Ubc - 1991 - A7 G73 PDF

OXIDATIVE PRESSURE LEACHING
OF CHALCOCITE IN SULPHURIC ACID

by
Ishwinder Singh Grewal
B.A.Sc, The University of British Columbia, 1989
A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF
THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF APPLIED SCIENCE
in
THE FACULTY OF GRADUATE STUDIES
Department of Metals and Materials Engineering
We accept this thesis as conforming
to the required standard
THE UNIVERSITY OF BRITISH COLUMBIA
October 1991
Ishwinder Singh Grewal, 1991
In presenting this thesis in partial fulfilment of the requirements for an advanced
degree at the University of British Columbia, I agree that the Library shall make it
freely available for reference and study. I further agree that permission for extensive
copying of this thesis for scholarly purposes may be granted by the head of my
department or by his or her representatives. It is understood that copying or
publication of this thesis for financial gain shall not be allowed without my written
permission.
Department of (V\gjbn\< \ - Mc\ e*. qU Bvqcê^nWj
The University of British Columbia
Vancouver, Canada
Date O C T - M
DE-6 (2/88)
ABSTRACT
At INCO's Copper Cliff Copper Refinery, a copper sulphide residue containing precious
metals is subjected to a pressure leach at 115C Copper occurs predominantly as G12S and
Cu
: %
S. The leach produces a slurry of copper sulphate solution and basic copper sulphate and
precious metals solids. The basic copper sulphate is dissolved in spent acid from the
electrowinning tankhouse leaving a precious metals residue for further processing. The leach
periodically develops a problem referred to as a "slow cook" where leaching times are greatly
extended and/or incomplete leaching of copper is encountered.
Based on earlier work, chalcocite leaching was proposed to occur sequentially via the
following reactions:
1. Cw,S + //
2
S0
4
+10
2
- CuS + CuS<9
4
+ H
2
0
2. CUTS + CuSO
A
+^0
2
+H
2
0 ->CuS + Cu{OH\ CuSO
A
3. Cw
1
S+^0
2
+H
2
0 -*^CuS+^(2Cu(OH)
2
'CuSOt)
4. CuS + 20
2
-+CuSOt
5. CuS+H^ + ^-^CuSO^+H^ +S
The exact reaction path is determined by the initial solution conditions (copper sulphate
and sulphuric acid concentrations). Under normal batch makeup conditions, all of the CU2S is
oxidized to cupric ions and sulphate via reactions 1,2 and 4. If the solution becomes depleted in
copper and acid, reaction 3 could occur. Elemental sulphur can be produced via reaction 5.
Experimental studies showed that the reactions were nearly sequential. Reactions 1 and 2
were found to be very fast relative to the rate of reaction 4. No slow cook conditions were
observed in the laboratory under normal leaching conditions. There is evidence suggesting that
-ii-
the slow cooks are caused by oxygen mass transfer limitations under conditions where the
slurry becomes highly viscous and pseudoplastic due to formation of finely divided basic
copper sulphate.
-iii-
Table of Contents
ABSTRACT ii
Table of Tables vi
Table of Figures vii
Acknowledgements xi
CHAPTER 1 - Introduction 1
CHAPTER 2 - Background and Literature Review 4
2.1 Overview of the INCO-CRED Process 4
2.1.1 Background of the Second Stage Leach 7
2.1.2 The Second Stage Leach 10
2.2 The UBC Screening Model 12
2.3 Scope of the Study 21
2.4 Literature Review 22
2.4.1 Copper Sulphides - Chalcocite to Covellite 22
2.4.2 Leaching of Chalcocite and Covellite 23
2.4.3 Electrochemical Studies 30
2.4.4 E
h
- pH Relationships and Phase Systems 33
2.4.5 Gas-Liquid Mass Transfer in Oxidative Leaching 38
2.5 Summary 41
CHAPTER 3 - Experimental Methods 43
3.1 Part A: Study of the sequential nature of the reactions 44
3.1.1 Batch make-up chemistry 44
3.1.2 Experimental procedure 45
3.1.3 Additional experiments in Part A 46
3.2 Part B: Kinetic Experiments 47
3.3 Part C: Leaching CuS in the presence of basic copper sulphate 48
-iv-
CHAPTER 4 - Results and Discussion 50
4.1 Part A: Study of the sequential nature of the reactions 50
4.1.1 The behavior of copper dissolution 50
4.1.2 Iron and Arsenic 58
4.1.3 Nickel and Cobalt 61
4.1.4 Additional Observations of Part A Experiments 63
4.2 Part B: Kinetic Experiments 63
4.3 Part C: Leaching CuS in the presence of basic copper sulphate 66
4.3.1 Discussion of ORP Measurements 71
4.4 Comparison of Leaching Rates - Part A and Part C 72
4.5 Additional Observations 73
CHAPTER 5 - Conclusions and Recommendations 76
5.1 Conclusions 76
5.2 Recommendations for further work 77
REFERENCES 79
APPENDIX A - Detailed Flowsheet of the CRED Plant 82
APPENDIX B - Planned Experiments for Part B-1 83
APPENDIX C - Assay results of Part A experiments 84
APPENDIX D - Part B experimental results 90
APPENDIX E - Part C experimental results 101
APPENDIX F - Part C experimental results - Effect of iron plots 107
-v-
Table of Tables
Table 2.1 Typical Assay of IPC Residue 4
Table 3.1 Assay of First Stage Residue used in Part A Experiments 44
Table 3.2 List of part C experiments performed 49
Table 4.1 X-Ray Diffraction Results 54
Table 4.2 Degree of sulphur oxidation 65
Table 4.3 Time taken to leach to 10,15 and 20% oxygen consumption 66
Table 4.4 Potential and pH measurements of the leach slurry after leaching and the
approximate temperatures at which they were measured 69
Table 4.5 Comaparison of oxygen flow rates 73
Table Bl. List of the planned experiments for part B 83
Table Cl . Amount of the indicated species in the leach solution at various oxygen
consumption levels '. 84
Table C2. Amount of the indicated species in the releach solution at various oxygen
consumption levels : 85
Table C3. Amount of the indicated species in the releach cake at various oxygen
consumption levels 86
Table C4. Total amount of species (calculated as a sum of tables C1-C3) in the process
87
Table C5. Distribution of species of experiments performed with the "copper
depleted cake" 88
Table C6. The pH and ORP values of the slurry after leaching to a given level of
oxygen consumption 89
-vi-
Table of Figures
Figure 1.1 Classification of leaching methods 2
Figure 2.1 General processing route of the IPC residue at the INCO-CRED plant in
Copper Cliff 6
Figure 2.2 Second Stage Leaching Circuit at INCO's - Copper Cliff Copper Refinery... 10
Figure 2.3 Approximate shape and dimensions of the Second Stage Autoclaves 11
Figure 2.4 Distribution of species as predicted by model for case (i) conditions 16
Figure 2.5 Oxygen flow rates as predicted by model for case (i) conditions 16
Figure 2.6 Distribution of species as predicted by model for case (ii) conditions 18
Figure 2.7 Oxygen flow rate as predicted by model for case (ii) conditions 18
Figure 2.8 Distribution of species as predicted by model for case (iii) conditions 19
Figure 2.9 Oxygen flow rate as predicted by model for case (iii) conditions 19
Figure 2.10 Distribution of species as predicted by model for case (iv) conditions 20
Figure 2.11 Oxygen flow rate as predicted by model for case (iv) conditions 20
Figure 2.12 Crystal structures of copper sulphide minerals relevant to this study 22
Figure 2.13 Leaching morphology for a chalcocite particle (a)0-20% copper extraction
03)20-50% copper extraction (c) 50-100% copper extraction 26
Figure 2.14 Evans diagram of applicable polarization curves during oxygen pressure
leaching of chalcocite 27
Figure 2.15a-b Potential-pH diagram for the Cu-S-H
2
0 system 34
Figure 2.16a-b Thermal precipitation diagrams for the CUSO4- H2SO4- H2O system ....... 35
Figure 2.17 Thermal precipitation diagram for the CUSO4- H2SO4- H2O system at 100C
for 3cu2+
= a
S04 2- 36
Figure 2.18a-b Phase diagrams of the Cu-S system. The blaubleinder covelUte is
abbreviated as "be" 37
Figure 2.19 Models for oxygen adsorption during oxidative leaching 40
Figure 3.1 Schematic of the experimental setup 43
Figure 4.1 The distribution of copper during leaching of chalcocite 52
Figure 4.2 Similar to Figure 4.1 - no copper in solids shown to magnify scale 52
Figure 4.3 Comparison of the model results to the actual behavior 53
-vii-
Figure 4.4 "Reaction" temperature versus pH^ change during precipitation from 1 M
CuS0
4
solution. The "equihbrium" boundary for 1 M solution is also shown 56
Figure 4.5 Comparison of sulphur levels in the leach residue between the model and
actual results 57
Figure 4.6 Distribution of iron during leaching. 59
Figure 4.7 SEM photomicrographps - Effect of iron on agglomerate size of the
precipitate 60
Figure 4.8 Distribution of arsenic during leaching 61
Figure 4.9 Distribution of nickel during leaching 62
Figure 4.10 Distribution of cobalt during leaching 62
Figure 4.11 Oxygen consumption rate at various initial copper concentrations with
[Fe]=0.25 g/L. Each curve represents a different level of oxygen consumption
.- 67
Figure 4.12 Oxygen consumption rate at various copper concentrations with [Fe]=0
g/L. Each curve represents a different level of oxygen consumption 68
Figure 4.13 The effect of initial copper concentration on the measured ORP at [Fe]=0
and [Fe]=0.25 g/L 70
Figure 4.14 Evans diagram of applicable polarization curves during pressure
leaching of CuS (schematic) 70
Figure 4.15 A schematic highlighting areas believed to be well mixed in the second
stage autoclave. The poorly mixed zones are thought to be the result of the
observed pseudoplastic behavior of the slurry 75
Figure Al . Detailed flowsheet of the CRED Plant 82
Figure DI. Rate of oxygen consumption for the condition where (x
2
,x
3
,x
4
)=(l,l,0) and
x
t
=0 91
Figure D2. Rate of oxygen consumption for the condition where (x
2
,x
3
,x
4
)=(l,0,l) and
x,=0 91
2
,X3
/
x
4
)=(l
/
-l
/
0) and
x,=0 92
2
,x
3/
x
4
)=(l/0,-l) and
x,=0 92
2/
X3/X
4
)=(0,l,-l) and
x
1=
0 93
2
,x
3/
x
4
)=(0,0,0) and
x
1=
0 93
-viii-
2/
x
3/
X4)=(0,l
/
l) and
x,=0 94
2/
x
3
,X4)=(0
/
-l
/
l) and
x
1=
0 94
2
,x
3
,x
4
)=(0,-l,-l)
andxÔ 95
2/
x
3/
X4)=(0,0,0)
andx,=0 95
Figure DTI. Rate of oxygen consumption for the condition where
( x ^x ^M- l ALO) 96
Figure D12. Rate of oxygen consumption for the condition where
(x
1
,x
2
,x
3/
x
4
)=(-l,0,-l,0) 96
(x
1/
x
2/
x
3
^
4
)=(-l,0J3
/
-l) 97
( x^x^M- l AO, ! ) 97
2/
x
3/
x
4
)=(-l,0,l)
and x
:
=0 98
2
,x
3
,x
4
)=(-l
/
0,-l)
andx,=0 98
2
,x
3/
X4)=(-l,l,0)
and x
1=
0 99
2
,x
3/
x
4
)=(-l,-l,0)
andx
1=
0 99
(x
:/
x
2
,x
3/
X4)=(-l,-l,0,0) 100
Figure El . Rate of oxygen consumption where initial [Cu]=0 g/L and [Fe]=0.25 g/L
102
Figure E2. Rate of oxygen consumption where initial [Cu]=80 g/L and [Fe]=0.25 g/L
102
Figure.E3. Rate of oxygen consumption where initial [Cu]=10 g/L and [Fe]=0.25 g/L
> 103
Figure E4. Rate of oxygen consumption where initial [Cu]=40 g/L and [Fe]=0.25 g/L
103
- i x -
Figure E5. Rate of oxygen consumption where initial [Cu]=l g/L and [Fe]=0.25 g/L
104
Figure E6. Rate of oxygen consumption where initial [Cu]=0 g/L and [Fe]=0 g/L 104
Figure E10. Rate of oxygen consumption where initial [Cu]=l g/L and [Fe]=0 g/L 106
Figure Fl . Rate of oxygen consumption for various initial copper concentrations at
the 10% oxygen consumption point 108
Figure F2. Rate of oxygen consumption for various initial copper concentrations at
the 70% oxygen consumption point Il l
the 80% oxygen consumption point Il l
-x-
ACKNOWLEDGEMENTS
I would like to thank Dr. David Dreisinger for his constant encouragement and support
and Dr. Ernest Peters for his thought provoking discussions and ideas throughout the course of
this project.
I wish to thank INCO; without their financial support and faculties, this project would not
have been possible. Thanks are also extended to all of the people associated with INCO who
helped in various ways in the completion of the experimental work.
I wish to thank my mother who has always encouraged me to press on and has shown me
the value of perseverance. I also wish to thank my wife for believing in me more than I believed
in myself throughout this endeavor.
And a final thanks is extended to the Cy and Emerald Keyes Foundation for their financial
support.
-xi-
CHAPTER 1 -Introduction
Copper is one of the less abundant base metals found in the earth's crust occurring at
levels of approximately 7 ppm (compared to aluminum and iron at approximately 80 000 and 60
000 ppm respectively) [1]. Approximately 90% of the world's supply of copper occurs as
sulphidic ores. Pyrometallurgical techniques have historically been the dominant processing
method. However, pollution problems associated with sulphur dioxide emissions from
pyrometallurgical operations has resulted in a considerable research effort in
hydrometallurgical processing of copper and other sulphide ores.
Some of the main advantages that hydrometallurgical processes offer are that:
1. Hydrometallurgy allows the processing of complex ores with multiple recoverable metals.
By controlling solution conditions, it is possible to recover various metals in separate unit
operations. These metals can be sold for additional revenues.
2. Hydrometallurgical operations are performed at lower temperatures and generally use less
energy compared to the high temperatures often employed in pyrometallurgical
operations. This is especially true for low grade ores.
3. Hydrometallurgy has often been found to be more economically viable in the treatment of
low grade ores especially if the crushing and grinding steps can be minimized as in
percolation leaching methods.
4. Hydrometallurgical operations produce little or no air pollution. The liquid waste
generated at hydrometallurgical plants is often easier to contain and treat than effluent
gases.
5. Solutions and slurries in hydrometallurgical plants are easily transported by pipeline
systems as opposed to moving of molten slags and mattes between furnaces using heavy
refractory ladles in pyrometallurgical processes.
-1-
Successful hydrometallurgical processes for copper extraction from sulphide concentrates
have been proposed and designed but they have not been able to compete commercially with
pyrometallurgical processes. Although hydrometallurgical processes have demonstrated many
advantages as listed above, they are not a panacea for extractive metallurgy. But
hydrometallurgy does have an important role to play in the treatment of specific ores such as
low-grade ores, complex mineral ores and secondary materials produced from other
pyrometallurgical and hydrometallurgical operations.
The most common hydrometallurgical step is the leaching process which serves to free the
desired constituents from the gangue material via dissolution. In general, leaching methods can
be classified into percolation leaching and agitated leaching (see Figure 1.1). The method used
depends upon the nature of the ore and the mineral deposit.
f
In-situ
Leaching
Percolation Leaching
t
Heap or
Dump
Leaching
Leaching Method
t
Vat
Leaching
Agitated Leaching
Thin Layer
Leaching
Slime (Pulp)
Leaching
Pressure
Leaching
t
Baking
Process
Figure 1.1 Classification of leaching methods [2].
-2-
The leaching reagents used must dissolve the ore minerals as rapidly as possible and be
substantially inert towards the gangue minerals. Extensive reaction with the gangue minerals
causes excessive reagent consumption and causes the solution to become fouled with
impurities. The reagent must also be readily available and as inexpensive as possible.
Leaching in the presence of sulphuric acid is one of the most common methods in leaching
copper sulphides. Sulphides are insoluble in dilute sulphuric acids but can be solubilized if
oxidizing species are present in solution. These oxidizing agents include oxygen, sulphate and
chloride salts of iron and copper and aqueous chlorine (ie. hypochlorous acid and hypochlorite).
Acids, present as concentrated solutions, are sometimes also powerful oxidizing agents.
Increasing temperature and oxygen pressures have been found to contribute significantly to the
rate of copper extraction.
One process for the leaching of copper from a sulphide residue is the CRED
1
Second Stage
Leach at INCO's Copper Cliff Copper Refinery. The second stage leach processes secondary
material, mostly CujS, generated from a preceding metathetic leach. The objective of this thesis
is to investigate the poor leaching behavior that has occasionally been encountered in this
process. The problem of slow copper leaching kinetics has existed for approximately 15 years
occasionally becoming severe enough to warrant investigation. The research work contained in
this thesis was designed following some initial mathematical modelling work done by
Dreisinger and Peters [3] at U.B.C. which pointed to a possible metallurgical explanation for the
poor leaching behavior.
This thesis is organized in the following way. Chapter 2 contains a brief literature survey
on the leaching behavior of copper sulphides. Chapter 2 also contains the investigations done
in the past by INCO and the model developed at U.B.C. Chapter 3 covers the experimental
methods and chapter 4 contains the results and discussions. In chapter 5, some conclusions and
recommendations are offered.
1 CRED - Copper Refinery Electrowinning Department
-3-
CHAPTER 2 - Background and Literature Review
2.1 Overview of the INCO-CRED Process
INCCs Copper Cliff Nickel Refinery extracts nickel via the INCO Pressure Carbonyl
(IPC) process. This process produces a residue that contains mostly copper along with the other
constituents shown in Table 2.1. Approximately 50 tons of this residue are processed daily in a
hydrometallurgical plant (CRED-Copper Refinery Electrowinning Department) at the Copper
Cliff Copper Refinery. The purpose of the CRED plant is to separate the various constituents of
the IPC residue through a number of hydrometallurgical operations (see Figure 2.1) [4]. The
process steps include pressure leaching, cementation, precipitation, thickening, filtration and
electrowinning. A detailed process flowchart is provided in Appendix A.
Table 2.1 Typical Assay of IPC Residue [4].
Weight Percent Oz/Ton
Cu Ni Co Fe S Se Te PGM + Au
Ag
55-60 6-10 4-8 4-9 13-19 0.06-0.10 0.06-0.10 20-30 25-45
The IPC residue is first treated via a metathetic pressure leach in sulphuric acid (100-200
g/L) and copper sulphate (40-90 g/L) solution at 150C. This batch process, referred to as First
Stage Leaching, is used to dissolve nickel, cobalt and iron and separate these metals from
copper, selenium, tellurium and precious metals which remain in the solid phase. The overall
reactions taking place in the leaching process are:
MeO(s) + H
2
SO
A
= MeS0
4
+H
2
0
Me(s) + CuSOt = MeSO
A
+ Cu(s)
-4-
MeS(s) + CuSO
A
= MeSO
A
+ CuS(s)
where Me =Ni,Co,Fe
Approximately 95-98% of the base metals, other than copper, are leached out of the solids
in this step. The copper entering the first stage leach is present predominantly in the form of
CujS (chalcocite) and passes through to the second stage leach unmodified. The first stage leach
slurry is filtered. The filtrate is put through a copper clean-up circuit to remove some copper
which still remains in solution after the leach. The first stage leach residue is treated in a total
oxidative pressure leach at 115C. This step is referred to as Second Stage Leaching.
The first stage cake obtained from the filtration step is combined with water and spent
electrolyte from the plant to produce a slurry of approximately 30% solids. This slurry is
charged into the second stage autoclaves. The chalcocite is batch-leached to form a slurry of
neutral copper sulphate (CuS0
4
) solution (pH of -2.5-3.0) and basic copper sulphate
(CuS0
4
-2Cu(OH)
2
) solids. The slurry is then mixed with spent electrolyte to dissolve the basic
copper sulphate to leave a residue containing precious metals and lead sulphate. Selenium,
tellurium and most of the base metals are also solubilized during the leaching process. The
unleached solids are filtered out for processing at another INCO plant to recover the precious
metals. The solution is treated for selenium-tellurium removal and then pumped to the
tankhouse for copper recovery via electrowinning.
Selenium and tellurium removal is essential because these impurities tend to co-deposit
with the copper during electrowinning and contaminate the cathodes. The removal of Se and
Te is achieved by heating the solution to 95 C and passing it through a column filled with
copper shot. This promotes the formation of selenide and telluride precipitates that form as fine
black particulates. The solution and solids are passed through four aging towers in series in
which the solids settle out. The Se and Te concentrations are reduced to less than 1 mg/1 in
solution. The overflow from the aging towers is passed through polishing filters and sent to the
electrowinning circuit.
-5-
PM Residue
Spent Electrolyte
Sulphuric Acid
Oxygen . .
Second Stage
Pressure
Leaching
First
Stage
Cake
IPC Residue
from INCO
Pressure Carbonyl
Process ^
First Stage
Pressure
Leaching
Spent
Electrolyte
First
Stage
Filtrate
NaSH '
Filter Aid
Copper
Clean-up
CuS to Second
Stage Pressure
Leaching
Se, Te Residue
Filtrate
Selenium,
Tellurium
Removal
CuShot
Filter Aid
Steam
Sulphuric Acid
Steam
Oxygen
Lime
Filter Aid
Filtrate
Iron/Arsenic
Removal
Iron hydroxide-
Gypsum Solids
to Effluent
Filtrate
Copper
Electrowinning
Titanium Blanks
Lead Anodes
Reagents
Water/Steam
Soda Ash
Steam
Filtrate
Nickel-
Cobalt
Recovery
Copper
Cathodes
Spent
Electrolyte
Nickel/Cobalt
* Carbonate
Vacuum
Bosh Pond
Figure 2.1 General processing route of the IPC residue at the INCO-CRED plant in Copper
Cliff
The filtrate from the first stage leach is processed through a copper clean-up circuit to
remove any copper which exists in solution in the form of copper sulphate. The removal is
necessary to prevent copper losses to the effluent during the iron/arsenic removal step and to
prevent copper contamination of the nickel/cobalt carbonate. The copper is removed by the
addition of a 30% NaHS solution at 70 C. Most of the copper is precipitated as CuS. The process
is controlled so as to prevent the evolution of H
2
S gas. A thickener is used to thicken the CuS
precipitate. The solids are returned to the first stage filters and the overflow solution is sent to
the iron/arsenic removal circuit.
-6-
The objective of the iron/arsenic removal circuit is to produce environmentally stable
compounds of iron, arsenic and sulphur and discard them to the effluent stream without
excessive loss of nickel and cobalt. The feed solution to this circuit contains 0.02 g/L copper,
25-35 g/L nickel, 15-25 g/L cobalt, 20-35 g/L iron, 1-2 g/L arsenic, and 40-70 g/L sulphuric
acid. It is processed continuously at a rate of 150 L/min. Lime slurry is added to the solution as
it is passed through two autoclaves operating under oxygen pressure at 90-95 C. The iron and
arsenic precipitate out and the solids are separated by filtration to produce an iron-gypsum
cake. The filtrate is sent to the nickel/cobalt recovery step. The iron-gypsum cake is partially
redissolved to remove co-precipitated nickel and cobalt and then filtered. The filter cake is sent
to the tailings and the filtrate is returned ahead of the iron precipitation circuit.
The filtrate from the iron removal circuit is mixed with a 200 g/L solution of sodium
carbonate (Na
2
C0
3
) in two reaction vessels in series. The pH is controlled in the ranges 7.6-7.8
and 8.1-8.3 in the two vessels respectively. The reaction product is a precipitate of basic nickel
and cobalt carbonates which is thickened to 20-25% solids. The nickel/cobalt carbonate is
shipped to the cobalt refinery and the barren solution is pumped to the waste pond.
2.1.1 Background of the Second Stage Leach
When the CRED plant first became operational in the early 70's, the second stage leach
was designed to leach CU2S completely in the presence of excess acid (H2SO4) and under
oxygen pressure at 110C. The products of the leaching process were CuS0
4
(aq) and
elemental sulphur. The equation governing the process was reported as [5]:
Cu + 2HO
t
+ 0
2
-> 2CuSO, + 2H
2
0 +S
The leach products typically analyzed 90% elemental sulphur and 10% precious metals and
unreacted sulphides. The factors affecting the reaction rate were determined to be the iron
content of the solution, oxygen pressure, temperature and feed particle size. The acid and
copper concentrations were not found to be critical factors in the leaching rate. The iron
-7-
content of the solution was identified as being an important variable. With iron in solution,
the reaction proceeds rapidly according to the reaction above to form elemental sulphur.
However in the absence of iron, the reaction proceeds more slowly and consumes up to 4
times as much oxygen and the sulphide sulphur is oxidized to sulphate according to the
reaction:
CifjS + H2SOA+\o
2
^> 2CuS0
4
+H
2
0
The leaching process was operated by this method for a few years. However, in the
mid-seventies, historical reports [6] show that a proposal was made to change the leaching
process. It was suggested that all the sulphide sulphur should be oxidized to form sulphate
as opposed to elemental sulphur by leaching in a low-acid solution. Based on laboratory
work, the product from this leaching method would produce a precipitate of basic copper
sulphate (CuS0
4
-2Cu(OH)
2
) in a solution of copper sulphate. The slurry would have to be
mixed with spent electrolyte containing sulphuric acid to dissolve the precipitate and leave
a residue containing precious metals and a small amount of gangue materials. The
operating conditions of the process were set at 150 psi oxygen pressure at 105'C. The batch
feed to the autoclave would be a mixture of spent electrolyte containing sulphuric acid,
copper and iron in solution with first stage residue to form a slurry containing -40% solids
by weight.
The process was eventually changed to a total oxidative leach in 1975 with some
modifications being continually made to improve the process. Howver, the second stage
leach residue occasionally showed high levels of copper still remaining in the solids even
after extended leaching times [7]. Extensive examination of IPC residue, first stage residue
and poorly leached second state leach residue was carried out to determine the nature of the
poor leaching behavior. The results showed that the presence of Cu
2
0 in the feed to second
stage, associated with high levels of oxygen in the IPC residue, was linked to the poorly
leached batches. The presence of Cu
2
0 was proposed to cause an adhering film of basic
-8-
copper sulphate at the point of basic copper sulphate formation. This would block oxidizing
species from reaching the copper sulphide particles and hinder further leaching.
Photomicrographs were presented to support this theory.
During 1986, slow leaching and high copper in the residue became a severe problem
and warranted further investigation of the process [8]. A complete leach should nominally
take 5 hours based on plant reports and experimental tests. However, the length of leach
times almost always exceeded 5 hours with the occasional leach time taking longer than 20
hours. For example, from plant data for the month of January 1988 [9], out of 93 leaches, 33%
of the leaches exceeded 8 hours. A calculation in one report [10] gives the cost of downtime
as approximately $25 000 /hr for deferred revenues from precious metals. It is apparent
from this calculation how even small improvements in leaching times can make a significant
difference to the revenues over one year.
One laboratory study [11] of the second stage leach shows some interesting results on
the behavior of the process with respect to pulp density, particle size of precipitate, and
agitation speed. It was found that higher solids density feeds lowered the leaching rate of
copper considerably due to higher viscosity of the solution. In lab tests with normal solids
densities, higher viscosities were observed on the material which leached poorly in the plant
as opposed to material which leached quickly. The higher viscosities observed in this case
were associated with a finer particle size of the precipitate. The agitation speed of the slurry
also had a significant effect on the leaching rate. All these factors appear to indicate that
oxygen dispersion in the autoclave is severely affected by changing viscosities and agitation
speed.
The autoclaves have no level meter, so the impeller depth varies considerably between
leaches. Impeller depth was suggested to be an important parameter in the leaching rate in
one study and so the slurry level was lowered (amount unknown) and was found to
improve the leaching process for a short while. However, this did not cure the problem
permanently.
-9-
2.1.2 The Second Stage Leach
The equipment used in the second stage leaching process consists of a batch make-up
tank/2 titanium autoclaves, a dissolving tank, 2 pressure filters and a rotary vacuum filter
(Figure 2.2) [4]. There are also product holding tanks between various stages of the process.
PM residue
slurry storage
Figure 2.2 Second Stage Leaching Circuit at INCO's - Copper Cliff Copper Refinery [4].
The autoclaves were originally designed for leaching in excess acid as described
earlier but were modified in the mid-seventies when the process was changed. The major
change to the autoclaves was the installation of vertical cooling coils around the inside
-10-
perimeter of the vessels (see figure 2.3) [12]. The agitator system consists of two 45'
pitched-down, 4 bladed turbine impellers attached to a single 18 cm diameter shaft rotating
at 68 rpm. The internal parts are made out of 316L stainless steel.
Oxygen
Sparger
Figure 2.3 Approximate shape and dimensions of the Second Stage Autoclaves [12].
-11-
The feed is prepared as a 30% solids slurry by mixing spent electrolyte from the
electrowinning plant, water and first stage residue in the batch make-up tank. The slurry is
then pumped into one of the second stage autoclaves. The autoclave is then pressurized
with oxygen to 150 psi while the slurry is being agitated. The temperature is maintained at
115C during the leach. The leaching process is assumed to be complete when there is no
more oxygen consumption, no more heat being generated and there is no temperature
increase when cooling is off. The slurry is then pumped to the redissolving tank where it is
mixed with spent electrolyte and filter aid. The acid in the spent electrolyte dissolves the
basic copper sulphate. The unleached solids are then recovered by pressure filtration and
the filtrate is sent to Se/Te removal. The solids are repulped in water and refiltered to
recover the precious metals residue. The final residue is shipped to Port Colborne for
precious metals recovery.
2.2 The UBC Screening Model
The studies in the past have been inconclusive in determining the cause of the long
leaching times and incomplete leaching in the second stage autoclaves. A mathematical model
of the CRED second stage leach was developed at UBC by Dreisinger and Peters [3] in an
attempt to evaluate possible metallurgical causes of the "slow cook" conditions occurring in the
process. This screening model was a first approximation to possibly highlight some of the
conditions that may lead to slow cook conditions. The model was developed on a number of
important assumptions based on work previously done by Peters and Mao [13] on the leaching
of Cu
2
S under slightly acidic conditions. Their work produced the following results:
i. Cu^ leaches very quickly to CuS.
ii. The CuS produced by leaching Cu
2
S tends to fracture and become finely disseminated.
iii. Cu^ conversion to CuS proceeds very quickly relative to the leaching of CuS.
iv. A small amount of iron in solution promotes elemental sulphur formation during leaching.
The leaches with no iron showed little or no elemental sulphur in the leach residue.
-12-
Since CuS leaching proceeds slowly relative to Cu
2
S conversion to CuS, it is possible to
separate the leaching steps of Cu
2
S conversion to CuS and CuS leaching to CuSGv In
developing the model, a number of discrete leaching reactions were proposed which would
proceed one at a time depending on the prevailing solution conditions and the character of the
unreacted solids. These reactions are:
1. Cu
x
S +{x- l]H
2
SO<+^(x- l)0
2
-*CuS + (x- \)CuS0
4
+ (x- \)H
2
0
2. Cu
x
S +^(x - WuSOt + îx - l)0
2
+ 2(x - \)H
2
0 -> CuS +^(x - 1)2CM(0//)J CuS0
4
3. Cu
x
S +^(x - \)0
2
+ (x -\)H
2
0 -> ^(3-x)CuS +^(x- l)(2Ca(0//), CuSOj
4. CuS + 20
2
-+CuSOt
5. CuS+H
2
SO
i
+^0
2
^,CuSOi+H
2
0 + S
where Cu,S refers to the average Cu/S mole ratio in the feed, not to any particular mineral
form and the value of is approximately 2.
There are five reaction pathways possible under various initial batch recipes.
i. Begin with copper sulphate and acid in solution.
Reaction 1 proceeds until acid depletion.
Reaction 2 proceeds until only CuS is left in the residue
Reaction 4 proceeds to total oxidative endpoint.
ii. Begin with copper sulphate in solution and no acid.
Reaction 2 proceeds until only CuS is left in the residue.
iii. Begin with copper sulphate and excess acid in solution. ,
Reaction 5 proceeds to acid depletion.
-13-
iv. Begin with acid and low copper in solution.
Reaction 1 proceeds until acid depletion.
Reaction 2 proceeds until copper sulphate is depleted.
v. Begin with low copper and no acid in solution.
Reaction 2 proceeds until copper sulphate is depleted.
The kinetic routine in the model was divided into a two-step process. The first step is
gas-liquid mass transfer defined by the following equation,
d[0
2
]
- ^ - = *,([OJ -[Oz])
where kg is the gas-liquid mass transfer coefficient for the system
[OJ" is the saturated oxygen cone, in solution at the oxygen partial pressure in the
autoclave
[0
2
] is the oxygen concentration in the bulk solution
The next step is controlled by chemical reaction defined by the following empirical equation:
= k^Cu
2
*] [OJ + ^[CM
2 +
] [OJ [Cu
x
S]
where k
t
and k
2
are empirical rate constants.
The equation is defined on the basis of copper catalysis which is first order in cupric and
dissolved oxygen concentrations and a solids leaching term which is first order in cupric,
dissolved oxygen and unreacted CuJ$ concentrations. The first term recognizes the significant
role of copper ion catalysis and the second term accounts for the fact that the rate will drop as
the solids concentration goes to zero.
-14-
The kinetic equations suggest that the amount of copper in solution at any given time is
very important to the rate and that lower copper concentrations will cause slower leaching rates.
If the copper in solution is depleted, the rate is expected to go to zero. This is the anticipated
slow leaching behavior observed in the plant known as the "slow cook" condition.
In this preliminary model, the rate constants were treated as fixed values because of the
unavailability of additional data. These values probably change due to changing conditions
during leaching.
Figures 2.4-2.11 show some sample outputs of the model generated from various initial
concentrations of acid and copper in solution. It can be seen that the slow cook condition occurs
only when there is a depletion of copper in solution.
Figure 2.4 shows the model output from a case when there are acid and copper in solution
at a level which will cause the reactions to proceed as described in case (i) above. The output can
be split into 3 sections. In the first section, according to reaction 1, acid is being consumed to
leach copper from Cu and the copper concentration is increasing in solution. When the acid is
depleted, at around the 16-minute mark, the process proceeds according to reaction 2 and
produces basic copper sulphate from Cu
x
S and CuS0
4
. The copper concentration decreases as
shown. Eventually, when all the Cu^S is transformed to CuS, the leaching proceeds according
to reaction 4 until all the CuS is leached. Figure 2.5 is the corresponding oxygen consumption
rate curve. This shows that the initial rate of reaction rises very quickly as the amount of copper
in solution rises and the rate drops as the copper is depleted via reaction 2. The reaction rates
never drop to low levels because there is always a lot of copper in solution available for
catalysis. The complete leach time is approximately 5 hours and is close to the times observed
in plant operations for a normal leach.
Figures 2.6 and 2.7 represent case (ii) in which the there is no acid available at the
beginning of the leach and the initial copper concentration is approximately 100 g/L. The
-15-
320 -
280 -
240 -
^ 200 -
c
o
a
s
160 -
c
-
120 -
8
80 -
40 -
0 -
Concentration Profiles Predicted by Model
_ \
\
\
\
Cu
x
s
V
\
V
\
\
\ 2Cu(OH)2.CuS04
- Y
/ \
/
/
/
;
Cu
N
W- H2S04
1 1 1 I 1 1 1 I
_ _ " " ~ r
40 80 120 160 200 240 280
Time (min)
Figure 2.4 Distribution of species as predicted by model for case (i) conditions.
0.04
0.035
Oxygen Flowrate Predicted by Model
280
Time (min)
Figure 2.5 Oxygen flow rate as predicted by model for case (i) conditions.
-16-
model predicts a higher amount of basic copper sulphate formation via reaction 2 until all Cu,S
is converted to CuS. The kinetics are good in this case because the copper in solution never
drops below 50 g/1.
Figures 2.8 and 2.9 shows the effect of excess acid in solution at the beginning of leach.
Because there is still acid present after all the Cu
x
S has been converted to CuS, sulphur
formation is expected via reaction 5 and no basic copper sulphate is produced. Near the end of
the leach process, the solubility of copper sulphate is exceeded resulting in the precipitation of
CuS0
4
.5H
2
0.
The model was operated under conditions which would cause a copper deficiency during
operation. This was done by setting a high copper to sulphur ratio in the feed solids and less
acid in the feed solution. The resulting output is shown in Figures 2.10 and 2.11. The acid and
copper in solution drop very quickly and the result is a severe drop in the leaching rate. It is also
important to note that a significant amount of basic copper sulphate solids is produced. This
high amount of solids could cause a significant drop in gas-liquid mass transfer although the
model does not incorporate the effect of solids loading into the gas-liquid mass transfer rate.
The total leach time is predicted to exceed 25 hours.
The model predicts slow leaching conditions under copper depleted conditions but the
model requires verification. Firstly, the sequential reaction chemistry proposed in the model
needed to be verified through experimental work. Secondly, better kinetic relationships need to
be developed because the model used an empirical relationship for the rate of reaction. The
objective of this thesis project was to obtain experimental data to improve the understanding of
the leaching process and eventually to develop a better model.
-17-
c
o
03
4=
C
o
o
280
240
200
160
120
80
r
i
i
\
I \ C"xS
/ ^
2Cu(OH)2.CuS04
r
i
i
\
I \ C"xS
/ ^
/ \
/
/
" " ^ " Cu
1 \,
100 200
Time (min)
300 400
Figure 2.6 Distribution of species as predicted by model for case (ii) conditions.
200
Time (min)
Figure 2.7 Oxygen flow rate as predicted by model for case (ii) conditions.
-18-
320 -i
280 -
240 -
i 200 -
r
i
t
r
a
t
i
o
t

160 -
n
c
e
i

120 -
8
80 -
40 -
0 -
\CujS
Cu
CuS04.5H20
Time (min)
Figure 2.8 Distribution of species as predicted by model for case (iii) conditions.
0.05
0.04
c
!
o
0.03 -
s
f 0.02

0.01
0 I i i i i i i i i i i i i i i i i i i i -
0 20 40 60 80 100 1 20 140 160 180 200
Time (min)
Figure 2.9 Oxygen flow rate as predicted by model for case (iii) conditions.
-19-
c
o
s
c
500
450
400
350
300
250
200
150
100
50
0
\ i
I
^ 2Cu(OH)2.CuS04
CU x S
Cu
'Tf
r
r
TrT
1
500 1000
T I I 1
1500
Time (min)
Figure 2.10 Distribution of species as predicted by model for case (iv) conditions.
Oxygen Flowrate Generated by Model
0.04 -n
0.035 -
.g 0.03 -
| 0.025 -
| 0.02 -
o
c 0.015 -
I
I" 0.01 -
0.005 -
0 " I I I \ 1^ I I I I I I I I I 1^
0 500 1000 1500
Time (min)
Figure 2.11 Oxygen flow rate as predicted by model for case (iv) conditions.
-20-
2.3 Scope of the Study
A review of the history of the second stage leached has shown that a number of variables
have been considered in trying to improve the leaching process. Clearly, the dificulties with the
process have not been satisfactorily overcome. The most recent attempt at analyzing the
problem was the UBC screening model discussed earlier.
The present study was designed based on the results of the UBC screening model and the
earlier work done at INCO labs. The main objetives of this study are:
1. to understand the reaction chemistry and check if the reactions are indeed
sequential as suggested in the UBC screening model.
2. to identify any intermediate copper sulphide products formed.
3. to investigate chemical kinetics of copper leaching for the first stage residue cake.
4. to provide a basis for further work to improve the present mathematical model or
develop a new mathematical model.
-21-
2.4 Literature Review
2.4.1 Copper Sulphides - Chalcocite to Covellite
One of the most important economic copper minerals, chalcocite (CujS), is produced
by the reduction of CuS0
4
solutions descending from oxidation zones of copper rich
deposits in the earth [14]. Covellite (CuS), similarly, is usually found as an oxidation
product of chalcocite or other primary copper sulphides like chalcopyrite as a zone of
secondary enriched copper deposit. The oxidation of chalcocite does not lead to the direct
formation of covellite. The decomposition process produces many intermediate sulphides
such as djurleite (Cu
196
S), digenite (Cu,
76
., g^S), blue-remaining covellite (Cu,,.
14
S) and
covellite (CuS). Potter [15] has shown the existence of numerous intermediate phases and
provided free energy data for these phases. These phases are Cu^S, Cu, o^S, Cu,
7 6 5
S,
Cu,
4
S, Cu, ,S and CuS. Figure 2.12 shows the crystal structures of chalcocite, covellite and
digenite.
Chalcocite (hexagonal) Digenite (cubic) Covellite
Figure 2.12 Crystal structures of copper sulphides relevant to this study [14].
-22-
In chalcocite and djurleite, the sulphur species are arranged in a hexagonal close
packed structure [14]. The copper ions are located near the triangular faces of the tetrahedral
sites as opposed to being in the center of the tetrahedral interstices. The structure of digenite
is a cubic close packed arrangement of the sulphur species and the copper ions are located
off-center in the tetrahedral interstices. One eighth of the tetrahedra are unoccupied [14].
Natural digenite has 1 at.% iron to maintain a stable solid solution composition but a stable
iron-free "low digenite" called anilite (Cu^S) is also found.
The structure of covellite is more complex as can be seen in Figure 2.12. The base
structure consists of three layers of hexagonal close packed sulphur species. The copper ions
occupy the centers of the equilateral triangles and the centers of tetrahedral sites in the
layers.
2.4.2 Leaching of Chalcocite and Covellite
The leaching of chalcocite has often been reported as a two-step process according to
the following reaction sequence:
Cu** -> CuS + Cu
1+
+ 2e~
CuS ->Cu
2+
+ S + 2e~
A variety of leaching processes have been investigated in the laboratory and classified
according to the leaching steps and the types of reagents used. The most common oxidizing
agents are:
Ferric sulphate in acid
Ferric chloride in acid
Oxygen in sulphuric acid
Oxygen in ammoniacal solutions
Nitric acid
-23-
There are other oxidizing agents but they have not received much attention, mostly because
of their cost and commercial availability.
Sullivan [16] studied the leaching chemistry of chalcocite in acidified ferric sulphate
solutions using bottle roll tests at temperatures below 50 C The dissolution process was
found to occur in two steps. The first step was rapid until about 50% copper dissolution and
the second step, oxidation of CuS, was relatively slow. The two reactions involved in the
leaching process were reported as:
CujS + Fe
2
(SOJ
3
-> CuSO
A
+ 2FeSO
A
+ CuS
CuS + Fe
z
(SO,\ -> Cu50
4
+ IF eSO
A
+ S
The study showed that the dissolution rate was independent of the strength of ferric
sulphate provided sufficient reagent was present. At a constant ferric concentration, the rate
was also independent of acid strength. Various particle size fractions in the range of
-10-mesh to 200-mesh were also studied. Although there is considerable difference in
surface area per unit weight in this range, there was almost no difference in the leaching
rates (ie. time taken to dissolve a given amount of copper) observed, provided that the
particles were open to solution attack. The rate of dissolution was greatly affected by
temperature. For example, 73% copper dissolution required 1, 5 and 15 days at 50 C, 35 C,
23 C respectively. Sullivan reported no information on intermediate copper sulphide
phases.
Thomas et al. [17] examined the kinetics of dissolution of synthetic chalcocite and
digenite in acid ferric sulphate solutions using a rotating sintered disc technique. The study
found that digenite and chalcocite dissolved at similar rates. The dissolution was reported
to occur in stages where chalcocite is progressively converted into djurleite, digenite,
blaubleibender covellite (also known as blue-remaining covellite) and normal covellite. The
covellite is transformed to elemental sulphur according to the second of two equations
above. The rate of dissolution was found to be directly proportional to ferric ion
concentration between the ranges tested (0.025 M - 0.2 M). This ferric ion concentration
-24-
dependency was not found in the studies by Sullivan. This difference is probably due to the
differences in experimental methodology. The rate was also found to depend significantly
on the temperature.
Mao and Peters [13] studied the leaching of chalcocite under autoclave conditions and
found the same two-stage leaching behavior reported in ferric sulphate leaching. During the
first stage, 50% of the copper is extracted and up to 100% of the chalcocite is converted to
covellite. The first stage is also separated into two steps which involves the initial
conversion of chalcocite to digenite and then subsequent conversion of digenite to covellite.
A leaching model to explain the leaching kinetics was based on three parts shown in Figure
2.13. The first step is a shrinking core kinetics model, the second includes particle break-up
and third is the effect of elemental sulphur morphology on kinetics. The leaching process is
described as a mixed-potential electrochemical model in which the first stage kinetics are
predominantly cathodically controlled. The presence of iron in solution leads to higher
leaching rates and decreases sulphur oxidation during the second stage. The second stage
kinetics are explained by the passivation of covellite by oxygen leading to a high mixed
potential. The Evans diagram in figure 2.14 shows a schematic of the applicable polarization
curves. Depassivation occurs in the presence of Fe
2+
ions where the process operates at point
D and leads to a higher exchange current (leaching rate) and a lower mixed potential.
-25-
First Step: Stage I Leaching
Cathodic:
0
2
+4H
+
+4e -^WiO (Cu & Cu^ Surface)
Anodic:
CUTS -> CKgS + 0.2Cu
2+
+ OAe (Cu^S only)
Volume Reduction: 7.6%
Second Step: Stage I Leaching
Cathodic:
0
2
+ 4H
+
+ 4e
Anodic:
CU2S - Cu
lJS
S + 0.2Cw
2+
+OAe (CiijS only)
Cumulative Volume Reduction: 24.4%
2H
2
0 (CuS Surface)
Stage II Leaching
Catnodic:
0
2
+4H
+
+4e^2H
2
0 (CuS Surface)
Anodic:
CuS-*Cu
2+
+S + 2e
CuS + 4H
2
0 -> Cu
+
+SOl'+ 8/T + Se
Cumulative Volume Reduction: 43.6%
(or more depending on degree of sulphur
oxidation)
Figure 2.13 Leaching morphology for a chalcocite particle (a) 0-20% copper extraction
Ob) 20-50% copper extraction (c) 50-100% copper extraction [13].
-26-
Otfluston - l \
limited Otygen i ^
hi Fww i \
0!
n _ A - B First SleO- Stag I teacftatg
C Secofic Sm. Slage I teaching
D Slags II Leaching (Fa * present)
Stage 11 Leaching(Fe' absent]
Legl-Cabin* Cumrtt [lenemalk)
Figure 2.14 Evans diagram of applicable polarization curves during oxygen pressure
leaching of chalcocite [13].
Oxygen pressure leaching experiments in an iron containing solution done by
Chmielewski and Charewicz [18] show that the partial pressure of oxygen governs the
process rate. The oxygen increased the kinetics mainly by oxidizing the ferrous iron to ferric
iron, the main leaching agent, and not directly by interaction with the copper mineral.
King et al. [19] studied the leaching of chalcocite by acidic ferric chloride solutions and
found the same two stage leaching process observed in other studies. The first stage of the
reaction, to approximately 50% copper dissolution, was complete in less than 4 minutes at
temperatures between 40C and 80C. However, the second stage of leaching was strongly
affected by temperature as the kinetics were much more rapid at higher temperatures. The
apparent activation energy, Ea, for the first stage and second stage was 3.43 kj/mol and
101-122 kj/mol respectively. This difference in Ea was attributed to a difference in the
-27-
charge transfer process between the two reactions. The first stage is probably controlled by
diffusion of copper ions in the particles and the second stage is chemically controlled by the
reaction of S
2
' ions in CuS to form sulphur.
The first stage of the process proceeded more slowly with the larger particle sized
material due to a larger diffusion layer for the copper to travel through in the solid. The
second stage was less affected by particle size. There was no effect of acid (HCl) strength on
the leaching rate. An increase in ferric concentration up to 0.25 M produced an increase in
the dissolution rate of the first stage but was independent of concentration beyond this
point. The addition of ferrous chloride to ferric chloride solutions showed the exact same
net increase that would have been found if the same amount of ferric chloride had been used
instead. Use of ferrous chloride alone (ie. no ferric chloride) produced slow leaching.
Particle size fractions tested were 425-600 um, 150-300 um, and 75-106 um. These size
fractions were similar to the ones Sullivan studied. There was almost no difference observed
in the leaching rates, a result similar to that of Sullivan. Particle sizes of 1.18-1.70 mm and
2.36-4.76 mm produced much slower leaching rates. These were attributed to a larger
diffusion distance required by the copper to travel in the solid.
The most interesting observations of this study were based upon the X-ray diffraction
data. The results show that a whole range of intermediate non-stoichiometric copper
sulphide phases are formed as copper is leached out of the solid matrix. The basic chalcocite
crystal structure does not change until the copper level is below Cu
1- g91
S which is outside the
digenite stoichiometric range. There appears to be a similar behavior as digenite transforms
to covellite. This could be caused by some local areas and particles becoming more depleted
of copper and achieving compositions at which phase transformations occur before others.
This would explain the mixtures of phases observed.
The leaching of chalcocite and covellite was studied by Grizo et al. [20] at pH values
between 0.7 and 2 in the presence of sulphuric acid and ferric sulphate. They divided the
leaching process into three stages. The three stages were identified by changes in kinetics
-28-
from linear to non-linear and back to linear dissolution rates. This is unlike previous studies
which divided the stages according to the formation of intermediate species such as digenite
and covellite. They do, however, suggest that during the second stage, leaching of
chalcocite, digenite and covellite is occurring in parallel. The activation energies were found
to progressively increase in each stage but the rise in activation energy is higher between the
second and the third stage. This increase in activation energy suggests a change in
mechanism from diffusion control to chemical kinetics control. An increase in particle size
decreases the rate at which copper is leached but does not affect the kinetic mechanism in the
three stages. The leaching data on various particle size fractions were also found to show
that the second stage was controlled by the diffusion of species through a product layer.
Cheng and Lawson [21] investigated the leaching of synthetic chalcocite and covellite
in oxygenated acidic sulphate-chloride solutions. The leaching was described in terms of a
shrinking core model with the rate being surface chemical reaction controlled in the first and
second stages. The late second stage was accompanied by pore diffusion control. Elemental
sulphur formation on the surface of the particles was found to retard the dissolution rate
during covellite leaching.
Thomas and Ingraham [22] studied the kinetics of dissolution of synthetic covellite in
aqueous acidic ferric sulphate solutions via a rotating sintered disk technique in the
temperature range 25 to 80C. They identified two rate controlling steps. The first, below
60 C, was surface chemical reaction controlled and the second, at higher temperatures, was
solution transport controlled. The respective activation energies were 92 kj/mol and 33
kj/mol. The leaching rate was directly proportional to the ferric concentration below 0.005
M but not sensitive to higher ferric sulphate concentrations.
Dutrizac and MacDonald [23] also studied the dissolution of synthetic CuS and
high-grade natural covellite in the temperature range 25 to 95C in acidified ferric sulphate
solutions. They found little difference in the leaching rate between natural and synthetic
covellite. Other leaching observations were similar to those of Thomas and Ingraham [22].
-29-
2.4.3 Electrochemical Studies
A number of researchers have investigated the electrochemical dissolution of copper
sulphide ores and mattes in order to develop a process for the direct electrorefining of these
materials. Etienne [24] studied the electrochemical aspects of aqueous oxidation of copper
sulphides using rotating disk anodes of digenite and chalcocite. The results showed that the
rate of chalcocite oxidation was under the control of diffusion of the cupric ions through the
solution in the pores of the covellite-sulphur product layer. Etienne also explained the cause
of large overpotentials observed by many researchers that occurred at some time into the
electrolysis process. She theorized that the polarizations causing the overpotentials were
due to the precipitation of copper sulphate in the pores formed from the leaching of copper
out of the matrix. This blocked the transfer of current to the reactive surface sites where the
electrolyte contacts the solid surface thus setting up a high electrical resistance.
Biegler and Swift [25] also investigated the dissolution of copper sulphide anodes and
the results supported Etienne's theory for the cause of the polarization. They also used other
electrolytes besides copper sulphate and found that the time at which polarization occurs is
directly related to the time at which the hmit of solubility of the copper salt in the solution is
reached. They also noted that the structure of the product layer is poorly understood and
further investigation of the non-equilibrium products formed during dissolution would be
required to understand the leaching process.
The study of the mechanism of the anodic dissolution of CU2S was performed in the
presence of sulphuric acid under galvanostatic and potentiostatic conditions by Winand et
al. [26]. In all cases, a layer of digenite, Cu
:
gS, was found to form on the surface according to
the following reported reaction.
SCu^S - 5Cu
lx
S+Cu
2+
+ 2e
A concentration gradient of copper was observed through the digenite layer. This digenite
layer stays at a constant thickness after the Cu
1;1
S layer appears on the surface. The reaction
in this step was reported as
-30-
3C,5 -> 4Cu
1A
S+Cu
2+
+2e
If the anodic potential is low during the electrolysis process, the next reaction proceeds as
follows
WCu
Ll
S - llCu
2+
+10.S+2r?
However, if the current density is sufficiently high to achieve a sharp increase in anodic
potential or the potential is kept high, the reaction path is given by the following two
reactions
lOCu
lA
S -> \QCuS + Cu
2+
+ 2e
followed by
CuS -+Cu
2+
+S+2e
Furthermore, sulphate is also found to be formed to some extent at high anodic potentials
according to the following reactions.
CuS+AH
2
0 - Cu
2+
+ S0
2
-+W
+
+8e
It must finally be noted that the formation of a copper sulphate precipitate on the
surface was stated not to be the cause of the sharp rises in anodic potential observed in the
experiments because the calculated current density for such a film on the surface was a
factor of ten higher than the current densities used in the study.
McKay [27] studied the anodic decomposition of copper-rich mattes using particulate
electrodes. Anodic decomposition of synthetic chalcocite was defined as a three-stage
process according to the following reactions:
1. Cu^ -+Cu
2
_
x
S+xCu
2+
+ 2xe~, 1.75 < (2-x) < 1.83
2. Cu
2
_
x
S-+Cu
2
_
y
S + {y-x)Cu
2
*+2(y-x)e-, 0.7<(2-y)<0.9
3. Cu^S - (2-y)Cu
2+
+ S + 2(2-y)e'
-31-
Stage 1 is associated with crack formation along grain boundaries and in stage 2, the grains
begin to deteriorate as copper is depleted from them. Total-bed polarization occurs because
of the deterioration of the electrode and a reduction in conducting reaction interfaces
between the electrolyte and the solid surface due to sulphur formation in stage 3.
The electrochemical dissolution of copper sulphides was investigated by Hillrichs et
al. [28,29,30] through cyclic voltammetric methods. The anodic dissolution of Q^.^S in
sulphuric acid pointed to three factors controlling the current density. These are, (a) solid
state diffusion through the CuS product layer, (b) pore diffusion in the product layer and (c)
resistance polarization due to CuS0
4
precipitation in the pores formed during dissolution.
The formation of a thin metastable copper oxide layer was also thought to affect the
dissolution of CuS. Further studies [29] confirmed the formation of this metastable,
non-stoichiometric copper oxide/hydroxide layer.
MacKinnon [31] investigated the anodic dissolution of chalcocite using a fluidised-bed
anode method. The intermediate formation of "blue-remaining" covellite (Cu
u
S) was
observed. The dissolution process became inhibited after about 50% copper removal and
was accompanied by increased oxygen evolution on the platinum current distributor. This
inhibition was inferred to be caused by sulphur formation on the surface of the reactive sites.
-32-
2.4.4 E
h
- pH Relationships and Phase Systems
Potential-pH diagrams show chemical equilibrium relationships for aqueous systems.
The plots are generated from hydrolysis and oxidation reduction reactions. Figures 2.15a
and 2.15b are E-pH diagrams for the Cu-S-H
2
0 system at 25 and 100 "C generated at unit
activity for all species [32].
Figures 2.16a-b and 2.17 [32] are thermal precipitation diagrams to show shifts in
solution-solid equihbria with respect to temperature and pH.
Figures 2.18a-b [33] are phase diagrams for the Cu-S system to show the stability
ranges for the various species. This phase diagram does not show some of the metastable
phases that have been observed by many researchers.
-33-
-34-
Figure 2.16a-b Thermal precipitation diagrams for the CuSO
4
-H
2
S0
4
-H
2
0 system [32].
-35-

Figure 2.17 Thermal precipitation diagram for the CuSO^HjSCvHjO system at
100-Cfora
CiiJt = V
. [ 32] .
-36-
J20Cv,
1
i
r
1000 I
N
8 0 0 -
r-
<
H 400r
2
200r
-crystalline S
0
1

100
Cu melt
1105' ~~
sulfide melt
813"
high digenite j
507*
covellite -
120
Wt. %S 80 60 40
700h
600h
500h
.400h
tr
cr300(-
UJ
covellite
507
s
covellite
200h
\00\-
157*
be
CuS
Cu|7S
\
\
Cu
\
i -435*
hex.
Cu.
chalcocite
Cu.
103.5*
digenite-I
orth.
chalcocite Cu
Wt.% S
CuxS X-
1.70
-t-r-n
T.80
21
1.90 2.00 2.10
Figure 2.18a-b Phase diagrams of the Cu-S system [33]. The abbreviation "be" refers to
"blaubleinder covellite".
-37-
2.4.5 Gas-Liquid Mass Transfer in Oxidative Leaching
Molecular oxygen has poor solubility in aqueous solutions, particularily under
atmospheric conditions, so agitation and/or sparging systems must continually be able to
transfer enough oxygen into solution to maintain high leaching rates. There are three
important steps in allowing oxygen to perform its objective. The first is that oxygen must
dissolve into solution (or create a surrogate oxidant in solution). The second is that the
dissolved oxygen or a surrogate oxidant must reach the mineral surface by mass transport
and finally, the oxidant must react on the surface. In general, dissolved oxygen itself is not
very reactive on most mineral surfaces because electrochemical reduction of oxygen is slow
on metal sulphides [34].
Peters [34] has suggested four methods by which oxygen is utilized during oxidative
leaching. The four models are shown in Figure 2.19 with mechanisms being described as
follows:
1. The simple model suggests that dissolved oxygen is transported to the particle surface
where it reacts directly to oxidize the metal (Figure 2.19a).
2. Oxygen can react homogeneously with reduced species in solution to form a surrogate
oxidant. An example of this is the oxidation of Fe
2+
to Fe
3
* in solution. Since it is
possible for iron to be present in higher concentrations than dissolved oxygen, it is
more readily available to react on the mineral surface (Figure 2.19b).
3. A surrogate oxidant can also be formed when a reducing agent generated through
mineral decomposition is oxidized at the gas/liquid interface. An example of this type
of a mechanism occurs in ammoniacal leaching where Cu(NH
3
)
2
+
is known to oxidize
very quickly to provide a surrogate oxidant Cu(NH3)
n
2+
. There is little dissolved
oxygen under these conditions and the surrogate is responsible for mineral oxidation
as well as homogeneous oxidation of other reducing agents generated by mineral
decomposition (Figure 2.19c).
-38-
4. Theoretically, the quickest oxygen transfer rate that can be achieved is when a highly
soluble surrogate oxidant is formed in the gas phase. In Figure 2.19d, the surrogate
oxidant is labelled as QO
z
.
As will be discussed later, case 2 may be an important mechanism in the leaching of
chalcocite.
Dawson-Amoah [35] investigated gas-liquid mass transfer in oxygen pressure
leaching systems. Variables such as impeller type, size, speed and immersion depth were
investigated. The effect of baffles and volumetric power consumption rates were also
studied. Dawson-Amoah found that unsymmetrical, unbaffled tanks yielded higher mass
transfer rates. Impeller depth was found to be the most important variable for determining
the minimum required tip speed of the impellers. Mass transfer is significantly enhanced at
shallow depths and higher critical tip speeds were required at greater depths.
The most efficient impeller for oxygen mass transfer was found to be the flat 6-bladed
disc impeller. It was found to be at least 2.8 times as efficient as the pitched-up axial
impeller. The pitched-down axial impeller was the least efficient. Although the radial
impeller consumes the most energy, it has the highest mass/energy ratio (kg oxygen/kW-h)
for oxygen mass transfer.
It was also suggested that shallow impellers pump gas and create numerous small
bubbles. The values of mass transfer coefficients were high for shallow impellers, further
suggesting that spargers are not necessary to achieve high gas-liquid mass transfer. Bubbles
created from spargers may simply rise to the surface with little oxygen depletion. Under gas
pumping conditions, bubbles that rise to the surface and mix with the freeboard gas can be
recycled back into solution.
-39-
Dissolved
Metal
Dissolved
Metal
Dissolved
Metal
Figure 2.19 Models for oxygen absorption during oxidative leaching [34].
-40-
2.5 Summary
The second stage leach at INCO's Copper Cliff Copper Refinery has ocassionally
experienced problems in leaching copper from a chalcocite concentrate received from the first
stage leach. The poor leaching behavior is identified by the extended leaching times required
for some batches. Incomplete leaching results in significant levels of copper reporting to the
residue. The residue is a precious metals concentrate in which unleached copper is an
undesirable impurity. The INCO-CRED process and the chemistry of the second stage leach is
described in section 2.1.
A mathematical model was developed by Dreisinger and Peters [3] to investigate
metallurgical causes of the slow leaching behavior. The model was based on information from
data and historical research reports from INCO and other studies on chalcocite and covellite
leaching. The given reactions were proposed to occur in sequence with the reaction path
dependent upon the initial solution conditions. The model predicted that the leaching rate was
dependent upon the copper concentration and that a depletion of soluble copper would result
in the leaching rate reaching a value close to zero. The proposed reactions and the predicted
catalytic role of copper required verification through experiments. The role of this study was to
verify the assumptions made in the development of the model and attempt to discover any
other parameters which may affect the leaching process.
There is unanimous agreement among the various studies that the leaching of chalcocite
is a multi-step process. There is also general agreement that intermediate copper sulphide
compounds are formed during the leaching process. In oxygen leaching experiments, higher
oxygen pressures and higher temperatures were found to increase the leaching rate. The
presence of ferric ion increases the leaching rate but if a sufficient amount is present, there is no
increase in rate realized by increasing the ferric ion concentration. In oxygen pressure leaching
the ferric ion is believed to serve as a surrogate oxidant and acts as an intermediary between
oxygen and the copper sulphide mineral.
-41-
Surrogate oxidant formation can increase leaching rates considerably because it is usually
available in higher concentrations than dissolved oxygen. Surrogate oxidants are generally
more reactive on mineral surfaces than dissolved oxygen.
In terms of physical properties of agitation systems, shallow mounted impellers are more
efficient for gas-liquid mass transfer. Flat-bladed impellers are more efficient also at good gas
dispersion. The pitched-down impeller was found to be the least efficient.
-42-
CHAPTER 3 - Experimental Methods
The experimental program consisted of three parts designated as part A, part B and part
C. All experimental work was performed in Sudbury at the Copper Cliff Copper Refinery. The
objectives and procedures for each part are described in the following sections.
The experimental apparatus consisted of a Parr 2-liter titanium autoclave fitted with an
internal cooling coil and a magnetic stirring drive. The oxygen delivery to the process was
monitored using electronic flow meters connected to a personal computer via a data acquisition
system. The temperature and stirring speed were controlled and monitored using a Parr
controller unit. A schematic of the general layout of the experimental apparatus is shown in
Figure 3.1.
Oxygen
Data Aquisistion
System
and Computer
Valve
Electronic
Mass Flowmeter
Temperature
and Stir Speed
Controller
Magnetic
Stirrer
O O
Autoclave
- CD
Valve
Cooling
Water
Figure 3.1 Schematic of the experimental setup.
-43-
3.1 Part A: Study of the sequential nature of the reactions.
The objective of the part A experiments was to test whether the leaching process follows
the reactions proposed in the model discussed earlier. The copper was predicted to leach
sequentially to form basic copper sulfate and CuS as intermediate products. The theory was
tested by performing interruptive experiments. These experiments were stopped at various
times into the leaching process. The products were separated and analyzed.
3.1.1 Feed preparation
Synthetic electrolyte was prepared using analytical-grade reagents in distilled water
with analytical grade sulphuric acid (95-98 wt%). The initial electrolyte composition was 40
g/L Cu, 5 g/L Fe and 200 g/L sulphuric acid. All the analysis of solutions and solids were
done by an ICP scan at the INCO Central Lab in Copper Cliff unless otherwise indicated.
Numerous samples of solids (first stage residue) were obtained from the plant. The
sample that was found to contain a "typical" assay of metal values was chosen for the part A
experiments. The cake was thoroughly washed using a Buchner funnel apparatus to remove
all entrained electrolyte and was stored wet in sealed containers to prevent oxidation. The
assay of the cake is given in table 3.1.
Table 3.1 Assay of First Stage Residue used in Part A Experiments.
Weight Percent (dry basis)
Cu Ni Co Fe S As
80.0 0.18 0.04 0.08 18.1 0.54
-44-
3.1.2 Experimental procedure
A feed slurry was prepared by adding 510 g of solids (dry basis) and 500 mL of the
prepared electrolyte to the lab autoclave. Distilled water was then added to the autoclave to
achieve a total volume of 1.2 liters. The autoclave was then sealed and heated to 115C while
being stirred at a speed of 820 rpm. This stirring speed was chosen to prevent excessive
splashing onto the autoclave walls which made it difficult to recover all of the solids. This
stirring speed may not overcome gas-liquid mass transfer limitations but since the leaching
rates were not studied in part A, this was not an issue
2
.
When the desired temperature (115C) was achieved, the oxygen feed was engaged
and monitored using an electronic mass flow meter connected to a personal computer. The
operating pressure was set at 150 psig.
In the first experiment, the leaching was allowed to proceed until the oxygen flow rate
dropped to zero. The total oxygen consumed to this point was considered the 100% oxygen
consumption level. This value was verified by calculation of the oxygen demand based on
the initial solids analysis. All following part A experiments were performed by shutting
down the experiment at intermediate levels of oxygen consumption. This was done by
terminating the oxygen flow to the autoclave, rapidly quenching the slurry to a temperature
of 80 C and bleeding excess oxygen out of the autoclave quickly.
The autoclave was opened and the internal parts were washed into the autoclave to
the prevent loss of slurry. The temperature, pH and ORP (oxidation-reduction potential-via
a calomel electrode) were measured using an Orion pH/ORP meter. The slurry was then
filtered hot and washed by pouring hot water over the solids. The leach solution (filtrate)
was analyzed via an ICP scan.
2 The oxygen consumption rate was found to be sensitive to the agitation speed in the
neighborhood of the stirring speed used.
-45-
The recovered solids were reslurried in water and sulphuric acid was added to
dissolve all the basic copper sulphate formed. The acid was added slowly until the slurry
pH reached a value of 0.5. The slurry was then filtered again to separate the unleached
solids from the solution. This solution is later referred to as the "releach solution". The
solids were dried in a vacuum desiccator at room temperature to prevent further oxidation
prior to analysis.
The analyses performed on the experimental products were as follows:
1. Leach solution: ICP Scan
2. Releach solution: ICP Scan
3. Unleached solids: ICP Scan, X-Ray Diffraction
elemental sulphur, total sulphur
sulphate sulphur and sulphide sulphur
The sulphur assays on the solids were done only if enough material was available after
performing other tests.
3.1.3 Additional experiments in Part A
A number of additional experiments were performed to investigate the affect of other
variables. These experiments are described below.
1. The effect of the iron content in the electrolyte: These experiments were performed
with iron-free synthetic electrolyte. In these experiments, the solids were leached to 4,
20 and 100% oxygen consumption. All other variables were kept constant.
2. The effect of "copper depletion" in the first stage solution: This product is referred to
as "copper-depleted" cake. This first stage cake is produced in the plant when copper
is depleted from solution during the first stage leaching step. It is frequently
associated with high levels of arsenic. Copper-depleted cake was investigated because
difficulties in leaching have appeared in the plant during second stage leaching of this
material. Two leaches were carried out to 20 and 100% oxygen consumption.
-46-
3. The effect of arsenic: High arsenic (5 g/L) was added to the synthetic electrolyte
initially. The cake was leached to 20 and 100% oxygen consumption.
4. A leach with high Cu/S ratio solids (Cu/S ratio = 5.5)
3
was performed. The higher
copper levels were achieved by adding fine copper powder to the cake.
3.2 Part B: Kinetic Experiments
The main objective of the kinetic experiments was to try to determine how fast the solids
leached under a variety of solution conditions. These experiments were designed to maintain
approximately constant solution conditions by using small pulp densities. A slurry volume of
1.8 Uters was chosen to minimize the oxygen inventory in the autoclave relative to the amount
of oxygen required to oxidize the solids. This volume was the maximum that could be used
safely. An overfilled autoclave could be dangerous because, as the solution is heated, the liquid
could expand to the point of creating hydraulic pressure in the autoclave.
The amount of solids used in these experiments was 15 g. The quantity of oxygen
required for the total oxidation of 15 g of solids is approximately 0.22 mole and the amount of
oxygen occupying the free space in the autoclave is less than 0.064 mole Cbased on less than 0.2
liter of free space) at the operating temperature and pressure. These numbers were considered
to be acceptable for these experiments.
A factorial design was chosen for this part of the experimental program. The following
variables were chosen to be studied and were coded according to the following formulae:
X, (Cu/S ratio) = semi-quantitative variable, l(high), O(average), -l(low)
X
2
(Acid) = ([H
2
SO
4
]-60)/60
X
3
(Copper) = ([Cu]-20)/20
X
4
(Iron) = ([Fe]-2.5)/2.5
3 The solids being used in the experiments have a Cu/S ratio of 4.4 and a low Cu/S ratio is
considered to be values below 4.
-47-
Three values (-1,0,1) of each variable were chosen. For example, acid concentration was varied
at values of 0, 60, and 120 g/L H2S04 to give values of X
2
of -1, 0 and 1 respectively. The
complete list of planned experiments is given in Appendix B. Unfortunately, no high Cu/S ratio
cake was available during the experimental program. All experiments to be run at high Cu/S
ratio were therefore cancelled.
The stirring speed was set at 1350 rpm to ensure that oxygen mass transfer would not be
a rate controlling factor. The temperature and pressure were the same as in part A. Blank
experiments (no solids in the batch) were performed so that the experimental results could be
adjusted to obtain net leaching rates.
The leach solution was filtered and analyzed via an ICP scan. The solids were weighed
and recovered for an ICP scan and x-ray diffraction analysis. If enough solids were available, a
sulphur analysis was also performed.
3.3 Part C: Leaching CuS in the presence of basic copper sulphate
Since the slow leaching conditions are predominant during the leaching of CuS in the
presence of basic copper sulphate, it was decided that this process stage should be investigated
further. A series of experiments were conducted to measure the leaching rate of CuS in the
presence of added basic copper sulphate under a variety of solution conditions. The tests were
performed in a similar method to that of part B.
The CuS was obtained by leaching first stage cake to 50% oxygen consumption at which
point all remaining solids are expected to be CuS based on part A results. Basic copper sulphate
was obtained by running a leach to 100% oxygen consumption. Both solids were filtered and
washed prior to use.
The copper concentration was varied from 0 to 80 g/1 and the iron concentration was set
at 0 or 0.25 g/1. Basic copper sulphate (50 g) was added to each batch. Two blank experiments
were performed with no CuS present. The list of experiments is given below in table 3.2.
-48-
Table 3.2 List of part C experiments performed.
Experiment [Cu] (g/L) [Fe] (g/L) CuS present
1 0 0.25 No
2 0 0.25 Yes
3 80 0.25 Yes
4 10 0.25 Yes
5 40 0.25 Yes
6 1 0.25 Yes
7 0 0 No
8 0 0 Yes
9 80 0 Yes
10 10 0 Yes
11 40 0 Yes
12 1 0 Yes
-49-
CHAPTER 4 - Results and Discussion
4.1 Part A: Study of the sequential nature of the reactions
The results of the experiments in this section are presented as graphs of the amount of
metal species reporting to either the leach and releach solutions or the solids residues. The raw
data used to generate the graphs are provided in Appendix C.
4.1.1 The behavior of copper dissolution
Analyzing the behavior of copper during the leaching process provides the most
important clues as to how the leaching process proceeds. The model's first premise is that
copper leaches out of the sulphide particles sequentially according to the reactions shown
earlier. These equations are given here again and will be referred to by their respective
numbers in following sections.
1. Cu
x
S + (x- l)H
2
SO
A
+ ^(x- l)0
2
->CuS + (x- l)CuS0
4
+ (x-\)H
2
0
2. Cu
x
S +^(x - l)CuSO, + ^(x - l)0
2
+ 2(x - \)H
2
0 -> CuS +^(x - IftCuiOH^ CuS0
4
3. Cu
x
S - \)0
2
+ (x - \)H
2
0 -> |(3-x)CuS +^(x - l)(2Cu(OH)
2
CuS0
4
)
4. CuS + 20
2
-+CuSO
A
5. CuS+H
2
SO
A
+^0
2
^CuSO
A
+ H
2
0 +S
The results for the copper distribution are shown in Figures 4.1 and 4.2. In Figure 4.1,
the leach solution assay is the level of copper in solution as soon as the leaching process is
stopped. The releach solution is representative of the amount of basic copper sulphate
formed since this is found by redissolving the basic copper sulphate precipitate using
sulphuric acid. The amount of the copper shown in the solids is obtained from the assay of
the "unreacted" cake. Figure 4.2 is a magnification of the vertical scale achieved by not
plotting the amount of copper in the solids residue.
-50-
By analyzing the copper in solution, it can be seen that the copper in solution rises as
expected if reaction 1 is proceeding up until 5% oxygen consumption. At this point, all acid
should be depleted and reaction 2 should proceed. Since reaction 2 consumes copper to
form basic copper sulphate, the copper in solution should begin decreasing. This
observation is consistent with the expected behavior. After reaching a minimum, the copper
in solution should begin to increase again as CuS dissolution begins eventually according to
reaction 4. It must also be noted that the initial rate of reaction is very fast and the time taken
to reach 20% oxygen consumption is less than 30 minutes. This means that all CUxS is
converted to CuS in less than half an hour. Total leaching times to 100% oxygen
consumption in the lab were approximately 4.5 hours. The part A experiments were
sensitive to agitation speed suggesting that the gas-liquid mass transfer is an important
variable.
The model was run with the same initial batch recipe as used in the experiments to see
which reactions are predicted to proceed under the experimental leaching conditions. The
comparison of the model to the actual results is shown in Figure 4.3. The model predicts that
the reactions 1,2,3 and 4 proceed in order given the batch recipe used in the lab. This would
mean that copper in solution should become depleted just beyond the 20% oxygen
consumption point and reaction 3 should proceed until all of the Cu
x
S is transformed into
CuS.
However, by analyzing the comparison of the model and the actual results, it appears
that the copper in solution never reaches as low a level as predicted. There are two possible
reasons why the amount of copper in the leach solution always appears higher in the actual
results.
The first explanation is that the leaching reactions proceed with a small degree of
overlap. As the leaching process starts, some of the CuS formed under reaction 1 reacts with
the acid according to reaction 5 to produce elemental sulphur and copper sulphate. This
would also explain the small amount (1-2%) elemental sulphur observed in the residue.
-51-
500.0
Distribution of Copper
As a Function of Oxygen Consumption
40 60
Percent Oxygen Consumption (%)
Leach Sol'n
Releach Sol'n
Solids
Figure 4.1 The distribution of copper during leaching of chalcocite.
-52-
After the acid is depleted (-5% oxygen consumption), reaction 2 proceeds rapidly but
reaction 4 may also proceed at a relatively slow rate. Reaction 4 causes some copper
dissolution and prevents complete depletion of copper in solution. Reaction 4 proceeding
would also cause the minimum point to move well beyond the 20% oxygen consumption
point and cause some Cu
x
S to exist beyond the 20% point as well. By looking at Figure 4.2
and the x-ray diffraction results in Table 4.1, it can be seen that this is consistent with the
observations. The x-ray diffraction results show that Cu
x
S disappears somewhere between
25 and 30% oxygen consumption.
Comparison of Model to Actual Results
500 | =
% Oxygen Consumed
Cu in Solids (Actual) A Cu in Releach Solution (Actual) Cu in Solution (Actual)
Figure 4.3 Comparison of the model results to the actual behavior.
-53-
Table 4.1 X-Ray Diffraction Results
Oxygen
Consumption
Relative Strength
of XRD Pattern Compounds Observed
0.0% Very Strong
Medium
Medium
Chalcocite (CujS)
Copper I Sulphide (Cu,.
%
S)
Cuprite (Cu
2
0)
5.0% Strong
Strong
Cu
x
S(1.96<x<1.86)
Copper Sulphide (Cu,.
765
S)
10.9 % Very Strong
Medium
Digenite (Cu,
76
S)
Covellite (CuS)
17.9 % Very Strong
Weak
Covellite (CuS)
Digenite (Cu,
76
S)
20.0 % Very Strong
Medium
Medium
Weak
Covellite (CuS)
Digenite (Cu,
76
S)
Copper Sulphate Hydroxide Hydrate
Copper Hydroxide Sulphate
25.1 % Very Strong
Weak
Covellite (CuS)
Digenite (Cu,
76
S)
30.0 % Very Strong
Medium
Weak
Covellite (CuS)
Copper Sulfate Hydroxide Hydrate
Copper Sulphate Penta Hydrate
37.7 % Very Strong
Possible (v. Weak)
Covellite (CuS)
Digenite (Cu,
76
S)
47.9 % Very Strong Covellite (CuS)
75.0 % Very Strong
Weak
Weak
Covellite (CuS)
Copper Sulphate Penta Hydrate
Lead Sulphate (PbS0
4
)
100% Very Strong Anglesite (PbS0
4
)
-54-
Table 4.1 X-Ray Diffraction Results cont.
Oxygen
Consumption
Relative Strength
of XRD Pattern Compounds Observed
No iron in leach solution.
20.0 % Very Strong
Medium
Weak
Covellite
100% Strong
Strong
Medium
Covellite (CuS)
Anglesite (PbS0
4
)
Copper Sulphide (Cu
18
S)
High arsenic in solution
20.0 %
Very Strong
Medium
Weak
Covellite (CuS)
100%

(Not enough solids recovered for analysis.)
The other reason that the copper in solution appears higher in solution is possibly
because some of the basic copper sulphate may dissolve upon cooling by back reacting with
H
+
ions according to the following reaction [32]:
3Cu
2+
+ 3S0
2
' + 4H
2
0 <r> 2Cu{OH\-CuSO
A
+ 2HSO; + 2H
Jf
The equihbrium of this reaction shifts to the left as it is cooled. Figure 4.4 from Kwok and
Robins [32] shows that as a solution of copper sulphate is heated, the basic copper sulphate
precipitates resulting in an increase in acidity. However, considering that the average pH of
the slurry is 2.8, there is not enough of a change in pH to account for the discrepancy
observed in the results.
The amount of copper in the solids is very close to the predicted behavior during the
leaching process. Figure 4.5 shows a comparison of the amount of sulphur remaining in the
-55-
300
u
o
u 200
a.
2
100
CuS0
4
- 2Cu( OH)
2
PRECIPITATION
COMMENCES HERE
pH
25
Figure 4.4 "Reaction" temperature versus pHjs change during precipitation from lm
CuS0
4
solution. The "equilibrium" boundary for lm solution is also shown
[32].
solids as a function of oxygen consumption. There should be no sulphur oxidation before
the 20% oxygen point but the results show that there is a slight amount. This again is
probably due to the fact that reaction 4 proceeds prior to the complete disappearance of
Cu^.
-56-
Comparison of Model to Actual Results
Figure 4.5 Comparison of sulphur levels in the leach residue between the model and
actual results.
Although the reactions are not completely sequential as predicted, they appear to be
very close to being sequential. Reaction 4 proceeds prior to the predicted time. This is
verified by the comparison made between the model and actual results. The x-ray
diffraction results show the formation of intermediate compounds of copper sulphide
during the leaching process. The leaching of Cu
x
S (2>x>l) is very fast compared to the
leaching of CuS because the leach times to 20% consumption were less than 30 minutes and
-57-
the remaining 4 hours of leaching were devoted mostly to CuS dissolution. The lower than
expected amount of basic copper sulphate observed can only be explained as result of the
reactions not occurring sequentially.
The most important result was that there was no slow leaching behavior exhibited in
the laboratory experiments. This result is consistent with other experiments done under
normal leaching conditions previously at INCO labs.
4.1.2 Iron and Arsenic
The iron is slowly leached into solution during the reaction time (Figure 4.6).
However, most of the iron in solution precipitates rapidly with the basic copper sulphate to
a stable level by the 25% oxygen consumption point. The level of iron in the precipitate
begins to decrease slightly by the end of the leach process probably due to some iron being
resolubulized into the leach solution.
The role of iron in the leaching process is very important. As discussed in the
literature review section, iron was found to increase the leaching rates in most studies
primarily by acting as a charge carrier between the oxygen and the copper sulphide
particles. Iron is also thought to have an important affect on the precipitation behavior of
basic copper sulphate. The experiments with no iron in solution showed some very
interesting behavior. The resulting basic copper sulphate slurry was much more viscous
and the agglomerate size of the precipitate was finer (see Figure 4.7). The rate of oxygen
consumption also slowed down considerably at approximately 15% oxygen consumption
and was very sensitive to stirring speeds. This suggests that gas-liquid mass transfer is
severely affected by the increased viscosity.
Arsenic in the solids is initially leached very quickly to the 5% oxygen consumption
point but then precipitates out to report to the releach solution (Figure 4.8). All the arsenic
that is leached out steadily for the remaining leaching time reports to the releach solution
and not to the leach solution. There appears to be an error in the assay of the releach solution
at the 5% point because the mass balance at this point does not add up to the total amount of
-58-
Distribution of Iron
3.0
3
$ 2.0
ID 1
J
2
Leach Sol'n
Releach Sol'n
Solids
0 20 40 60 80 100
Figure 4.6 Distribution of iron during leaching.
arsenic in the system. The releach solution assay is thought to be incorrect because the
arsenic is expected to be in the leach solution before it can precipitate. The other reason that
this point is thought to be in error is because the results of the experiment with no iron in
solution show that arsenic first reports to the leach solution and then to the precipitate
beyond the 5% oxygen point (see assay results in Appendix C).
-59-
(a) With Iron-xl 500 (c) Without Iron-xl 500
-60-
Distribution of Arsenic
3.0 |
0 20 40 60 80 100
Figure 4.8 Distribution of arsenic during leaching.
4.1.3 Nickel and Cobalt
The leaching behavior of nickel and cobalt is very similar (Figures 4.9 and 4.10). Both
metals leach very quickly and stay in the leach solution without any appreciable amount of
precipitation. Nickel leaches quickly in the presence of acid and reaches a steady state by
20% oxygen consumption. Cobalt also leaches quickly in the presence of acid but continues
to leach slowly until the end of the process. Neither metal is thought to affect the leaching
process significantly at the levels at which they are present in the system.
-61-
1.0
Distribution of Nickel
Figure 4.9 Distribution of nickel during leaching.
Distribution of Cobalt
As a Function ot Oxygen Consumption
-62-
4.1.4 Additional Observations of Part A Experiments
The experiments done with excess arsenic in solution or using the "copper depleted"
cake yielded no unusual leaching behavior. Only the experiments done with high Cu/S
cake and no iron in the electrolyte showed significant differences in leaching behavior.
The experiments done with a high Cu/S ratio cake showed significant sensitivity to
agitation speed and the slurries were higher in viscosity due to more basic copper sulphate
being formed. The higher viscosity observed was not measured but was just based on visual
observations in comparison to other experiments.
The effect of no iron in the original electrolyte was discussed earlier and reported as
having a significant effect on the viscosity probably as a result of the finer precipitate
formation. After six hours of leaching time, there was 4 times as much unleached material
as expected with copper sulphides still appearing in the x-ray diffraction results (see Table
4.1). The slow leaching in these experiments appears to be more a function of high viscosity
and therefore mixing/gas-liquid mass transfer rather than chemistry. It must be noted that
the "no-iron" condition is almost impossible in the plant because there is always significant
levels of iron present in the spent electrolyte and entrained in the first stage cake liquor.
4.2 Part B: Kinetic Experiments
The part B experiments can be divided into 2 sections; those performed with and without
acid in solution. The two types of experiments must be considered distinct because they take
different reaction paths in the leaching of chalcocite. For this reason, the originally suggested
factorial design analysis was not carried out on the results. The experiments done with acid in
the initial solution are not very representative of the leaching path in the plant because the acid
is present during the whole leaching time in these experiments. The leaching rates that are of
interest are the ones in which the acid is depleted early in the process.
-63-
The leaching rate versus percent oxygen consumption plots are provided in Appendix D
for the acid and no-acid experiments. These graphs were generated by subtracting the blank
experiments (no solids added) from the actual experiments to obtain net rates. The "loops"
formed at the initial part of the plot are caused by the subtraction of the two runs.
The experiments that begin with acid in solution proceed initially via reaction 1 where
Cu
x
S is converted to CuS. This is followed by the leaching of CuS via reaction 5. However,
reaction 4 must occur to a limited degree because some of the sulphur is oxidized. The chemical
analyses of the leach residues contained approximately 90% sulphur and the x-ray diffraction
results show very strong elemental sulphur patterns. The degree of sulphur oxidation is shown
in Table 4.2 for the various runs performed with acid. It should be noted that those experiments
with no copper and/or iron in solution showed higher levels of sulphur oxidation. This is
consistent with the work done by Mao and Peters [13]. They found that the presence of iron
lowered the levels of sulphur oxidation. They observed 90.6% elemental sulphur in their
residues, values very similar to the ones observed in these experiments. All of the sulphur was
found to oxidize in the experiments done with no acid in the solution.
The times taken to 10,15 and 20% oxygen consumption are given in Table 4.3. They show
very clearly that the initial leaching rates are very fast where Cu
x
S is being converted to CuS.
The time to 20% oxygen consumption is usually less than 3 minutes and is a very short duration
relative to the total reaction time of most of these experiment of 2.5-3 hours. This initial rapid
leaching of chalcocite is consistent with the work of Mao and Peters [13] as well as other
researchers.
-64-
Table 4.2 Degree of sulphur oxidation at various initial acid, copper and iron concentrations.
Cu/S
[HjSOJ
[Cu] [Fe] % Sulphur
Ratio
(g/D
(g/U
(g/D
Oxidized
Medium 60 40 5 7.6
Medium 60 40 0 15.9
Medium 60 0 0 31.6
Medium 60 0 5 21.4
Medium 60 20 2.5 16.0
Medium 60 20 2.5 10.4
Medium 120 0 2.5 23.9
Medium 120 40 2.5 1.6
Medium 120 20 5 9.6
Medium 120 20 0 28.4
Low 60 20 0 28.5
Low 60 0 2.5 26.6
Low 60 20 5 15.3
Low 60 40 2.5 15.4
In the experiments with no acid in the initial batch recipe, the material is expected to leach
via reaction 2 followed by reaction 4. The reactions are not expected to be entirely sequential as
the results of part A have indicated. In these experiments, all of the sulphur was to oxidize. The
times to 20% oxygen consumption are very fast in the no-acid experiments also.
The total leaching times in these experiments were much shorter than part A. This is most
likely due to the fact that the agitation speed was higher and the pulp density was lower
contributing to better mixing and much higher gas-liquid mass transfer rates.
-65-
Table 4.3 Time taken to leach to 10, 15 and 20% oxygen consumption at various initial
acid, copper and iron concentrations.
Cu/S [HjSOJ [Cu] [Fe] Time (s) to %consumption
Ratio
( g/ U ( g/ u (g/D
10% 15% 20%
Medium 0 20 5 90 142 305
Medium 0 0 2.5 100 175 334
Medium 0 40 2.5 80 105 186
Medium 0 20 0 162 332 499
Medium 60 40 5 78 92 107
Medium 60 40 0 89 110 143
Medium 60 0 0 84 110 174
Medium 60 0 5 95 109 122
Medium 60 20 2.5 115 129 146
Medium 60 20 2.5 90 108 129
Medium 120 0 2.5 168 284 306
Medium 120 40 2.5 83 98 116
Medium 120 20 5 100 116 137
Medium 120 20 0 90 113 141
Low- 0 20 2.5 230 399 559
Low 60 20 0 137 250 640
Low 60 20 2.5 89 105 125
Low 60 20 5 92 110 136
Low 60 20 2.5 132 152 180
4.3 Part C: Leaching CuS in the presence of basic copper sulphate
Figures 4.11 and 4.12 show the oxygen consumption rates at regular intervals during the
leaching of CuS in the presence of basic copper sulphate. The rate of oxygen consumption at
low copper concentrations, between 1 and 10 g/L, appears to be slower. A minimum point
probably exists somewhere in this range but it is not possible to depict without more data. This
dip in rate is apparent in both the experimental conditions of iron and no-iron in solution.
Beyond the minimum point, the rate of oxygen consumption (CuS leaching) generally appears
-66-
to be copper catalyzed and increases with increasing copper in solution.
Oxygen Consumption Rate
Al Various Copper Concentrations
0.0 I
1 1 1 1
:
1 1 1
' 0.0
0 20 40 60 80
Initial Copper Concentration (g/L): [Fe]=0.25
Figure 4.11 Oxygen consumption rate at various initial copper concentrations with initial
[Fe]=0.25 g/L. Each curve represents a different level of oxygen consumption.
Comparing the leaching rates of experiments done with and without iron in solution, it
appears that iron in solution increases the leaching rate. Appendix F contains plots of rates at
various oxygen consumption points with and without iron in solution. There is a crossover of
rates between the 0 and 10 g/L Cu points.
Table 4.4 and Figure 4.13 show that increases in the initial copper concentration or iron
concentration results in an increase in the oxidation-reduction potential (ORP). This is
consistent with the Nernst equation, e.g.:
-67-
Figure 4.12
At Various Copper Concentrations
20 40 60
Initial Copper Concentration (g/L): [Fe]=0
10%
20%
30%

40%
50%
60%
70%
80%
Oxygen consumption rate at various initial copper concentrations with initial
[Fe]=0 g/L. Each curve represents a different level of oxygen consumption.
Cu
2+
+ e'^Cu
+
R T [Cu
+
1
EL = E - I n -
1
nF [Cu
2+
]
A higher solution potential will tend to increase the leaching rate by imposing a higher
exchange current on the mineral. Figure 4.14 shows a schematic of an Evans E>iagram of the
possible polarization curves during CuS leaching. The reversible potential of CuS leaching as
shown on Figure 4.14 at 388 K is approximately 0.21 V. The actual ferric and cupric polarization
curves will be a result of the mixed potential caused by both iron and copper in solution. The
iron in solution is reported to be easily oxidized from ferrous to ferric in the presence of copper
as the cupric-cuprous couple is thought to catalyze the oxidation of the ferrous species [36].
-68-
The increase in the leaching rate observed at higher copper concentrations and higher iron
concentrations is now more understandable. The increase in the cupric/cuprous, ferric/ferrous
ratios or a net increase of the cupric or ferric concentrations will increase the mixed solution
potential and as a result increase the anodic current (leaching rate).
The dip in the solution potential, and consequently the leaching rate, observed at
approximately 10 g/L copper concentration was not explainable. This point is not likely to be
in error because it occurs in both the experiments (ie. [Fe]=0 and [Fe]=0.25 g/L).
Table 4.4 Potential and pH measurements of the leach slurry after leaching
and the approximate temperatures at which they were measured.
Initial Initial pH ORP (mV) Temperature CO
[Cu] (g/L) [Fe] (g/L)
0 0.25 2.84 350 80.1
1 0.25 2.79 353 77.9
10 0.25 2.53 319 81.5
40 0.25 2.51 491 84.6
80 0.25 2.43 499 83.0
0 0 2.78 314 85.9
1 0 2.68 360 82.9
10 0 2.50 321 84.0
40 0 2.68 445 86.9
80 0 2.43 449 85.1
-69-
>
E
550.0
500.0 -
g 450.0 -
o
cu
g 400.0 -
o
350.0
300.0
Solution Potential
at Various Copper Concentrations
10 20 30 40 50 60
Initial Copper Concentration (g/1)
80
Figure 4.13 The effect of initial copper concentration on the measured ORP at [Fe]=0 and
[Fe]=0.25 g/L.
Evans Diagram Schematic of Applicable
Polarizations Curves During CuS Leaching
1.0
0.8
0.6
o
> 0.4
0.2
0.0
-0.2
Increasing ferric or cupric ion
concentration
CuS+ 4HjO-- Cu + SO*+ 8H
+
+ 8e
_
Log I - Galvanic Current (Schematic)
Figure 4.14 Evans diagram of applicable polarization curves during pressure leaching of
CuS (schematic).
-70-
4.3.1 Discussion of ORP Measurements
Since there is a small amount of solids present in the slurry when the ORP is measured,
the value obtained is really a "mixed potential" because it is affected by both the solids
present and the prevailing solution conditions. However, since the solids concentration is
very low in the part C experiments, the measured ORP value is much closer to the solution
potential. A simple calculation shows that the solid potential changes very little as a result
of the change in copper concentration.
The equilibrium reaction is:
Cu
2+
+ SOl~ + 8/Y
+
+ &e <=> CuS + 4H
2
0
This potential will vary as a function of [Cu
2+
]:
ie RT 1
' E = E- 2.303log
a
Cu**
a
*-
a
+
And assuming: a
sol
- = a
Cu
i
t
2.303(8.314) (298.15),
2
2.303(8.314) (298.15)
E = E +
8^965001
l 0 g a
(96500)
p H
E = E + 0.0148 \oga
Cult
- 0.059\6pH
Therefore, the "solid potential" will vary by -15 mV per order of magnitude change in
copper concentration.
The cathodic reaction is:
0
2
+ 4ht+4e -*2H
2
0
However, it is also possible for other reactions to catalyze the reaction:
Fe
3+
+ e -> Fe
2+
Cu
2+
+ e -> Cu
-71-
The observed changes in the ORP measurements are large (Table 4.4). However,
according to the calculation above, the "solid potential" can only change by -15 mV per
order of change in the Cu
2 +
concentration. It is therefore more likely that the observed
change in the ORP measurement is a result of the Cu
2 +
/ Cu
+
and/or Fe
3+
/Fe
2+
couples. An
increase in potential of these couples increases the rate of electrochemical dissolution and
hence increases the rate of leaching. This observation is important since it indicates that the
levels of copper and iron in solution are important as catalysts and. may be serving as
surrogate oxidants.
4.4 Comparison of Leaching Rates - Part A and Part C
A comparison of leaching rates between part A and part C experiments was performed to
determine an empirical relationship between them (see Table 4.5). The main difference between
these experimental section was the pulp density and agitation speeds. The comparison of rates
is done at 60 and 70% oxygen consumption for the following reasons:
1. The copper concentrations are similar in these experiments.
2. The predominant material (solids) remaining is CuS.
3. The flow rates are extremely stable and are not affected by initial transients.
4. There is no manual oxygen flow control, as was practiced in the early stages of the
part A experiments
4
.
If the ratio of rates is taken between these two parts, it can be seen that the rate of leaching
is 4.5 and 4.2 times as high in the 60% and 70% runs respectively in the part C experiments. This
lends further credence to the fact that the rates must be dependent upon agitation and/or pulp
density both of which significantly affect gas/liquid mass transfer.
4 The oxygen flow rates in the part A experiments had to be limited by a flow valve in the
early stages to keep the flow within the range of the flow meter. Beyond approximately 40%
oxygen consumption, the valve was opened totally to allow the system to receive oxygen as
needed.
-72-
Table 4.5 Comparison of oxygen flow rates
Weight of
Solids
Remaining (g)
[Cu]
(g/D
[Fe]
( g/
Oxygen
How Rate
(cc/s)
Ratio of
Flow rate / Wt.
Remaining
At 60% Part A 159 92 <0.1 23.5 0.15 At 60%
PartC 6 86 <0.1 4.1 0.68
At 70% Part A 115 112 <0.1 19.5 0.17 At 70%
PartC 4.5 87.6 <0.1 3.26 0.72
4.5 Additional Observations
An experiment was performed to produce basic copper sulphate for part C experiments.
The solids loading was increased to 600 g and 40 g of fine copper powder was added. The
oxygen consumption rate dropped significantly at the basic copper sulphate point and
displayed behavior that could be classified as "slow cook". The rate was very sensitive to
agitation speed. The products of this leach were not subsequently used in the part C
experiments and a new experiment was performed in its place. This experiment did, however,
prove very dramatically the significant effect of slurry density (or as a result, viscosity) on the
rate of leaching.
Some temperature measurements [37] were made on the plant autoclave walls during
leaching. Since the autoclave is thin walled, the surface temperature was expected to be quite
close to the slurry temperature in the autoclave. Since the autoclave is thought to be well mixed,
the surface temperature was also expected to be uniform at various points on the surface of the
autoclave. However, the temperature measurements on the surface of the autoclave were quite
variable and well below the 115C set point. The surface temperature ranged from 85 to 105C
at various points. This suggests that there may be a problem with mixing in the autoclave and
if that is the case, then the gas-liquid mass transfer can probably considered to be poor also.
-73-
Viscosity measurements [38] were made on the basic copper sulphate slurry produced in
the plant using a Brookfield viscometer. The results suggested that the viscosity between
batches varied considerably and that the slurry displayed a "pseudoplastic" behavior.
Pseudoplastic fluids display a decrease in viscosity with an increasing velocity gradient.
Commonly encountered examples, as given in most fluid dynamics textbooks [39], of
pseudoplastic fluids are slurries, muds, polymer solutions and blood. This would mean that
slurry near the impeller area would be quite fluid while the slurry remote from the areas
affected by the impeller would be significantly more viscous.
In some leaches there is a significant amount of copper found to be remaining in the
residue even when it appears that the leaching is complete (ie. no temperature rise or oxygen
consumption detected). This could also be a function of poor mixing. If there are any "dead
spaces" in the autoclave, then there would be unleached solids trapped in these areas that would
report to the residue. This is very possible given the pseudoplastic behavior of the slurry. In
fact, the area behind the cooling coils may be even be stagnant or experiencing very little mixing
once high concentrations of basic copper sulphate are formed in the autoclave. Figure 4.15 is a
hypothetical diagram to show how the well mixed and poorly mixed zones may appear in the
autoclave. Further investigations must study the effects of viscosity on fluid flow to provide a
better picture of the mixing in the autoclave.
-74-
Figure 4.15 A schematic highlighting areas believed to be well mixed in the second stage
autoclave. The poorly mixed zones are thought to the result of the observed
pseudoplastic behavior of the slurry.
-75-
CHAPTER 5 - Conclusions and Recommendations
5.1 Conclusions
The leaching of chalcocite can be divided into a number of nearly sequential reactions.
The reaction path is determined by the prevailing solution conditions which are in effect
controlled by the initial batch recipe. The predominant reactions, as proposed in the screening
model, were verified as being accurate in defining the leaching process. These reactions are:
1. CuJ + (x- WtSOt + îx -\)0
2
-+CuS + (x- \)CuS0
4
+ (x - \)H
2
0
2. Cu
x
S +^(x - l)CuSOt + ^(x - l)0
2
+ 2(x - \)H
2
0 -> CuS +^(x - l)2Cw((9//)
2
CuSO
A
3. Cu
x
S + | ( J C - 1)0
2
+ (x - l)H
2
0 -> ^(3-x)CuS +^(x - l)(2C(0//)
2
-CuSOJ
4. CuS + 20
2
^CuSO
i
5. CuS + /7
2
50
4
+10
2
-CuSO
A
+ H
2
0+S
The reactions were found not to be entirely sequential. It is believed that reactions 4 and
5 proceed slowly before all of the Cu^ is completely converted to CuS. However, reactions 1
and 2 were found to be very fast and the degree to which reactions 4 and 5 can occur in this short
time is small and so the leaching process can be modelled as being sequential.
The screening model based the leaching kinetics on two steps; gas-liquid mass transfer of
oxygen and copper catalysis. Slow leaching kinetics that were expected under copper depletion
in solution were not realized. Copper in solution, although shown to increase the leaching rate,
does not inhibit the leaching process to the point of creating the "slow cook" conditions. Also,
the copper in solution is never depleted because of reactions 4 and 5 proceeding before other
reactions have stopped. The "slow cook" condition observed in the plant cannot be a result of
-76-
loss of copper catalysis.
The chalcocite leaches progressively to form various intermediate copper sulphide
compounds such as djurleite (Cu,
%
S), digenite (Cu
1765
S Cu
176
S), and covellite (CuS). Various
intermediate compounds observed by other researchers were not observed in this study.
Deficiency of iron in solution increases the viscosity of the slurry by promoting
precipitation of a finer precipitate. The result is slower leaching. Incomplete leaching also
results with a lack of iron in solution. The iron is most likely the dominant leaching agent
because it is available in higher concentrations around the particles than dissolved oxygen. The
lack of iron has a two-fold effect on the leaching process by promoting the formation of a higher
viscosity slurry and reducing the concentration of the surrogate oxidant.
The distribution of arsenic, nickel and cobalt during leaching was reported and was found
to have no discernible effect on the leaching process.
High solids loading in the process was also found to increase the viscosity of the slurry
and cause the leaching process to slow down. Significantly higher leaching rates are realized as
a result of leaching at lower pulp densities.
Observations made on the surface temperature on the of the plant autoclave appear to
suggest that there is also poor mixing in the autoclave. The pitched-down impeller design is not
the optimum based on oxygen mass transfer studies done at U.B.C. [35]. The cause of the slow
and incomplete leaching observed in the plant is most likely caused by poor gas-liquid mass
transfer and/or poor mixing.
5.2 Recommendations for further work
This study has shown that the major rate controlling parameter is not based on the
chemical kinetics of the leach but rather the poor gas-liquid mass transfer in the plant
autoclaves. Further research on the investigation of this leaching process must address the
following issues:
1. The effect of iron on the precipitate particle size and viscosity of the slurry.
-77-
2. The effect of viscosity on the limits of dissolved oxygen concentration and gas-liquid
mass transfer.
3. The effect of impeller design and impeller depth on gas-liquid mass transfer.
4. The effect of autoclave shape and baffling created by the cooling pipes.
-78-
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30. Hillrichs E., Greulich H., Bertram R., "Investigations of the Electrochemical Dissolution of
Copper Sulfide Ores in Sulfuric Acid Solutions", Hydrometallurgy Reasearch,
Development and Plant Practice, eds. K. Osseo-Asare and J.D. Miller, TMS-AIME, 1983,
277-287.
31. MacKinnon, D.J., "Fluidised-Bed Anodic Dissolution of Chalcocite", Hydrometallurgy, 1,
241-257, (1976).
32. Kwok O.J. and Robins R.G., "Thermal Precipitaion in Aqueous Solutions", International
Symposium on Hydrometallurgy, eds. D.J.I. Evans and R.S. Shoemaker, 1033-1080,1973.
33. Roseboom E.H. Jr., "An Investigation of the System Cu-S and Some Natural Copper
Sulphides Between 25 C and 700 C", Econ. Geol., 61,641-672,1966.
34. Peters E.,"Oxygen Utilization in Hydrometallurgy: Fundamental and Practical Issues",
Proc. of the International Symposium on the Impact of Oxygen on the Productivity of
Non-Ferrous Metallurgical Processes", eds. Kachaniwsky G. and Newman C, Pergamon
Press, New York, 151-164,1987.
35. Dawson-Amoah J., "Gas-Liquid Mass Transfer Rates by Gas Pumping Agitators in
Oxygen Pressure Leaching Systems", M. A.SC Thesis, The University of British Columbia,
1991.
36. Dreisinger D.B. and Peters E., "The Oxidation of Ferrous Sulphate by Molecular Oxygen
under Zinc Pressure-Leach Conditions", Hydrometallurgy, 22,101-119,1989.
37. Shelegey J. and Grewal I., unpublished data, August 1990.
38. Shelegey J. and Grewal I., unpublished data, September 1990.
39. De Nevers N., Huid Mechanics, Addison Wesley Publishing Company, Reading,
Masachusetts, pp 9-10,1970.
-81-
APPENDIX A - Detailed Flowsheet of the CRED Plant.
-82-
APPENDIX B - Planned Experiments for Part B-1.
The following is a list of the experiments that were originally planned for the Part B
experimental program. All of the following experiments were performed except for the ones in
which the value of X,=l (high Cu/S ratio) because this material was not available from the plant
at the time the experiments were being performed.
Table Bl. List of the planned experiments for part B.
Experiment
x
2 x
3 *4
Experiment
(Cu/S) (Acid) (Copper) (Iron)
1 -1 -1 0 0
2 1 -1 0 0
3 -1 1 0 0
4 1 1 0 0
5 0 0 -1 -1
6 0 0 1 -1
7 0 0 -1 1
8 0 0 1 1
9 0 0 0 0
10 -1 0 0 -1
11 1 0 0 -1
12 -1 0 0 1
13 1 0 0 1
14 0 -1 -1 0
15 0 1 -1 0
16 0 -1 1 0
17 0 1 1 0
18 0 0 0 0
19 -1 0 -1 0
20 1 0 -1 0
21 -1 0 1 0
22 1 0 1 0
23 0 -1 0 -1
24 0 1 0 -1
25 0 -1 0 1
26 0 1 0 1
27 0 0 0 0
-83-
APPENDIX C - Assay results of Part A experiments.
The assay results from part A experiments are shown in the following tables. The percent
oxygen is the fraction of oxygen used compared to the total amount required to leach the
sample. The assays reported as <0.0> represent a "very low" value; it was below the detection
limit of the analytical method.
Table Cl . Amount of the indicated species in the leach solution at various oxygen
consumption levels.
Percent Oxygen Amount of species in the leach solution (g).
(%)
Cu Ni Co Fe As S
0.0 18.5 0.00 0.00 2.65 0.00 38.8
5.0 79.1 0.54 0.08 2.29 0.80 43.8
10.9 61.4 0.63 0.10 0.57 0.00 31.6
17.9 39.6 0.66 0.11 0.28 0.00 20.6
20.0 39.0 0.62 0.11 0.15 <0.0> 20.3
25.1 36.3 0.65 0.13 0.13 0.01 18.9
30.0 43.6 0.58 0.12 0.10 <0.0> 22.6
37.7 61.3 0.67 0.15 0.17 0.03 31.5
47.9 80.6 0.66 0.16 0.13 0.06 38.7
75.0 145.0 0.61 0.16 0.07 0.11 73.0
100.0 194.3 0.76 0.20 0.06 0.14 104.3
Experiments with no iron in leach solution
4.0 74.6 0.49 0.09 0.08 0.85 19.4
20.0 38.0 0.61 0.11 <0.0> 0.03 19.6
100.0 180.7 0.63 0.16 <0.0> 0.12 92.6
Experiments with high arsenic in leach solution
20.0 48.5 0.64 0.14 0.13 0.01 25.2
100.0 197.6 0.29 0.17 <0.0> 0.15 103.3
-84-
Table C2. Amount of the indicated species in the releach solution at various oxygen
consumption levels.
Percent Oxygen Amount of species in the releach solution (g).
(%) Cu Ni Co Fe As
5.0 2.87 <0.0> <0.0> 0.09 0.80
10.9 73.3 0.009 0.002 1.98 0.96
17.9 162.9 0.035 0.008 2.36 1.18
20.0 161.9 0.029 0.004 2.28 1.20
25.1 201.8 0.040 0.013 2.54 1.44
30.0 204.1 <0.0> <0.0> 2.31 1.48
37.7 218.1 0.041 0.010 2.44 1.65
47.9 226.1 0.064 0.012 2.54 1.88
75.0 224.6 <0.0> 0.010 2.37 2.10
100.0 235.7 0.065 0.019 2.22 2.40
4.0 0.26 <0.0> <0.0> <0.0> 0.05
20.0 176.3 <0.0> 0.009 0.11 1.23
100.0 239.0 <0.0> <0.0> <0.0> 2.53
20.0 152.5 <0.0> 0.008 2.55 3.82
100.0 249.5 <0.0> <0.0> 2.19 5.18
-85-
Table C3. Amount of the indicated species in the releach cake at various oxygen
consumption levels.
Percent Oxygen
Amount of species in the leach cake (g).
(%) Cu Ni Co Fe As S
0.0 408.1 0.94 0.20 0.40 2.76 92.3
5.0 341.3 0.31 0.11 0.24 1.85 91.2
10.9 292.0 0.28 0.09 0.40 1.81 91.9
17.9 230.5 0.26 0.08 0.26 1.61 88.3
20.0 221.9 0.23 0.08 0.21 1.55 87.3
25.1 193.6 0.21 0.06 0.21 1.37 83.3
30.0 175.5 0.27 0.06 0.16 1.30 76.2
37.7 155.2 0.23 0.04 0.29 1.11 69.6
47.9 125.8 0.20 0.03 0.13 0.87 58.2
75.0 52.9 0.21 0.03 0.10 0.49 24.8
100.0 0.13 0.18 0.02 0.34 0.27 0.65
4.0 355.3 0.44 0.12 0.29 1.94 93.8
20.0 220.8 0.28 0.08 0.16 1.59 87.4
100.0 13.5 0.16 0.02 0.07 0.19 5.33
20.0 226.6 0.27 0.09 0.34 1.65 86.5
100.0 0.03 0.18 0.02 0.19 0.27 0.56
-86-
Table C4. provides a sum of all the species in the three phases as check to see if the assays
added upto the original amounts added into the process (ie. a mass balance). The totals in each
column should be approximately equal to the value given at zero oxygen conssumption.
Table C4. Total amount of species (calculated as a sum of tables C1-C3) in the process.
Percent Oxygen Amount of species in the process (g).
(%)
Cu Ni Co Fe As
0.0 426.6 0.94 0.20 3.05 2.76
5.0 423.2 0.85 0.19 2.62 3.45
10.9 426.6 0.93 0.19 2.95 2.77
17.9 433.0 0.95 0.20 2.89 2.79
20.0 422.8 0.88 0.19 2.64 2.75
25.1 431.6 0.90 0.20 2.88 2.81
30.0 423.2 0.85 0.17 2.57 2.78
37.7 434.6 0.94 0.20 2.90 2.78
47.9 432.4 0.93 0.20 2.81 2.80
75.0 422.5 0.82 0.19 2.54 2.70
100.0 430.1 1.01 0.24 2.63 2.81
4.0 430.2 0.93 0.20 0.36 2.84
20.0 435.1 0.89 0.20 0.27 2.85
100.0 433.2 0.79 0.18 0.07 2.83
20.0 427.6 0.92 0.23 3.03 5.48
100.0 447.1 0.47 0.19 2.39 5.59
-87-
Table C5. Distribution of species on experiments performed with the "copper depleted
cake".
Percent Oxygen Amount of species in the process (g).
(%)
Cu Ni Co Fe As
Leach Solution
0.0 20.0 0.00 0.00 2.50 0.0
20.0 61.8 1.63 0.39 0.46 0.01
100.0 234.5 2.59 2.53 0.02 0.005
Releach Solution
20.0 127.0 0.056 0.01 2.92 2.70
100.0 191.3 0.092 0.03 3.08 3.85
Leach Cake
0.0 392.7 2.70 2.63 0.28 4.06
20.0 227.6 1.28 2.28 0.21 1.47
100.0 0.0
s
0.0 0.0 0.0 0.0
Totals
0.0 412.7 2.698 2.63 2.78 4.06
20.0 416.3 2.961 2.68 3.59 4.18
100.0 425.8 2.679 2.56 3.10 3.85
5 The amount of residue in this experiment was very small and the quantity of species listed in
the table could be approximated as zero at 100% oxygen consumption.
-88-
Table C6. The pH and ORP values of the slurry after leaching to a given level of oxygen
consumption.
Percent Oxygen ORP
(%)
pH (mV)
5.0 1.69 366
10.9 2.80 65
17.9 2.93 295
20.0 2.68 332
25.1 2.94 285
30.0 2.76 285
37.7 2.76 300
47.9 2.85 321
75.0 2.97 323
100.0 2.20 182
No iron
4.0 1.41 290
20.0 2.62 390
100.0 2.41 182
High arsenic
20.0 2.57 336
100.0 1.99 458
-89-
APPENDIX D - Part B experimental results
The following pages contain the plots of the part B experimental results. They are
presented as plots rather than numerical data because the data files are too large to print
numerically and would occupy too many pages.
Blank experiments, done with no solids present in solution, were performed for each case.
These blank experiments were subtracted from the actual experiments to obtain a net leaching
rate. The plots on the following pages are the net leaching rate plots. The plots have negative
values of oxygen consumption. This is the result of the subtraction and has no interpretable
meaning. The initial peaks (erratic behaviour) is caused by the initial rapid kinetics and the
filling of the autoclaves with oxygen. The necessary data was extracted from the corresponding
numerical files where the process was stable.
In the plots labelled as (x
2
,X3,x
4
), the value of xl is zero. The other plots are labelled as
(x
1
,X2,x
3
,x
4
). The concentration values for the variables is provided in the experimental
procedures sections.
The plots are arranged as follows:
Figures DI. to DI4: Experiments in which acid was present in the solution at the
beginning of the experiment.
Figures D15. to D20. Experiments in which there was no acid present in the
solution at the beginning of the experiment.
-90-
Rate of Oxygen Consumpti on
Run Type: (1,1,0)
40 60
Percent Oxygen Consumed
Figure DI. Rate of oxygen consumption for the condition where (x
2/
x
3/
x
4
)=(l
/
l
/
0) and x
:
=0.
Rat e of Ox y g e n Cons umpt i on
Run Type: (1.0,1)
a.
2
,x
3/
X4)=(l,0,l) and x
t
=0.
-91-
Run Type: (1,-1,0)
2/
X3,x
4
)=(1,-1,0) and \y=0.
Run Type (1,0,-1)
20 1 ,
-5 -
-10 ' 1 1 1 I I | |
-10 0 10 20 30 40 50 60 70
2
,x
3
,x
4
)=(l,0,-l) and x,=0.
-92-
Figure D5.
0 20 40 60 80 100
Rate of oxygen consumption for the condition where (x
2/
x
3/
X4)=(0,1,-1) and x
t
=0.
Run Type: (0,0,0)
-20 0 20 40 60 80 100
2/
x
3/
x
4
)=(0,0,0) and x
t
=0.
-93-
Run Type: (0,1,1)
-
" 1
i i - i
-20 0 20 40 60 80 100
2
,x
3
,xi)=(0,\A) and xÔ.
Run Type: (0,-1,1)
30 i 1
Figure D8.
2
,x
3/
x
4
)=(0
/
-l
/
l) and x
:
=0.
-94-
Rate of Oxygen Consumption
Run Type: (0,-1,-1)
Figure D9.
2
,x
3
,x
4
)=(0
/
-l
/
-l) and xÔ.
Run Type: (0,0,0) #1
Figure D10. Rate of oxygen consumption for the condition where (x2,x3,xi)=(0,0,0) and xÔ.
-95-
Ox y g e n Cons umpt i on Rat e
Run Type: (-1,0,1,0)
; /
- V
-20 0 20 40 60 tO 100
Figure Dl l . Rate of oxygen consumption for the condition where (X
U
X
2/
X2,XA)=(-\,0,1,Q).
Run Type: (-1,0,-1,0)
-20 0 20 40 60 80 100
1
,x
2/
x
3/
X4)=(-l/0
/
-l,0).
-96-
Run Type: (-1,0,0,-1)
Perceni Oxygen Consumed
1/
x
2/
x
3/
x
4
)=(-l,0,0,-l).
Run Type: (-1,0,0,1)
1/
x
2
,X3
/
x
4
)=(-l
/
0
/
0,l).
-97-
Run Type: (-1,0,1)
-
1 1 1 ' 1 J 1 1 J 1 1
-10 0 10 20 30 40 50 60 70 80 90 100 110
2
,x
3
,X4)=(-i/0,l) and xÔ.
Run Type: (-1,0,-1)
15
E o
-5
-
\
\
-
, ==_
i i i i i i i i i i
10 0 10 20 30 40 50 60 70 80 90 100 110
Figure D16. Rate of oxygen consumption for the condition where ( x^x^M- l A- D and xÔ.
-98-
Run Type: (-1.1.0)
Perceni Oxygen Consumed
2/
x
3
/X
4
)=(-l,l
/
0) and x,=0.
Run Type: (-1,-1,0)
40 60
2r
x
3
,X4)=(-1/-i/0) and xÔ.
-99-
Run Type: (-1,-1,0,0)
30 I
0 10 20 30 <0 50 60 70 80 90 100 110
Percent Oxygen Consumption
Figure D19. Rate of oxygen consumption for the condition where (xjpc^x^M-l/-! AO).
-100-
APPENDIX E - Part C experimental results
The plots on the following pages are generated from the part C experiments in which CuS
is leached in the presence of basic copper sulphate. The levels of copper and iron in solution at
the beginning of the leach is given for each plot.
Blank experiments, done with no solids present in solution, were done for each case.
These blank experiments were subtracted from the actual experiments to obtain a net leaching
rate. The plots on the following pages are the net leaching rate plots. The plots have negative
values of oxygen consumption. This is the result of the subtraction and has no interpretable
meaning. The initial peaks (erratic behaviour) is caused by the initial rapid kinetics and the
fining of the autoclaves with oxygen. The necessary data was extracted from the corresponding
numerical files where the process was stable.
-101-
Modified B: Exp. #2
30 - -
Percent Oxygen COnsumed
Figure El . Rate of oxygen consumption where initial [Cu]=0 g/1 and [Fe]=0.25 g/1.
Modified B: Exp #3
Figure E2. Rate of oxygen consumption where initial [Cu]=80 g/1 and [Fe]=0.25 g/1.
-102-
Modified B: Exp.#4
Figure E3. Rate of oxygen consumption where initial [Cu]=lO g/1 and [Fe]=0.25 g/1.
Modified B: Exp. #5
40 I
at.
Figure E4. Rate of oxygen consumption where initial [Cu]=40 g/1 and [Fe]=0.25 g/1.
-103-
Ra t e of Ox y g e n Co ns umpt i o n
Modified B: Exp. #6
Figure E5. Rate of oxygen consumption where initial [Cu]=l g/1 and [Fe]=0.25 g/1.
Modified B: Exp. #8
10 .in -
-104-
Modified B: Exp. #9
Figure E7. Rate of oxygen consumption where initial [Cu]=80 g/1 and [Fe]=0 g/1.
Modified B: Exp. #10
10 |
-5 I 1 1 1 1 1
0 20 40 60 80 100
-105-
-10 0 10 20 30 40 50 60 70 90 100 110
Figure E10. Rate of oxygen consumption where initial [Cu]=l g/1 and [Fe]=0 g/1.
-106-
APPENDIX F - Part C experimental results - Effect of iron plots
The following pages contain plots of the leaching rates at various oxygen consumption
points as a comparison between the experiments done at [Fe]=0 g/L and [Fe]=0.25 g/L.
-107-
Ox y g e n Co ns u mp t i o n Rat e
At 10% Oxygen Consumption
05
Copper Concentration (gpl)
_,_[Fe]=0.25 __[Fe]=0
Figure Fl. Rate of oxygen consumption for various initial copper concentrations at the 10%
oxygen consumption point.
Ox y g e n Co ns umpt i o n Rat e
0*
30 40 50
Copper Concentration (gpl):
. [Fe)=0.25
.[Fe]=0
Figure F2. Rate of oxygen consumption for various initial copper concentrations at the 20%
-108-
. [Fe]=0.25 .[Fe]=0
Figure F4.
Copper Concentration (gpl) .
. [Fe]=0.25 .[Fe]=0
Rate of oxygen consumption for various initial copper concentrations at the 40%
-109-
_^[Fe]=0.25 _ _ [ Fe ] =0
__[ Fe] =0. 25 _ _ [ Fe ] =0
-110-
Al 70% Oxygen Consumption
. [Fe]=0.25 .[Fe]=0
_^[Fe]=0.25 _o_[Fe]=0
- Il l -

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OXIDATIVE PRESSURE LEACHING

OF CHALCOCITE IN SULPHURIC ACID

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