper sulfides. As these
are acid deficient, the initial acid is supplied in the lixiviant.
Cu2S + H2SO4 + 0.5O2 CuS + CuSO4 + H2O
(32)
Cu9S5 + 4H2SO4 + 2O2 5CuS + 4CuSO4 + 4H2O
(33)
Cu7S4 + 3H2SO4 + 1.5O2 4CuS + 3CuSO4 + 3H2O
(34)
Cu5FeS4 + 2H2SO4 + O2 3CuS + FeS + 2CuSO4 + 2H2O
(35)
During the course of the leach, ferrous iron is oxidized to ferric and is subsequently reduced by
reaction with the remaining sulfides.
The acid demand is supplemented by that produced during the oxidative dissolution of fletcherite
and/or polydimite. Acid generated in this way is of fundamental importance in reducing the acid demand of
the copper pressure leach, and consequently so too is the production of a nickel non-oxidising leach residue
with a Cu:Ni ratio of between 6:1 and 8:1.
Ni3S4 + 7.5O2 + H2O 3NiSO4 + H2SO4
CuNi2S4 + 7.5O2 + H2O 2NiSO4 + CuSO4 + H2SO4
(36)
(37)
The next phase of the leach involves oxidation of sulfide sulfur to sulfate and dissolution of the
associated metals.
FeS + 2O2 FeSO4
(38)
NiS + 2O2 NiSO4
(39)
CuS + 2O2 CuSO4
(40)
The acid requirements for the reaction of the cuprous sulfides are met by direct addition of acid
and that formed by the reactions of polydimite and fletcherite. Excessive amounts of acid may lead to the
formation of elemental sulfur which is detrimental to the leach. The leach temperature used is tolerant of
acid concentrations of up to 60 g/L and rarely led to the formation of elemental sulfur. An acid deficiency
in the leach will not affect the conversion of cuprous sulfide to covellite, but will result in the precipitation
of basic copper sulfate
Figure 5 shows the major reaction taking place as the oxidative dissolution of copper.
Acid consumption is initially low with the decomposition of fletcherite supplementing the
demand, tailing off towards the end of the leach where the major contribution to dissolved copper is from
covellite.
453
80
16
70
14
60
12
50
10
40
30
20
10
0
0
50
100
150
Ni and Fe Concentration (g/L)
Cu and H2SO4 Concentration (g/L)
200
Time (minutes)
Cu
Acid
Fe
Ni
Figure 5 - Copper, iron, nickel and acid profiles for copper pressure leach solutions
Copper Polishing Leach
The polishing leach is effectively an extension of the copper pressure leach and serves to leach
any remaining copper and nickel bearing mineral phases present in the copper pressure leach residue to
completion. Notwithstanding the fact that the feed to the polishing leach should contain mainly copper as
covellite, the polishing leach has been shown to be capable of dealing with up to 30% elemental sulfur,
should it be present, as well as mineral phases such as bornite, idaite and fletcherite. The process will
produce a concentrate containing high value PGMs as well as residual copper and sulfur and a leachate
comprising mainly copper and sulfur.
Mineralogy
Regular samples from each of the main four successive leaching stages were examined
mineralogically by X-ray diffractometry, SEM-EDX analysis and MLA technology. The resultant
distribution of mineral phases during progressive leaching stages is depicted in Figure 6.
Basic copper sulfate refers to species such as copper sulfate hydroxide, examples being
Cu3(OH)4SO4, chalcanthite as well as copper bearing nickel sulfate hydrate, (Cu,Ni)5(SO4)2(OH)6.6H2O.
The term intermediate copper sulfides refers to specifically, but not necessarily exclusively, to
chalcocite, diginite and anilite. During the copper removal process, fletcherite and godlevskite are the
predominant nickel bearing mineral phases whilst copper is predominantly present as intermediate copper
sulfide (chalcocite) with basic copper sulfate becoming more evident as the leach progresses. During the
nickel atmospheric leach heazlewoodite and godlevskite are converted to millerite. Millerite is in turn
converted to fletcherite, specifically in the more oxidising potion of the leach. The basic copper sulfates are
rapidly dissolved in the early stage of the nickel atmospheric leach consuming acid generated in the nickel
non-oxidising leach. Bornite is not leached to any extent in both the copper removal and the nickel
atmospheric leach. It is however, leached to near completion in the nickel non-oxidising leach. During the
nickel non-oxidising leach nickel is leached further as millerite is leached to completion by conversion to
fletcherite. Copper is removed from solution by metathesis of soluble copper with covellite, millerite and
fletcherite/polydimite to produce the intermediate copper sulfides diginite and anilite, which are the
predominant phases present in the reside produced from the nickel non-oxidising leach. During the copper
pressure leach diginite and anilite are converted to covellite which continues to leach. The acid demand
from the conversion of diginite and anilite to covellite is somewhat mitigated by acid produced during the
454
leaching of the remaining fletcherite. The copper polishing leach serves to leach any mineral phase
remaining, ideally covellite, to extinction, producing a low mass PGM concentrate.
100
Copper
Removal
Modal Abundance (Mass %)
90
Nickel
Atmospheric
Nickel Non-Oxidising
Copper Pressure
Copper Polishing
80
70
60
50
40
30
20
10
0
0
200
400
600
800
1000
1200
1400
Time (minutes)
Intermediate CuS
Covellite
Fletcherite
Bornite
Heazlewoodite
Millerite
Godlevskite
Basic copper sulfate
Figure 6 Copper and nickel bearing mineral phases over the five leaching stages
CONCLUSION
The combination of the five leaching stages discussed lends itself to a robust and partially selfsustaining leaching process for the mineral composition discussed, producing a nickel-rich liquor at the
nickel atmospheric leach stage, and a copper-rich liquor copper in the pressure leach stage. Both of these
liquors are suitable for further processing for the recovery of both nickel and copper by electrowinning.
Overall extractions of nickel and copper are favourable up to 99% in both cases. Similarly, overall mass
loss from the matte was greater than 98%. Given the changing nature of the feed mineralogy, these results
compare well with those obtained previously by Sherrit. The introduction of a mass reducing polishing
leach produces a relatively high grade PGM residue.
The deportment of PGMs and impurity elements was generally favourable in all processes.
Selenium and tellurium has a tendency to dissolve, specifically during oxidative processes. These can
however be removed from the copper pressure and copper polishing liquors by subsequent downstream
reduction.
Although PGMs are generally not extracted during the polishing leach stage, additional test work
is envisaged in order to better understand the deportment of other minor elements.
455
REFERENCES
Bryson, L.J., Hofirek, Z., Collins, M.J., Stiksma, J. and Berezowsky, R.M. (2008). New Matte Leaching
Developments at Anglo Platinums Base Metal Refinery. In C.A. Young, P.R. Taylor, C.G.
Anderson and Y. Choi (Eds.), Sixth International Symposium on Hydrometallurgy (pp. 570
579). Phoenix, AZ.
Crundwell, F.K., Moats, M.S., Ramachandran, V., Robinson, T.G. and Davenport, W.G. (2011).
Separation of the Platinum-Group Metals from Base Metal Sulfides, and the Refining of Nickel,
Copper and Cobalt. In Extractive Metallurgy of Nickel, Cobalt and Platinum Group Metals (pp.
457-487). Elsevier.
Hofirek, Z. and Kerfoot, D.G.E. (1992). The Chemistry of the Nickel-Copper Matte Leach and its
Application to Process Control and Optimisation. Hydrometallurgy, 29, 357-381.
Hofirek, Z. and Nofal, P.J. (1995). Pressure Leach Capacity Expansion Using Oxygen-Enriched Air at
RBMR (Pty) Ltd. Hydrometallurgy, 39, 91-116. And references therein.
Hundermark, R.J., Mncwango, S.B., de Villiers, L.P.vS. and Nelson, L.R. (2011). The Smelting Operations
of Anglo Americans Platinum Business: An Update. In R.T. Jones & P. den Hoed (Eds),
Southern African Pyrometallurgy 2011 (pp. 295-307). Johannesburg, South Africa.
457
THE LONMIN PLATINUM BASE METAL REFINERY

OPERATIONS AND CONTINUAL IMPROVEMENTS 1985 TO 2012
*N. Steenekamp, M. Turner-Jones
Lonmin Platinum
South Africa
Private Box X508, Marikana, 0284, South Africa
(*Corresponding author: nico.steenekamp@lonmin.com)
ABSTRACT
The Lonmin Base Metal Refinery treats converter matte from the Lonmin Smelter to produce
nickel sulphate crystals, copper cathode as well as a concentrate containing the platinum group (PGM)
metals. The original process employed a Sherritt design and utilizes atmospheric and pressure leaches for
the dissolution of base metals. This paper describes the original flow sheet and the improvements made to
enhance PGM recoveries, product quality and to increase capacity. Changes include the introduction of
flash recycle cooling on the autoclave, batch leaches to improve the quality of the PGM concentrate and
the implementation of solid-liquid separation with centrifuges.

Niagara, ON, Canada
Edited by
458
INTRODUCTION
The Lonmin Base Metal Refinery (BMR) is about 100 km north-west of Johannesburg and treats
converter matte from the Lonmin Smelter to produce nickel sulphate crystals, copper cathode and a
concentrate containing the PGMs. The plant was commissioned in 1985 based on a Sherritt design to treat
12 tonnes converter matte per day. The original flow sheet consists of a milling circuit, an atmospheric
leach and a pressure leach to produce a PGM concentrate which is despatched by helicopter to the Lonmin
Platinum refinery in Brakpan, about 40 km east of Johannesburg. The liquor from the atmospheric leach is
treated by crystallization to produce a nickel sulphate hexa-hydrate crystal. The leach liquor from the
pressure leach is treated by a selenium removal step followed by electro-winning to produce copper
cathode. The spent solution from the copper electro-winning is recycled to both the atmospheric and
pressure leach steps to provide sulphuric acid for the leaching reactions.
Modifications were made to the original circuit to increase the plant capacity, to improve the
PGM recoveries and to improve the quality of the PGM concentrate. Capacity increases included all the
unit operations, new mill, new first stage, additional autoclaves, additional nickel sulphate crystallizers,
new copper electro-winning and new batch leach reactors for upgrading the PGM concentrate. The current
circuit is described in this paper and not the detailed history of each plant change.
The original pressure leaching step was modified to include flash cooling, and the implementation
of a continuous third stage leach step. This enabled better temperature control on the autoclave, without
sacrificing residence time.
Batch leaches were introduced on the third stage leach residue to improve the grade of the PGM
concentrate. A high pressure caustic leach to leach remaining selenium is followed by a formic acid leach
to remove oxidised iron and nickel species (magnetite and trevorite) from the PGM concentrate.
The solid/liquid separation after the second stage leach was originally by thickening, but has been
changed to a centrifuge, to reduce the PGM lock-up in the process. It also results in less entrained base
metals in the residue fraction and a cleaner third stage leach.
Internal investigations, sponsored research at universities and investigations with technology
suppliers with the objective to improve the understanding of the BMR process and ultimately to improve
the operational performance was undertaken. Results and outcomes of the investigations are described in
the paper.
PROCESS OVERVIEW
A simplified flow sheet of the BMR is shown in Figure 1. A description of the original (1985)
flow sheet and the developments of the process have been given by Brugman and Kerfoot (1986) and
improvements and modifications to the circuit until 1999 by Steenekamp and Dunn (1999).
Granulated converter matte (about 2 mm particles) is received from the smelter in 1.5 tonne bulk
bags and milled in a closed circuit ball mill. Typical converter matte analysis is shown in Table 1. After
thickening the slurry matte slurry is pumped to the first stage leach. The slurry from the first stage leach is
pumped to a thickener. The first stage leach solution (thickener overflow) is clarified by filtration and
pumped to a crystallizer to produce nickel sulphate hexahydrate crystals.
The first stage leach residue is treated by two further continuous pressure leach steps, the second and third
stage leaches where the remaining nickel in the residue and the copper is leached. The second stage leach
is fitted with a flash recycle cooling arrangement. The discharge slurry from the second stage leach is
thickened or centrifuged, the thickened slurry is repulped in water and fresh acid and pumped to the last
compartment of the autoclave for a third stage leach to remove more copper. The discharge slurry from the
third stage leach is filtered. The solids are further treated in batch leaches.
459
Figure 1 - The Base metal refinery flow sheet

The discharge solution from the autoclave
autoclave is pumped to a selenium removal section where it is
heated to 90 O C and mixed with aqueous sulphur dioxide solution before it iiss passed through a pipe
reactor,
reactor, where the selenium and tellurium in the solution are precipitated as copper selenide and te
telluride.
lluride.
The solution is filtered and pumped to the copper electro winning where copper is plated as cathodes. The
spent solution is recycled back to the first and second stage leaches where the sulphuric acid (and copper
sulphate in the first stage leach) is used for leaching.
460
Table 1 Typical Lonmin converter matte analysis

Element
Ni
Cu
Fe
S
Co
Total PGM
As
Se
Te
Pb
Composition
46 48%
26 30%
0.5 2.0%
19 22%
0.3 0.6%
0.4 0.7%
~300ppm
~400ppm
~100ppm
~200ppm
The solids from the third stage leach is treated in two batch leaching steps, first a high pressure
caustic leach to remove more selenium, and a formic acid atmospheric leach to remove spinel phase
(magnetite and trevorite) and any possible ferric precipitates. The concentrate after the formic acid leach is
filtered, vacuum dried and despatched to the Lonmin Precious Metals Refinery.
The original plant was designed for 12 tonne per day matte and produced a 30% PGM concentrate
grade. The plant was expanded and modified to allow for an increased matte throughput, as well as to
improve the quality of the PGM concentrate. The current nameplate capacity is 37 tonne per day matte
producing a 65% PGM concentrate.
MILLING CIRCUIT
The original milling circuit was designed for a 12 tonne per day throughput. A second milling
circuit was installed in 1991 with a capacity of 42 tonne per day. The larger milling circuit is currently in
use, with the smaller mill on standby. The milling circuits consist of standard rubber lined ball mills, with
closed circuit cyclones. The cyclone overflow slurry is thickened in a thickener, the thickener underflow is
the feed material to the first stage leach, and the overflow water is recycled to the mill. The mill product is
about 75% passing 75 m.
FIRST STAGE LEACH
The first stage leach consists of five agitated cascading atmospheric tanks in series. Copper spent
solution is added to the first tank, and provides the sulphuric acid and copper sulphate which are the
leaching reagents. Oxygen is sparged into the first three tanks. The slurry from the last tank is pumped to a
thickener. A portion of the thickener underflow is recycled back to the first leach tank. A nickel extraction
of about 70% is achieved. The thickener overflow solution is filtered through press filters followed by a
clarifier filter and pumped to the nickel sulphate crystallizer. A second leach train was installed in 1991 to
increase the plant capacity. The second train also consists of five tanks and a new thickener. The old first
stage leach reactors had an operating volume of 25 m3 in the five tanks; the second leach train has a total
operating volume of 70 m3.
Leaching reactions of matte under atmospheric conditions with sulphuric acid and copper solution
has often been described and discussed in detail in various reports and publications. Only the major
reactions will be described here. The reactions below are as described by Crundwell, Moats,
Ramachandran, Robinson and Davenport (2011). The major mineralogical phases in the matte are:
Alloy: Iron, Nickel and Copper

Nickel sulphide as Heazelwoodite: Ni3S2
Copper sulphide as Djurlite: Cu2S
461
The metals present as alloys in the matte leached very rapidly, in a manner similar to the
following reaction:
Ni (s) + H2SO4 (aq) + 0.5O2 (g) NiSO4 (aq) + H2O (l)
(1)
Nickel is leached by dissolution with sulphuric acid and oxygen and by metathesis with copper:
Ni3S2 (s) + H2SO4 (aq) + 0.5O2 (g) NiSO4 (aq) + 2NiS (s) + H2O (l)
(2)
Ni3S2 (s) + 2CuSO4 (aq) 2NiSO4 (aq) + Cu2S (s) + NiS (s)
(3)
The operation of the first stage leach requires a balance between a high leaching efficiency for
nickel and removing the copper from solution with the metathesis type reaction, such as equation 3.
The alloy leaching reactions (reaction 1) is the most rapid and proceeds to completion (of the
alloy phase). The acid leaching reaction (reaction 2) is faster than the metathesis reaction (reaction 3).
Reactions 2 and 3 both react with the heazelwoodite (Ni3S2). If the rate of reaction 2 is not controlled by
controlling the oxygen addition rate, there will be insufficient heazelwoodite to remove all the copper via
reaction 3.
Note that the above is a simplification and does not describe all the leaching reactions. There is
clear evidence of further leaching of the millerite (NiS) to form polydemite (Ni3S4).
In the pressure leaches to follow the atmospheric leach, some of the rhodium, ruthenium and
iridium (OPMs) dissolve with the base metals. These OPMs follow the copper solution and reports in the
spent solution to the first stage leach.
The OPMs in the spent solution are normally effectively removed from solution in the first stage
leach. The OPM removal reaction has been described as a hydrolysis reaction, but it is the authors view
that it is more likely to be a metathesis type reaction (as reaction 3). It is also an important objective in the
first stage leach to remove all the copper and the OPMs in the spent solution to prevent these metals
reporting to the crystallizer and being lost with the nickel sulphate crystals.
An internal team has investigated the first stage leach with the objective to reduce the copper and
OPM losses to the nickel sulphate stream. One idea was to change the first stage leach to a two-stage
counter-current operation of leaching and solution purification. As part of the investigation, Lonmin
sponsored a master study by Van Schalkwyk (2011) at Stellenbosch University. A model of the first stage
leach was developed using Cycad Process simulation software. The model was developed together with
Crundwell Management solutions. The first stage leach capacity and operation under different process
conditions were simulated using the model. Eventually no changes were made to the process, these studies
have resulted in an improved understanding of the first stage leach and a significant reduction of copper
and OPMs reporting to the nickel solution, achieving the original objective of the studies.
The practise of recycling a portion of the thickener underflow back to the first tank has often been
debated and discussed. This recycle resulted in a higher solid concentration in the first stage leach tanks,
resulting in a higher lock-up of PGMs in the process. Minimising the lock-up of PGMs is an important
operational objective, and therefore the recycling practise has been questioned. However, operational
practise has illustrated that without the recycle the nickel extraction on the leach is less, and the ability to
remove copper from the solution is reduced. The Cycad model of the process has assisted to explain this
operational experience.
462
PRESSURE LEACHING
The first stage leach residue is further treated in an autoclave in two continuous pressure leach
steps to remove the remainder of the nickel and the copper. A schematic and pictorial overview is provided
in Figure 2 and 3, respectively.
Flash
Slurry feed
Cu spent
PGM filtrate
Mixing
tank
Flash
Centrifuge
Acid
Water
Flash
Recycle
tank
Mixing
tank
PGM
filtration
Vent
Oxygen
2nd stage
3rd stage
Figure 2 The second and third stage pressure leaches

There are normally two (10m long by 2,2m diameter) autoclaves in use, with a third autoclave on
standby. The autoclaves are standard carbon steel, lead lined vessels with two courses of brick lining. The
normal operating pressure is 600 kPa, the temperature 130 to 145 O C and the sulphuric acid concentration
20 to 30 g/l.
The following leaching reactions are as described by Crundwell et al. (2011).
The remaining nickel in the residue is mainly in the form of millerite (NiS), which dissolves in the
autoclave as follows:
463
Figure 3 Autoclave
NiS (s) + 2O2 (g) NiSO4 (aq)
(4)
Copper in the residue is mainly in the form of Djurlite (Cu2S), which dissolves by the following
reactions:
2Cu2S (s) + 2H2SO4 (aq) + O2 (g) 2CuSO4 (aq) + 2CuS (s) + 2H2O (l)
CuS (s) + 2O2 (g) CuSO4 (aq)
(5)
(6)
The leaching reactions are exothermic. In the original circuit the cooling was done by quenching
with spent solution. While this achieved temperature control, it did increase the sulphuric acid
concentration and reduce the retention time.
Flash recycle cooling was implemented to make temperature control independent of the sulphuric
acid concentration and retention time. At the same time an additional continuous pressure leach was added
to the process. The original autoclave was divided into two discrete duties. The first and larger part consists
of a large first compartment with three agitators, followed by two smaller compartments. The final
compartment was modified to a polishing duty to increase the grade of the PGM concentrate. Fresh
sulphuric acid (not from recycle spent) and water is used as the leach solution in the third stage leach.
Oxygen is sparged into the last two compartments (the third stage leach compartment and the last
second stage leach compartment. Unused oxygen from the third stage leach flows through a vapour vent
opening from the third stage compartment to the second stage, and counter current through the second
stage to vent discharge in the first compartment. The oxygen is drawn from the vapour phase into the liquid
phase with aerofoil impellors.
The change to the flash recycle cooling and continuous third stage leach has previously described
in detail by Steenekamp and Dunn (1999).
464
The pressure leaching was investigated in a PhD study at the University of Stellenbosch by
Dorfling (2011). The improved understanding as a result of this study has assisted in a significant reduction
in dissolving of the OPMs. The original flash recycle circuit was designed to operate at 145 OC and 700
kPa. As a result of the study the operating temperature and pressure of the autoclave have been
successfully reduced without impacting the leach efficiencies but resulting in a significant drop in the
OPMs that dissolve in process.
CENTRIFUGE
When the autoclave was modified to the flash cooling with continuous third stage leach as
described above, the discharge slurry from the second stage leach (the first pressure leaching step) was
treated by thickening. The thickener underflow stream was repulped with sulphuric acid and water, and
pumped back to the third stage leach. The PGM grade of the second stage leach residue is already high
(above 20% PGM grade) and a small volume lock-up of material represents a large lock-up of PGMs. The
thickener was replaced with a centrifuge to reduce this lock-up of PGM rich material. A Flotweg decanter
centrifuge was selected for this duty and commissioned in 2010. The project was described in detail by
Snyders and Schwartz (2010).
The centrifuge had the additional advantage to produce entrain much less solution with the solids
than the thickener underflow material. This has resulted in an improved third stage operation and notable
improvement in the PGM concentrate quality.
After commissioning erosion problems of the centrifuge scroll were experienced. This was largely
overcome with application of a sacrificial layer of ceramic paste on the scroll surface. The continuous
operation of the centrifuge however remains a maintenance challenge.
HIGH PRESSURE CAUSTIC LEACH
Some of the selenium and tellurium present in the matte dissolves in the continuous pressure
leaches, but a large portion reports to the leach residue. To reduce the selenium and tellurium content of the
PGM concentrate further, a high pressure caustic leach step was implemented. The selenium and tellurium
is leached under higher temperature and pressure. The leaching reactions are thought to be as follows:
Cu2Se (s) + 2NaOH (aq) + 2.5O2 (g) 2CuO (s) + Na2SeO4 (aq) + H2O (l)
(7)
The tellurium reaction is similar.

The leach solution is dispatched to a toll refiner where any PGMs are recovered, the solution
inerted and disposed of safely.
UPGRADING OF THIRD STAGE RESIDUE: ACID WASH
When the copper concentration on the third stage residue was analysed and found to exceed
specification limits, a further batch oxidising pressure leach (a fourth stage leach) would be undertaken on
the third stage leach residue. After the implementation of the high pressure caustic leach it was discovered
that the remaining copper in the residue readily dissolves under atmospheric pressure using sulphuric acid
after the high pressure caustic leach. The practise of upgrading the third stage leach residue with a fourth
stage leach was therefore stopped and replaced with an acid wash after the high pressure caustic leach.
However, this is only required during plant upset conditions i.e. during start up or shut down conditions.
FORMIC ACID LEACH
The formic acid leach was introduced to remove oxidised iron and nickel species. The matte
contains spinel phases, magnetite (Fe3O4) and trevorite (NiFe2O4). These oxidised species do not leach in
465
the oxidising leach conditions, and formerly would report to the PGM concentrate. A reducing leach was
developed and implemented to remove these spinel phases. The acid concentration in the circuit is
normally too high for the precipitation of ferric precipitates (goethite or Jarosite) but if these do however
form under localised conditions, they are dissolved by the formic acid leach.
The leaching reactions:
Fe3O4 (s) + HCO2H (aq) + 3H2SO4 (aq) 3FeSO4 (aq) + 4H2O (l) + CO2 (g)
(8)
NiFe2O4 (s) + HCO2H (aq) + 3H2SO4 (aq) 2FeSO4 (aq) + NiSO4 (aq) + 4H2O (l) + CO2 (g) (9)
The leach solution from the formic acid leach is returned back to the autoclave feed make-up tank.
NICKEL SULPHATE CRYSTALLIZER
The first stage leach solution is treated in a nickel sulphate crystallizer plant where hexahydrate
nickel sulphate crystals are produced.
The original crystallizers were draft tube units where the solution evaporated and the crystals
formed in a single evaporator/crystallizer step. Additional crystallizer capacity was required and a new
crystallizer unit was erected and commissioned in 2008, as illustrated in Figure 4. The new unit consist of
separate evaporator and crystallizer units.
Figure 4 New NiSO4 crystallizer

In the evaporator unit the solution is concentrated by evaporation passing the solution through a
falling film evaporator where the bulk of the water is removed. The evaporated vapour is removed by a
mechanical vapour recompressing (MVR) fan. The compressed vapours are used to heat the solution in the
falling film evaporator.
466
The concentrated, hot solution is pumped to the crystallizer unit where more water is evaporated
and the solution is cooled to 50 OC which results in crystallization. The crystals are removed from the
crystal slurry by a centrifuge and then dried in a fluidised bed dryer.
The falling film and MVR fan arrangement is an efficient design an ideal for evaporating clean
solutions. The nickel sulphate contains some iron and ferric precipitates; these have proved to be
problematic in the evaporator circuit. To achieve the design capacity on the new crystallizer the iron will
have to be removed from the nickel sulphate solution, or the iron precipitate will have to be managed by
some other means e.g. regular cleaning and removal of precipitated solids from the evaporator unit. An
iron removal step on the nickel sulphate solution is currently being investigated.
SELENIUM REMOVAL
A large fraction of the selenium and tellurium in the converter matte is leached in the second and
third stage pressure leach and have to be removed from the solution before copper electro winning. The
solution from the second and third stage leaches is contacted with sulphurous acid to precipitate the
selenium and tellurium from solution. This is done in a pipe reactor at 90 OC, followed by an aging tank.
The following reactions are as described by Crundwell et al. The effect of the sulphurous acid is to reduce
the copper to the cuprous state, Cu+. This reaction, which occurs rapidly in the pipe reactor, is given as
follows:
2CuSO4 (aq) + H2SO3 (aq) + H2O (l) Cu2SO4 (aq) + 2H2SO4 (aq)
(10)
The cuprous ions Cu+ react with the Se4+ to produce copper selenide by the following reaction:
4Cu2SO4 (aq) + H2SeO3 (aq) + 2H2SO4 (aq) Cu2Se (s) + 6CuSO4 (aq) + 3H2O (l)
(11)
Some of the selenium may be present as Se6+, which reacts with the Cu+ ions by the following
reaction:
5Cu2SO4 (aq) + H2SeO4 (aq) + 3H2SO4 (aq) Cu2Se (s) + 8CuSO4 (aq) + 4H2O (l)
(12)
The precipitation of tellurium is by similar reactions.

After precipitation the precipitate is filtered off and the solution is pumped to copper electro
winning.
Some of the OPMs in solution co-precipitates with the selenium precipitate. The precipitate has to
be treated to separate the value metals from selenium and tellurium. The copper selenide and telluride
residue is repulped in a sodium hydroxide liquor and leached at 50 kPa at 85 OC in an oxygen atmosphere.
The reactions:
Cu2Se (s) + 2NaOH (l) + 2O2 (g) + H2O (l) Na2SeO3 (l) + 2Cu(OH)2 (s)
(13)
Cu2Te (s) + 2NaOH (l) + 2O2 (g) + H2O (l) Na2TeO3 (l) + 2Cu(OH)2 (s)
(14)
The solution is filtered and dispatched to a toll refiner where the residual PGMs and copper are
recovered; the solution is inerted and disposed of safely. The recovered solids, containing the value metals
(PGMs and copper) are recycled back to the third stage leach.
COPPER ELECTRO WINNING
After the selenium removal step the solution is pumped to the electro winning tankhouse where
the copper is removed from the circuit as copper cathode. Copper is plated on stainless steel cathodes.
467
Sulphuric acid is produced at the anodes which are made of cast lead. The overflow spent solution from the
tank-house contains copper sulphate, sulphuric acid as well as nickel sulphate. The spent solution is
recycled to both the first and second stage leaches to provide the sulphuric acid and copper sulphate
required for the leaching reactions.
CONCLUSION
The Lonmin Base Metal Refinery has proved to be a reliable operation to produce a high quality
PGM concentrate product and saleable nickel sulphate crystals and copper products. Process investigations,
both internal and in partnerships with universities and technology suppliers have resulted in a better
process understanding, demystifying the complexities of the chemistry and increasing the versatility to
fluctuations in the feed from the Smelter.
Successful modifications to the process have been made over the past 27 years of operations with
regard to installation of new equipment, modifications to the existing installed equipment and improved
operating practice. These changes have resulted in an increased plant capacity and significant
improvements in product quality and metal recoveries across the Base Metals Refinery complex. Figure 5
shows a trend of the final PGM concentrate grade since the plant was commissioned.
80%
70%
60%
50%
Caustic Leach
40%
30%
Formic Leach
20%
10%
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
2011
2012
0%
Year
Figure 5 - PGM concentrate grade
AKNOWLEDGEMENTS
The authors wish to thank the management of Lonmin for the permission to publish this paper.
The contributions of the BMR personnel, specifically Viljoen van der Merwe, Eddie Rankou and Manja
Horne, for testing and implementing the process improvements are appreciated. Assistance, advice and
encouragement from colleagues in writing the paper, specifically Rian Bezuidenhout, are acknowledged.
468
REFERENCES
Brugman, C.F. and Kerfoot, D.G. (1986). Treatment of nickel-copper matte at Western Platinum by the
Sherritt acid leach process. Proceedings of Nickel Metallurgy, Volume 1. Canadian Institute of
Mining and Metallurgy, pp. 512-531.
Crundwell, F.K., Moats, M.S., Ramachandran, V., Robinson, T.G., & Davenport, W.G. (2011). Extractive
metallurgy of the platinum-group metals. In, Extractive Metallurgy of Nickel, Cobalt and
Platinum-group Metals, pp. 457-458. Great Britain: Elsevier.
Dorfling, C., Akdogan, G., Bradshaw, S.M., & Eksteen, J.J. (2011). Determination of the relative leaching
kinetics of Cu, Rh, Ru and Ir during the sulphuric acid pressure leaching of residue derived from
Ni-C converter matte enriched in platinum group metals. Minerals Engineering, 24, pp. 583-589.
Snyders, C.A., Eksteen, J.J., & Scharwtz, N. (2010). Implementation of decanter centrifuge technology in
the recovery of high grade platinum group metals concentrates. Proceedings of Precious Metals
2010, Falmouth, United Kingdom, Mineral Engineering International (June 15-16, 2010).
Steenekamp, N., G. Dunn, G. (1999). Operations of and improvements to the Lonrho platinum base metal
refinery. Proceedings of the 1999 EPD Congress, The Minerals, Metals & Materials Society
(TMS), pp. 365-378.
Van Schalkwyk, R.F. (2011). Leaching of Ni-Cu-Fe-S Peirce Smith converter matte: Effects of the Feendpoint and leaching conditions on kinetics and mineralogy. (Masters thesis). Retrieved from
Stellenbosch University library.
469
Author Index
Alfantazi, A. .......................................................... 269
Anderko, A. ........................................................... 105
Antonio, M. ............................................................... 3
Asselin, E. ............................................... 31, 241, 269
Azimi, G. ............................................................... 105
Barr, G................................................................... 427
Barrette, E. ............................................................ 367
Becze, L. ............................................................... 143
Blais, D.................................................................... 15
Brooks, K. ............................................................. 327
Brown, J.A. ........................................................... 427
Bruce, R. ............................................................... 281
Buhan, K. .................................................................. 3
Carlos, M. .............................................................. 105
Choi, Y. ................................................................... 41
Collins, M.J. .............................................................. 3
Craig, D.C. ............................................................ 443
Crundwell, F.......................................................... 391
Dani, A. ................................................................... 53
Demopoulos, G.P. ........................................... 15, 281
Dinham, P.............................................................. 443
Dixon, D.G. ........................................................... 229
Donohue, I. ............................................................ 367
Dowling, S. ........................................................... 443
Dreisinger, D.B. ............................................ 121, 229
Evans, G. ............................................................... 143
Faris, M. .................................................................... 3
Ferron, C.J. ............................................................ 143
Fleming, C.A. ........................................................ 427
Fuentes, G. ............................................................ 257
Gorst, J.A. ............................................................. 413
Guerra, E. .............................................................. 137
Guerrero G., P. ........................................................ 63
Guo, F. .................................................................. 187
Habashi, F. ............................................................ 295
Haneman, B. .......................................................... 413
Heidel, A. .............................................................. 281
Helberg, R.G. ........................................................ 313
Hosken, T. ............................................................. 211
Jackson, M. ........................................................... 211
Jiang, J..................................................................... 41
Jonas, R.K.............................................................. 379

Jung, J. ..................................................................... 91
Keller, W. ................................................................ 91
Klein, B.................................................................. 121
Kong, L. ................................................................. 153
Latva-Kokko, M.J. ................................................. 335
Li, J. ............................................................... 121, 211
Li, L. ...................................................................... 153
Li, Q....................................................................... 163
Li, Y....................................................................... 163
Li, Y.J. ................................................................... 153
Liu, J. ..................................................................... 269
Liu, Z. .................................................................... 163
Liu, Z. ............................................................ 163, 163
Martin, P. ............................................................... 401
Masters, I. .................................................................. 3
Mayhew, K. ........................................................... 281
McCulloch, N. ....................................................... 443
McDonald, R. ........................................................ 211
Mihaylov, I. ........................................................... 199
Moldoveanu, G. ..................................................... 105
Nazari, G................................................................ 229
Papangelakis, V.G. .................................. 53, 105, 153
Paraga T., J.R........................................................... 63
Parisien-La Salle, J.-C. ............................................ 15
Pearson, M. ............................................................ 367
Peek, E. .................................................................. 143
Quiroz C., L.S. ......................................................... 63
Reading, K. ............................................................ 143
Rebelo, S.M. .......................................................... 313
Riihimki, T.J. ....................................................... 335
Robinson, D. .......................................................... 211
Rodriguez, M. ........................................................ 211
Salomon-de-Friedberg, H. ....................................... 31
Sauve, P. .................................................................. 31
Shairp, S. ............................................................... 305
Singhal, A. ............................................................. 199
Slabbert, W. ........................................................... 413
Steenekamp, N. .............................................. 391, 457
Steyl, J.D.T. ............................................................. 75
Summerton, G.C. ................................................... 443
470
Tong, L. ................................................................. 121

Turner-Jones, M. ................................................... 457
Valenzuela G., J.L. .................................................. 63
Valenzuela G., P.J. .................................................. 63
Van Weert, G. ......................................................... 41
Vials, J................................................................. 257
Wang, C. ....................................................... 175, 187
Wang, O. ................................................................. 41
White, D.T............................................................. 343
Wrana, D. .............................................................. 199
Wu, C. ................................................................... 163
Xu, C. .................................................................... 153

Xu, Z. ..................................................................... 175
Xue, T. ................................................................... 199
Yue, G.K................................................................ 241
Zhang, Y. ............................................................... 175
Zu, Z. ..................................................................... 187
Zucht, A. .................................................................. 91

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Hydrothermal Production of Gallium Oxide ............................................................................................... 143

DESIGN OF THE AGA BRASIL REFRACTORY GOLD PRESSURE OXIDATION PLANT

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Figure 1 Process flow diagram for treatment of Crrego do Stio concentrate

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Improved gold extraction with POX treatment at 230C compared to 220C;

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Au3+ + 3e- Au(s) e = 1.498 V

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