Chloride Leaching for Chalcopyrite

by

Jenni Anne Liddicoat

B.Sc., The University o f Sydney, 1997

A THESIS SUBMITTED IN P A R T I A L F U L F I L M E N T OF
T H E REQUIREMENTS FOR T H E D E G R E E OF

M A S T E R OF SCIENCE

in

THE F A C U L T Y OF G R A D U A T E STUDIES

Department o f Metals and Materials Engineering

We accept this thesis as conforming

to the required standard

The University of British Columbia

December 2003

Jenni Liddicoat, 2003

In p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t o f t h e r e q u i r e m e n t s
f o r an a d v a n c e d d e g r e e a t t h e U n i v e r s i t y o f B r i t i s h C o l u m b i a , I
a g r e e t h a t t h e L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r r e f e r e n c e
and s t u d y . I f u r t h e r agree t h a t p e r m i s s i o n f o r e x t e n s i v e c o p y i n g o f
t h i s t h e s i s f o r s c h o l a r l y p u r p o s e s may be g r a n t e d b y t h e h e a d o f my
department o r by h i s o r her r e p r e s e n t a t i v e s . It i s u n d e r s t o o d t h a t
c o p y i n g or p u b l i c a t i o n of t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not
be a l l o w e d w i t h o u t my w r i t t e n p e r m i s s i o n .

Department of

The U n i v e r s i t y o f B r i t i s h C o l u m b i a
V a n c o u v e r , Canada
A B S T R A C T

Two new process flowsheets have been developed which combine chloride leaching for
chalcopyrite with solvent extraction, to selectively transfer copper to a conventional
sulfate electrowinning circuit. Both models were designed to address the common
chloride hydromet problem of product impurity, and they differ with respect to iron
deportment. Chloride leaching offers significant advantages for copper hydrometallurgy
including increased solubility, increased rates of leaching and stabilization of Cu(I)
through chloride complexation. A mass balance was completed for both models and
enabled the determination of recycle leach liquor concentrations of copper and iron
species for the countercurrent leach tests.

To assist with solid-liquid (S-L) separation a bench size mini-thickener was designed and
tested in the continuous countercurrent,leach experiments. One mini-thickener was used
for leach stage 1 (LSI) S-L separation in a smooth, clean and semi-continuous manner.
The leach tests were performed using a chalcopyrite concentrate, from Antamina in
northern Peru, which contained a low to moderate amount of gangue material.

The successful completion of mass balances for both circuits demonstrates potential for
these two new chloride leach flowsheets particularly in addressing current purification
difficulties and waste management issues.

The goethite model leach experiments, in which oxygen was injected to leach stage 2
(LS2) to aid iron oxidation and precipitation, were unsuccessful in achieving >95%
copper extraction in the atmospheric conditions tested. It is believed that further
intensification of conditions could produce >95% copper extraction.

The hematite model, in which no air is added to the leach, was successful in
demonstrating the effect of varying particle size, leach time and temperature to achieve
copper extractions >95%. Three hematite process variations achieved >95% copper
extraction and these involved fine grinding of the concentrate, and either a 3h residence

ii
time at 95C (98% extraction), a 2h residence time at 95C (96% extraction) or a 3h

residence time at 85C (96% extraction).

One final experiment, based on the hematite model, was successfully conducted at

optimum leach conditions employing Rosario concentrate from Chile, which contains

chalcopyrite, chalcocite and a significant amount o f pyrite. Copper extraction exceeded

99% for this experiment.

iii
 TABLE OF CONTENTS
ABSTRACT ii

T A B L E OF CONTENTS iv

LIST OF FIGURES vii

LIST OF T A B L E S ix

ACKNOWLDEGEMENTS xi

1 INTRODUCTION 1

2 LITERATURE REVIEW 4

2.1 Aqueous copper and chloride chemistry 4

2.1.1 Chloride complexes 4

2.1.2 Solubility 8

2.1.3. Ionic Activity 10

2.1.4 Redox Chemistry 12

2.2 Chalcopyrite leaching i n chloride 17

2.2.1 Thermodynamics and kinetics 17

2.2.2 Sulfur 23

2.2.3. Iron Deportment 25

2.3 Overview o f chloride leach processes for copper 29

2.4 Summary 34

3 EXPERIMENTAL 35

3.1 Mass balance spreadsheet preparation for the leach models 35

3.2 Feed concentrates 35

3.3 Feed solutions 37

3.3.1 Feed liquor for the hematite model 38

3.3.2 Feed liquor for the goethite model 38

3.3.3 Feed liquor analysis 38

3.4 Experimental Apparatus 39

3.4.1 Leach vessels 39

3.4.2 Temperature control 40

3.4.3 Solid-liquid separation 40

3.4.4 Compressed air/oxygen addition to L S 2 43

iv
 3.5 Experimental procedures 44

3.6 p H and redox potential measurements 48

3.6.1 p H 48

3.6.2 Redox potential 49

3.7 Sampling and Analysis 49

3.7.1 Sample Collection 49

3.7.2 Preparation and Analysis 50

3.7.3 Calculation o f copper and iron extraction 51

4 RESULTS A N D DISCUSSION 52

4.1 Excel mass balance outputs for the hematite and goethite process flowsheets 52

4.1.1 The hematite process 53

4.1.2 The goethite process 55

4.1.3 Feed liquor outputs 57

4.2 Overview o f continuous countercurrent leach experiments 58

4.3 Results o f hematite model experiments 62

4.3.1 Potential, p H and free acid 63

4.3.2 Copper and iron extraction 66

4.3.3 Speciation 69

4.3.4 Hematite experiment discussion 71

4.4 Results o f goethite model experiments 71

4.4.1 Potential, p H and free acid 73

4.4.3 Speciation 78

4.4.4 Goethite experiment discussion 79

4.5 Application o f hematite leach model to Rosario concentrate 79

4.5.1. Potential, p H and free acid 80

4.5.2 Copper and iron extraction 81

4.6 Sulfur balance 83

4.7 Trace Metals 85

5 CONCLUSIONS A N D RECOMMENDATIONS 86

5.1 M o d e l mass balances 86

5.2 Implementation o f the mini-thickener 86

 5.3 Countercurrent leach experiments 87

5.4 Recommendations for further work 87

6. REFERENCES 89

Sample identification guide for Appendices 1 and 2 93

Appendix 1 Certificates o f Analysis (IPL) 94

Appendix 2 Certificates o f Analysis (ChemMet) 121

Appendix 3 Certificates o f Analysis (Malvern Mastersizer) 131

Appendix 4 X R D Spectra 135

Appendix 5 Methods 136

Appendix 6 Experimental Logs 143

Appendix 7 Calculations 147

Appendix 8 Mass balances for experimental accountability 151

Appendix 9 Experimental Profiles 164

vi
 LIST O F FIGURES

Figure 1 The Hematite Process 3

Figure 2 The Goethite Process 3

Figure 3 C u - H 2 0 E h p H Diagram at 25C (1 atm, 1M) [12] 6

Figure 4 C u - C l - H 2 0 E h p H Diagram at 25C (1 atm, 1M) [12] 6

Figure 5 C u - H 2 0 E h p H Diagram at 25C (1 atm, C u 1 M , C l 5M)[12] 6

Figure 6 C u C l Solubility [1] 9

Figure 7 PbC12 Solubility [1] 9

Figure 8 Altered redox potentials i n chloride solution [3] 13

Figure 9 E h vs L o g a C l [23] 15

Figure 10 C u - F e - S - H 2 0 E h - p H diagram at 25C [24] 18

Figure 11 C u - F e - S - C l - H 2 0 E h - p H diagram at 25C [24] 19

Figure 12 Chloride leach processes for copper 30

Figure 13 Experimental Set-up 39

Figure 14 Mini-thickener design 42

Figure 15 Photo o f mini-thickener 42

Figure 16 Photo o f titanium rake 42

Figure 17 Photo o f countercurrent leach set-up 44

Figure 18 Mass and volume transfers 46

Figure 19 Thickening operation 47

Figure 20 Hematite Process 53

Figure 21 Goethite Process 55

Figure 22 E profile for H4(75um, 3h, 95C) 64

Figure 23 E profile for H5(41um, 3h, 95C) 64

Figure 24 p H profile for H4(75um, 3h, 95C) 64

Figure 25 p H profile for H5(41um, 3h, 95C) 64

Figure 26 H 4 : C u & Fe (%) Extraction ; 68

Figure 27 H 5 : C u and Fe (%) Extraction 68

Figure 28 H 4 : Concentration vs Time 68

Figure 29 H 5 : Concentration vs Time 68

Figure 30 H 4 : C u and Fe i n L S 2 Residue 68

vii
Figure 31 H 5 : C u and Fe i n L S 2 Residue 68

Figure 32 E profile for G2(75um, 2h, 85) 74

Figure 33 E profile for G3(41um, 3h, 95C) 74

Figure 34 p H profile for G2(75um, 2h, 95C) 74

Figure 35 p H profile for G3(41um, 3h, 95C) 75

Figure 36 G l : C u & Fe (%) Extraction 77

Figure 37 G 2 : C u & Fe (%) Extraction 77

Figure 38 G 3 : C u & Fe (%) Extraction 78

Figure 39 E profile for H9(37um,3h,95C) 81

Figure 40 p H profile for H9(37uni,3h,95C) 81

Figure 41 C u & Fe (%) Extraction for H 9 82

Vlll
 LIST OF TABLES
Table 1 Metal-chloro complexes with increasing chloride concentration [3] 7

Table 2 M e a n activity (a) o f H and Cl" in 2 M HC1 and several salts [1]
+
11

Table 3 Summary o f chloride leaching kinetics 22

Table 4 Summary o f iron compound precipitation [36,37] 28

Table 5 Process Review: Chloride Leach Summary Table 31

Table 6 Process Review: Summary Table 32

Table 7 C u , Fe and S % i n feed concentrates 36

Table 8 Feed concentrate particle size 37

Table 9 Hematite Process: L S 2 streams 53

Table 10 Hematite Process: L S I streams 54

Table 11 Hematite Process: Solvent Extraction streams 54

Table 12 Hematite Process: Autoclave streams 55

Table 13 Goethite Process: L S 2 streams 56

Table 14 Goethite Process: L S I streams 57

Table 15 Goethite Process: Solvent extraction streams 57

Table 16 Feed liquor concentrations 57

Table 17 Order o f experiments 59

Table 18 Hematite model - feed conditions 62

Table 19 E , p H and free acid output for hematite experiments 65

Table 20 Results o f hematite model experiments 67

Table 21 Total reduced species o f exit P L S and L S 2 liquors 69

Table 22 Feed conditions for goethite model experiments 72

Table 23 E , p H and free acid output for goethite experiments 74

Table 24 Output concentrations (solution and solids) for goethite model experiments... 76

Table 25 Total reduced species in goethite experiments 79

Table 26 Feed conditions for Rosario experiment 80

Table 27 E , p H and free acid 81

Table 28 Output concentrations (solution and solids) for the Rosario experiment 82

Table 29 Sulfur species in Final L S 2 residues 83

Table 30 Sulfur recovery 84

ix
Table 31 Trace metal analysis 85

Table 32 Sample identification guide 93

Table 33 Concentrate sample identification 93

Table 34 Comparing I P L free acid results with test titration value 138

x
ACKNOWLDEGEMENTS

I would like to sincerely thank Professor David Dreisinger for both the opportunity to

undertake this masters and for the guidance over the past two years. The Tim-Tam

biscuits brought from Australia were also very much appreciated. I also thank

Falconbridge L t d for the opportunity and importantly for the project funding. In

particular Mohammed Buarzaiga, from Falconbridge, was a gem i n assisting with the

design and prompt manufacture o f the mini-thickener and rake component. Other

department faculty and staff have also been helpful i n advising and assisting with not

only my studies but also my social enjoyment. I owe thanks to D a v i d D i x o n for the

chemistry instruction, Steve Cockcroft (in particular for the B B Q and Softball funding),

and the kind staff i n the M M A T workshop and stores who were always there to help me

put things back together and working again. These guys deserve a special mention Serge,

Ross, Carl, Dave and Glenn. I would also like to thank the U B C Department o f M i n i n g

and Department o f Geological Sciences for their cooperation i n allowing me to use their

analytical instruments.

I owe a great deal o f thanks to Prabhjit Bhatia, m y trusty research aid, who took care o f

my experiment during the daytime shift, when I was sleeping to rejuvenate for the night

shift. The Department o f Metals and Materials Engineering at U B C has been an

enjoyable place to work, and the other graduate students and staff have indeed made it a

friendly place to be. I would like to say a special thanks to all o f my lab and office mates

in the hydromet group, both passing and permanent. In particular, there was one

thoughtful visitor who kept me going during my early struggles with apparatus and

procedure development, and who later helped me to revise m y thesis.

xi
1 INTRODUCTION

Within the past 150 years a number of hydro-metallurgical techniques have been proposed
for the extraction of base metals, copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn), and
precious metals, silver (Ag) and gold (Au), from sulfide minerals [1,2]. An alternative
method to smelting was initially sought to combat the emission of acidic sulfur dioxide
( S O 2 ) gas to the atmosphere and the loss of associated precious metals to slag [3,4].

Now, for copper, approximately 20% of total primary production is achieved via
hydrometallurgical processing [5], and hydrometallurgy potentially offers advantages
over smelting with respect to lower capital and operational costs, in the recovery of
precious metals, recycling of process streams, and the production of inert,
environmentally stable, waste residues. The advantage also of constructing a small-scale
hydrometallurgy plant at the ore processing site is of increasing importance where
transport costs are significant and for newly discovered deposits in remote locations [4].

Currently, commercial hydromet processes for copper largely feature sulfate-based heap
or pressure leaching combined with solvent extraction and recovery via electrowinning,
and are generally suitable for processing copper oxides or secondary copper sulfides,
such as covellite (CuS) or chalcocite (CU2S). Chalcopyrite ( C u F e S 2 ) , the most abundant
copper mineral, is however difficult to leach and competing sulfate based leach systems
are currently investigating fine grinding and addition of surfactants to overcome
passivation effects and product layer diffusion obstruction [6,7].

Chloride leaching, however, has been extensively proven to extract >95% of copper from
CuFeS2 at temperatures around the boiling point and at atmospheric pressure [3,4,8].
Chloride leaching offers significant advantages for hydrometallurgical processing, in
supporting high metal solubility, enhanced redox behaviour, and increased rates of
leaching. In this system, both the cuprous ion, Cu , which is sparingly soluble in sulfate
+

systems, and cupric ion, Cu , as well as a host of other metal ions are stabilized through
2+

complexation with varying arrangements of chloride ions [3]. The result is that high

1
recoveries of both the primary metal of interest and associated precious metals can be
achieved, by leaching at fairly modest temperatures, and thus has potential for treating
complex ores and concentrates.

Other attributes of a chloride system include the minimization of sulfate formation and
the formation of predominantly elemental sulfur that remains in the leach residue, and
that pyrite is generally left undisturbed in the leach solids [4]. Concentrated chloride
solutions also induce high ionic activities that can play a beneficial role in the
precipitation and separation of metal chloride salts [1]. The chemistry behind the chloride
system is complex but it is this complexity that potentially allows for selective separation
and recovery of valuable metals from process liquors or waste material.

Yet despite the effectiveness of chloride leaching, there has been a definite lack of
progression toward commercial activity. The reasons for this are largely due to problems
with product purity and morphology, in addition to changes in the market value of copper
and competition with existing smelting techniques [4].

In this thesis work chloride leach experiments are conducted with respect to two process
flowsheets, shown in Figures 1 and 2. Both process models, feature chloride leaching of
chalcopyrite combined with solvent extraction, an effective method for the selective
removal of copper, and copper recovery by conventional sulfate electrowinning, to
address the issue of pure product recovery. They differ however with respect to iron
deportment. The hematite model, in which no air is introduced to the leach, allows
separate sulfur and iron residues to be produced, thus making waste treatment and
disposal potentially easier. The goethite model, however, offers simplicity in overall
flowsheet design, and air is added to the leach to precipitate iron as goethite (FeOOH) for
disposal with the leach residue.

This work builds upon previous experiments undertaken at UBC [9] in which a number
of experimental difficulties were encountered performing a four stage countercurrent
leach, particularly with respect to S-L separation. For simplification this work has

2
reduced the number o f leach stages to two and examined the use o f a novel apparatus to

aid smoother S-L transfer.

Figure 1 The Hematite Process Figure 2 The Goethite Process

Air to LS2
CuFeS,
2 Stage O,
Leach CuFeS 2

EW
EW 2 Stage
Cu S X (from
(from Leach
Cu S X sulfate)
Residue (Sulfur) sulfate)

Residue A/clave
-O,
T T Cu
(Fe 0 - Fe Cu
2 3
Residue (S &
hematite") removal
FeOOH-goethite)

The goals o f this investigation were:

1. to complete mass balances for both models to determine feed liquor requirements

for leaching;

2. to perform continuous 2 stage countercurrent leach experiments for both models

varying residence time, temperature and particle size to determine optimum leach

conditions;

3. design and implement a bench scale, glass "mini-thickener" to improve

countercurrent transfer o f the solids and liquids

4. to assess speciation i n the pregnant leach solution with respect to downstream

processing.

3
2 LITERATURE REVIEW

2.1 Aqueous copper and chloride chemistry

2.1.1 Chloride complexes

One o f the most significant features o f the chloride system for copper hydrometallurgy is

that the cuprous, C u , ion becomes stable through complexation with chloride ions. In a
+

pure water or sulfate solution C u ions are not stable and the cupric, C u , ion is the
+ 2 +

dominant species [10]. In water at 25C cuprous chloride solubility is o f the order 2 x 1 0 "
7
( however this solubility increases significantly with increasing total chloride

concentration [11]. Figure 3[12] shows the relative thermodynamic stabilities o f the

copper ions i n the C u - H 0 system at 25C in a Pourbaix (Eh-pH) diagrams, and Figures
2

4[12] and 5[12] show the C u - C l - H 0 system at 1 M CI and 5 M CI, respectively.

2

The ability to support both C u and C u + 2 +

ions has major process implications for chloride

systems with respect to the solubility limit o f copper, the redox potential o f the process

liquor, and product recovery, particularly the decreased energy requirement to electrowin

C u i n comparison with C u .
+ 2 +

The key issues for chloride complexation are complex stability, the comparative strengths

o f metal chloride complexes and the expected variations for metals in different chloride

concentrations.

For many metal chloride complexes, the maximum number o f chlorides is usually four

[13]. In the case o f the cupric ion, substitution takes place with the four strongly bound

equatorial water molecules [2], thus forming a complex with a square planar geometry

[2,14].

4
Figure 3 Cu-H 0 E pH Diagram at 25C (1 atm, 1M) [12]
2 h

Eh (Volts)

1 1 1 1 1 1 1 1 1 1 1 1 1

" _Cu20

Cu

I I I I I I 1 I I I I I I

0 2 4 6 8 10 12 14
pH

Figure 4 Cu-Cl-H 0 E pH Diagram at 25C (1 atm, 1M) [12]

2 h

Eh (Volts)

1 1 1 i i i i i 1 1 1 1

CuCl(+a) CuO

CuCI ^"""l _____

L____Cu20 -______-

Cu

0 2 4 6 8 10 12 14
PH

5
Figure 5 Cu-H 0 E pH Diagram at 25C (1 atm, Cu 1M, Cl 5M) [12]
2 h

Eh (Volts)

1 1 1 1 1 1 1 1 1 1 1 1 1

CuO

CuCI3(-2a)
I^TuM?

Cu

1 I I I - I I

0 2 4 6 8 10 12 14
pH

In general, metal ion complexes (MLn) are formed by the successive addition of ligands
(L), and the complex formation reactions can thus be written (a = activity) [10].
cl

M z +
+ L" <t> M L "
1 2 1
K , = ( 2 . 1 )
V + a
L '

Thus for cupric chloride complexes the following exist:

Cu 2 +
+ Cl" C u C l +
K, = A C U C 1 +
(2.2)
a
cu 2+a
cr

cucr + c r <=> Cuci 2 K = 2

A C U C
' 2
(2.3)
cl 1 ci
Cuci +
cr

C u C l + Cl" CuClj
2 K = 3
A C U C L ;
(2.4)
a
CuCl 2
a
C l-

C u C l j + C l ' o CuClJ- K = 4
A q v C i 1
' (2.5)
a a
Cuci; cr

6
K =i_4 represent the stepwise stability constants for each separate ligand addition, but
n

cumulative stability constants, p\, are also often quoted and are defined by:

M z +
+ riL" M L "
1 z
n
n
yfti = M L
" (2.6)
a
L-

M a n y studies have been undertaken and data tabulated for the stability constants o f

metal-chloro complexes [2,10,11, 15-18]. This information allows for the determination

of complex speciation for various concentrations o f chloride and the proposal o f relative

strengths o f chloro-complexes [10,11].

From these studies, the following order o f strength has been suggested for metal-chloro

complexes, from the strongest (Cl" acceptors): A g C l > C u C l > P b C l > Z n C l > C u C l > 2 2 2

FeCl 3 > FeCl 2 > NiCl 2 > H C I , N a C l , K C 1 (Cl" donors) [11]. Table 1 [3] provides an

overview o f metal-chloro complexes and indicates which species are dominant with

respect to changes in chloride concentration.

Table 1 Metal-chloro complexes with increasing chloride concentration [3]

Low Cl" concentration High Cl" concentration

Cu (II) Cu 2+
CuCf CuCl 2 CuCl " 3 CuCl " 4
2

Cu(I) CuCl " 2 CuCl " 3

2
CuCl " 4
3

Fe (III) Fe 3+
FeCl 2+
FeCl 2
+

Fe (II) Fe 2+
FeCf
Zn Zn 2+
ZnCf ZnCl 2 ZnCl "
3 ZnCl " 4
2

Pb PbCf PbCl 2 PbCl "

3 PbCl " 4
2

Ni Ni 2 +
NiCf
Co Co 2+
cocr
Mn Mn 2+
MnCf
Cd Cd 3+
CdCl +
CdCl 2 CdCl " 3 CdCl " 4
2

Sb SbCl 2+
SbCl 2
+
SbClj SbCl " 4 SbCl " 5
2
SbCl " 6
3

Bi BiCl 2+
BiCl 2
+
BiCl 3 BiCl " 4 BiCl "
5
2
BiCl "
6
3

As AsCl 3

Ag AgCl " 2 AgCl " 3

2

Hg HgCf HgCl 2 HgCl "3 HgCl " 4

2

7
The formation o f chloro-complexes is largely dependent on the chloride concentration, as

can be seen by the above equilibrium equations, and tends toward higher substitution by

chloride at higher concentrations [2,3,11]. For cupric chloride, C u , C u C l and C u C k ,

2 + +

and possibly CuCh," and Q1CI4 ", are observed with increasing chloride concentration, and

similarly for the cuprous ion, C u C V , C u C ^ " and C u C U " , are observed.
2 3
Also,

polynuclear cuprous chloride complexes, i.e. CU2CI

4 ", 2
Cu Cl6 ",
3
3
CU2CI
3 ", have been

suggested [3,16] as probable species and a spectrophotometric study o f a highly

concentrated C u C l - N a C l - H C l - H 0 system has most likely identified

2 CU2CI
4 ",
2
rather than

CuCl "[3]. 4
3

It is important to note that complexes may have a variety o f charges (positive, negative or

neutral) and that the chlorides may be replaced with other ligands, i.e. substituted, or the

complexed species themselves may be complexed by other ligands, which can be useful

in solvent extraction techniques [2].

The relative strengths o f each o f the metal ion complexes become important i n chloride

solution leach liquors.

2.1.2 Solubility

It is important that the primary metal o f interest for a certain process has an appreciable

solubility to allow fast leaching and efficient movement through the process, particularly

for economical reasons. Most o f the metal ions important to copper chloride systems

have greater solubilities than i n sulfate solutions, e.g. C u 2 +

(five times), F e , N i 2 + 2 +
and

Zn 2 +
[1,20].

Particularly for the generally water insoluble chloride salts, i.e. PbCl2, C u C l and A g C l ,

much greater solubilities can be achieved i n highly concentrated chloride solutions. For

example the solubility o f C u C l in cold water is 0.6 m g / L but in concentrated brine

solutions >100g/L can be achieved (see Figure 6 [1]). The solubility o f PbCL. i n 25C

water is 1 g/L but a solubility increasing ten times can be achieved at 6 M total chloride

(see Figure 7 [1]).

8
Figure 6 CuCl Solubility [1]

LEGEND

1501- -5C 27C 95C

FeCI, A 0
a
+0-25 HCI 9
+0-50 HCI m
+0-25 MgCI, C n
+ 0-50 MgCI, O a
o 100

5
50

2 3 4 5 6
Total C l " ( E q u i v a l e n t s per litre)

Figure 7 PbCl Solubility [1]

2

9
Though usually present i n smaller amounts i n the concentrate, A g recoveries have been

high in most chloride extraction processes as it possesses a high solubility in strong brines

at the moderately high temperatures used, e.g. above 85C.[1]

A s shown by the above two figures the effect o f temperature is quite significant, with

solubility increasing with higher temperatures. This effect has been used i n the recovery

o f these metals i n piloted chloride processes [3,4], where by simply reducing the

temperature the chloride crystals, i.e. C u C l and P b C h , precipitate out o f solution, with

purity relative to the contents o f the process solution.

It has been shown that solubility limits vary not only with the total chloride concentration

but also with the type o f chloride salt added to the solution. The reason for this is that

different metal cations form chloride complexes o f differing strengths thereby changing

the availability o f chloride ions for complexation with typically water insoluble species.

For example, Fe forms weak complexes in chloride solutions therefore leaving the

chloride ions available to complex with C u , and thus increases the solubility o f the
+

cuprous ion. Conversely, Z n 2 +

ions form strong complexes with chloride ions and thus

decrease the solubility o f the cuprous ion [11].

In conclusion, for chloride hydrometallurgy it is then desired that a high background

concentration o f chloride salts (e.g. K , N a , M g , Ca) be present i n the leach/process liquor

at a moderately high temperature (e.g. near boiling point) for maximum extraction o f

copper and other valued metals. Despite the possible negative effect on copper solubility

by other metal cations present, as long as a significant amount o f chloride ions are

present, impurities in the leach liquor are generally not a concern. Impurities however

w i l l cause concern during product recovery stages.

2.1.3. Ionic Activity

In dilute solutions, e.g. < 1 M , the chemical potential, or activity (a), o f a species can be

approximated by the M o l a r concentration ( M , mol/L), or molal concentration (m, m o l / K g

H2O). Therefore by the following relationship the activity coefficient (y) is 1 [1,13].

10
 Activity (a) = Activity Coefficient (y) x Concentration (m,M) (2.7)

However i n very concentrated solutions, e.g. > 2 M chloride (i.e. concentrations typically

used i n chloride hydrometallurgy), there is a significant effect on the activity o f the

species present (shown i n Table 2 [1]). In summary, a very concentrated solution can

greatly increase the activity (or chemical potential) o f species present. A s an example, a

very small amount o f acid can be used to keep the p H very low i n a concentrated chloride

solution.

Table 2 Mean activity (a) of H and Clin 2M HCI and several salts [1]
+

Salt Concentration NaCl CaCl 2 MgCl 2

_ 2.02 2J02 2.02

2N 4.03 4.89 5.23

4N 7.28 12.05 13.4

6N 12.4* 27.50 30.6

* Supersaturated i n N a C l

In addition, cations that have higher charge densities (e.g. M g > C a > N a ) and are
2+ 2+ +

present as undissociated species, have a higher hydration number, i.e. have a greater

number o f interactions with water molecules, and thus decrease the activity o f the water

and increase the activity o f ionic species present.

W i t h respect to the oxidative leaching o f chalcopyrite i n a concentrated chloride solution,

the influence o f chloride ion activity is quite important. For cupric leaching the final

reaction may be stated as [ 1 ].

C u F e S + 3 C u + 8C1- - 4 C u C l " + F e
2
2 +
2
2 +
+2S (2.8)

A n d at equilibrium, the equilibrium constant K is defined:

11
 log K = 4 log a(Cuci2-)+ log ^ 2 + ) - 8 log a<ci-) - 3 log ^ 2 + ) (2.10)

The aim o f the leach is generally to achieve high cuprous and low cupric ion, i.e. to go to

completion. This is thermodynamically favoured only at high chloride ion activities

[1,10].

2.1.4 Redox Chemistry

The standard potentials for many species are altered i n chloride solutions as a result o f

their chloro-complex formation (see Figure 8 [3]) [1,3]. The formation o f strong

complexes, e.g. C u , P b + 2 +
and Z n , decreases the potential at which these metal species
2 +

are reduced to their metallic state.

This can be observed by using the Nernst equation (2.11) to calculate the reversible

potential for the species M C l " / M i n chloride solution, with respect to the standard
n
z n

potential for M / M at 25C.

z +

F =F - 0 5 9
i l>cr m n

Z a
M C l -

A t higher B, i.e. for stronger complexes, the deposition potential decreases. A s an

example the potential for cuprous deposition decreases from 0.521 i n water to 0.084 in

concentrated chloride solution [3,13,21].

The advantage o f maintaining copper in the cuprous state is that it allows deposition o f

copper v i a a one-electron transfer, i f direct electrowinning is used, and therefore offers

potential energy savings when compared to cupric deposition, requiring 2 electrons per

copper atom. A l s o , the theoretical cell potential is decreased relative to electrowinning

Cu 2 +
i n sulfate via reducing C u at the cathode and oxidizing C u to C u
+ + 2 +
at the anode. In

addition, the C u / C u deposition is faster, having only to transfer one electron, with an
+

12
exchange current density, j 0 (rate o f electron transfer), in chloride solution ( 5 M N a C l )

determined to be 2 4 0 0 A / m at 25C, when compared to that o f the Cu(U)/Cu deposition

2

in sulfate which can be between 20-200A/m [3].

Figure 8 Altered redox potentials in chloride solution [3]

Reversible potentials in a 4M NaCl - Eh (mV) Standard potentials

0.5M HCI solution at 30C 1600 - j
- 1500 Au(lll)/Au
1400 -
- 1360 e v e r
Cl /Cr - 1242
2
1200 -

Au(lll)/Aiu 1012 1000 -

800 - Fe(lll)/Fe(ll) - 771- 779 Ag(l)/Ag

Fe(lll)/Fe(ll)- 681
Cu(ll)/Cu(l) - 5 8 4 600 -
- 521 Cu(l)/Cu
400
Ag(l)/Ag - 335 Cu(ll)/Cu- 337_ 320 i(lll)/Bi
B

200 -
- 153 Cu(ll)/Cu(l)
Bi(lll)/Bi- 9 - 84 Cu(l)/Cu
1

o
Ni(ll)/Ni - -58 u

-200 -
_. 50
2 Ni(ll)/Ni

-400 i
_ -441 Fe(ll)/Fe
Fe(ll)/Fe - -458
-600 -

-800 -

Despite the ability to deposit copper at a fast rate at the cathode, and although this is good

for process efficiency, the downside is that the copper is not smooth and fine metallic

crystals o f copper are formed instead. It should also be noted that the potential ohmic

drop for chloride solutions is larger than in sulfate, i.e. the loss o f energy as current

travels through the electrolyte is greater.

13
The growth o f finer copper crystals (e.g. dendrites, nodules or metallic powder) may lead

to greater contamination due to the exposure o f a greater surface area to the process

liquor, and generally these morphologies also make the product harder to handle.

Investigations have consequently been made into the use o f additives to aid i n better,

smoother, product formation [3,16]. However, greater product purity problems arise

from the presence o f more noble elements i n the cell feed solution, e.g. selenium (Se),

tellurium (Te) and most notably silver (Ag), and these w i l l even i n small concentrations

deposit at potentials required for C u deposition, as this potential w i l l be below the

+

reduction potential for these elements [4].

O f particular interest for gold bearing concentrates, is the significant decrease in the

standard potential for the A u / A u couple i n concentrated chloride solutions, from 1.5 V
3+

to 1.012V i n 4 M N a C l - 0 . 5 M H C I (Figure 8) [3].

However o f overall importance is the effect o f the concentration o f chloride on the

oxidation potential o f the couples Fe and C u , both o f which are commonly used i n

the oxidative leaching o f copper sulfide minerals.

The standard reduction potentials (at 25C) for F e 3 + / 2 +

and C u 2 + / +
are 0.77 and 0.153,

respectively, and therefore the ferric ion has a far greater oxidizing potential i n pure

water solutions [3,22]. In 4 M N a C l , 0 . 5 M H C I solutions the oxidizing potential o f the

iron ion couple falls to 0.681 and the copper ion couple increases to 0.584, both o f these

potentials are high enough for oxidizing most metal sulfides [3].

These changes are again due to the complexation behaviour o f the ions. For copper i n

chloride solution the electron transfer from C u 2 +

to form the reduced C u species, i.e. +

Cu 2 +
+ e <=> C u , can be more correctly written as: C u
+ 2 +
+ 2C1" + e 1_
<=> CuCLf.

Cuprous is more strongly complexed than the cupric ion, which forms weaker complexes

and remains largely uncomplexed to high chloride concentrations. Therefore the ratio o f

free C u : C u
+ 2 +
decreases with increasing concentrations o f chloride and according to the

Nemst equation the potential o f the C u 2 + / +

couple w i l l thus increase [13,21]:

14
 RT a
E ^ c ^ ^ - T l n - ^ (2.12)
r d
Cu 2 +

Conversely, for the Fe /Fe couple the oxidizing potential decreases with increased

chloride concentration as the ferric ion forms stronger complexes with the chloride ions

than does the ferrous ion. Therefore the ratio o f free F e : F e 3 + 2 +

decreases with increasing

chloride concentration and thus the solution potential decreases. Similarly the

relationship can be observed [13,21]:

E
=K*^-^-^ -
(2 13)

Figure 9 [23] shows the effect o f chloride activity on the potential o f species common to

copper chloride hydrometallurgy solutions.

Figure 9 Eh vs Log a a [23]

- 2 - 1 0 1 2

log cr

15
The importance o f a concentrated chloride solution for the oxidative leaching o f

chalcopyrite by cupric is that a high oxidation potential can be maintained as the leach

progresses. A high ratio o f cuprous, reaction product, to cupric can be present, and the

reaction still be driven to near completion. This is because cuprous is associated only as

chloro-complexed species, effectively reducing the free cuprous ion concentration.

16
2.2 Chalcopyrite leaching in chloride
2.2.1 Thermodynamics and kinetics
To determine the suitable aqueous conditions i n which leaching o f a particular mineral

can be carried out, an E h - p H (or Pourbaix) diagram assists by indicating the predominant

species, o f metal and metal compounds, present at equilibrium with respect to reduction

potential and hydrogen ion concentration. B y following the progression from mineral to

soluble metal species on the diagram leaching pathways can be determined, i.e. what

adjustments in p H and/or solution potential are required to liberate the metal ions

contained in the mineral [22].

E h - p H diagrams represent only thermodynamic equilibria however and so alone do not

indicate which leaching pathway w i l l work best. The kinetic factors o f each reaction

must also be considered and are especially important when considering process design.

This kinetic information comes from experimentation and observation, and leaching rates

are generally influenced by reactant concentration, temperature, particle size (surface

area) and product layer formation.

In this study the copper sulfide mineral chalcopyrite (CuFeS2) is o f particular importance

as it is presently the most abundant source o f copper [22]. B y observation o f the Cu-Fe-

S-H2O E h - p H diagram at 25C, which has been simplified to include only laboratory

observed reactions (See Figure 10 [24]), it is also confirmed to be quite refractory, being

quite resistant to acid attack and requiring strong acid oxidizing conditions [6]. The

stability o f chalcopyrite has been attributed to its face-centered tetragonal lattice

structural configuration [25].

17
Figure 10 C u - F e - S - H 0 E - p H d i a g r a m at 25C [24]
2 h

18
F i g u r e 11 C u - F e - S - C l - H 0 E h - p H d i a g r a m at 25C [24]
2

19
A s this study is also focused on chloride solutions, Figure 11 [24] shows that when

chloride (at 1M) is added to the C u - F e - S - H 0 E h - p H diagram at 25C the regions o f

2

sulfide stability are not significantly affected and the only difference appears to be i n

soluble copper and oxide regions. Thus during leaching the presence o f chloride appears

to prevent oxide formation, that could possibly slow the leach reaction [24].

A s a strong acidic oxidizing solution is required, studies and processes for chalcopyrite

leaching [1,3,4,10,21, 26-33] have so far employed ferric and/or cupric chloride and have

successfully demonstrated the effective leaching o f copper at atmospheric pressure in

solutions near boiling point. Consequently, the following two leaching reactions are

generally accepted:

CuFeS + 4FeCl
2 2
+
- C u 2 +
+ 5 F e + 2S + 8C1"
2+
(2.14)

CuFeS + 3 C u
2
2 +
+ 8C1" - 4 C u C l " + F e
2
2 +
+ 2S (2.15)

Not predicted by the E h - p H diagram is the recovery o f predominantly elemental sulfur

(S) instead o f the oxidized sulfate species. In fact less than 5% o f the S i n chalcopyrite

generally oxidizes to sulfate in atmospheric chloride leaching, and it is when pressure

leaching is employed that greater sulfate formation may become a concern [34]. The

formation o f a S product layer around the mineral particles has not been observed to

affect the rate o f leaching [34], and more discussion regarding the fate o f sulfur i n

chloride leaching is presented i n a section 2.2.2.

To further complicate the reaction kinetics and mechanisms involved, and despite the

reporting o f separate studies for ferric and cupric leaching, the two oxidant species are

closely linked as ferric leaching w i l l produce cupric ions, cupric leaching w i l l produce

ferrous ions, and ferric ions w i l l oxidize cuprous ions to form ferrous and thus regenerate

cupric for further leaching, as in the following reaction:

FeCl 2
+
+ C u C l " - F e
2
2 +
+ Cu 2 +
+ 4C1" (2.16)

Before discussing the findings o f kinetic leaching studies it is important to note that, by

simple observation o f the above reactions, there is flexibility i n which form the copper

20
ion may be attained during or at the end o f the leach, and this may ultimately be

important for downstream processing. A l s o due to the role chloride plays i n stabilization

o f the cuprous ion, copper solubility and the C u / C u 2 + +

redox potential, chloride

concentration is to be a significant factor in the leaching rate and extent o f leaching.

It was discovered early on that the ferric oxidation o f chalcopyrite i n chloride solution

was much faster than i n sulfate solution [21,27]. However it was not until the

development and testing o f hydrometallurgical chloride processes for copper i n the early

1970s [3,4] that there was significant interest i n determining the reaction mechanism and

kinetics behind leaching in chloride media. It was then found that the presence o f cupric

substantially increased the rate o f leaching [21,32].

Table 3 below summarizes the main findings o f chalcopyrite leaching studies i n chloride

media and following the table is a brief discussion on important leaching aspects.

The two requirements that enable optimum leaching with cupric ions (Equation 2.15)

include the presence o f a significant concentration o f chloride and also that the potential

is low enough to support the cuprous ion [10,21,32]. However, as stated previously, i n a

chloride solution the C u 2 + / +

redox potential is raised due to chloro-complexation, and

therefore the potential required for cupric leaching does not have to be too low, provided

the chloride concentration is high.

It has also been reported that to leach to completion, a high chloride concentration, high

temperature and short leaching time must be employed to lessen the reduction o f

elemental sulfur by the cuprous reaction product (Equation 2.17) [30].

2 C u C l " + S - C u S
2 (s) + Cu +4Cr
2+
(2.17)

21
Table 3 Summary of chloride leaching kinetics

Linear kinetics observed [10,21]:

Extraction rate was shown to increase with temperature; this is an indication o f surface

rate control (i.e. rate controlled by electron transfer across mineral surface) as reaction

products do not affect leaching rate; activation energies (>40kJ/mol) determined from

temperature experiments also indicate surface control o f dissolution rate.

Temperatures near boiling point are therefore best to achieve maximum extraction, higher

temperatures would cause sulfate formation (See Section 3b.).

Smaller particles increase rate [10,21,28]:

Following from the above, as the surface is rate controlling, an increase i n surface area

would therefore increase the rate o f particle dissolution, and this has been demonstrated.

Rate dependent on [10,21,28]:

Oxidant concentration (i.e. cupric or ferric), cuprous and chloride concentration; also the

cupric leaching rate has shown to be greater than ferric.

Rate independent of [21,28]:

Hydrochloric acid concentration, ferrous concentration and completely dissociated

chloride salts; p H should however remain l o w enough to avoid the precipitation o f

copper-oxy chloride or iron compounds; rate is also independent o f stirring rate, which

needs only be sufficient to suspend particles.

The presence o f air, or stronger oxidants, i n the leach can assist also i n oxidizing the

cuprous i o n product to subsequently prevent cuprous reduction o f sulfur and/or

regenerate cupric for further leaching. Oxidation o f cuprous by air may occur either

directly (Equation 2.18) or v i a the oxidation o f ferrous to ferric (Equation 2.19) which

may then catalyze the oxidation o f cuprous to cupric (Equation 2.20).

2 C u + 2 H + 0.5O -> 2 C u
+ +
2
2 +
+H 0
2 (2.18)

2Fe 2+
+ 0.5O + 2 H -> 2 F e
2
+ 3+
+H 0 2 (2.19)

Cu +
+ Fe 3 +
Cu 2 +
+ Fe 2 +
(2.20)

22
The conversion o f ferrous to ferric may also allow for the removal o f iron as goethite at

ambient pressure during the leach process v i a the following reaction (see section 2.2.3 on

iron deportment):

Fe 3 +
+ 2 H 0 - 3 H + F e O O H
2
+
( s ) (2.21)

It is not always desirable for the iron to be removed with the leach residue and so to

prevent the above from occurring oxidant addition needs to be controlled.

Despite the possible array o f proposed intermediary Cu/S compounds, from the reaction

o f chalcopyrite with either ferric and/or cupric ions, generally i n concentrated chloride

solutions there is observed to be a simultaneous rapid extraction o f both copper and iron.

This indicates that potentially hindering reactant products are not formed for either

species.

In summary, there are a number o f factors that contribute to the rate o f C u F e S leaching
2

and an atmospheric leach at boiling point, low p H , with relatively fine particles and a

high concentration o f both oxidant and chloride are important for efficient and effective

leaching.

2.2.2 Sulfur

Both fundamental studies and developed hydrometallurgical processes involving

chalcopyrite leaching with FeCi3 or C u C l have generally reported >95% o f the sulfur
2

reaction product forming as elemental sulfur, and hence <5% oxidation o f sulfur to

sulfate [4,34,35]. Even when long retention times (up to 90hr) were employed, or large

amounts o f oxidant or acid were used, at temperatures below 100C there was still found

to be predominantly elemental sulfur as the sulfur leach reaction product [34].

The advantages in the recovery o f sulfur in its elemental form include the following

[4,34,35]

fugitive emissions o f S 0 are avoided, unlike i n smelting;

2

easy storage and handling;

23
 limited environmental hazards (in waste residues sulfate hydrolysis causes

acidic conditions in the environment);

oxidant is consumed only by the desired mineral reaction, thereby maximizing

the release o f the metal o f interest (i.e. no oxidant is wasted on S oxidation);

the precipitation o f sulfate containing jarosite is avoided (Jarosite is typically

a process waste residue for the removal o f iron and tends to be less stable i n

the environment- see section on Fe deportment). However, i f so desired

jarosite may be formed with the aim o f removing sulfate from the process

liquor; and,

i f sulfate forms the leaching rate o f the chloride system w i l l be much slower.

Generally, sulfate forms when temperatures are employed above the melting point o f

sulfur (119C) [35]. This explains the increased sulfate levels (up to 25% o f sulfur

product) o f chloride hydrometallurgy processes which involve pressure leaching, e.g. i n

the C L E A R process. However, although for relatively few processes, 5-25% sulfur

oxidation has still been reported for systems that remain below 100C and it has been

suggested, that although not precisely clear, it is likely that the mineralogical composition

of the concentrate tested was a factor [4]. For example some sulfate may originate from

the superficial oxidation o f the sulfides prior to leaching (e.g. PbS04 on galena, PbS) or

by the sulfide leaching reaction itself. In addition, it has been shown that despite the

presence o f air i n the leach there is no significant effect on the relative amounts o f

elemental sulfur and sulfate produced and the relative amount o f elemental sulfur formed

is independent o f chalcopyrite particle size [34].

The most likely mechanism o f elemental sulfur formation appears to be v i a the dissolved

intermediary reaction product H S . This mechanism is reasoned by the presence o f well-

2

formed euhedral sulfur crystal growth that indicates the elemental sulfur was deposited

from aqueous solution, as opposed to conversion o f the sulfide remaining on the mineral

surface. A variety o f morphological arrangements o f these sulfur crystals have been

observed (dependent on mineral particle size and preparation) ranging from large

globules to continuous films. However, due to observed linear leaching kinetics

24
sufficient porosity must exist i n this product layer to allow passage o f reactants and thus

does not cause passivation [34].

One advantage o f the sulfur coating o f particularly fine CuFeS2 particles is to cause

agglomeration thus improving thickening and filtration properties o f leach residues [4].

The addition o f calcium to process liquor, as either a chloride salt (CaCL:) or carbonate

(Limestone, C a C 0 3 , typically employed for p H adjustment) is a very good method o f

removing sulfate, as gypsum (CaS04), from solution. Jarosite may also be precipitated at

moderate leaching temperatures and i n acid concentrations but this reaction w i l l still

leave a background concentration o f sulfate (e.g. lOg/L) [4].

2.2.3. Iron Deportment

Iron is the fourth most abundant element i n the earth's crust and as a consequence is

usually present i n most metal ores, including those o f copper. Iron may be present as an

essential constituent o f the ore mineral (i.e. the material containing the metal o f value),

e.g. chalcopyrite CuFeS2, bornite Cu5FeS4 and cubanite CuFe2S3, and therefore i n

extracting the metal o f interest the associated iron w i l l also accumulate i n the leach

liquor, and w i l l have to be removed prior to recycling o f the stream for leaching.

Iron may also be present i n gangue minerals (i.e. materials that do not bear metals o f

value for the process) either as an essential constituent or partially substituted for an

essential constituent. The most common iron-bearing gangue mineral i n sulfide ores, and

in particular for the chalcopyrite ores this study is interested in, is pyrite FeS2. For oxide

ores the most common include hematite Fe203 and magnetite F e 0 4 . In addition, owing
3

to iron's similarities i n chemical properties with many elements (in particular the first

series transition metals) it may substitute for an essential element into the crystal lattice

of either ore or gangue mineral [36].

Whilst it is generally unavoidable to accumulate iron i n the leach liquor, i f iron is present

in the ore mineral, it is possible to avoid dissolution o f gangue materials by selective

25
leaching conditions. For example a chloride leach for chalcopyrite operating at

atmospheric pressure enables this strategy as pyrite is generally left unattacked. Pyrite i n

fact reacts much more slowly than chalcopyrite even i n oxygen pressure leaching

(especially <170C [36]) and this may be due to the formation o f elemental sulfur around

the pyrite and/or galvanic protection by less noble minerals such as galena, covellite, and

sphalerite [22].

Iron still however makes up an appreciable content o f the chalcopyrite leach liquor owing

to its 1:1 Cu:Fe ratio, and the most common method for removing iron from

hydrometallurgical processes is via the precipitation o f iron compounds. The

precipitation can occur during the leach stage, and therefore iron is removed with the

leach residues, or separated at another stage o f the process, which may be preferred so as

not hinder the removal o f sulfur or precious metals from the leach residue or for the

production o f a separate saleable iron product.

The three predominant iron compounds that are precipitated i n hydrometallurgical

processes are goethite FeOOH, hematite Fe 03,

2 and jarosite

(H 0,K,Na,NH4).Fe3(S04)2(OH) compounds, i f sulfate is present [36].

3 6

The precipitation o f these iron compounds occurs when the iron is present as ferric ion

and there is low acid. When oxygen is added to convert ferrous to ferric, as seen by the

following equation, then this consumes acid, and can thus raise the p H to initiate

precipitation.

2Fe 2+
+ 0.5C-2 + 2 H +
- 2Fe 3+
+ H 02 (2.22)

If the p H is raised too quickly, with poor agitation at low temperatures [22] ferric

hydroxide w i l l form and due to the polymeric nature o f this gel colloid precipitate, which

contains cross-linked hydroxyl bridges, it is poorly filtered and w i l l not be successfully

separated from the process. O n the other hand a steady p H increase, high temperatures

and good agitation w i l l result i n the well-structured, easily filtered iron compounds,

26
goethite, hematite and jarosite. In a chloride leach stream the iron is often produced as

ferrous and therefore by careful mixing with oxygen, to convert ferrous to ferric, the rate

o f p H increase can be controlled, and therefore a filterable iron compound is easily

achieved.

Table 4 [36,37] summarizes process requirements for precipitation o f these compounds,

with comments on their stability as waste residues in the environment, and their role i n

hydrometallurgical processing.

It is important to comment on one study [37] that showed by increasing the chloride

content o f solutions with chloride salts that completely dissociate, e.g. N a C l or CaCb;, the

proton activity increased, thereby decreasing the quantity o f hematite produced, without

however effecting the composition o f the product. When salts which formed complexes

with chloride, e.g. ferrous or zinc ion, were added there was no effect o f the amount o f

hematite formed, as the free chloride did not change and therefore the proton activity did

not change.

27
T a b l e 4 S u m m a r y of i r o n c o m p o u n d precipitation [36,37]

Iron Compound Process Requirements Comments

Hematite F e 0 3 2 Generally formed at Though more costly to produce, it is

(Fe ~ 70%) T>130C i n an autoclave very stable and good for ponding and

(T>100C i f hematite seed possible resale.

is present). Stability demonstrated in natural

When formed i n chloride environment, by its occurrence as a

solutions C l found to be weathering product.

<1% o f product. H i g h F e % requires less solids to be

handled.

A study has shown also that by

seeding precipitation a more coarse

grain is formed which is easier to

filter.

Goethite F e O O H Generally formed at Precipitation can occur at atmospheric

(Fe ~ 63%) T<120C. pressure.

When formed i n chloride Goethite has also been shown to be

solutions product may environmentally stable, after hematite,

contain - 8 % C l . particularly i n wet conditions. In fact

the weathering o f hematite i n a humid

environment usually produces

goethite, 2 F e O O H <=> F e 0 + H 0 . 2 3 2

Jarosite Precipitates over a range o f The iron content is low. Thus more

M*Fe (S0 ) (OH)

3 4 2 6 temperatures and is product is required to remove a

M*= H , Na, K , dependent on the content comparative amount o f iron.

NH 4
+
of sulfate. C a n be formed There are problems with long term

Fe ~ 35%) at a lower p H . stability as acid w i l l leach out:

NaFe (S0 ) (OH)

3 4 2 6 + 3H 0 2 ->

'/JNfoSCU + 3 F e ( O H ) + 3 / 2 H S 0
3 2 4

28
2.3 Overview of chloride leach processes for copper
Over the last thirty years a number o f hydrometallurgical processes that employ chloride

leaching for copper have been tested at the laboratory, pilot plant and/or demonstration

plant [2,4]. These processes have been quite successful i n exhibiting efficient extraction

of copper, v i a leaching at atmospheric pressure and boiling point, but only one process,

the Duval Corporation's C L E A R process, has been operated commercially. This process

operated for a period o f six years until it was closed due to various technical and

economic reasons, noting that their product still required further costly refining to

achieve wirebar- or cathode-grade material [4,38]. Product impurity (especially due to

silver contamination) has i n fact been a major hindrance towards commercial

development o f these processes along with technological constraints faced i n the

handling o f corrosive process liquors [38].

Figure 12 provides an overview o f the various methods o f recovering copper from

chloride leach liquor that have been investigated, and includes the chloride leach process

proposed i n this thesis work. Tables 5 and 6, on the following pages, summarize the leach

and process characteristics o f these processes, which were mostly designed to leach

chalcopyrite (CuFeS2) concentrates.

29
Figure 12 Chloride leach processes for copper

Chloride Leaching

Recovery from Electrowinning from Solvent Extraction

crystals chloride

CYMET [3,4,39] - U.S. Bureau Mines [i,4,13,21,24]

UBC-Cominco [1,4,24] - Duval C L E A R [1-4,21,40]

Outokumpu [39] - Elkem [3,38]

- Intec Copper [41,42]

GCM [4] '

Electrowinning Electrowinning
from chloride from sulfate

Cuprex C M E P [2-4,38,43,44] - Minemet Recherche [45,46]

- Phelps-Dodge [47]
- Henkel Corporation [4,48,49]

- *Falconbridge Copper
Chloride Process [9]

30
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Table 5 shows process variations investigated for CuFeS2 leaching in chloride with, employing

and/or ferric i n a background o f N a C l or CaCb., and these have all reported high extractions.

Similar lixiviant characteristics and leach conditions were employed i n this thesis work.

Regarding the variations i n copper recovery for each o f the different processes, initial aims to

crystallize pure crystals o f copper salt, as cuprous chloride, found that silver was a major

contaminant. Even when metallic copper was added to reduce cupric to cuprous, and cement

noble impurities [1,4], this technique was not successful in completely removing the silver.

A l s o , the temperature adjustments required and handling o f the crystals may have potentially led

to technological problems during process scale up. A s an example, evolved HC1 must be kept dry

to prevent corrosion.

Later attempts to electrowin copper from the cuprous state i n chloride solution, attempting to

reduce operating costs v i a electrowinning C u , encountered the same product purity problems
+

with respect to silver ( U S B M , Intec, Elkem, C L E A R ) [3,4,38,40]. These processes were also

susceptible to product contamination by insoluble compounds as well as other noble impurities,

such as antimony [13]. In addition, due to the high rate o f winning i n a chloride medium, the

product was fine, either dendritic or powder-like, and thus created handling difficulties.

Solvent extraction so far appears to be the best method o f selectively removing copper from the

leach solution, for preparation o f a pure cell feed for electrowinning from either a chloride or

sulfate solution. Organic extractants are generally highly selective for the cupric ion [49-51] and

impurity transfer along with the copper is therefore minimal. However, it is important to wash

the chloride from the loaded solvent to prevent transfer o f chloride to the sulfate electrowinning

cell, which may even in small quantities lead to corrosion [49-51].

Electrowinning copper i n chloride solutions from the cupric state seems to negate the advantage

of using chloride. Electrowinning cuprous, which is only stable in concentrated chloride

solutions, would require only one electron and therefore half o f the energy required to reduce

cupric to metallic copper. A l s o partial and incomplete reduction o f cupric to cuprous may occur.

Electrowinning copper from sulfate solutions is a well-developed technology for producing

smooth, high purity copper cathodes, and conventional cell designs are now well established.
33
However, commercial development o f these chloride leach/sulfate electrowinning processes has

likely been hindered by process complexity and uncertainty regarding the capital and operating

costs required to compete with existing sulfate based leaching plants.

The flowsheets o f the three chloride leach processes in Table 6 that have proposed copper

recovery v i a solvent extraction and sulfate electrowinning have flowsheets which differ with

respect to this thesis work. The closest design is that o f the Minemet Recherche process, i n

which the pregnant leach solution is split, one half going to solvent extraction and the other to

atmospheric goethite precipitation, and then both streams combine to return to the leach.

2.4 Summary
The two process models developed i n this work combine chloride leaching with solvent

extraction and electrowinning o f copper from sulfate solution, and evolved from reviewing the

various chloride processes previously attempted, see Figure 12. Although the experimental work

in this thesis focuses on the leaching step, i n hydrometallurgy it is important to consider

downstream processing steps and recycling o f the liquor to the leach to determine the suitability

o f a process. Mass balances were completed for both circuits, and leach experiments were

performed with respect to the calculated feed liquor requirements.

The leach conditions chosen for the countercurrent leach experiments were based on

recommendations i n the literature investigating the kinetics o f chalcopyrite leaching. The

literature indicates that an atmospheric leach, near boiling point, at a low p H , using relatively

fine particles and a high concentration o f chloride and oxidant are important for effective and

efficient leaching o f chalcopyrite. A s the reaction is linear with temperature and the rate

determined to be surface reaction controlled, particle size, temperature and leach time were

varied i n the experiments to achieve higher extractions o f copper.

34
3 EXPERIMENTAL
3.1 Mass balance spreadsheet preparation for the leach models
For the two chloride leach process models considered i n this thesis work, the "hematite" (no air

in leach) model and the "goethite" (air in leach) model, simplified'mass balance spreadsheets

were developed in E x c e l to determine recycle feed liquor requirements for the leach. These mass

balances considered the leach with respect to downstream purification and recovery steps. In

particular, the concentration o f oxidants cupric and ferric were determined to allow 100%

extraction o f copper and iron from CuFeS2 and enable recycling o f the process liquor to the leach

following copper recovery. These recycle concentrations provided the basis for preparing feed

liquors for continuous countercurrent leach experiments.

Assumptions for performing the mass balance included identification o f reactions taking place i n

each process unit and that 100% o f the leach liquor moved countercurrently to the leach residues.

3.2 Feed concentrates

The copper concentrate tested i n all but the final experiment originated from Antamina in

northern Peru, and 30kg was shipped v i a Falconbridge Ltd. For the final experiment chalcopyrite

concentrate from the Rosario deposit at Collahuasi in Chile was tested, and 4kg was provided by

Falconbridge.

Both concentrates contained chalcopyrite (CuFeS2), with differing amounts o f gangue material,

and the Rosario concentrate also included chalcocite (CU2S). To obtain a representative sample

o f the Antamina concentrate, for the leach tests, the complete concentrate sample was mixed and

divided using an automatic splitter i n the U B C Department o f M i n i n g Coal Lab. The splitter was

then used to produce smaller packages, e.g. 2.5kg lots, suitable for testing. The Rosario

concentrate was sent for grinding and then divided equally on a bench to select a representative

sample for testing.

Prior to use in the leach experiments both concentrates were air dried, over approximately one

week, and rolled with a stainless steel rolling pin to break up clumps. For some o f the

experiments i n which finely ground concentrate was employed, a portion o f both concentrates

was sent to Process Research Associates ( P R A ) in Vancouver to perform grinding to 20-

35
25microns. The final and only experiment that employed Rosario concentrate had undergone

fine grinding.

Initial characterization o f the concentrates involved analysis o f 30 elements (including C u and

Fe) by Inductively Coupled Plasma (ICP) spectrometry (via aqua-regia digestion), total sulfur

analysis and Si02 analysis. These analyses were performed by International Plasma Laboratories

(LPL), a contract laboratory i n Vancouver. G o l d analysis was also performed by ChemMet

Consultants i n Vancouver. The results o f these analyses can be found i n Appendices 1 and 2 and

a summary o f the C u , Fe and S% are shown i n the following table for the three experimental

concentrate feeds. The 3 feeds include the as-received coarse Antamina concentrate and the

Antamina and Rosario concentrates that had undergone fine grinding.

Table 7 Cu, Fe and S % in feed concentrates

Feed Concentrate Cu % Fe % S%
Antamina (as received) 28.8 28.4 32.1

Antamina (fine grind) 28.5 28.7 , 32.4

Rosario (fine grind) - 26.8 26.8 35.5

Particle size analysis included wet sieving for the as-received coarse material, as a significant

proportion o f particles were larger than the smallest sieve size o f 38um. For analysis o f the finely

ground concentrates a Malvern Mastersizer laser analyzer was used to assess particle size

distribution. The Mastersizer is an instrument that determines particle sizes v i a the detection o f

light refracted by the various sized mineral particles, and is well suited for particles <38um. The

coarse material was also tested using the Mastersizer to provide a comparison. Both particle size

analyses were performed i n the U B C Department o f M i n i n g Coal Lab and the results are shown

in the following table. Reports for the Mastersizer analyses can be found i n the Appendix 3.

36
Table 8 Feed concentrate particle size

Feed Concentrate Method Results

Wet Sieving p90 = - 7 5 p m
Antamina (as received)
Malvern Mastersizer p50= 42pm, p90=106pm

Antamina (fine grind) Malvern Mastersizer p50= 16pm, p90=41pm

Rosario (fine grind) Malvern Mastersizer p50= 16pm, p90=37pm

p50 or p90 = size under which 50% or 90% of particles exist

Characterization o f both concentrates also included x-ray diffraction spectrometry ( X R D ) , and

was performed i n the U B C Geology Department. The X R D spectra have been included i n

Appendix 4. The Antamina spectrum reveals that the concentrate consists largely o f chalcopyrite

with a low-moderate amount o f gangue material consisting o f pyrite, silica, sphalerite, zinc oxide

and molybdenite. The Rosario spectrum reveals that the concentrate consists o f two copper

minerals chalcopyrite and chalcocite with a significant amount o f gangue material, largely o f

pyrite and lesser amounts o f silica, molybdenite, and sphalerite.

3.3 Feed solutions

Feed solutions were prepared in deionised water (DI water) using technical grade ferric chloride

(FeCl ) powder and 4-14 mesh calcium chloride ( C a C l ) pellets obtained in bulk quantities from
3 2

Anachemia Science. Laboratory grade cupric chloride dihydrate (CuCl2.2H 0) was obtained
2

from Fisher Scientific or A l d r i c h and concentrated hydrochloric acid (HCI) from Fisher

Scientific. To achieve the reduced ferrous solution for the goethite model feed liquor powdered

iron was used to reduce ferric chloride.

Feed liquor concentrations were based on the mass balance outputs o f the model. For both

models, an approximate background concentration o f free acid (as H C I ) was aimed at around

3g/L, either to approximate the expected free acid concentration i n liquor recycled from hematite

precipitation i n an autoclave or to keep acid sufficiently low to promote goethite precipitation.

Total chloride concentration was aimed at greater than 5 M with additional free chloride

contributed by either 1 lOg/L or 220g/L C a C l . 2

37
3.3.1 Feed liquor for the hematite model
To prepare the hematite model feed liquor ferric chloride was added first to generate heat to then

aid dissolution o f cupric and calcium salts. Finally, hydrochloric acid was added and, to

determine the actual free acid concentration, an undiluted sample was sent to I P L for analysis v i a

oxalate masking N a O H titration. Following the reporting o f two anomalously high free acid

concentrations by I P L , additional free acid titrations were performed at U B C and for all other

experiments the results were comparable. Appendix 5 contains the Free A c i d method used for

the U B C titrations and shows a table comparing I P L and U B C titration results.

3.3.2 Feed liquor for the goethite model

The feed liquor for the goethite experiments contained iron as predominantly ferrous. To

prepare the liquor, ferric chloride and calcium chloride were first dissolved i n D I water and then

powdered iron added to achieve the desired ferrous concentration, according to the following

reaction (3.1).

2 F e C l + Fe -> 3 F e C l
3 2 . (3.1)

A higher calcium chloride concentration, o f 220g/L, was used, following the first experiment, to

make up for the reduced amount o f metal chloride salt added. Following completion o f the

reduction reaction, indicated by stabilization o f the redox potential at 450mV /Agci (at room
Ag

temperature), cupric chloride and hydrochloric acid were added. The final solution was then

titrated with acidic certified cerium sulfate solution (0.1M) to determine total reduced iron, and

the method used can be found i n Appendix 5. The ferric concentration was thus calculated as the

difference between the total iron and reduced iron.

3.3.3 Feed liquor analysis

In addition to free acid analysis, two diluted samples o f the feed liquor (d.f.xlOO), one with 2 %

HC1 and one with only D I water, were prepared and sent to I P L for I C P 30 element analysis and

total chloride ion analysis respectively. Total chloride was analyzed by P L using an ion

selective electrode (ISE) and reported as g/L HC1. Certificates o f analysis for the I P L results can

be found in Appendix 1.

38
3.4 Experimental Apparatus
The layout o f the two-stage countercurrent leach circuit is shown i n Figure 13. For solid-liquid

(S-L) separation one mini-thickener ( T h l ) , was incorporated between Leach Stage 1 ( L S I ) and

Leach Stage 2 (LS2) and pressure filtration (P.F.) was used to separate final leach residues. The

filtrate from pressure filtration (LS2 liquor) was then transferred countercurrently to L S I .

The equipment and apparatus used is detailed i n the following sections.

Figure 13 Experimental Set-up

Leach liquor
Fresh Leach to LSI
Concentrate Exit PLS Solution
Feed

LSI LS2

Solids

Leach Residue - Final Filtration

3.4.1 Leach vessels
The experiments were conducted using 2 L glass water-jacketed leach vessels, approximately

11cm i n diameter, for containing 1L leach volumes for Leach Stages 1 and 2 ( L S I and L S 2 ) .

These tanks had indents, to act as baffles, and were sealed with a removable high-density

polyethylene ( H D P E ) l i d . The l i d , important to prevent evaporation loss, had several stoppered

openings for the temperature probe, p H and E measurement, sampling, stirrer shaft and

connection to a condenser. Water condensers were used to maintain atmospheric pressure and

prevent water loss due to evaporation.

39
A s the lixiviant, containing ferric and cupric i n a total chloride concentration > 5 M , was

extremely corrosive and corrodes stainless steel, equipment was largely made o f either glass,

titanium, or i n some cases plastic was used (e.g. the lids and tubing). The titanium stirrers were

made o f grade 2, 8mm (5/16 inch) diameter rod, featuring a 6 blade radial design, and were

attached via overhead motors. The stirrer was suspended approximately 2.5cm from the bottom

o f the leach vessel, which was 25cm deep, and each radial blade was 2cm long. The stirrer speed

was set at lOOOrpm, sufficient to suspend all particles.

Pumping o f the leach slurry was conducted using peristaltic pumps and three types o f Masterflex

tubing, C-Flex, Teflon and polycarbonate.

3.4.2 Temperature control

To achieve a leach temperature o f 85C or 95C a Haake C l water bath was used to heat and

pump water to the water jacket o f each leach vessel. To inhibit evaporation o f water from the

water bath an insulated l i d was used i n addition to float balls and slow refilling o f the bath, at a

low flow rate so as not to decrease the bath temperature. The water bath took about two hours to

heat prior to the start o f the experiment with the aid o f additional heaters, which were removed

once the experiment had started.

A copper pipe delivered the hot water from the water bath pump outlet to reinforced plastic

tubing, wrapped in insulation tape, which was used to circulate the water from water bath to L S 1 ,

from L S I to L S 2 and then from L S 2 back to the water bath. Hose clamps were used to tightly

secure connections and a water circulation test was performed a day in advance o f each

experiment to check for leaks.

Teflon coated thermocouples, connected to an external digital reader, were inserted via screw

fittings through the lids o f both L S I and L S 2 to monitor temperature. Readings were noted at the

beginning, middle and end o f the residence time for each leach cycle.

3.4.3 Solid-liquid separation

The original intention for the countercurrent circuit was to incorporate two mini-thickeners for S-

L separation for L S I and L S 2 slurries. This was hoped to achieve a more continuous process

and reduce the errors and difficulties previously associated with using pressure filters for all S - L
40
separation. However as this mini-thickener was a new design and had not been used before, it

has was only used for L S I S - L separation in this work to investigate function capabilities.

3.4.3.1 Mini-thickener for LSI slurry S-L separation

A glass mini-thickener (see Figures 14 and 15) 20cm i n length, featuring a domed l i d (with an

internal feed well and four available inlet/outlet ports), a cylindrical glass separating column and

a cone shaped underflow exit, was designed for bench-scale S - L separation. The glass l i d and

body were manufactured by Canadian Scientific Glassblowing L t d , i n Vancouver. A slow

moving internal titanium rake, featured i n Figure 16, was designed and manufactured v i a

Falconbridge and delivered with an overhead motor, to operate slowly at 6 rpm to aid moving the

settled solids through the bottom exit.

A support-stand for the mini-thickener was made i n the U B C Department o f Metals and

Materials Engineering ( M M A T ) workshop. The support consisted o f a curved aluminum backing

plate attached to a retort stand and large (15cm) diameter hose clamps were used to hold the

thickener to the stand. Clamps were used to hold the l i d in position.

A thick, clear, half inch diameter piece o f P V C tubing 10cm long was attached to the end o f the

underflow port which was then connected to smaller diameter tubing before reaching a peristaltic

pump. This tube was pinched closed with clamps whilst solids settled.

41
Figure 14 Mini-thickener design Figure 15 Photo of mini-thickener
The original design o f the thickener included side overflow ports to assist i n achieving

continuous operation (i.e. slurry continually fed to the thickener would result i n clarified solution

exiting v i a the overflows). These side ports were sealed and not used i n the current work due to

bench scale limitations, largely with respect to liquor volumes, and instead a semi-continuous

type operation was performed. This was generally achieved by pumping slurry into the central

feed well, v i a an inlet port i n the lid, and after the solids had settled fully the clarified liquor (the

P L S ) was removed by pumping liquor from above the mudline. Once the P L S was removed the

underflow exit tube was undamped and underflow slurry pumped out the bottom exit.

3.4.3.2 Pressure filtration for LS2 slurry S-L separation

A 1.5L capacity pressure filter, manufactured by Advantec M F S Incorporated and lined with

polyurethane, was used to filter solids using N at 30-45psi. It was found that for filtering finer
2

solids two filter papers were required to prevent blowout and loss o f solids.

3.4.4 Compressed air/oxygen addition to LS2

For goethite model experiments air or oxygen was required for leach stage two to regenerate the

oxidant species. The gas ran from a cylinder through clear P V C tubing v i a a flow meter and then

bubbled through a stoppered flask o f water before reaching L S 2 , to signal blockages. The air

tube inside the leach vessel was a 9.5mm (3/8 inch) diameter polycarbonate tube about 21cm

long.

43
3.5 Experimental procedures

The original idea for incorporating the mini-thickener in the experimental set-up was to achieve

continuous S-L separation. Whilst the mini-thickener did enable an inline, smooth

countercurrent transfer o f L S 1 slurry, into partially leached solids and pregnant leach solution

(PLS), the actual experiments in this thesis were performed semi-continuously. This means that

within each experiment a series o f leach cycles were performed as batch operations i n continuous

succession. This was largely due to limitations of bench scale work, i.e. with respect to volumes

o f solution and space, and due to this being the first ever commissioning o f the mini-thickener,

upon which further tests can build. A photo o f the set-up is shown i n Figure 17.

Figure 17 Photo of countercurrent leach set-up

44
The continuous countercurrent leach experiments began with 135g o f feed concentrate and 1L o f

feed liquor in both L S I and L S 2 . A t the end o f the designated residence time countercurrent

transfer would occur, new feed concentrate was added to L S I and fresh feed liquor added to

L S 2 , and this leach/transfer pattern would repeat for 5 or 6 cycles. The first three cycles allow

the countercurrent system to reach steady state operation and the following cycles were expected

to approach "steady state" and thus indicate true extraction behavior.

Further details o f the procedures for the leach experiments follow in three sections, 1) prior to

start-up, 2) during the leach cycle and 3) S - L separation and countercurrent transfer.

1) Prior to start-up

The feed liquor was prepared at least a day in advance, allowing time for the solution to cool.

The redox potential and p H o f the feed solution were then measured at room temperature. The

water bath generally took 2hrs to heat (with additional heaters) and circulate water at the

operating temperature before the experiment could start. During this time, 1L o f feed liquor was

added to both L S I and L S 2 .

2) During the leach cycle

Once the leach temperature had stabilized, redox potential and temperature were recorded i n

each leach vessel and then concentrate was added. Temperature and redox potential were then

recorded at the midpoint and end o f each leach cycle. The p H was measured only i n samples

taken from each leach stage once they had cooled to room temperature on the bench.

During the leach the following were monitored:

waterbath operation, temperature and water level;

stirrer connections;

thickener rake motor off between transfers, and underflow clamp secured before next

loading o f the mini-thickener;

water condenser water flowing; and

hose clamps secured on water jacket tubing connections.

About 15 m i n prior to transferring L S I slurry to the thickener, 10-15mL o f 1000 ppm

Superfloc A 1 1 0 anionic flocculant was added to enable quick and complete settling o f solids.
45
This approximated a dosage o f 100-150g per ton o f leach solids. The higher dosage (15mL

A110) was found necessary for experiments employing finer particle sizes.

3) S - L separation and countercurrent transfer

A t the end o f the leach residence time, all o f the L S 1 slurry was pumped from L S 1 to the glass-

thickener. A t the same time, all o f L S 2 slurry was pumped to a flask for immediate pressure

filtration, separating final L S 2 leach residues (for further washing and drying) and liquor for

transfer to L S I . The L S 2 filtrate was measured and recorded prior to addition to L S I , whilst

allowing solids in the thickener to completely settle. Figure 18 shows the countercurrent transfer

operation and volumes generally transferred.

Figure 18 Mass and volume transfers

~1.1L to
135g feed cone. PLS - 0 . 8 L 1L feed liquor L
^ l

Pressure
LSI ~1.1L Thickener LS2-1.2L
Filter

U/F -0.2L Final Residue

100% L S I solids
[* = 80mL sample]
s.d. 40-50%'

Pre-heated fresh feed liquor, 1L, was then added to L S 2 and, following complete settling o f

thickener solids (see Figure 19), the clarified P L S was pumped from above the solids bed,

generally leaving around 180-200mL o f liquor with 100% o f solids for underflow transfer to

L S 2 . After the P L S had been removed and measured, the underflow was pumped to L S 2 . This

process required the operation o f the slow moving internal rake to effectively move all settled

solids through the underflow bottom exit and prevent any solids clinging to walls or cone o f the

glass thickener. Reverse pumping was sometimes used to recollect solids that were left behind.

Total transfer time took between 20-30min. Slightly before the underflow transfer to L S 2 was

complete, fresh concentrate (135g) was added to L S I and this signaled the beginning o f the next

leach cycle. The temperature o f both L S 1 and L S 2 at the start o f the next leach stage was

46
recorded, and generally this was slightly lower (-5-1OC) than the designated leach temperature.

However, within 5-10min the leach temperature had been reached.

Figure 19 Thickening operation

47
A n example o f the experimental logs used to record temperature, redox potential and p H

measurements, samples, and mass and volume transfers can be found i n Appendix 6.

3.6 pH and redox potential measurements

Due to problems o f probe fouling i n previous chloride leach experiments performed at U B C ,

probes were not left i n the leach vessels for any length o f time. Hot chloride solutions are very

aggressive and combined with solids the resulting slurries are very harsh environments for glass

and platinum sensors. Care was taken with both p H and redox electrodes to keep them clean

between readings.

When refillable probes were used the hole was covered with tape, to prevent slurry or solution

entering the inside chamber o f the probe.

3.6.1 pH
Due to the difficulty o f preventing p H fouling i n hot concentrated chloride solutions, it was

determined best to take p H measurements only at room temperature i n the filtered samples.

Measurements o f p H were initially taken with plastic gel filled p H probes that had a paper

junction for equilibrium ion transfer. However, the high concentrations o f iron i n the leach

solutions quickly fouled these junctions, turning them brown, and performance rapidly

deteriorated. For example, calibration was very slow and soon drift and shortening o f the range

made calibration nearly impossible. A new probe was then purchased, a ThermoOrion refillable

combination electrode with a glass-body, rugged bulb (protected with a plastic shell), and

ceramic junction. Cleaning o f this probe was significantly, better, v i a disposing o f the

contaminated inner solution and soaking o f the ceramic junction. Refilling o f the electrode with

4 M K C 1 (saturated with A g C l ) restored the inside environment and maintained electrode

operation.

The p H measurements quoted i n the results section have not been corrected for liquid junction

potential, largely due to the complexity o f the concentrated chloride leach solution. Therefore,

p H readings mainly serve to indicate comparative trends between the experiments and possibly

the values at which copper or iron precipitation may occur. Readings were also generally at ~

p H 0 or lower, significantly under the lowest p H buffer o f 1. Free acid measurements i n the feed

and final P L S provide a better indication o f acid consumption and behaviour.

48
3.6.2 Redox potential

Redox potential, E , measurements were originally performed using a glass body combination

A g / A g C l electrode with a ceramic junction and fine platinum sensor. Not only did the fine

platinum sensor bend i n the hot leach slurry, after only a few trial experiments the glass body

cracked without warning simply upon insertion o f the probe into the slurry. This happened twice

and for one experiment a Saturated Calomel Electrode was thus used as an immediate backup.

A n epoxy body A g / A g C l combination electrode ( V W R Symphony Brand) with a flat bottom

platinum sensor and free flow junction was subsequently purchased. The filling solution used

was 4 M K C 1 saturated with A g / A g C l , suitable for use i n concentrated solutions (>0.2M). Light's

solution (see Appendix 5) was used to check redox electrode performance.

Redox potential readings were taken in-situ i n the leach vessels at the start o f the experiment,

before addition o f concentrate, and at the middle and end o f each residence time. During the

leach Light's solution was used to check performance o f the electrode, and whether drifting or

fouling o f the electrode had occurred. Generally readings were satisfactory and only sometimes

the K C 1 filling solution would need renewing.

Redox potential measurements were not corrected for temperature and have been quoted i n this

thesis as m V vs A g / A g C l at either room or experimental temperature. The measurements have

also not been corrected for Light's solution changes during the experiments, unless in one or two

cases where they were out by greater than 30 m V . E readings can therefore generally be accepted

as accurate to within 20-30mV.

The leach solutions i n this research work are highly concentrated and depart significantly from

ideal solution behaviour. Therefore, the redox measurements largely serve a comparative

purpose between experiments in this thesis.

3.7 Sampling and Analysis

3.7.1 Sample Collection

L S I and L S 2 80mL slurry samples were collected at the end o f each residence time, during

transfers to the thickener and pressure filter. Approximately 200mL was first allowed to flush

49
through the pump line and then 80mL was collected i n a beaker. The samples were then set-

aside on the bench for filtration.

Both L S 1 and L S 2 samples were prepared i n the following manner. The sample was filtered v i a

water vacuum filtration and the filtrate was collected in a small (60mL) plastic sample bottle.

The sample was cooled to room temperature, prior to dilution for external analysis and p H

measurement.

The solids were then washed with lOx diluted concentrated hydrochloric acid (1/10 H C I ) until

the filtrate ran colorless. This chloride wash solution was collected for all residue washes, and

the total volume was recorded arid sent for external analysis. Final washing o f the filter cake was

with D I water and the cake was then transferred to an oven to dry. Once dry, the weight o f the

residues were recorded and sample bagged for external analysis.

The final L S 2 leach residue sample, collected i n the pressure filter, was also treated in the same

manner as the residue in the slurry samples. For this residue the weight o f the wet cake was

recorded in addition to the washed and dried product.

A l l solution and residue samples were prepared accordingly and sent to LPL for analysis. The

final L S 2 residue was sent to ChemMet for sulfur group analysis.

3.7.2 Preparation and Analysis

The following samples were sent to I P L for analysis.

The feed liquor and L S I and L S 2 liquor samples from each cycle were diluted lOOx (2mL i n

200mL) with - 2 . 5 % H C I and analyzed for 30 elements (including C u and Fe) by I C P . In

addition, undiluted samples o f the feed liquor and final exit P L S were sent for free acid analysis

and ICP 30 element analysis.

Dilutions with only D I water for the feed (lOOx dilution) and final exit P L S (lOOOx dilution)

were also prepared for total chloride ion analysis v i a ion selective electrode (ISE).

50
A l l solids were sent for 30 element ICP analysis (via aquaregia digestion). The feed concentrate

was also analyzed for Total S and Si02. T w o further samples were sent to ChemMet Consultants,

the feed concentrate was analyzed for A u and the final L S 2 exit residue analyzed for sulfur group

analysis (including total sulfur, elemental sulfur, sulfide and sulfate).

3.7.3 Calculation of copper and iron extraction

A n example calculation for determining the extraction o f copper and iron can be found i n
Appendix 7.

51
4 RESULTS AND DISCUSSION

4.1 Excel mass balance outputs for the hematite and goethite process flowsheets
This section reports the input and output streams o f the mass balance for the two chloride process

models. For both models 135g pure CuFeS2 concentrate was introduced to the circuit and it was

assumed that 100% o f the C u and Fe i n CuFeS2 was leached and subsequently all o f the

extracted C u was removed via S X and all extracted Fe was precipitated (i.e. steady state was

maintained), either as goethite or hematite. The models were simplified to include only major

reactions, assumed from previous experimental work and the literature. These reactions are

reported and discussed. A l s o , the simplified models consider complete countercurrent transfer o f

liquor with respect to solids. The models do not account for the small portion o f L S I liquor that

would return with thickener underflow to L S 2 .

For each stream, the copper and iron species are written as single, uncomplexed cations (i.e. C u ,+

C u , F e , F e ) but are assumed to be associated with chloride. These copper and iron species
2 + 2+ 3+

would generally be added to the leach liquor as metal chloride salts and thus contribute to the

total background chloride concentration. A concentration o f 110 g/L CaCL. was used to ensure a

concentrated chloride medium >5M. In these simplified models, gypsum (CaS04) precipitation

is not considered, as minimal sulfate production is expected. A background concentration o f HC1

was also included in both models although remained constant through the balancing o f acid

consuming and generating reactions. The result o f ensuring this acid balance also assisted i n

regenerating the oxidant species for recycling to Leach Stage 2.

52
4.1.1 The hematite process
This model focuses on 3 major process units (see Figure 20), a 2 stage countercurrent leach,

copper solvent extraction and iron precipitation in an autoclave. Thus separating the leach

residue from iron deportment and producing two waste residues. The input and output streams

for L S I , L S 2 , S X and Autoclave, determined from the mass balance for this flowsheet, are

shown below alongside the assumed reactions. The mass o f each species is given i n grams (g)

and the total amount o f water, lOOOg, is comparable to the quantity used in the experiments and

is maintained constant, assuming evaporation o f water produced.

Figure 20 Hematite Process

Feed Concentrate, 100% CuFeS 2

135g C u F e S (added to L S I ) : C u = 46.7g; Fe = 4 1 . l g ; S = 47.2g

2

Assumed extent o f extractions: L S I = 51.5 %; L S 2 = 48.5 %

Leach Stage 2 (LS2)

C u F e S + 4 F e C l - 5 F e C l + C u C l + 2S
2 3 2 2 (4.1)

Liquor, rich in ferric and cupric, is recycled from the autoclave and fed to L S 2 . Ferric is

consumed in the oxidation o f C u F e S , leaving some ferric and cupric for further leaching in L S I .
2

Table 9 Hematite Process: L S 2 streams

Stream Cu +
Cu 2 +
Fe 2 +
Fe J +
CaCl 2 HCI H 0
2

In 0 50.3 0 80.2 110 2 1000

Out 0 73.0 99.6 0.53 110 2 1000

53
Leach Stage 1 (LSI)

C u F e S + 4 F e C l -> 5 F e C l + C u C l + 2S
2 3 2 2 (4.2)

C u F e S + 3 C u C l - 4 C u C l + F e C l
2 2 2 + 2S (4.3)

Ferric is completely consumed in L S I while the remaining C u F e S is leached with cupric. Sulfur 2

oxidation and atmospheric oxidation o f cuprous or ferrous is not considered i n this simplified

model. A s the feed is 100% C u F e S 2 the consumption o f acid by soluble minerals is not

considered. The exit stream is predominantly reduced species, i.e. cuprous and ferrous.

Table 10 Hematite Process: LSI streams

Stream Cu +
Cu 2 +
Fe Fe CaCl 2 HC1 H 0
2

In 0 73.0 99.6 0.53 110 2 1000

Out 95.5 1.54 121.3 0 110 2 1000

Solvent Extraction (SX)

2 C u C l + 0.5O + 2 2HRo r g CuR 2 o r g + CuCl + H 0 2 2 (4.4)

Addition o f oxygen to the aqueous phase facilitates 100% extraction o f the leached copper (i.e.

- 5 0 % o f the copper i n solution) into the organic phase. To balance acid generated, from the

donation o f protons from the organic extraction, an equal amount o f cuprous is oxidized to

cupric.

Table 11 Hematite Process: Solvent Extraction streams

Stream Cu +
Cu 2 +
Fe 2 +
Fe J +
CaCl 2 HC1 H 0
2

In 95.5 1.54 121.3 0 110 2 1000

Out 2.01 48.3 0 80.2 110 2 1000

54
Hematite Precipitation in Autoclave (A/C)
2 F e C l + 0.5O + 2 H 0 - Fe 0 (s) + 4HC1
2 2 2 2 3 (4.5)

2 C u C l + 0.5O + 2HC1 -> 2 C u C l + H 0

2 2 2 (4.6)

2 F e C l + 0.5O + 2HC1 -> 2 F e C l + H 0

2 2 3 2 (4.7)

Oxygen is added to the autoclave to enable the precipitation o f 100% o f leached iron as hematite

( F e 0 ) v i a ferrous oxidation.
2 3 This reaction produces a surplus o f acid that is subsequently

consumed by cuprous and further ferrous oxidation. This acid balance also achieves 100%

regeneration o f the required ferric and cupric for recycle to L S 2 .

Table 12 Hematite Process: Autoclave streams

Stream Cu +
Cu 2 +
Fe 2 +
Fe J +
CaCl 2 HCI H 0
2

In 2.01 48.3 121.3 0 110 2 1000

Out 0 50.3 0 80.2 110 2 1000

4.1.2 The goethite process

This process focuses only on 2 major process units (see Figure 21). Though the leach is more

complex than the hematite model, as oxygen is added to precipitate goethite i n L S 2 , and thus a

mixed sulfur/iron residue is produced. The input and output streams for L S I , L S 2 and S X ,

determined from the mass balance for this flowsheet are shown below alongside the reactions

considered. A s above with the hematite model, the mass o f each species is given i n grams (g)

and the total amount o f water, lOOOg, is comparable to the quantity used i n the experiments and

is maintained constant, assuming evaporation o f water produced. Oxygen addition is not

included below but is assumed to be equal to that required.

Figure 21 Goethite Process

55
Feed Concentrate, 100% CuFeS2
135g C u F e S (added to L S I ) : C u = 46.7g; Fe = 4 1 . l g ; S - 47.2g
2

Assumed extractions: L S I = 55 %; L S 2 = 45 %.

Leach Stage 2 (LS2)

C u F e S + 3 C u C l - 4 C u C l + F e C l
2 2 2 + 2S (4.8)

2 F e C l + 0.5O + 2HC1 ^ 2 F e C l + H 0
2 2 3 2 (4.9)

2 F e C l + 4 H 0 - 2 F e O O H
3 2 (s) + 6HC1 (4.10)

Overall - 2 F e C l + 0.5O + 3 H 0 - 2 F e O O H
2 2 2 (s) + 4HC1 (4.11)

Cupric in solution, recycled from solvent extraction, facilitates leaching o f C u F e S . Oxygen is 2

added to enable oxidation o f ferrous and subsequent precipitation as goethite. W i t h the excess

acid generated from goethite precipitation, cuprous and further ferrous oxidation occurs. The

oxygen input required is 17.65g.

Table 13 Goethite Process: LS2 streams

Stream Cu +
Cu 2 +
Fe Fe J +
CaCl 2 HCI H 0
2

In 0 48.7 31.1 0 110 2 1000

Out 0 69.7 0.27 8.21 110 2 1000

Leach Stage 1 (LSI)

C u F e S + 4 F e C l - 5 F e C l + C u C l + 2S
2 3 2 2 (4.12)

C u F e S + 3 C u C l -> 4 C u C l + F e C l
2 2 2 + 2S (4.13)

The small amount o f ferric generated i n L S 2 is consumed i n C u F e S leaching and then the 2

remainder o f the leach is conducted using cupric. The pregnant leach solution is rich i n copper,

as cuprous, and the iron content is the same as fed to L S 2 , as there are no further downstream

reactions involving iron.

56
Table 14 Goethite Process: LSI streams

Stream Cu +
Cu 2 +
Fe 2 +
Fe i +
CaCl 2
HC1 H 0
2

In 0 69.7 0.27 8.21 110 2 1000

Out 93.5 1.93 31.1 0 110 2 1000

Solvent Extraction (SX)

2 C u C l + 0.5O + 2 2HRo r g -> C u R 2 o r g + CuCl + H 0

2 2 (4.14)

This step is the same as for the previous hematite model. V i a the addition o f oxygen, cuprous is

oxidized to enable extraction into the organic phase and complete cupric regeneration, for

recycle to L S 2 .

Table 15 Goethite Process: Solvent extraction streams

Stream Cu +
Cu 2 +
Fe 2 +
- Fe 3 +
CaCl 2 HC1 H 0
2

In 93.5 1.93 31.1 0 110 2 1000

Out 0 48.7 31.1 0 110 2 1000

4.1.3 Feed liquor outputs

For both process models, the concentrations o f copper and iron species i n the recycled L S 2 feed

stream, as calculated from the above mass balance, are summarized i n the following table. These

were used for the preparation o f feed liquor for the countercurrent leach experiments.

Table 16 Feed liquor concentrations

Model Feed Requirements

Hematite Fe J +
80 g/L, C u 2 +
50g/L, HC1 ~ 3 g / L

Goethite Fe J +
0 g/L, F e 2 +
30 g/L, C u 2 +
50g/L, HC1 L o w (<3g/L)

57
For the hematite model, sufficient ferric and cupric must be fed to L S 2 to enable 100%

extraction o f C u and Fe from CuFeS2, as there is no additional oxidant addition during L S I or

LS2. For the goethite model, ferric is not required i n the L S 2 feed as oxygen is added to

produce ferric for goethite precipitation and regenerate cupric for further leaching.

One aspect o f these models is that ferric is consumed i n leaching prior to cupric. Whilst this may

be true for a medium with a total chloride concentration o f - 4 . 5 M , where the standard F e 3 + / 2 +

potential is at 668mV and C u 2 + / +

at 581mV, at higher chloride concentrations it is predicted that

the copper couple w i l l become more oxidizing than the iron couple. W i t h respect to the models,

in which 100% o f CuFeS2 occurs and there is no excess oxidant i n the feed, it does not matter for

the output feed which oxidant is consumed first. For example, i n the hematite model both

oxidants are completely consumed, and i n the goethite model only a small amount o f excess

ferric is produced, which is subsequently consumed i n CuFeS2 leaching.

4.2 Overview of continuous countercurrent leach experiments

Twelve continuous countercurrent leach experiments have been performed. The order,

experimental identifier ( ' H ' or ' G ' ) and conditions used are shown in Table 17. The

experimental identifier indicates upon which process model the leach was based, ' H '

representing the hematite (no air i n leach) process and ' G ' the goethite process (with air/oxygen

addition to LS2). The residence time (RT) quoted in the table is per each o f the two leach stages.

The first eleven experiments were conducted using Antamina concentrate, varying conditions o f

residence time, temperature and particle size. The final experiment was performed using fine

grind Rosario concentrate, at optimum conditions determined from the eleven previous

experiments. For all experiments, to start each experiment 135g o f feed concentrate was added to

volumes o f 1L feed solution, and the background concentration o f total chloride, contributed by

110 or 220 g/L C a C ^ , was aimed at greater than > 5 M .

The aim o f these experiments was to find conditions to achieve maximum copper extraction

(>95%) by varying conditions o f residence time, temperature and particle size, with both leach

models to be investigated. The first four experiments were important i n establishing

experimental procedures and providing direction for subsequent experiments.

58
Table 17 Order of experiments

Feed RT Total Temp. Air/0 to LS2

Order Expt 2

Concentrate (h) Time (h) '(Q (flow rate)

Antamina
1 HI 2 10.75 85 No
(p90=75um)
2 Gl 2 10 85 A i r (200mL/min)

3 H2 2 10 95 No

4 G2 2 10 95 A i r (2.5L/min)

5 H3 3 18 85 No

6 H4 3 18 95 No
r
Antamina
7 H5 3 18 95 No
(p90=41um)

8 H6 2 12 95 No

9 H7 3 18 85 No

10 H8 2 12 85 No

11 G3 r 3 18 95 0 2 (2.5L/min)
Rosario
12 H9 3 17.5 95 No
(p90=37um)

For the first four experiments 5 leach cycles were performed, but for subsequent experiments 6

cycles were performed. The first three cycles are necessary for the system to reach steady state,

and then actual trend data can be collected. Thus it was considered better to have three end

cycles rather than two to provide the trend data.

Some anomalies i n total experiment duration exist for two experiments, H I and H 9 , due to

problems with the waterbath. In both cases the total leach time was extended, to make up for

leach time when temperatures were depressed, but overall did not significantly affect the output

of the experiments. This is discussed further i n the following results sections.

A l s o i n the first experiment, H I , redox measurements were taken using an S C E probe due to a

glass body probe breaking immediately before start-up. For all subsequent experiments an epoxy

body A g / A g C l probe was acquired and proved to better withstand leach conditions. For the first
59
two experiments, H I and G l , p H measurements were measured on the bench at temperatures

slightly above room temperature. However for the remainder o f experiments p H was consistently

measured only at room temperature.

For the goethite experiments, G l and G 2 , oxygen addition was required and this was achieved

via sparging compressed air to L S 2 , in accordance with previous U B C chloride leach

experiments. A similar flow rate to those previous experiments, o f 200mL/min, was used for

experiment G l but upon recalculation, was later found to be inadequate. It was determined then

that 535mL/min would deliver the exact amount o f air required (containing - 2 1 % oxygen) over

two hours and so a 4.7x excess should be used i n experiment G 2 to overcome inefficiencies, i.e.

2.5L/min. The impact o f the greater airflow delivery to the small leach vessel resulted i n a

depression i n leach temperature o f - 4 C in L S 2 to around 91C. This excess air, however, still did

not achieve a significantly greater extraction and so the experimental focus shifted to the

hematite leach model for the next 6 experiments. For flow rate calculations see Appendix 7.

The next 2 experiments, H 3 and H 4 , were also performed using the coarse Antamina concentrate

completing a series o f four hematite model experiments comparing residence time (2h vs 3h) and

temperature (85 vs 95C).

Then four experiments, H 5 - H 8 , again based on the hematite (no air in leach model) were

performed using Antamina concentrate that had undergone fine grinding. These four reflected

the experimental matrix o f the four previous coarse material experiments (i.e. 2 or 3 h R T at 85

or 95 C ) .

The final two experiments were performed at optimum conditions determined for the hematite

model experiments, using fine grind concentrate, a temperature o f 95C and residence time o f 3h,

applied to the goethite model and an alternate concentrate.

This included one further goethite model experiment (G3) but this time oxygen (98% pure) at a

flow rate o f 2.5L/min (an excess o f 33x) was sparged to leach stage two. The final experiment,

H 9 , was conducted based on the hematite (no air i n leach) model at optimum conditions (3h,

95C) using finely ground Rosario concentrate.

60
The following sections in this chapter present the results of the countercurrent leach experiments.
Certificates of analysis for all samples can be found in Appendices 1 and 2, and the Cu and Fe
mass accountability performed for all experiments, based on feed material in and samples taken
out, can be found in Appendix 8. Profiles of measurements over time for each individual
experiment, can be found in the Appendix 9.

61
4.3 Results of hematite model experiments
Eight experiments based on the hematite leach model were conducted and conditions are shown

in Table 18. The first four experiments employed the as received Antamina concentrate (p90 =

75pm), varying residence time (2 or 3 hour per leach stage) and temperature (85 or 95C). The

successive four (H5-H8) employed fine grind Antamina concentrate (p90 = 41pm), similarly

varying residence time and temperature. Thus an experimental matrix was completed observing

the effect o f particle size, residence time and temperature on copper extraction.

Table 18 Hematite model - feed conditions

EmV Free Acid

Cl Cu 2 +
Fe 3+

Experiment Concentrate X (as HCI)

[M] Ag/Ag/CI g/L g/L
(RT, Temp.) g/L
(a = vs S C E )

HI Antamina
(p90=75um) 7.19 626 a
-0.48 47.8 76.7 5.74
(2h, 85C)
H2 Antamina
7.39 650 a
-0.24 47.2 79.9 5.28
(2h, 95C) (p90=75um)

H3 Antamina
(p90=75um) 7.19 639 a
-0.36 52.9 87.2 4.04
(3h, 85C)
H4 Antamina
(p90=75um) 7.95 661 -0.35 55.8 90.6 4.04
(3h, 95C)
H5 Antamina
(p90=41um) 6.29 677 -0.16 45.0 76.0 2.71
(3h, 95C)
H6 Antamina
(p90=41um) 6.35 660 -0.25 41.1 70.2 1.94
(2h, 95C)
H7 Antamina
(p90=41um) 8.01 659 -0.68 47.7 80.1 2.96
(3h, 85C)
H8 Antamina
(p90=41um) 7.17 661 -0.67 48.0 75.3 3.69
(2h, 85C)
"measured at room temperature

After the first four experiments it was observed that the best conditions for copper extraction

involved using a 3h R T at 95C. Therefore for the fifth experiment these conditions were used

when first testing the fine grind concentrate i n order to see potentially what the maximum

extraction would be and i f further experiments with this model were worthwhile. Upon

achieving very good extractions, >98%, the final three experiments were pursued.

62
The feed liquor cupric and ferric concentrations, with respect to the mass balance output, were

aimed to be 50g/L and 80g/L respectively. In a few o f the experiments these concentrations

were slightly lower, however as the feed concentrate was not 100% CuFeS2 (unlike i n the model

mass balance calculations) this decrease o f oxidant i n the feed liquor was not a concern. A

recalculation o f oxidant i n the feed (see Appendix 7), based on the actual CuFeS2 content o f the

Antamina feed shows that 70g/L ferric and 40g/L cupric are sufficient oxidant concentrations for

the feed.

Temperature was maintained within 1-2C from the target leach temperature, except i n

experiments H I and H 3 when there were slight deviations (due to problems with the water bath).

In H I the temperature i n the second cycle dropped, thus the leach was extended for 45 m i n to

compensate, and at the end L S 2 was slightly elevated at 88C for the last hour. In H 3 there was a

slight drop o f 2-4C i n the last cycle for a period o f ~20min, due to a water jacket hose clamp

connection loosening. These deviations are not considered significant.

The copper and iron mass balance was calculated for each experiment based on the total in feed

materials and outgoing samples, solutions and residues. A l l o f the balances were within

acceptable limits, o f 95-105%) accountability, except for copper i n H I , for which copper

accountability was 94%, and H 3 , for which.copper accountability was 93%. A s these were only

out by 2% they were not considered significant.

4.3.1 Potential, pH and free acid

A l l 8 hematite model experiments, involving Antamina concentrate, exhibited similar potential

and p H profiles and trends i n free acid consumption. The input feed and final output L S 1 and

L S 2 streams are summarized i n Table 19. The E and p H profiles for each experiment are found

i n Appendix 9 and some representative profiles have been included below.

In accordance with the trend predicted for countercurrent leaching, potential decreased from L S 2

to L S I . L S 2 is expectedly higher in the countercurrent system due to the fresh feed liquor

meeting the partially leached solids from L S I . In these experiments there was a general redox

potential gradient o f 50-100mV from L S 2 down to L S I , with in-situ redox measurements for

L S 2 at 4 5 0 - 5 5 0 m V / A c i and L S I at 4 0 0 - 4 5 0 m V / A c i Examples o f representative E profiles

Ag g Ag g

for experiments H 4 and H 5 are shown below i n Figures 22 and 23.

63
Figure 22 E profile for H4(75um, 3h, 95C) Figure 23 E profile for H5(4lum, 3h, 95C)

The p H profiles for all hematite model experiments revealed a similar trend, showing only slight
deviations from the feed value. For all hematite model experiments the free acid was measured
in the exit PLS stream and found to be completely consumed. The p H therefore was not affected
by the decrease in free acid, owing to the extremely high concentrations of chloride and metals.
The free acid was likely consumed in the oxidation of reduced species.

64
Table 19 E, pH and free acid output for hematite experiments

E mV Ag/Ag/ciX
pH Free Acid
Expt Stream (except a = vs SCE)
(at room temp,
as HC1 (g/L)
except b = at 35C)
Feed 677 a
-0.48 5.74

HI LSI 416 a
-0.01 b
not measured

LS2 509 a
-0.04 b

Feed 733 -0.24 5.28

H2 LSI 453 -0.39 0.18

LS2 530 -0.41

Feed 750 -0.36 4.04

H3 LSI 451 -0.34 O.01

LS2 530 -0.31

Feed 747 -0.35 4.04

H4 LSI 440 -0.55 O.01

LS2 537 -0.37

Feed 754 -0.16 2.71

H5 LSI 415 -0.27 O.01

LS2 492 -0.13

Feed 735 -0.25 1.94

H6 LSI 428 -0.42 <0.01

LS2 497 -0.33

Feed 748 -0.68 2.96

H7 LSI 388 -0.77 <0.01

LS2 468 -0.71

Feed 733 -0.67 3.69

H8 LSI 400 -0.41 O.01

LS2 462 -0.73

"At reaction temperature

65
4.3.2 Copper and iron extraction
The following Table 20 summarizes solids and solution concentrations i n the feed and final L S 1

and L S 2 output streams. The calculated copper and iron extraction values i n the final L S I and

L S 2 residues are also shown. The profiles o f solution and residue concentrations for each

experiment can be found i n Appendix 9 and representative profiles have been included i n the

following discussion o f the results.

These experiments revealed a consistent trend with respect to CuFeS2 leaching i n varying

temperature and residence time with respect to particle size. The copper extraction at steady

state in the first four experiments (H1-H4), employing p90 = 75um concentrate, show that

increasing the temperature from 85C to 95C had a greater impact on extraction than increasing

the residence time from 2h to 3h. Observing the final L S 2 extraction data, for experiments H l -

H 4 , the copper extractions were 80% (2h,85C), 87% (2h,95C), 83% (3h,85C)and 93% (3h,95C)

respectively.

A s >95% copper extraction i n chloride media has been well demonstrated by others, the

subsequent experiments (H5-H8) were performed using a concentrate o f a finer particle size, p90

= 41 um, i n order to achieve higher copper extraction. The first experiment i n this series, H 5 ,

was thus performed using conditions o f 3h residence time and 95 C. This experiment was very

successful and an average o f ~ 98% copper extraction was achieved. The final three

experiments, H 6 - H 8 , were then completed to mirror the experimental matrix performed for the

p90 = 75um Antamina concentrate, i.e. varying residence time (2 and 3h) and temperature (85

and 95C). The lowest average copper extraction was 90% when a 2h leach stage residence time

was employed and conducted at 85C, see H 8 . Interestingly, experiments H 6 (2h, 95C) and H 7

(85C), both reported similar copper extraction behavior and a final value o f 96%.

The lower values reported for iron extraction have been examined and found to represent iron

remaining from unleached CuFeS2 and iron remaining as undisturbed pyrite (FeS2).

Examples o f representative profiles for solution concentration, C u and Fe i n L S 2 residue and C u

and Fe extraction for experiments H 4 and H 5 are shown i n Figures 26-31.

66
Table 20 Results of hematite model experiments

Solution Solids Percentage Extn

Expt Stream
Cug/L Feg/L Mass g Cu % Fe% Cu% Fe%
Feed 47.8 76.7 135 28.8 28.4
HI LSI 74.1 101.7 87.6 18.0 23.0 59 47
LS2 54.1 85.2 44.5 17.5 22.1 80 74
Feed 47.2 79.9 135 28.8 28.4
H2 LSI 81.8 114.3 79.3 17.9 19.6 64 59
LS2 60.1 93.1 63 8.1 12.4 87 80
Feed 52.9 87.2 135 28.8 28.4
H3 LSI 86.3 125.1 88.9 20.7 22.0 53 49
LS2 63.0 100.7 57.7 11.3 16.2 83 76
Feed 55.8 90.6 135 28.8 28.4
H4 LSI 94.6 127.9 46.6 21.4 24.3 74 70
LS2 68.1 102.9 46.9 6.1 12.5 93 85
Feed 45.0 76.0 135 28.3 28.8
H5 LSI 86.0 118.0 114 25.0 24.7 27 28
LS2 71.0 100.0 41 2.0 8.5 98 91
Feed 41.1 70.2 135 28.5 28.7
H6 LSI 75.3 103.9 100.1 25.2 24.8 34 36
LS2 60.8 87.4 46.6 3.7 9.6 96 88
Feed 47.7 80.1 135 28.5 28.7
H7 LSI 81.1 112.9 71.5 20.7 21.8 61 60
LS2 65.4 96.9 43 4.0 10.2 96 89
Feed 48.0 75.3 135 28.5 28.7
H8 LSI 80.4 106.5 87 23.0 24.9 48 44
LS2 63.8 91.5 49.1 7.9 13.36 90 83

67
Leach Conditions: H4 = 75p.m, 3h, 95C and H5 = 41ujn, 3h, 95C
Figure 26 H4: Cu & Fe (%) Extraction Figure 27 H5: Cu and Fe (%) Extraction

93.4 94.0 91.2 9 2 9

5 10 15 20
Time (h)

Figure 28 H4: Concentration vs Time Figure 29 H5: Concentration vs Time

140 140

120

100

! 80

60
-4LSlFe
40 - LS2 Fe
-LSlCu
20
LS2Cu

5 10 15 20
Time(h)

Figure 30 H4: Cu and Fe in LS2 Residue Figure 31 H5: Cu and Fe in LS2 Residue

68
4.3.3 Speciation

Both models predict that the exit P L S w i l l contain predominantly reduced species, o f iron and

copper, and hence downstream purification and recovery steps were balanced accordingly.

Theoretical calculations (based on the actual feed concentrate, feed liquor and completeness o f

leaching) for total reduced species (TRsp) content i n the P L S have been performed (an example

calculation is included i n Appendix 7) and presented i n Table 21 along with actual titration

values. Both results are compared and variations from the model are discussed, as are

implications for downstream processing.

Table 21 Total reduced species of exit PLS and L S 2 liquors

TRsp Titration TRsp

Final TRsp TRsp
CuFeS CuFeS Ttl Ttl Difference (titration)
Cu
reacted (theoretical) theo. (titration) actual (Theoretical - TRsp % of
2 2
Expt in
extn LSI LSI Titration) LS2
(mol) (mol) M M Theoretical
% (M) (M) (M) (M)
H2 0.612 87 0.532 2.66 3.24 2.44 3.33 0.22 92 1.02
H3 0.612 83 0.508 2.54 3.41 2.28 3.60 0.26 90 0.78
H4 0.612 93 0.569 2.84 3.64 2.60 3.78 0.24 91 0.88
H5 0.605 98 0.593 2.97 3.26 2.60 3.47 0.37 88 0.88
H6 0.605 96 0.581 2.91 3.07 2.53 3.05 0.38 87 1.48
H7 0.605 96 0.581 2.91 3.35 2.62 3.30 0.29 90 1.22
H8 0.605 90 0.545 2.72 3.19 2.39 3.17 0.33 88 1.30

The calculation for determining the theoretical reduced species concentration takes into account

the feed liquor oxidant concentrations and the actual CuFeS2 reacted for each experiment. It does

not matter which oxidant, ferric or cupric, is consumed first i n leaching, as both reactions

produce the equivalent amount o f reduced species, i.e. 5 m o l reduced species per m o l CuFeS2

reacted, as shown i n equations 4.15 and 4.16.

C u F e S + 4Fe
2
3+
-> 5Fe + C u
2+ 2 +
+ 2S Reduced = 5 m o l ferrous (4.15)

CuFeS + 3Cu
2
2+
4Cu + F e
+ 2 +
+ 2S Reduced = 4 m o l cuprous and 1 m o l ferrous (4.16)

69
The titration values reported in the above table are all lower than the theoretical calculation by

0.22-0.33M, and in both cases oxidant was still found remaining in the P L S . To explain the

difference between theoretical and titration total reduced species values two things were

considered, additional oxidation occurring in the leach liquor during the experiment and error in

the titration method.

The first considers that additional cuprous or ferrous may be oxidized by atmospheric oxygen,

available in the headspace o f the leach vessel, with available acid, HC1. However a calculation

of air volume and acid required indicate that between 7-12L o f air would be the exact amount o f

air required to deliver the required oxygen and 8-12g/L HC1 would be required. Whilst there

may certainly be acid available in the leach solution it is not feasible that the solution would

meet with such a volume o f ambient air, considering that there is only 1L o f headspace i n both

leach stages. A l s o an excess o f air, above the stoichiometric ratio, would be required to

overcome gas transfer limitations. Although not all o f the difference can be attributed to

atmospheric oxidation a small amount is certainly possible.

It is more likely that cuprous, being incredibly unstable in more dilute solutions o f chloride on

exposure to air, may have been oxidized during dilution for the titration. In either case, both

results indicate that copper and iron species i n the P L S stream are not likely to be fully reduced

as predicted i n the models and downstream implications must be considered.

Complete reduction o f the liquor could be achieved by adding copper metal to the stream to

reduce the oxidized species prior to downstream processing. This however would not only

increase the cost o f production but also increase the copper tenor, which is already high.

Another alternative is to investigate what the actual impact would be o f sending this liquor

containing oxidized copper as well as reduced species direct to solvent extraction. The result is

actually not detrimental as the following discussion suggests.

The uptake o f copper by the organic extractant is actually in the form C u 2 +

and thus oxidized

species would be available without requiring addition o f oxygen. However without the complete

balance o f oxidation o f cuprous to cupric there would be an excess o f acid produced. Though

ferrous is still available and may be oxidized thus consuming acid produced by copper

extraction. The following equations (4.17-4.19) demonstrate these reactions.

70
 Cu 2 +
+ 2HRo r g CuR 2 o r g + 2H +
(4.17)

2 C u C l + 0.5O + 2HC1 - 2 C u C l + H 0
2 2 2 (4.18)

2 F e C l + 0.5O + 2HC1 - 2 F e C l + H 0
2 2 3 2 (4.19)

Thus the stream leaving S X would contain cupric, ferrous and some ferric, which is then

available for hematite precipitation.

2 F e C l + 3 H 0 - F e 0 ( s ) + 6HC1
3 2 2 3 (4.20)

as opposed to

2 F e C l + 0.5O + 2 H 0
2 2 2 Fe 0 2 3 ( s ) + 4HC1 (4.21)

This may produce a slight excess o f acid i n the autoclave.

4.3.4 Hematite experiment discussion

Conditions for achieving the highest extraction o f copper involved employing a fine grind

concentrate, 95 C and leaching for 3h i n each leach stage. Depending on the copper recovery

necessary there may be some flexibility with respect to leach design, due to fairly high extraction

rates reported at the lower temperatures or leach residence times. For example, i f >95%

recovery is sufficient, then using fine grind concentrate and either a 2h residence time at 95C or a

3hr residence time 85C may be sufficient. Should fine grinding o f the concentrate be avoided

then it may be possible to conduct the leach at 95 C with a 3h leach residence time and still

achieve a satisfactory copper extraction o f around 93%.

4.4 Results of goethite model experiments

Three experiments based on the goethite leach model have been performed and conditions are

shown i n Table 22. In the first two experiments air (-21% 0 ) was added to leach stage 2 to 2

regenerate cupric for further leaching and ferric for goethite precipitation. These first two

experiments were not successful in achieving high copper extractions and so for the third

experiment fine grind Antamina concentrate was tested and 98% oxygen used as the oxidant

source. The flow rate for the third experiment was kept the same as for the second, i.e. 2.5L/min.

This was to ensure that an excess (circa. 3 Ox) o f oxygen was delivered to overcome

inefficiencies and solubility limitations. The calculations for oxygen delivery are contained i n

Appendix 7.
71
Table 22 Feed conditions for goethite model experiments

Free A c i d
Flow rate to Cl EmV Cu 2 +
Fe 3+
Fe 2+
CaCl 2

Experiment 3

X
pH (as HC1)
LS2 [M] g/L g/L g/L g/L
Ag/Ag/Cl g/L

Gl Air
4.5 463 0.02 54.1 7.9 27.1 110 0.72
(2h, 85C) (200mL/min)
G2
Air (2.5L/min) 5.7 457 -0.47 55.9 11.6 22.9 220 10.02
(2h, 95 C)
G3
0 (2.5L/min)
2 5.6 443 -0.29 47.4 4.9 25.1 220 <0.01
(3h, 95C)

(residence time per leach stage, temperature); measured at room temperature

In accordance with the calculated feed requirements, liquor concentrations approximated 50g/L

cupric, with 30g/L iron as ferrous and a low concentration of ferric. Although experiment G3

had a slightly lower cupric concentration, this was not important as there was additional oxidant

available in the feed as ferric and the feed was not 100% CuFeS2, unlike the mass balance model.

In experiment G l the background concentration of HOg/L C a C ^ provided just under 5M total

chloride, as a result of the lower content of metal chlorides used in the feed compared to the

hematite feed. Thus for further goethite model experiments the background CaCL. concentration

was raised to 220g/L to ensure a total chloride concentration of 5M. A high chloride content is

important for supporting high metal concentrations and maintaining a low pH, however this

increase was not thought to be significant for comparison of these experiments.

It was intended that the feed liquor contain a low (<3g/L) concentration of free acid as HC1 to

promote goethite precipitation. The second experiment G2 however was prepared with a

significantly higher HC1 content. Whilst this was not a concern regarding copper extraction it

was interesting to observe the effect on iron extraction behavior.

The temperatures for the experiments were kept within 1-2C of the set conditions, except for LS2

in experiments G2 and G3 where the temperature was depressed ~4C due to the high flow rate

(2.5L/min) of air and oxygen addition.

72
The copper and iron mass balance was calculated for each experiment based on the total feed

liquor and concentrate i n and outgoing samples, solutions and residues. A l l o f the balances were

within acceptable limits, o f 95-105% accountability, except for experiment G l i n which C u

accountability was 88% and iron accountability was 86%. One problem that may have

contributed to this poor recovery was the difficulty processing and filtering the sticky, orange

goethite residue. Another problem with this experiment was that insufficient oxygen was

delivered to L S 2 and so overall this experiment can only serve to provide an approximate guide

for goethite model leaching. The results o f the above goethite model experiments are reported

below.

4.4.1 Potential, pH and free acid

The measurements o f redox potential, p H and free acid for the input feed and final output L S I

and L S 2 streams for the three goethite experiments are summarized i n Table 23. Similarly, i n

accordance with the trend predicted by countercurrent leaching, potential decreased from L S 2 to

L S I . A s the potential o f the feed liquor was quite low and the air ( - 2 1 % 0 ) addition was not
2

very high i n the first experiment the E gradient from L S 2 to L S I was not very large. In

experiment G 2 when air addition was substantially increased, the resulting potentials o f L S I and

L S 2 were still not observed to increase and did not differ from G l . The resulting extraction

results, as discussed below, were not very high either and this is further discussed below. Thus

air delivery, even i n excess, did not seem successful at regenerating oxidant species or even

restoring potential to that o f the feed value.

A significantly higher oxidation potential was however achieved i n the final experiment, G 3 ,

with L S 2 between 550-600mVAg/A ci, when almost pure oxygen (98%) was added to L S 2 at a
g

rate o f 2.5L/min and thus delivering a 20 times excess. A substantial E gradient was observed

across L S 2 / L S 1 . This E increase also paralleled a greater copper extraction. Figures 32 and 33

show the E profiles for experiments G 2 and G 3 . This experiment confirmed that copper

extraction could be improved by increasing oxidation potential i n L S 2 and it is likely that >95%

copper leach extraction could be achieved with longer leach residence time and further fine

grinding o f the concentrate.

73
Table 23 E, pH and free acid output for goethite experiments

E mV Ag/Ag/ciX Free Acid as HCI

Expt Stream PH
(LS1/LS2 for feed) (g/L)

Feed 504/524 0.02 0.72

Gl LSI 439 0.75 y

1.5

LS2 451 0.64 y

Feed 534/571 -0.47 10.02

G2 LSI 439 -0.04 2.8

LS2 456 0.54

Feed 515/580 -0.29 <0.01

G3 LSI 409 -0.24 <0.01

LS2 606 0.32

x
A t reaction temperature; measured at 50C.
y

Figure 32 E profile for G2(75|im, 2h, 85) Figure 33 E profile for G3(41u.m, 3h, 95C)

580
560
540
LS1
5 520
I< 500
LS2

<n 480
|> 460
| LU 440
* *
420
400
4 6 8 10 12
Time (h)

74
Fairly similar p H profiles were observed for all goethite experiments, as shown i n Figures 34 and

35. A s expected there was greater fluctuation in p H for the goethite experiments, compared to

the hematite model, due to L S 2 reactions involving acid, i.e. ferrous and cuprous oxidation and

iron precipitation reactions. During the first leach cycle, prior to steady state, the p H i n L S 2 rose

sharply but then returned to stabilize at a lower p H . This reflects acid consumption reactions

dominating, i.e. oxidant regeneration, until a sufficient acid deficit can drive goethite

precipitation. This occurs significantly in G 3 , in which the feed liquor already had a lower free

acid content. In G 3 , the p H was observed to rise sharply to a value o f 2, which is the value at

which iron is expected to precipitate i n concentrated chloride solutions. Following this first cycle

a better balance was achieved between oxidation and precipitation reactions stabilizing the p H at

a lower value. A slightly different situation occurred i n experiment G 2 due to the feed liquor

containing a greater concentration o f free acid. A s a result it appears that p H is stabilized at a

moderately low value, and it is likely that oxidation regeneration dominated due to the available

concentration o f free acid i n the feed, and only a small amount goethite precipitation could occur

when sufficient acid had been consumed.

Figure 34 pH profile for G2(75u,m, 2h, 95C) Figure 35 pH profile for G3(4lu,m, 3h, 95C)

75
4.4.2 Copper and iron extraction

The following table summarizes solids and solution concentrations i n the feed and final L S I and

L S 2 output streams. The calculated copper and iron extraction values i n the final L S I and L S 2

residues are also shown. The profiles o f solution and residue concentrations for each experiment

can be found i n Appendix 9. The results o f sulfur analyses are given i n section 4.6.

Table 24 Output concentrations (solution and solids) for goethite model experiments

Solution Solids Percentage Extn

Expt Stream
Cug/L Feg/L Mass g Cu% Fe% Cu% Fe%

Feed 54.1 35.0 135 28.8 28.4

Gl LSI 55.5 27.6 90 25.5 25.4 41 40

LS2 67.3 29.6 112 13.9 29.8 60 13

Feed 55.9 34.5 135 28.8 28.4

G2 LSI 87.9 59.7 93 29.1 26.9 30 35

LS2 76.7 48.5 78 16.6 23.2 67 53

Feed 47.4 30.0 135 28.5 28.7

G3 LSI 93.9 26.2 88 24.5 26.5 44 40

LS2 79.3 11.3 108 4.0 38.4 89 -7

Experiments G l and G 2 , at 2h R T and 85C and 95C respectively, were able to demonstrate

leaching only to 60% and 67% copper extraction. Therefore i n these conditions, despite

delivering a 4.7 times excess o f oxygen i n experiment G 2 , copper extraction was not acceptable.

Oxygen solubility in hot liquor at atmospheric pressure is likely to be the limiting factor.

W i t h respect to iron, precipitaion o f goethite i n G l successfully recovered all but 13% o f iron,

driven by a low free acid i n the feed liquor. However, i n G 2 , iron precipitation was inhibited by

the presence o f lOg/L HC1 i n the feed liquor, although this had no apparent consequence on

copper extraction. The increase o f 8% copper extraction from experiment G l to G 2 mirrors the

7%) increase i n the hematite experiments when a 2h leach stage residence time was used at 85C

76
the 95C, i.e. H I and H 3 . The extraction profiles for copper and iron i n experiments G l and G 2

are shown in Figures 36 and 37.

The best result for the goethite model was experiment G 3 using Antamina fine grind concentrate

(3h R T , 95C) and oxygen (98%) sparging to L S 2 , instead o f air. Following the first three cycles,

copper extraction stabilized at 89% and a much higher oxidation potential i n L S 2 was recorded.

The extraction profiles for copper and iron in experiment G 3 is shown i n Figure 38. A longer

residence time and/or finer grinding may lead to achieving >95% copper extraction. Interestingly

however iron precipitation was too high i n G 3 , i.e. greater than the amount o f iron contained in

the feed concentrate, resulting in a negative -7% iron extraction. A greater amount o f acid in the

feed would reduce iron precipitation, however the value o f free acid would be fixed by solvent

extraction step for this model. The current precipitation value may however be acceptable

providing a greater overall extraction o f C u and Fe from CuFeS2 can be achieved, or by ensuring

that further cycles through the system w i l l achieve an overall iron balance.

77
 Figure 38 G 3 : C u & Fe (%) E x t r a c t i o n

-80 J
Time (h)

4.4.3 Speciation

The following table presents the titration values for total reduced species concentrations, along

with total species determined from the addition o f copper and iron concentrations, for the feed

and final L S I and LS2 streams. Similarly as with the hematite model, the exit P L S streams all

contain a significant portion o f oxidized species. However, as the next process step in the

goethite model flowsheet is copper solvent extraction the impact on downstream process is

insignificant, as discussed previously for the hematite model experiments.

78
Table 25 Total reduced species in goethite experiments

Total
Total % Total
reduced
Expt Stream Species Reduced
species
(M) species
(M)
LSI 1.37 0.65 48
Gl
LS2 1.59 0.55 35

LSI 2.45 1.41 58

G2
LS2 2.08 0.94 45

LSI 1.95 1.12 58

G3
LS2 1.45 0.09 6

4.4.4 Goethite experiment discussion

The goethite experiments were not successful i n achieving greater than 95% copper extraction.

Even when conditions were used that had achieved the highest extraction in the hematite model,

i.e. fine grind concentrate, 3 hour leach and 95C, and an excess o f oxygen was delivered to the

leach the highest extraction achieved was 89%. This value was a significant improvement on the

experiments employing air addition to L S 2 , G l and G 2 , and by extending residence time and/or

finer grinding o f the concentrate there is potential for achieving >95% copper extraction.

Although such a large excess o f oxygen (circa. x20), as used i n experiment G 3 , would be very

unreasonable in scaling up o f the process. It is likely that there exists an industrial scale reactor

designed to increase oxygen utilization efficiency i n a commercial plant, thus improving upon

the bench scale system.

Another negative aspect o f this model was that the mixed, orange sulfur/goethite leach residue

was very sticky and difficult to filter. Not only was filtering slow but the residue encapsulated a

significant amount o f liquor which required large amounts o f 1/10 H C I for washing away soluble

copper and iron.

4.5 Application of hematite leach model to Rosario concentrate

The highest copper extraction from the Antamina concentrate i n this investigation was achieved

employing the hematite model with a fine grind concentrate (p90 = 41pm), leach residence time
79
o f 3h and a temperature o f 95C. The aim o f the final experiment, H 9 , was to achieve a similarly

high copper extraction from a different concentrate under the same conditions. The Rosario

concentrate was selected as it is currently o f interest. The Rosario concentrate contains a similar

amount o f copper (26.8%) as the Antamina (28.5%), but contains less CuFeS2 and an additional

copper mineral, chalcocite, CU2S. The Rosario concentrate underwent fine grinding prior to the

experiment, to a p90 o f 37p.m. The conditions o f the feed liquor for the Rosario experiment are

shown i n the following table, and are similar to the conditions for the previous hematite model

experiments, H I - 8 .

Table 26 Feed conditions for Rosario experiment

Free A c i d
Cl EmV Cu 2 +
Fe 3+
CaCl 2

Experiment 3
pH (as HC1)
[M] Ag/Ag/Cl* g/L g/L g/L
g/L

H9
7.08 659 -0.41 50.6 82.0 110 2.35
(37um,3h,95C)
(residence time per leach stage, temperature); measured at room temperature

During cycles 5 and 6 o f this experiment water bath circulation problems significantly disrupted

the temperature profile. Interestingly, copper extraction, as discussed below, was not

significantly affected.

The mass balance accountabilities for copper and iron, determined from feed and outgoing

samples and materials, were 95% and 97% respectively.

4.5.1. Potential, pH and free acid

The potential, p H and free acid trends were similar to those o f the other hematite experiments

and the results are shown in Table 27 and Figures 38 and 40. The free acid was similarly

depleted i n the P L S , the p H stayed close to the feed value and the range o f L S I and L S 2 E values

were 400-450mVAg/A ci and 450-550mVAg/A ci respectively.

g g

80
Table 27 E, pH and free acid

Free Acid as
Expt Stream E mV Ag/Ag/ciX pH HCl(g/L)

Feed 743 -0.41 2.35

H9
LSI 463 -0.51 <0.01
(37um,3h,95C)

LS2 562 -0.53

x
A t reaction temperature

Figure 39 E profde for H9(37um,3h,95C) Figure 40 pH profile for H9(37um,3h,95C)

800
750
700
650 LSI
600 I LS2

550
500
450 -

400
350
4 6 8 10 12 14
Time (h)

4.5.2 Copper and iron extraction

Table 28 reports the successful output data for the final hematite experiment. Not only was the

final copper extraction 98%, by the end o f the first leach stage 96% extraction had already been

achieved. The presence o f CU2S i n this material thus indicates that it is easier to leach than a

predominantly CuFeS2 concentrate, and, as a result thereof, the required leaching time is

significantly decreased. The following equation (4.22) is shown for CU2S leaching. The

unleached iron in the residue was examined and found to contain represent undisturbed pyrite.

C u S + 2 F e / C u / o x -> 2Fe /Cu /red- + 2 C u + S

2
3+ 2+ 2+ + 2 +
(4.22)

81
T a b l e 28 O u t p u t concentrations (solution and solids) for the R o s a r i o experiment

Solution Solids Percentage E x t n

Expt Stream
Cug/L Feg/L Mass g Cu% Fe% Cu% Fe%

Feed 50.6 82.0 135 26.8 26.8

H9
(37LUIL LSI 91.7 100.5 76.3 2.1 28.3 96 40
3h, 95C)
LS2 55.1 84.9 68.6 1.1 27.5 98 48

F i g u r e 41 C u & Fe (%) E x t r a c t i o n for H9(37Lim,3h,95C)

0 5 10 15

Tlme(h)

82
4.6 Sulfur balance
The feed concentrate was analyzed for Total sulfur (S), and the final L S 2 leach residue o f each
2 2
experiment was analyzed for total S, elemental S, sulfide (S ") and sulfate (SO4 ") The sulfur

group analyses i n the final L S 2 residue o f each experiment are shown i n Table 29.

Table 29 Sulfur species in Final LS2 residues

Elemental Sulfide Sulfate

Expt
(%) (%) (%)
HI 28.0 23.9 0.91

H2 50.4 15.0 <0.1

H3 39.6 16.6 <0.1

H4 42.0 13.9 <0.1

H5 49.8 9.91 <0.01

H6 56.5 11.8 O.01

H7 53.6 11.4 0.02

H8 46.8 14.4 O.01

H9 23.1 34.1 O.01

Gl 15.0 16.0 1.33

G2 24.2 21.3 0.12

G3 20.4 6.68 1.09

The residue (<10g) from the slurry sample taken from L S I was not however analyzed for sulfur,

and to calculate the sulfur mass balance an expected loss o f sulfur from L S I was determined

based on C u and Fe concentrations i n the sample. Table 30 reports these sulfur values and

presents the sulfur balance.

The generally very low amounts o f sulfate indicate almost 100% yield o f elemental sulfur. The

hematite model experiments produced a mainly elemental S residue, with some sulfide

remaining from unleached CuFeS2 and/or FeS2. For the goethite model experiments, elemental

sulfur was also the major reaction product left in the residue along with goethite (FeOOH). For

both models, there was no significant amount o f sulfate i n the exit leach residues. This correlates

83
previous reports o f minimal oxidation Of elemental sulfur to sulfate, which would precipitate

with gypsum i n these experiments. A small but insignificant amount o f sulfate was detected i n

the first and final goethite experiments, the two i n which goethite was successfully precipitated

with the residue.

Table 30 Sulfur recovery

Est'd
LS2 Total S out Final
Total S S out of Total MSN Sin-
Output Sulfur of Cu
Expt in LSI Sout out/in S out
Mass in LS2 LS2 ext'n
(g) sample (g) (%) (g)
(g) (%) (g) (%)
(g)
HI 43.3 44.5 53.2 23.7 4.0 27.7 64 15.6 80

H2 43.3 63.0 65.6 41.3 3.3 44.6 103 -1.3 87

H3 43.3 57.7 56.2 32.4 2.9 35.4 82 8.0 83

H4 43.3 46.9 55.9 26.2 2.5 28.7 66 14.6 93

H5 43.8 41.0 59.8 24.5 3.5 28.0 M 15.7 98

H6 43.8 46.6 68.3 31.8 3.4 35.2 So 8.6 96

H7 43.8 43.0 65.0 28.0 3.2 31.2 71 12.6 96

H8 43.8 49.1 61.1 30.0 3.7 33.7 MBSM 10.1 90

H9 48.0 68.6 57.2 39.2 6.1 45.3 95 2.6 98

Gl 43.3 112.4 32.6 36.6 2.8 39.4 VI 3.9 60

G2 43.3 77.8 45.5 35.4 2.4 37.8 87 5.5 68

G3 43.8 108.2 28.2 30.5 4.1 34.6 79 9.1 89

The sulfur balance for nearly all experiments does not lie within acceptable limits, 95-105%,

despite acceptable copper and iron balances. There appears to be a loss o f S i n the range o f 5-

15g across all experiments. Reasons for this are not clear other than to consider the possibility o f

loss o f residue or slurry.

It was observed i n the hematite experiments, that the light sulfur residue would tend to float to

the top and stick to the walls o f the flask or thickener. This indicates potential for loss o f sulfur

from the final residue and may have a significant effect on the balance. It is indeed the sulfur

84
balance o f the hematite experiments that report the greatest lack o f accountability o f sulfur (up to

15g).

The three goethite model experiments and the final Rosario leach experiment reported better

sulfur recovery figures, with a lack o f accountability between 2.6-9. l g . These residues contained

a significant amount o f goethite or pyrite that may have helped bond the residue together and

prevented floating or frothing o f the lighter sulfur.

In scaling up o f the process, attention to engineering design would address the lack o f sulfur

accountability in the leach residue.

4.7 Trace Metals

A l l the elements reported in I C P analysis were examined to determine which other elements

were leached with copper. The following table reports the extraction values o f these elements in

the final L S 2 residues o f three experiments, and includes copper and iron extractions for

comparison. Silver (Ag), chromium (Cr), lead (Pb), magnesium (Mg), nickel (Ni) and zinc (Zn)

all reported significantly high extractions, i.e. all generally above 90%. This indicates the

suitability o f chloride leaching for complex sulfides.

Table 31 Trace metal analysis

Extraction % in final L S 2 residue

Element
H5 (41um,3h,95C) G3(41um,3h,95C,O 2t0LS2 ) H9 (Rosario,3h,95C)

Ag 97.1 92.4 98.9

Cd not in feed not in feed 100.0
Cr 92.1 46.2 93.9
Cu 98.2 88.7 97.9
Fe 91.1 -7.0 47.7
Pb 99.9 99.7 94.3
Mg 96.7 93.4 95.5
Ni 93.0 90.1 92.4
Zn 98.9 98.4 98.7

85
5 CONCLUSIONS AND RECOMMENDATIONS
5.1 Model mass balances
Two new process flowsheets, the Goethite Process and the Hematite Process, were developed

and the successful completion o f mass balances shows potential for both circuits particularly i n

addressing current purification difficulties and waste management issues. Solvent extraction

( S X ) is known to be a very effective method o f selective uptake o f copper from sulfate leach

liquor, for transfer to the electrowinning circuit with minimal impurity transfer, and is expected

to work well for a chloride system. A s goethite (FeOOH) is a less stable iron residue in the

environment that hematite (Fe20s) it is important to have two process options because i n some

localities goethite w i l l not be accepted i n waste for disposal.

The mass balances were also useful i n determining feed liquor requirements for the leach.

Although these models were simplified, considering only major reactions and assumed complete

extraction o f chalcopyrite, they were still beneficial and successfully tested i n the continuous

countercurrent leach experiments. Whilst the aqueous processing assumptions were fairly

accurate with respect to the experimental outcomes, the delivery o f gas containing oxygen did

not perform as w e l l as the goethite model intended i n an atmospheric leach system. Both

Goethite and Hematite Processes did however improve upon a previously proposed flowsheet i n

which air was added to leach stage two i n addition to use o f an autoclave downstream for iron

recovery, thus requiring careful control so as not to precipitate iron i n the leach. In the two

current models investigated i n this thesis, either oxygen was added to the leach to precipitate iron

or an autoclave was incorporated downstream, therefore clearly defining at which part o f the

process iron deportment would occur.

5.2 Implementation of the mini-thickener

The mini-thickener proved very useful i n achieving consistent operation for all countercurrent

continuous-batch experiments. Complete transfer o f the solids was achieved from L S I to L S 2

and the transfer o f leach liquor volumes could be carefully tracked. In previous U B C chloride

leach testing, a more continuous countercurrent leach system was investigated i n which half the

slurry was removed and countercurrently transferred at each half-residence time. However, it

was difficult to accurately take out half each time and use o f the pressure filter, for S - L

separation, was difficult to peform cleanly. The transfer time i n this investigation was still
86
comparable to previous work, at 20-30min, but as the L S I S - L separation was achieved inline

via the mini-thickener the transfer operation was much smoother. Following from this initial

testing o f the mini-thickener, it is feasible that future work could potentially incorporate two

mini-thickeners, for both L S I and L S 2 S-L separation, in addition to working towards a more

continuous operation. This would likely involve slurry being continuously fed to the thickener

and the overflow ports being used to slowly remove clarified pregnant leach solution.

5.3 Countercurrent leach experiments

The countercurrent leach experiments performed for the hematite model were successful in

demonstrating the effect o f varying particle size, leach time and temperature to achieve copper

extractions >95%. There are three hematite process variations possible i f 96% extraction is

sufficient. A l l three involved fine grind concentrate (p90=41pm) with either a 2h residence time

at 95C (96% extraction), a 3h residence time at 85C (96% extraction) or a 3h residence time at

96C (98% extraction). The benefits o f this model include a relatively straightforward 2-stage

leach (in which all the oxidant required is fed as aqueous species to L S 2 ) and the separation o f

sulfur leach residue from iron precipitate, thus making reuse or waste treatment easier. The

substitution o f N a C l for CaCL; may be possible for the hematite model as there is no iron

precipitation in the leach, and hence there is no concern for jarosite formation, as in previous

Falconbridge Copper Chloride Process experiments undertaken at U B C . This substitution would

reduce processing cost. The goethite model experiments were unsuccessful in achieving >95%

extraction o f copper, with the highest extractions stabilizing at 89%. However a longer residence

time or finer grinding may be investigated to achieve higher extractions for this model.

Alternatively, use o f an autoclave for Leach Stage 2 may overcome oxygen solubility limitations

and i n turn may assist in the increase o f copper extraction. W i t h respect to fine grinding,

although potentially costly and energy intensive, grinding to 20microns is considerably more

feasible than grinding to lOmicrons or less, as is required for some competing sulfate based leach

processes.

5.4 Recommendations for further work

Following the success o f the leaching aspect o f the hematite model it would now be

recommended to test the subsequent process units with respect to the actual exit liquor arising

from the leach or relevant previous process unit. Thus for solvent extraction a feed should be

87
tested containing variations o f reduced and oxidized copper and iron species, instead o f a

assuming a feed containing only reduced species.

Further work should also involve development o f a more continuous countercurrent leach

employing the use o f two mini-thickeners for L S I and L S 2 S-L separation.

88
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92
Sample identification guide for Appendices 1 and 2
The following table provides a guide indicating to which experiment the samples i n the

certificates o f analysis belong, e.g. H I has an original experiment identification number o f 7 and

' M ' and ' N ' represent L S I or L S 2 samples respectively. The concentrate samples analyzed are

also identified i n Table 33.

Table 32 Sample identification guide

Original

Experiment Identifier Identification Samples L S 1 . L S 2

Number

1 HI 7 7M, 7N

2 Gl 8 8P, 8Q

3 H2 9 9K, 9L

4 G2 10 10J, 10K

5 H3 11 11C, 11D

6 H4 12 12M, 1 2 N

7 H5 13 13G, 13H

8 H6 14 14V, 14W

9 H7 15 15S, 15T

!0 H8 16 16X, 16Y

11 G3 17 17K, 17L

12 H9 18 18 A , 18B

Table 33 Concentrate sample identification

Concentrate Sample I.D.

Antamina AN

Rosario RO

93
Appendix 1 Certificates of Analysis ( I P L )

94
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Appendix 2 Certificates of Analysis (ChemMet)

121
Appendix 3 Certificates of Analysis (Malvern Mastersizer)

131
 A S T E R SIZE R

Result Analysis Report

Sample Name: SOP Name: Measured:
Ant - Whole - Average Monday, October 06, 2003 11:01:08 AM
Sample Source & type: Measured by: Analysed:
Factory contract Monday, October 06, 2003 11 01:09 AM
Sample bulk lot ref: Result Source:
Averaged

Particle Name: Accessory Name: Analysis model: Sensitivity:

Chalcopyrite Hydro 2000S (A) General "purpose Normal
Particle Rl: Absorption: Size range: Obscuration:
1.450 0 0:020 to 2000.000
1
um 18.04 %
Dlspersant Name: Dispersant Rl: Weighted Residual: Result Emulation:
Water 1.330 0.956 % \ Off

Concentration: Span : Uniformity: Result units:

0.0629 %Vol 2.267 o:72 Volume

Specific Surface Area: Surface Weighted Mean D[3,2]: Vol. Weighted Mean D[4,3]:
0.246 m /gJ
24.418 um 52.146 um

d{0.1): 10.613 d(0.5): 41.971 d(0.9): 105.757

Particle Size Distribution

1
! 1

V01 *- 1000 3000

01
Particle S i z e ( ^ m )
-Ant - Whole - Average, Monday, October 06, 2003 11 01 08 A M
Size(ijm) rVolumeln% .Size (um) Volume In % Stze (um) iVoiume In % Ssze(um) ^Volume ln% sStze (Mm)
0010 0071 0.501 3548 25119 177 828
390 057
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251 189
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56.234
.-
5.55
' 552
398.107
.004
0.04
0.025 0.00 '. 0.178
. 0.00
1:259
.0.00 / 8.913 63096
., ..5.35
446684
:0.03
0.00 1.413 10.000 '70.795 501 187
0.028 , -. 0.200 0.00 178 5.02 -0.00
0.00

.
0032
0.035
0.00
0.224
0.251
aoo
- -. Q00
1.565
1.778
0.00 -11:220
12589
.79.433
. 89.125
456
.. 562.341
630957
003
0.00 219 000
aoo
000 .1.995 100.000 707946
0.040 000 . 14.125
' .aoo
0.282 ' ' - 2.42, 333 0.00
, . 0.045 000 0.316 v .2239
0.00 .: 15849 267:
11Z202
-, ,265
" 794.328
.003
O050
; 000
: ; ' 0.355 .0.00 2512
0.00 17.783
12.94
125893
201,
891251
: 0,00
0.056
,000
0.00 0.398 " \
0.00
'0.00
2.818
0.00 1- ,19*953 141.254
, 142
' 1000.000
'3.162 i ';,324
0.053 0447: 0.07 , , 22.387 .158489 094
0.00 . >0.00 . 356
0.071 . 0501 3.548 , 25.119 . 177.828
0.14
0.26

132
 ASTERSIZER v _

Result Analysis Report

Sample Name: SOP Name: Measured:
Ant - Fine Grind - Average Monday, October 06, 2003 10:53:44 AM

Sample Source & type: Measured by: Analysed:

Factory contract Monday, October 06, 2003 10:53:46 AM
Sample bulk lot ref: Result Source:
Averaged

Particle Name: Accessory Name: Analysis model: Sensitivity:

Chalcopyrite Hydro 2000S (A) Generajpurpose Normal

Particle Rl: Absorption: Size range: Obscuration:

1.450 0 0.020 to 2000.000 um 16:22 %
Dispersant Name: Dispersant Rl: Weighted Residual: Result Emulation:
Water 1.330 1.495 % Off

Concentration: Span: Uniformity: Result units:

0.0279 %Vol 2.059 0:642 " Volume

Specific Surface Area: Surface Weighted Mean D[3,2]: Vol. Weighted Mean D[4,3]:
0.476 m'lg 12.597 , um 20:816 um

d(0.1): 6.136 d(0.5) : 16.861 d(0.9): 40.855

Particle Size Distribution

8 L J J LU.
7
6
5
i
A
3
r
> i
2 |
1 I

01 0.1 10 100 1000 3000

Particle S i z e (Mm)
- A n t - Fine Grind - Average, Monday, October 06, 2003 10.53 44 A M
Size(um} Volume In % Size (Mm) Volume In % Size (Mm): Size(pm) Size (Mm)
0010 0071 0501 3548 25119 177828
"'0.00 O.OO .0.00 ,1.09 544 000
O011- ,0.079
'ooo '0552:
000
1981
142
28184
4.95
199526
000
ooo
000 0.089 4467 31623 223872
0013 0.631: 1r78 437 000
. .0.014
0016
i*
0.00
0.00
0.100
. 0.112
000
- " 0.708"
0.794'
'.-"'. ooo
, ' ,0.00
5012
5623
216
35481
39811
' 373
251189
281838
000
0.00 000 256 307 000
".' aoo
'." 0.00 <0,126 '. ' 6:310 "44668 316228
0.018 - 000
0020
0.00
000
0141
0.158
000
1:000, aooaoo .;7.079
7943
298
342
60119
56.234
244
185
,354.813
398107
000
O022 '-. '.1.122 .388 135 000
0.00
Q025
: oo
.o
0.00
0.178
.. aoo 1:259 ;.. - aoo
'""--. 0.00
8913
'4.34
63.096
0.92
'446.684
000
O028
ooo
0.200
oo.o 1.413 10000
4.80
70795
059
501.187,
' 000
oo
.o .*0.00
aoo
.0.224 11.220 79.433 .662341
' .0032 ' 1.585 5.22 .038 000
0.00 .
0.035 . 0.251
oo
.o 1:778
'. 0.00
v 12589
6.59
'89.125"
014
630957
000
aoo
0.00 .0.282 .' 14.125 100.000 707.946
0040 : 1.995^ 5.88 000
aoi 001
0.045
j-0.00 0.316
. 0.00
2239 ' ' 0.10
15849
-6.06
112202
aoo 794.328
aoo
-0.050
. 000 .0.355 2512 - "17.783
-6.12
-"'125.893
ooo 891.251;

aoo
,0.00
ooo
000 0.398 2818 . 0.2B .19.953 -.141.254 '1000.000 000
. 0.056 6,03
0063 :oo
.o
0.00
:0447:
0.501 ooo 3162
3.548
0.52
-.' 0.77
22387
. 25.119
, 580 ' ooo
O071,

133
 ASTERSIZER

Result Analysis Report

Sample Name: SOP Name: Measured:
Ros - Fine Grind - Average Monday, October 06. 2003 10:40:43 AM

Sample Source & type: Measured by: Analysed:

Factory contract Monday, October 06,2003 10:40:44 AM
Sample bulk lot ref: Result Source:
Averaged

Particle Name: Accessory Name: Analysis model: Sensitivity:

Chalcopyrite Hydro 2OO0S (A) General purpose Normal
Particle Rl: Absorption: Size range: Obscuration:
1.450 0 0,020 to 2000.000 um 17.01 %
Dispersant Name: Dispersant Rl: Weighted Residual: Result Emulation:
Water 1.330 1.394 " % Off

Concentration: Span : Uniformity: Result units:

0.0283 %Vol 1.925 0:6 Volume

Specific Surface Area: Surface Weighted Mean D[3,2]: Vol. Weighted Mean D[4,3]:
0.492 m'/g 12.206 um 19.465. um

d(0.1): 6.041 um d(0.S): 16.243 um d(0.9): 37.306 um

Particle Size Distribution

01 0.1 10 1000 3000

Particle S i z e (pm)
- R o s - Fine Grind - Average, M o n d a y , October.06, 2 0 0 3 10:40:43 A M ;

Sizefum) Volume In* Volume In %' Size(um) Size(um) Volume ln,% 'Stze(um) Volume In % Size (urn) Volume In %
;0.010 00711 "0.501 ,"3548 25119 .177.828
000 . 000 ' 0.00 s 113 550 000
' O079 - 0.562 3981 28184 199.526
000 000^ 0.00 "'000
0069 0631 . 4467 145 31623 '.,223.872
ao\3 " 000
000 000 0706 179 419 , 000
0.014 0100 5012 35.481 SV 251'.189
000 ,000 ",00a 216 245 OOO
0016 ' 0112 0794 5623 39811 281638
000 000 "000 2.56 _27f - 000
0018 0126 t' 0891 6310 44668 316228
000 000 000 2.99 '204 ,000
0141 '1OOO 7079
: 0.020 QOO
600 1 122
ooo 347
50119
145
354813
; ,000
0022 0158 7943 58234 398107
ooo 000 3.97
'0.025 0178 00b 1.259
,000
8913 63096
096
' 446.684
> 000
000 000 . M1413 . 449 059 - "-000
:. ,0.023 0200 10000 70 795 501:167
0.00 000 000 502 035 000
0.032 0224 ! -1.585 11220 79433 ! 582.341-
;

I. '.OOO 000 M778 'obo 550 005 ' '_' . 000

: -0.O35 025V . :12.589 89125 630.957
000 poo . .1.995 -' :0.00 593 000 000
0.040 0282 ' 14.125 100.000 707.946
000 boo . 2.239 001 625 000 a'oo
0.046 0316 - , 15.843 112302 .,784.328
000 000 2.512 015 - 644 000 - .'000
0.050 0356 . '17.783 125893 :
891.251
ooo 000 '2.818 ox . 000 000
0056 .19.953 648 141354 1003.000
- 0.00 0.396 -000 ;0.58 . 631
0063 . 0.447
0.00
3162
-084
'.' 22.387' 15
^489 v .0.00
0.00
0.00 . 3548
0.071 ' ."0.501 25.119 ..'177.828

134
Appendix 4 XRD Spectra

Antamina XRD Profile

10 20 30 40 SO 60 7C

2-Theta - Scale

Rosario XRD Profile

3400 - .
3300 ~
3200 -

4 10 20 30 40 50 60

2-Theta - Scale

135
Appendix 5 Methods
A. Free Acid Titration
B . Cerium Titration
C. Light's Solution Preparation

136
Appendix 5A. Free Acid Titration (with oxalate masking)
The purpose o f this titration was to determine the free acid concentration o f the feed liquor.

Potassium oxalate (K2C2O4.H2O) was used to complex metal ions that would normally contribute

protons ( H ) , via complexation with hydroxyl ions (OH") i n water, e.g. C u

+ 2 +
+ 4(OH") ->

Cu(OH) ".
4
2

Method used

1. In a beaker containing ~ 6 5 m L D I water, add a 1 or 2 m L aliquot o f the feed liquor.

2. A d d 2 5 m L Potassium Oxalate solution (280g K o x . H 0 i n 1L)

2

3. Measure the p H o f the solution before and after addition o f K(ox).

4. Titrate solution with 0 . 1 M N a O H (accurately determined) and record p H changes with

volume added.

5. Plot p H vs volume N a O H added. The mid-point o f the steepest part o f the curve indicates

the volume required to neutralize the free acid. This volume can be used to determine

moles o f free acid i n the aliquot used, as shown in the following reaction.

OH~ + H - * H 0
+
2 (A5.1)

The results o f titrations performed at U B C , shown in the following table, indicate that for all but

H 3 and H 4 the results were in general agreement. There is still some slight variation from the

I P L data but as the concentration o f the feed liquor is extremely high in copper, iron and calcium

chloride this may impact on the method and output reproducibility. Example titration curves are

provided for experiment H 7 .

137
Table 34 Comparing IPL free acid results with test titration value

IPL result UBC titrations -

Expt
(g/LHCl) averages given (g/L HC1)
HI 5.74 Not performed

H2 5.28 Not performed

H3 12.97 4.06

H4 12.53 4.06

H5 2.71 3.04

H6 1.94 2.19

H7 3.01 2.96

H8 3.69 3.14

H9 2.35 2.55

Gl 0.72 Not performed

G2 10.02 Not performed

G3 <0.01 <0.1

Example free acid titration curves for experiment H 7 ( l m L and 2 m L aliquots)

Aliquot = 1 m L
Vol (mL) pH
7.6 6.73 Calculation:
7.8 6.85 Midpoint o f steepest section (between points i n bold):
8.0 6.97 V o l = 8.35mL
8.2 7.21
Titration V o l = 8.35-7.6 = 0.75mL
8.5 7.67
M o l N a O H = M o l HC1 = 0 . 1 M x 0.75mL = 0.075mmol
8.7 7.92
[HC1] = 0.075mmol/0.001L = 0.075M = 2.73g/L
9.0 8.13

138
 lmL aliquot

8.5
Midpoint
8
(8.35,7.4)
7.5
pH
7

6.5

6
7.0 7.5 8.0 8.5 9.0 9.5
Vol NaOH O.lM(mL)

Aliquot = 2mL
Vol (mL) pH Calculation:
9.5 6.21 Midpoint of steepest section (between points in bold):
9.7 6.26 Vol=11.25mL
9.9 6.35 Titration Vol = 11.25-9.5 = 1.75mL
10.2 6.46
Mol NaOH = Mol HC1 = 0.1M x 1.75mL = 0.175mmol
10.5 6.58
[HC1] =.0.175mmoV0.002L = 0.175M = 3.19g/L
10.7 6.75
11.1 7.05 2mL aliquot

11.4 7.44 9.00

8.50 Midpoint
11.7 7.69
(11.25,7.25)
11.9 7.80 8.00

12.2 7.94 7.50

12.5 8.00 pH 7.00
12.7 8.05 6.50
13.0 8.12 6.00
13.6 8.21 5.50
14.2 8.27 5.00
15.3 8.36 7.0 9.0 11.0 13.0 15.0 17.0
Vol NaOH 0.1M (mL)

Average of two free acid titrations = (2.73 + 3.19)/2 = 2.96 g/L HC1

139
Appendix 5B Cerium Titration (for reduced species determination)

This titration was used to determine reduced species i n the goethite feed liquor and i n the final

L S I (PLS) and L S 2 exit liquors o f selected experiments. Certified acidic cerium ( C e ) sulfate 4+

solution (0.1M) was used as the titrant, and as the C e / C e 4 + 3 +

redox potential is significantly high

(at +1.61V) it has the ability to oxidize many reduced metals ions, e.g. C u or Fe + 2 +
, v i a the

following reactions.

Ce 4 +
+ Cu +
Ce 3 +
+ Cu 2 +
(A5.2)

Ce + F e
4 + 2 +
^ Ce + Fe
3 + 3 +
(A5.3)

2Ce 4 +
+ Fe 2 +
+ C u -> 2 C e
+ 3 +
+ Fe 3 +
+ Cu * 2
(A5.4)

Method used

1. A 0.5, 1 or 2 m L aliquot was added to a beaker containing 80-100mL D I water.

2. A few drops o f H C I were then added, i f required, and a few drops o f Ferroin indicator.

3. The change i n redox potential was then recorded as 0 . 1 M C e 4 +

titrant was introduced into

the solution.

4. The endpoint was detected by a change in color o f the indicator as well as a sharp rise i n

the redox potential, i.e. >800mV /Agci- Ag

5. The concentration o f total reduced species was determined by calculating the moles o f

Ce 4 +
reacted using the titration volume, and then dividing by the aliquot o f test solution

added.

140
Example cerium titration curve for experiment H7 - Final PLS liquor
Aliquot = 0.5mL
V o l (mL) E (mV A g / A g ci) Calculation:
2.0 162 Titration Vol = 15.0-12.0mL = 13.0mL
2.5 176 M o l NaOH = M o l HCI = 0.1M x 13.0mL = 1.30mmol
2.7 181 [HCI] = 1.30mmol/0.0005L = 2.60M Total Reduced Species
3.2 190

3.5 199

3.9 209 Cerium titration H7 - Final PLS liquor - 0.5mL aliquot

4.3 227
600
4.5 248
550
4.8 320
500
5.4 389
450
5.6 405 U
400
6.2 415 en
< 350
>
6.5 421
> 300
6.8 426
250
7.1 430
200
7.4 434
150
7.7 438
100
8.2 443
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
9.0 450 Vol 0.1 M Cerium (mL)
9.3 453

10.1 460

11.1 469

12.3 481

12.6 486

13.1 493

13.6 502

14.0 512

14.4 523

14.9 553

endpoint
15.0
(>800mV)

141
Appendix 5C.Light's Solution Preparation

Redox probes cannot be recalibrated and thus performance must be monitored throughout the

duration o f its lifespan. A solution o f known potential, such as Light's solution, can be used to

check probe performance.

Dissolve 3 9 . 2 l g o f ferrous ammonium sulfate-6-hydrate and 48.22g o f ferric ammonium sulfate-

12-hydrate i n 800mL o f D I water. Then add 56.2ml o f concentrated sulfuric acid and adjust

volume to 1 liter with D I water. This solution has a p H near 0. It is a corrosive strong acid

solution and should be handled with care and kept stored away from light.

For a stable reading, the redox electrode should be placed into stirred light's solution for at least

30 minutes for equilibrium to be established. The value that should be obtained for A g / A g C l

(sat.KCl) probes is +476mV and Calomel (sat.KCl) probes is +430mV at 25C.

142
Appendix 6 Experimental Logs
A . Measurements (Temperature, p H and E)

B . Samples

C. Mass and Volume Transfers

143
 Date: Thursday 25 September 2003
Experiment#18 (H9) Continuous 18h Countercurrent Leach, Fine Grind, No Air to LS2,135g/L, 95C, RT 3h.
ROSARIO Concentrate Light's Soln: Start=
Concentrate fine grind filtered, dried and rolled with S S rolling pin. I End=
Leach Solution: 50g/L Cu2+, 80g/L Fe3+, 110g/L CaCI2, -3g/L HCI | Average=
RT - C ; E(mV/AgAgCI)=
pH =

LS1 LS2
Time Leach time Comments
T(C) h (mV Ag/AgCI) PH T(C) t (mVAg/AgCI) pH
I.
0

1.5h
2.75h A1.10toLS1 15mL
3h
Bench pH -
Transfer time =

II.
0

1.5h
2.75h A110toLS1 15mL
3h
Bench pH -
Transfer time =

III.
0

1.5h
2.75h A110toLS1 15mL
3h
Bench pH -
Transfer time =

IV.
0

1.5h
2.75h A110toLS1 15mL
3h
Bench pH -
Transfer time =

V.
0

1.5h
2.75h A110toLS1 15mL
3h
Bench pH -
Transfer time =

VI.
0

1.5h

3h
Bench pH -

144
 o
O
T3
c o
oo
|p's, O CM
X
T T o ^<
let <N CM CM CN [M M i - CM CN C N C N C N C N CN

co
Q- 0_ m o. D. CL
oo o o

o o o o o o
CNI CN CM CM CM CM
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o o o o
o o o o
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o o o o o
oo CO C O CO

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CL CL
a)
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CM CO LO
m m m m m
CO
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00 00 00
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ra
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152.
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col
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a> t j t c C D
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LU
ra (0 3
 Experiment:
Date :
Page:

Feed Liquor 3
1L CuFeS2= 135fl Feed
d Liquor 1L
3
IL C( u F e S 2 3
135g

.,._L_L LS2 ,

80mL Sample

<0mL Sample

Pressure Filter
Volume for L S 1

LR wet cake=>
C u F e S 2 135g vol. llquor?=
washed and d r i e d 3

\
Pressure Filter
Volume for LS1=

\.R wet caken

vol. liquor?=
washed and dried=

80mL Sample

Pressure Filter

Transfer Vnliimn fnr I S1a

rLR wet cake=

vol. llquor?=
washed and drled=

BOmL Sample

Pressure Filter

Transfer Vnlumft fnr LSI:

i. LR wet cake=
vol. l i q u o r ?
washed and d r i e d *
3

A11015mL LS1

\ ,80ml. Sargple

Pressure Filter

Volume for LS1

T LR wet c a k e 3

Feed Liquor 1L
3
vol. liquor?=
washed and d r i e d 3

l80njL Sample 80mL ^ample

Pressure Filter Pressure Filter

LR wet c a k e 3
LR wet cake=
vol. l i q u o r ? 3
vol. l i q u o r ?
3

washed and d r i e d 3
washed and d r i e d 3

146
Appendix 7 Calculations

A . Copper and iron extraction

B . Required oxidant concentration for hematite feed liquor

C. Oxygen addition to L S 2

D . Theoretical reduced species

147
Appendix 7A. Copper and iron extraction
The extraction o f copper and iron from the concentrate was calculated i n the following manner.

A n example for copper is provided for experiment H 5 (Antamina p90=41um, 3h, 95C).

C u % in feed = 28.8%, C u % in L S residue = 1.96%

Amount o f copper i n feed = 135g x 28.8% = 38.88g

Final mass o f L S 2 residue (80mL slurry sample and bulk pressure filter sample)

= 3.1 +37.8 = 40.9g

Copper in final L S 2 residue = 40.9g x 1.96% = 0.80g

Extraction o f Copper = (copper i n feed - copper i n L S 2 residue)/ (copper i n feed) x 100%

= (38.88 - 0.80)/38.88 x 100 = 97.9%

This calculation does not take into account the small residue sample taken from L S 1, which may

decrease the lower extraction values by no more than 1-2%.

Appendix 7B. Required oxidant concentration for hematite feed liquor

Calculation for determining i f 70g/L ferric ( F e ) and 40g/L cupric ( C u ) i n the feed liquor is
3+ 2+

sufficient for leaching 100% o f CuFeS2 i n the Antamina concentrate feed:

28.8% C u i n 135g feed concentrate = 38.9g C u = 0.61mol

If all o f the copper is contained in CuFeS2 this implies 0.61mol CuFeS2.

The ferric and cupric leach reactions are as follows:

C u F e S + 4 F e C l - 5 F e C l + C u C l + 2S
2 3 2 2 (A7.1)

C u F e S + 3 C u C l -i> 4 C u C l + F e C l + 2S
2 2 2 (A7.2)

If F e = 70g/L = 1.25 m o l in I L , then ferric can leach 1.25/4 = 0.31mol C u F e S and produce
3+
2

0.31 m o l C u .
2 +
If C u 2 +
is 40g/L (0.63 m o l in I L ) and is combined with the 0.31mol C u 2 +

produced by the ferric leach, this amounts to C u 2 +

= 0.94mol i n I L . This total C u 2 +
amount,

0.94mol, has the ability to leach 0.94/3 = 0.31mol C u F e S . 2

The total amount o f C u F e S that can be leached by 70g/L F e

2
3 +
and 40g/L C u 2 +
is therefore 0.31 +

0.31 = 0.62mol C u F e S , which is 0.01 m o l greater than the amount o f C u F e S delivered i n the
2 2

Antamina concentrate.
148
Appendix 7 C . Calculation for oxygen addition to L S 2 (Goethite model)
Delivery o f oxygen to L S 2 is required i n the goethite model experiments to regenerate cupric

and ferric species. The following calculation assisted in determining an appropriate flow rate

for air delivery.

. Leach time = 2h = 120min

A i r = assume 2 1 % oxygen

Oxygen requirement (determined from the flowsheet mass balance)

per 135 g pure chalcopyrite feed = 17.65g = 0.55mol

Moles o f air required = 0.55mol x 100/21 = 2.62 m o l

If 1 m o l gas approximates 24.5L at room temperature (298K),

2.62 m o l air = 64.2L

Over two hours the flow rate to deliver a stoichiometric quantity o f oxygen =

64.2L x lOOOmL/L / 120min = 535 m L / m i n

To ensure a sufficient amount o f oxygen is delivered to L S 2 a 5-10 times excess should be

considered, to overcome inefficiencies caused by transfer and solubility limitations. This would

mean an airflow rate o f 2.7L/min or 5.3L/min.

For experiment G 2 , a flow rate o f 2.5L/min was used, a 4.7 times excess. Although it would be

better to have a 10 times excess this would have lowered the temperature o f L S 2 too much, as

even this rate depressed the temperature by 4 C .

For experiment G 3 , almost pure oxygen (98%) gas was delivered at a flow rate o f 2.5L/min. A s

this gas is approximately 98/21 times more concentrated than the air and the residence time was

extended from 2 to 3 hours, the actual excess o f oxygen delivered is close to x33.

149
Appendix 7D. Theoretical reduced species
An example calculation follows for determining the theoretical reduced species concentration for
the exit PLS in experiment H2 (75um, 2h, 95C), assuming a 1L volume of feed liquor and PLS:

Feed CuFeS = 0.612mol

2

If copper extraction = 87%, then (assuming this is equivalent to CuFeS extraction) the amount
2

of reacted CuFeS = 0.87 x 0.612 = 0.532mol

2

The total reduced species produced via CuFeS leaching (i.e. 5mol per molCuFeS )
2 2

= 5 x 0.532mol = 2.66mol

Based on 1L of feed liquor (Cu = 0.743 M; Fe = 1.431 M)

2+ 3+

the theoretical total species would be

= Cu and Fe from CuFeS (0.532 x 2) + Cu and Fe in the feed (0.743 + 1.431)
2

= 3.24M

150
Appendix 8 Mass balances for experimental accountability

151
Experiment H1
Sample guide: LS1 = M, LS2 = N
Cu and Fe Input

Solids Description wgt (g) Cu (%) Fe (%) Cu(g) ... Fe (g)

Concentrate 6 x 135g 810.0 28.8 28.4 233.28 230.04

Solution Vol (L) [Cu] (g/L) [Fe](g/L). Cu (g) Fe (g)

Feed liquor 6x1L 6.0 47.8 76.72 286.56 460.32

Total Input | 519.84 690.36

I Input per 135g CuFeS2
Cu and Fe Output Cu = 38.88 g
Samples - balance solution reading with residue - record amounts (vol or wgt) and concentration Fe= 38.34 9
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe(g) . Cu % Fe%
7N1S bulk and sample 72.2 21 22.4767 15.16 16.23 61.0 57.7
7N2S bulk and sample 46 19 24 8.74 11.04 77.5 71.2
7N3S bulk and sample 51.3 16 20 8.21 10.26 78.9 73.2
7N4S bulk and sample 73.8 16.8 18.4174 12.40 13.59 68.1 64.5
7N5S bulk and sample 44.5 17.47 22.12 7.77 9.85 80.0 74.3
7M5S bulk and sample 87.6 18 23 15.77 20.15 59.4 47.4

Solutions Vol (L) [Cu] (g/L) [Fe](g/L) Cu (g) Fe (g)

7M1 bulk and sample 0.84 65 95.1 54.60 79.88
7M2 bulk and sample 0.74 86.04 113.77 63.67 84.19
7M3 bulk and sample 0.82 71.83 98.14 58.90 80.47
7M4 bulk and sample 0.88 76.9 107.6 67.67 94.69
7M5 bulk and sample 1.19 74.09 101.69 88.17 121.01
7N5 bulk and sample 1.13 54.06 85.19 61.09 96.26
Wash 1.1 3.45 4.8 3.80 5.28
A110 4x10mL 0.04
Estimated loss from samples not analyzed (see box below) 23.58 34.84
Total Vol PLS + samples + flocc Total Output 489.52 677.74
= 5.64 I
Total Expected Cu and Fe 519.84 690.36
in concentrate and solution
% Recovery 94.171 98.17
** Note this includes the estimated
copper and iron in samples not analyzed (see box below)

Unaccounted for mass output:

7M1-M4 residues = 33.2g

7N1-4 solutions = 320mL
I
Estimate additional mass of this output here:
Estimate average LS1 residue Cu and Fe % (from7M5)
Thus Est % Total g in 33.2g
Cu 18 5.976
Fe 23 7.636
Estimate average LS2 liquor Cu and Fe g/L (from7N5)
Est g/L Total g in 320mL
Cu 55 17.6
Fe 85 27.2
Total extra output (g)
Cu 23.576
Fe 34.836

152
Experiment H2
Sample guide: LS1 = K, LS2 = L.
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 6 x135g 810.0 28.8 28.4 233.28 230.04

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe(g)

Feed liquor 6x1L 6.0 47.2 79.5 283.48 476.84

Total Input 516.761 706.88

Input per135g CuFeS2
Cu and Fe Output Cu = 38.88 g
Fe= 38.34 9
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g) Cu% Fe%
9L1S bulk and sample 56.98 17.00 19.61 9.69 11.18 75.1 70.9
9L2S bulk and sample 34.8 13.41 15.81 4.67 5.50 88.0 85.7
9L3S bulk and sample 53.13 11.52 14.98 6.12 7.96 84.3 79.2
9L4S bulk and sample 40.9 7.62 11.10 3.12 4.54 92.0 88.2
9L5S bulk and sample 62.6 8.13 12.44 5.09 7.79 86.9 79.7
9K1S sample 5 16.16 19.72 0.81 0.99
9K2S sample 7.1 23.17 24.55 1.64 1.74
9K3S sample 5.2 16.28 19.11 0.85 0.99
9K4S sample 5.4 18.76 20.44 1.01 1.10
9K5S bulk and sample 79.3 17.85 19.57 14.16 15.52 63.6 59.5

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

9K1 bulk and sample 0.88 74.05 108.59 65.16 95.56
9K2 bulk and sample 0.66 86.16 120.15 56.87 79.30
9K3 bulk and sample 0.83 78.67 111.14 65.30 92.24
9K4 bulk and sample 0.97 81.76 114.75 79.31 111.30
9K5 bulk and sample 1.15 81.75 114.28 94.01 131.42
9L1 sample 0.08 75.64 110.40 6.05 8.83
9L2 sample 0.08 54.25 89.27 4.34 7.14
9L3 sample 0.08 66.32 100.84 5.31 8.07
9L4 sample 0.08 58.47 92.08 4.68 7.37
9L5 bulk and sample 1.21 60.11 93.09 72.73 112.64
Wash 3.1 4.17 6.35 12.91 19.67
A110 4x1 OmL 0.04
Sum of volumes = 6.06 Total Output I 513.82 730.85
I I I . .1
Total Expected C u and Fe I 516.76 706.88
in concentrate and solution |
I | % Recoveryl 99.43 103.39

153
Experiment H3
Sample guide: LS1 = C, L S 2 = D.
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) C u (g) Fe (g)

Concentrate 7x135g 945.0 28.8 28.4 272.16 268.38

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) C u (g) Fe (g)

Feed liquor 7x1L' 7.0 52.9 87.2 370.321 610.106

Total Input 642.48 878.49

Input per 135g C u F e S 2
Cu and Fe Output Cu = 38.88 g
Fe= 38.34 9
Extraction
Solids Description wgt(g) Cu (%) Fe (%) Cu (g) Fe (g) Cu % Fe%
11D1S bulk and sample 55.8 20.61 22.68 11.50 12.65 70.4 67.0
11D2S bulk and sample 49 17.66 20.36 8.65 9.98 77.7 74.0
11D3S bulk and sample 50.5 14.29 17.98 7.22 9.08 81.4 76.3
11D4S bulk and sample 44.8 15.22 19.31 6.82 8.65 82.5 77.4
11D5S bulk and sample 49.9 12.76 17.00 6.37 8.48 83.6 77.9
11D6S bulk and sample 57.7 11.32 16.24 6.53 9.37 83.2 75.6
11C1S sample 4.2 19.44 22.30 0.82 0.94
11C2S sample 5.9 25.30 25.86 1.49 1.53
11C3S sample 4.9 19.93 22.34 0.98 1.09
11C4S sample 4.9 22.41 24.06 1.10 1.18
11C5S sample 4.9 19.03 21.22 0.93 1.04
11C6S bulk and sample 88.9 20.73 22.02 18.43 19.58 52.6 48.9

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

11C1 bulk and sample 0.83 74.03 110.70 61.44 91.88
11C2 bulk and sample 0.75 90.71 130.22 68.03 97.67
11C3 bulk and sample 0.91 78.88 116.05 71.78 105.60
11C4 bulk and sample 0.87 85.34 123.39 74.25 107.35
11C5 bulk and sample 0.85 54.54 123.83 46.36 105.26
11C6 bulk and sample 1.09 86.28 125.09 94.04 136.34
11D1 sample 0.08 76.16 112.14 6.09 8.97
11D2 sample 0.08 57.72 93.34 4.62 7.47
11D3 sample 0.08 66.56 105.49 5.32 8.44
11D4 sample 0.08 61.37 96.52 4.91 7.72
11D5 sample 0.08 64.75 102.70 5.18 8.22
11D6 bulk and sample 1.08 63.03 100.70 68.07 108.75
Wash 3.75 5.12 7.68 19.19 28.81
A110 5x10mL 0.05
Sum of volumes = 6.83 Total Output 600.13 906.05
Gust PLS+sample not inside LS1) I I I
Total Expected C u and Fe 642.48 878.49
in concentrate and solution
I % Recoveryl 93.41 103.14

154
Experiment H4
Sample guide: LS1 = M, LS2 = N.
Cu and Fe Input
,.
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)
Concentrate 7x135g 945.0 28.8 28.4 272.16 268.38

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 7x1L 7.0 55.8 90.5 390.733 633.325

Total Input , 662.89 . 901.71

Input per 135g C u F e S 2
Cu and Fe Output Cu = 38.88 g
Fe= 38.34 g
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g) Cu% Fe%
12N1S bulk and sample 42.7 13.32 18.37 5.69 7.85 85.4 79.5
12N2S bulk and sample 35.9 7.10 12.84 2.55 4.61 93.4 88.0
12N3S bulk and sample 48.5 8.71 14.97 4.22 7.26 89.1 81.1
12N4S bulk and sample 40.6 5.78 12.39 2.35 5.03 94.0 86.9
12N5S bulk and sample 46.9 7.31 13.80 3.43 6.47 91.2 83.1
12N6S bulk and sample 45 6.14 12.48 2.76 5.61 92.9 85.4
12M1S sample 3.4 13.34 17.38 0.45 0.59
12M2S sample 9.7 26.99 29.65 2.62 2.88
12M3S sample 4.2 16.67 19.61 0.70 0.82
12M4S sample 4.2 20.56 22.23 0.86 0.93
12M5S sample 4 17.59 20.06 0.70 0.80
12M6S bulk and sample 46.6 21.37 24.33 9.96 11.34 74.4 70.4

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

12M1 bulk and sample 0.81 86.46 122.65 70.04 99.35
12M2 bulk and sample 0.66 102.52 133.30 67.66 87.98
12M3 bulk and sample 0.85 91.95 125.08 78.16 106.32
12M4 bulk and sample 0.9 93.27 125.93 83.94 113.34
12M5 bulk and sample 0.92 91.94 125.02 84.58 115.02
12M6 bulk and sample 1.1 94.59 127.92 104.05 140.71
12N1 sample 0.08 88.81 129.48 7.10 10.36
12N2 sample 0.08 66.13 103.07 5.29 8.25
12N3 sample 0.08 76.59 113.30 6.13 9.06
12N4 sample 0.08 68.18 104.11 5.45 8.33
12N5 sample 0.08 72.88 107.89 5.83 8.63
12N6 bulk and sample 1.2 68.09 102.95 81.70 123.53
Wash 3.5 5.80 8.37 20.29 29.28
A110 5x1 OmL 0.05
Sum of volumes = 6.89 Total Output 656.53 914.36
(just PLS+sample not inside LS1)
Total Expected Cu and Fe 662.89 901.71
in concentrate and solution
j % Recovery 99.04 101.40

155
Experiment H5
Sample guide: LS1 = G , LS2 = H.
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 7x135g 945.0 28.5 28.7 269.19317 271.367

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 7x1L 7.0 45.0 75.8 314.979 530.509

Total Input 584.17 801.88

Input per 135g CuFeS2
Cu and Fe Output Cu = 38.45617 g
Fe= 38.76667 9
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g) Cu% Fe%
13H1S bulk and sample 46.6 11.61 16.01 5.41 7.46 85.9 80.7
13H2S bulk and sample 15.2 1.40 7.73 0.21 1.17 99.4 97.0
13H3S bulk and sample 26.8 3.56 9.87 0.95 2.65 97.5 93.2
13H4S bulk and sample 36.8 0.94 7.65 0.35 2.81 99.1 92.7
13H5S bulk and sample 49 2.50 8.59 1.23 4.21 96.8 89.1
13H6S bulk and sample 40.9 1.96 8.50 0.80 3.48 97.9 91.0
13G1S sample 4.6 11.83 15.87 0.54 0.73
13G2S sample 11.2 27.80 25.86 3.11 2.90
13G3S sample 6.6 18.31 20.66 1.21 1.36
13G4S sample 10 22.71 23.14 2.27 2.31
13G5S sample 6.5 22.23 23.44 1.45 1.52
13G6S bulk and sample 113.9 25.03 24.73 28.50 28.17 25.9 27.3

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

13G1 bulk and sample 0.83 77.84 106.69 64.61 88.56
13G2 bulk and sample 0.67 80.44 114.40 53.89 76.65
13G3 bulk and sample 0.83 81.18 110.75 67.38 91.92
13G4 bulk and sample 0.83 82.79 111.76 68.71 92.76
13G5 bulk and sample 0.83 85.15 115.20 70.67 95.62
13G6 bulk and sample 1.28 86.08 118.04 110.18 151.09
13H1 sample 0.08 79.68 109.12 6.37 8.73
13H2 sample 0.08 57.19 85.11 4.58 6.81
13H3 sample 0.08 77.43 105.87 6.19 8.47
13H4 sample 0.08 59.86 87.60 4.79 7.01
13H5 sample 0.08 76.45 106.07 6.12 8.49
13H6 bulk and sample 1 71.08 100.25 71.08 100.25
Wash 6.94 10.11 0.00 0.00
A110 5x1 OmL 0.05 |
Sum of volumes = 6.72 Total Output | 580.61 795.12
(just PLS+sample not inside LS1) I |
I Total Expected C u and Fe 584.17 801.88
| in concentrate and solution
I | %Recovery| 99.39 99.16

156
Experiment H6
Sample guide: LS1 = V, LS2 = W.
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 7x135g 945.0 28.5 28.7 269.19317 271.367

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 7x1L 7.0 41.1 70.2 287.602 491.54

Total Input I | 556.80 762.91

Input per 135g CuFeS2
Cu and Fe Output Cu = 38.45617 9
Fe= 38.76667 9
Extraction
Solids Description Wgt(g) Cu (%) Fe (%) Cu (g) Fe (g) Cu% Fe%
14W1S bulk and sample 47.7 11.95 15.70 5.70 7.49 85.2 80.7
14W2S bulk and sample 34.39 1.86 8.04 0.64 2.76 98.3 92.9
14W3S bulk and sample 56.6 5.74 10.69 3.25 6.05 91.6 84.4
14W4S bulk and sample 43.5 3.05 9.18 1.32 3.99 96.6 89.7
14W5S bulk and sample 52 5.76 10.90 2.99 5.67 92.2 85.4
14W6S bulk and sample 46.6 3.69 9.59 1.72 4.47 95.5 88.5
14V1S sample 3.7 10.49 14.64 0.39 0.54
14V2S sample 10.9 27.32 25.22 2.98 2.75
14V3S sample 5.5 17.35 19.71 0.95 1.08
14V4S sample 8.6 25.99 25.05 2.24 2.15
14V5S sample 5.9 20.77 22.63 1.23 1.33
14V6S bulk and sample 100.1 25.21 24.76 25.23 24.79 34.4 36.1

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

14V1 bulk and sample 0.83 72.09 102.26 59.83 84.87
14V2 bulk and sample 0.62 75.13 107.06 46.58 66.38
14V3 bulk and sample 0.86 76.37 106.26 65.68 91.39
14V4 bulk and sample 0.82 73.47 98.22 60.25 80.54
14V5 bulk and sample 0.89 72.17 99.42 64.23 88.48
14V6 bulk and sample 1.13 75.27 103.88 85.05 117.38
14W1 sample 0.08 73.27 99.84 5.86 7.99
14W2 sample 0.08 52.77 79.11 4.22 6.33
14W3 sample 0.08 68.29 91.97 5.46 7.36
14W4 sample 0.08 57.37 85.08 4.59 6.81
14W5 sample 0.08 64.54 92.00 5.16 7.36
14W6 bulk and sample 1.23 60.76 87.44 74.74 107.55
Wash 3.6 5.92 8.33 21.33 29.99
A110 2x5mL+3x10mL 0.04
Sum of volumes = 6.820 Total Output 551.631 765.49
(just PLS+sample not inside LS1) I I
Total Expected Cu and Fe 556.80 762.91
in concentrate and solution
I % Recovery 99.07| 100.341

157
Experiment H7
sample guide: LS1 = S, LS2 = T.
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 7x 135g 945.0 28.5 28.7 269.19317 271.367

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 7x1L 7.0 47.7 80.1 333.97 560.826

Total Input I . 603.16 832.19

Input per 135g CuFeS2
Cu and Fe Output Cu = 38.45617 g
Fe= 38.76667 g
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g) Cu% Fe%
15T1 bulk and sample 54.1 11.73 15.58 6.35 8.43 83.5 78.3
15T2 bulk and sample 37.4 2.84 8.36 1.06 3.13 97.2 91.9
15T3 bulk and sample 59.1 7.60 12.35 4.49 7.30 88.3 81.2
15T4 bulk and sample 38.8 3.80 10.52 1.48 4.08 96.2 89.5
15T5 bulk and sample 43.3 7.79 12.72 3.37 5.51 91.2 85.8
15T6 bulk and sample 43 4.03 10.20 1.73 4.39 95.5 88.7
15S1 sample 3.6 11.06 15.29 0.40 0.55
15S2 sample 9.2 26.99 25.72 2.48 2.37
15S3 sample 5.5 16.07 18.66 0.88 1.03
15S4 sample 6 23.98 24.49 1.44 1.47
15S5 sample 5.3 18.68 20.45 0.99 1.08
15S6 bulk and sample 71.5 20.65 21.77 14.76 15.57 61.6 59.8

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

15S1 bulk and sample 0.85 79.08 112.11 67.22 95.30
15S2 bulk and sample 0.53 84.58 117.90 44.83 62.49
15S3 bulk and sample 0.68 81.47 114.83 55.40 78.08
15S4 bulk and sample 0.89 87.66 121.39 78.01 108.04
15S5 bulk and sample 0.78 85.25 117.55 66.49 91.69
15S6 bulk and sample 1.2 81.10 112.93 97.32 135.52
15T1 sample 0.08 79.81 113.13 6.39 9.05
15T2 sample 0.08 55.91 88.41 4.47 7.07
15T3 sample 0.08 74.05 107.17 5.92 8.57
15T4 sample 0.08 61.99 94.96 4.96 7.60
15T5 sample 0.08 67.27 100.44 5.38 8.04
15T6 bulk and sample 1.2 65.42 96.92 78.51 116.30
Wash 4 5.64 7.93 22.57 31.73
A110 5x1 (toil- 0.05
Sum of volumes = 6.580 Total Output 576.91 814.36
Qust PLS+sample not inside LS1) |
Total Expected Cu and Fe 603.16 832.19
in concentrate and solution
I % Recovery 95.65 97.86

158
Experiment H8
Sample guide: LS1 = X, LS2 = Y.
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 7x135g 945.0 28.5 28.7 269.19317 271.367

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 7x1L 7.0 48.0 75.3 336.105 526.792

Total Input 605.30 798.16

Input per 135g CuFeS2
Cu and Fe Output Cu = 38.45617 g
Fe= 38.76667 g
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g) Cu% Fe%
16Y1 bulk and sample 54.8 14.68 18.53 8.05 10.16 79.1 73.8
16Y2 bulk and sample 43.3 6.66 12.02 2.88 5.21 92.5 86.6
16Y3 bulk and sample 68.3 10.12 14.49 6.91 9.90 82.0 74.5
16Y4 bulk and sample 47.3 6.94 13.35 3.28 6.31 91.5 83.7
16Y5 bulk and sample 49 9.36 14.44 4.58 7.08 88.1 81.7
16Y6 bulk and sample 49.1 7.85 13.36 3.85 6.56 90.0 83.1
16X1 sample 4.6 14.60 18.26 0.67 0.84
16X2 sample 8.4 26.36 27.31 2.21 2.29
16X3 sample 5.8 18.57 21.71 1.08 1.26
16X4 sample 7.1 23.13 24.72 1.64 1.75
16X5 sample 6.7 21.58 23.69 1.45 1.59
16X6 bulk and sample 87 23.02 24.93 20.03 21.69 47.9 44.1

Solutions Vol (L) [Cu] (g/L) [Fe](g/L) Cu (g) Fe (g)

16X1 bulk and sample 0.82 76.62 104.92 62.83 86.03
16X2 bulk and sample 0.67 81.63 109.15 54.69 73.13
16X3 bulk and sample 0.8 78.90 104.68 63.12 83.74
16X4 bulk and sample 0.81 81.20 107.60 65.77 87.16
16X5 bulk and sample 0.8 80.58 107.48 64.46 85.98
16X6 bulk and sample 1.04 80.44 106.45 83.66 110.71
16Y1 sample 0.08 76.48 104.64 6.12 8.37
16Y2 sample 0.08 56.55 83.30 4.52 6.66
16Y3 sample 0.08 68.52 93.92 5.48 7.51
16Y4 sample 0.08 61.31 88.36 4.90 7.07
16Y5 sample 0.08 66.49 92.02 5.32 7.36
16Y6 bulk and sample 1.25 63.82 91.53 79.77 114.41
Wash 3.85 5.76 8.03 22.18 30.90
A110 2x10mL+3x15mL 0.065
Sum of volumes = 6.655 Total Output 579.46 783.68
(just PLS+sample not inside LS1) j
Total Expected Cu and Fe 605.30 798.16
in concentrate and solution
| % Recovery 95.73 98.19

159
Experiment H9
Sample guide: LS1 = A, LS2 = B.
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 7x135g 945.0 26.8 26.8 252.86499 253.569

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 7x1L 7.0 50.6 82.0 354.0228 573.806

Total Input 606.89 827.38

Input per135g CuFeS2
Cu and Fe Output Cu = 36.12357 g
Fe= 36.22415 g
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g) Cu% Fe%
18B1 bulk and sample 70.1 0.67 28.18 0.47 19.75 98.7 45.5
18B2 bulk and sample 63.5 0.40 29.42 0.25 18.68 99.3 48.4
18B3 bulk and sample 59.1 0.57 28.83 0.34 17.04 99.1 53.0
18B4 bulk and sample 65.8 0.51 28.00 0.34 18.42 99.1 49.1
18B5 bulk and sample 74.3 1.46 28.62 1.09 21.27 97.0 41.3
18B6 bulk and sample 68.6 1.09 27.47 0.75 18.85 97.9 48.0
18A1 sample 5.6 0.67 29.05 0.04 1.63
18A2 sample 9.1 14.10 30.14 1.28 2.74
18A3 sample 5.9 0.86 28.58 0.05 1.69
18A4 sample 7.2 5.34 29.71 0.38 2.14
18A5 sample 6 2.14 28.09 0.13 1.69
18A6 bulk and sample 76.3 2.07 28.26 1.58 21.56 95.6 40.5

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

18A1 bulk and sample - 0.82 86.81 96.35 71.19 79.00
18A2 bulk and sample 0.68 106.80 104.54 72.62 71.09
18A3 bulk and sample 0.88 90.53 102.09 79.66 89.84
18A4 bulk and sample 0.78 99.81 104.71 77.85 81.67
18A5 bulk and sample 0.9 88.23 100.93 79.41 90.84
18A6 bulk and sample 0.98 91.68 100.48 89.84 98.47
18B1 sample 0.08 87.20 100.22 6.98 8.02
18B2 sample 0.08 55.59 86.74 4.45 6.94
18B3 sample 0.08 68.29 90.82 5.46 7.27
18B4 sample 0.08 55.46 83.54 4.44 6.68
18B5 sample 0.08 61.38 91.45 4.91 7.32
18B6 bulk and sample 1.1 55.13 84.91 60.65 93.40
Wash 4.9 2.97 3.92 14.55 19.22
A110 5x15mL 0.075
Sum of volumes = 6.615 Total Output 578.70 805.21
(just PLS+sample not inside LS1) I I
Total Expected Cu and Fe 606.89 827.38
in concentrate and solution
I % Recovery 95.36 97.32

160
Experiment G1
Sample guide: LS1 = P, LS2 = Q
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 6x135g 810.0 28.8 28.4 233.28 230.04

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 6x 1L 6.0 54.1 35.0 324.35379 209.821

Total Input 557.63 439.86

Input per 135g CuFeS2
Cu and Fe Output Cu = 38.88 g
Fe= 38.34 9
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g) Cu% Fe%
8Q1S bulk and sample 90.8 15.89 31.72 14.43 28.80 62.9 24.9
8Q2S bulk and sample 60.8 11.38 32.28 6.92 19.62 82.2 48.8
8Q3S bulk and sample 97.1 13.99 31.27 13.58 30.37 65.1 20.8
8Q4S bulk and sample 102.8 14.32 30.32 14.72 31.17 62.1 18.7
8Q5S bulk and sample 112.4 13.87 29.80 15.59 33.49 59.9 12.6
8P1S sample 5 24.32 24.72 1.22 1.24
8P2S sample 7.3 26.69 27.14 1.95 1.98
8P3S sample 6.4 25.81 26.81 1.65 1.72
8P4S sample 5 26.42 27.33 1.32 1.37
8P5S bulk and sample 90.4 25.49 25.42 23.05 22.98 40.7 40.1

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

8P1 bulk and sample 0.85 62.66 41.61 53.26 35.37
8P2 bulk and sample 0.68 71.25 34.34 48.45 23.35
8P3 bulk and sample 0.78 69.05 35.45 53.86 27.65
8P4 bulk and sample 0.93 68.54 35.02 63.74 32.57
8P5 bulk and sample 1.05 51.99 25.36 54.59 26.63
8Q1 sample 0.08 71.22 31.62 5.70 2.53
8Q2 sample 0.08 60.23 27.78 4.82 2.22
8Q3 sample 0.08 69.10 32.34 5.53 2.59
8Q4 sample 0.08 68.77 31.45 5.50 2.52
8Q5 bulk and sample 1.18 67.32 29.55 79.43 34.87
Wash 3.57 6.05 4.27 21.61 15.25

SUM of volumes= 5.79 Total Output | 490.92 378.29

I I I
Total Expected Cu and Fe 557.63 439.86
in concentrate and solution
I | % Recoveryl 88.04 86.00

161
Experiment G2
Sample guide: LS1 = J, LS2 = K.
Cu and Fe Input

Solids Description Wgt(g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 6x135g 810.0 28.8 28.4 233.28 230.04

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 6x1L 6.0 55.9 34.5 335.304 207.036

Total Input 568.58 437.08

Input per 135g CuFeS2
Cu and Fe Output Cu = 38.88 g
Fe= 38.34 9
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe(g) Cu% Fe%
10K1S bulk and sample 102.2 16.25 26.60 16.61 27.18 57.3 29.1
10K2S bulk and sample 56.6 12.95 20.83 7.33 11.79 81.1 69.3
10K3S bulk and sample 35.5 10.25 21.51 3.64 7.64 90.6 80.1
10K4S bulk and sample 80.3 15.82 23.10 12.70 18.55 67.3 51.6
10K5S bulk and sample 77.8 16.55 23.17 12.87 18.03 66.9 53.0
10J1S sample 6.1 24.31 23.01 1.48 1.40
10J2S sample 9.4 30.30 27.78 2.85 2.61
10J3S sample 16.7 25.89 26.12 4.32 4.36
10J4S sample 8.4 26.90 25.30 2.26 2.12
10J5S bulk and sample 92.9 29.10 26.85 27.03 24.95 30.5 34.9

Solutions Vol (L) [Cu] (g/L) [Fe](g/L) Cu (g) Fe (g)

10J1 bulk and sample 0.81 77.40 55.10 62.69 44.63
10J2 bulk and sample 0.68 89.69 56.47 60.99 38.40
10J3 bulk and sample 0.88 84.79 56.65 74.62 49.85
10J4 bulk and sample 0.85 85.73 55.56 72.87 47.22
10J5 bulk and sample 1.08 87.95 59.73 94.98 64.51
10K1 sample 0.08 87.00 51.25 6.96 4.10
10K2 sample 0.08 71.71 44.89 5.74 3.59
10K3 sample 0.08 78.14 48.42 6.25 3.87
10K4 sample 0.08 75.67 48.43 6.05 3.87
10K5 bulk andsample 1.08 76.74 48.48 82.87 52.35
Wash 3.1 5.91 4.51 18.33 13.99
A110 4x1 OmL 0.04
Sum of volumes = 5.74 Total Output 583.45 445.02
Gust PLS+sample - not inside LS1) |
Total Expected Cu and Fe 568.58 437.08
in concentrate and solution
| %. Recovery 102.61 101.82|

162
Experiment G3
Sample guide: LS1 = K, LS2 = L
Cu and Fe Input

Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) Fe (g)

Concentrate 7x135g 945.0 28.5 28.7 269.325 271.215

Solution Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

Feed liquor 7x1L 7.0 47.4 30.0 332.045 209.825

Total Input 601.37 481.04

Input per 135g CuFeS2
Cu and Fe Output Cu = 38.475 g
Fe= 38.745 g
Extraction
Solids Description Wgt (g) Cu (%) Fe (%) Cu (g) |Fe_(9) Cu% Fe%
17L1 bulk and sample 134.6 1.35 43.24 1.81 58.20 . 95.3 -50.2
17L2 bulk and sample 112.9 2.88 40.79 3.25 46.06 91.6 -18.9
17L3 bulk and sample 136.9 2.59 43.52 3.55 59.58 90.8 -53.8
17L4 bulk and sample 116.3 3.72 40.04 4.33 46.57 88.8 -20.2
17L5 bulk and sample 104.5 3.93 40.12 4.10 41.93 89.3 -8.2
17L6 bulk and sample 108.2 4.04 38.42 4.37 41.57 88.6 -7.3
17K1 sample 7.1 23.40 26.11 1.66 1.85
17K2 sample 13.7 27.14 28.12 3.72 3.85
17K3 sample 8 25.18 26.84 2.01 2.15
17K4 sample 7.9 25.51 27.01 2.02 2.13
17K5 sample 8.7 24.90 26.59 2.17 2.31
17K6 bulk and sample 88.2 24.49 26.54 21.60 23.40 43.9 39.6

Solutions Vol (L) [Cu] (g/L) [Fe] (g/L) Cu (g) Fe (g)

17K1 bulk and sample 0.825 60.65 42.46 50.04 35.03
17K2 bulk and sample 0.39 107.42 15.95 41.89 6.22
17K3 bulk and sample 0.72 91.27 25.95 65.72 18.68
17K4 bulk and sample 0.74 97.26 20.29 71.97 15.02
17K5 bulk and sample 0.755 95.46 24.44 72.07 18.45
17K6 bulk and sample 0.8 93.91 26.18 75.13 20.94
17L1 sample 0.08 98.58 0.11 7.89 0.01
17L2 sample 0.08 71.62 10.75 5.73 0.86
17L3 sample 0.08 86.55 5.52 6.92 0.44
17L4 sample 0.08 79.09 9.00 6.33 0.72
17L5 sample 0.08 76.75 9.70 6.14 0.78
17L6 bulk and sample 0.89 79.33 11.34 70.61 10.09
Wash 6 9.42 1.06 56.50 6.38
A110 5x15mL 0.075
Sum of volumes = 5.595 Total Output 591.51 463.23
(just PLS+sample not inside LS1) | I
Total Expected Cu and Fe 601.37 481.04
in concentrate and solution
% Recovery 98.36 96.30

163
Appendix 9 Experimental Profiles

164
 Experiment H1: Coarse Antamina concentrate, 85C, 2h per leach stage

Temperature vs Time pH vs Time

89.0

88.0 LS1
87.0 -LS2
Temp
(C)86.0

85.0

84.0

83.0
5 10 15 5 10
Time (h) Time (h)

Potential, E (mV vs SCE@85C) vs Time Cu and Fe Concentrations vs Time

120 -

100 -
0 600
< 80 i

1 550
c 1
o
Ic 60 -
> <D ALS1 Feg/L
E O
40 -
o LS2 Fe g/L
LU
O
L S 1 Cug/L
20
L S 2 Cug/L
0
5
Time(h) 1 0 15 0 2 10 12
4
Timl(h) 8

Cu and Fe Extraction (LS2 Residue)

77.5 tti.H 6 8 * BU.Or

-Cu
-Fe

15

165
 Experiment H2: Coarse Antamina concentrate, 95C, 2h per leach stage

pH vs Time

0.00
-0.10
LS1
-0.20 LS2
pH -0.30
-0.40

-0.50
-0.60
4 6 8 10 12
Time (h)

Potential, E (mV vs Ag/AgCI@95C) Cu and Fe Concentrations vs Time

vs Time
750
700 , l ^ -1
a Lo\
o 650 --LS2
<
< 600
550
>
E 500
LU
450
400
4 6 8 10 12
Time (h) Time (h)

Cu and Fe Extraction (LS2 Residue)

B6.9~

- Cu
Fe

5 10 15
Time (h)

166
 Experiment H3: Coarse Antamina concentrate, 85C, 3h per leach stage

Potential, E (mV vs Ag/AgCI@85C) Cu and Fe Concentrations vs Time

vs Time
800

750

400
6 9 12 15 18 10 15 20
Time (h) Time (h)

Cu and Fe Extraction (LS2 Residue)

82,5 83.61
^3.2

-Cu
Fe

10 15 20
Time (h)

167
 Experiment H4: Coarse Antamina concentrate, 95C, 3h per leach stage

Temperature vs Time
100

99 LS1
-LS2
98

Temp
97
(C)

96
Bar

95

94
0 5 10 15 20
Time (h)

Potential, E (mV vs Ag/AgCI@95C) Cu and Fe Concentrations vs Time

vs Time
800

750

6" 700
CD

^ 650
< 600

5 10 15 20
10
Time (h) Time (h)

Cu and Fe Extraction (LS2 Residue)

94.0202.0

20

168
 Experiment H5: Fine grind Antamina concentrate, 95C, 3h per leach stage

Temperature vs Time pH vs Time

100
99
98
97
Temp 96
(C) 95
94 LS1
93 -LS2
92
91
90
5 10 15 20
Time (h)

Potential, E (mV vs Ag/AgCI@95C) Cu and Fe Concentrations vs Time

vs Time
800

20 5 10 15 20
Time (h)

Cu and Fe Extraction (LS2 Residue)

99.4 Q7 * 99..1 96.8 97.9

10 15 20
Time (h)

169
 Experiment H6: Fine grind Antamina concentrate, 95C, 2h per leach stage

p H v s Time

15

Time (h)

Potential, E (mV v s A g / A g C I @ 9 5 C ) C u and Fe Concentrations v s Time

vs T i m e

-LS1
LS2

5 T i m e (h) 10 15 5 T i m e (h) 1 0
15

C u and F e Extraction L S 2 R e s i d u e

100
90 85.2 y>^*^^t~-^+r----+
80
70
60
Cu
% 50
- - F e
40
30
20
10
0 II o.o
5 10 15
T i m e (h)

170
 Experiment H7: Fine grind Antamina concentrate, 85C, 3h per leach stage

Temperature vs Time

90 -
89 -
88 -
87 -

Tem 8 6 .
3

(C) 85 -
84 -
83 LS1
82 - -LS2
81
80 -
10 15 20
Time (h)

Potential, E (mV vs Ag/AgCI@85C) Cu and Fe Concentrations vs Time

vs Time

LS1
-LS2

20
15 20
Time (h]^

Cu and Fe % in LS2 Residue

- - C u

Fe

It

10 15 20
Time (h)

171
 E x p e r i m e n t H8: F i n e grind A n t a m i n a c o n c e n t r a t e , 8 5 C , 2h per l e a c h stage

Temperature vs Time

90
89
88
87
86
Temp
85
(C)
84
83 --LSI

82 --LS2
81
80
2 4 6 8 10 12 14
Time (h)

Potential, E (mV vs Ag/AgCI@85C) Cu and Fe Concentrations vs Time

vs Time
800
750
700 LS1
O 650 LS2
< 600
cn
< 550
>
500
>
E 450
400
350

6 8 10 12 14 10 12 14
Time (h)
4
x- 6
a
Time (h

Cu and Fe Extraction in LS2 Residue

-92r-

6 8 10
Time (h)

172
 Experiment H9: Fine grind Rosario concentrate, 95C, 3h per leach stage

Temperature vs Time

98
97 A A A A
a A w T *XL
96
95
II \
94
Temp
93
(C)
92
91 LS1
90
HLS2
89
88
10 15 20
Time (h)

Potential, E (mV vs Ag/AgCI@95C) Cu and Fe Concentrations vs Time

vs Time

800
750
0 700 LS1
650 LS2
600
5 550
| 500
uT 450
400
350
0 2 4 6 8 10 12 14
10 15 20
Time (h) Time (h)

173
 Experiment G1: Air to LS2 (200ml/min), Coarse Antamina concentrate,
85C, 2h per leach stage

Temperature vs Time pH vs Time

89 T

88 -
LS1
87 - LS2

Temp 86
(C)
85
<> PH
.11 ^
J
w =

84 -

83 -

82 - II

4 6 8 10 12
Time (h)

Potential, E (mV vsAg/AgCI@85C)

Cu and Fe Concentrations vs Time
vs Time
80

70 A _ _
-LSI
_ 60
--LS2
3 50

I 40 LS1 Cu
2 LS2 Cu
| 30 ""^ ^^^^xjE *LS1 Fe
20 LS2 Fe
o

400 10

0 2 4 6 8 10 12 0
0 2 4 6 8 10 12
Time (h)
/ u

Time (h)

Cu and Fe % in LS2 Residue

174
 Experiment G2: Air to LS2 (2.5L/min), Coarse Antamina concentrate,
95C, 2h per leach stage

Temperature vs Time pH vs Time

--LSI
LS2

8 10 1B

Time (h)

Potential, E (mV vs Ag/AgCI@95C)

Cu and Fe Concentrations vs Time
vs Time
100
580
90
560
~ 80 r^y^
s=> 540 LS1
o
S> 520
|j> 500
LS2
3 70
.2 6
IF
0
/s i A

A
Mr
2 50 1 1 A *
m
<n 480 1 40
if
y
LS1 Cu
> 460 30
L S 2 Cu
~ 440 0
20
LU 4LS1 Fe
10
420 L S 2 Fe
0
400 2 4 6 8 10 12
4 6 8 10 12
Time (h) Time (h)

Cu and Fe Extraction (LS2 Residue)

67.3 6 6 ,9

4 6 8 10 12
Time (h)

175
 Experiment G3: 0 to LS2 (2.5L/min), Fine grind Antamina concentrate,
2

95C, 3h per leach stage

pH vs Time

-LS1
LS2

IcT* 1% 20

Time (h)

Potential, E (mV vs Ag/AgCI@95C) vs Time Cu and Fe Concentrations vs Time

120

LS1 Cu
m LS2 Cu
* LS1 Fe
m

LS2 Fe

350
10 15 20 10 15 20
Time (h) Time (h)

Cu and Fe % in LS2 Residue Cu and Fe Extraction (LS2 Residue)

100 95.3 91.6 90.8 88.8 89.3 88.6

-Cu
Fe
-Cu

15 20

Time (h)

176