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hydrometallurgy

ELSEVIER Hydrometallurgy 47 (1998) 189-203

Thiourea leaching of a copper-gold ore using


statistical design
c,*
Pierre Lacoste-Bouchet a, Guy Deschenes b, Edward Ghali
a Agnico Eagle, Cadillac, Quebec, Canada
b CANMET, Ottawa, Ontario, Canada
c Laval University, Quebec City, Quebec, Canada

Received 16 September 1996; accepted 16 June 1997

Abstract

Thiourea was used to leach gold from ore containing 0,4% Cu and 5.6 gjt Au. The parameters
studied were acid pretreatment, leaching time, pH, thiourea concentration and the oxidizing agents
used. Gold extraction was 89% and thiourea consumption was 3.9 kgjt. No acid consumption was
observed during leaching at pH 3. Pretreatment by acid washing is recommended for improved
gold leaching and lower thiourea consumption. The best gold recovery results were obtained with
ferric sulphate as the oxidizing agent, although it is more expensive. Thiourea dissolves three
times less copper than cyanide does. The best leaching conditions achieved were as follows: acid
wash pretreatment, an average amount of added thiourea of 12 gj, a leaching duration of 72 hand
a pH of 3. The oxidation-reduction potential fluctuated between 410 and 450 mVjSHE. 1998
Elsevier Science B.V.

1. Introduction and objectives

Cyanidation is generally used in leaching gold ores, since the industry is very
proficient in this technology. Moreover, sodium cyanide and lime consumption are
relatively inexpensive. However, there are some drawbacks to cyanidation such as:
- gold ores with high copper concentrations cannot be leached economically;
- the cost of treating contaminated water increases production costs [l ,2].
The depletion of ores which lend themselves readily to cyanidation and the new
environmental regulations have led to the development of new technologies. One of the

, Corresponding author. Universite Laval, Cite Universitaire, Dept. de Mines et Metallurgic, Quebec.
Canada G IK 7P4.

0304-386X/98/$19.00 1998 Elsevier Science B.V. All rights reserved.


Pll S0304-386X(97)00043-1
190 P. Lacoste-Bouchet et al.j Hydrometallurgy 47 (1998) 189-203

pronusmg alternatives is the use of thiourea to leach gold ores especially for heap
leaching and underground applications. Its advantages are its effectiveness in processing
some ores which are refractory to cyanidation (copper sulphides); and rapid leaching
kinetics.
Cyanide has acute and harmful environmental effects. Thiourea is itself toxic and can
be a carcinogen, like several other organic compounds. However, the use of thiourea
causes high reagent consumption and it is this consumption of thiourea which seriously
limits its use.
The objectives of this study are to evaluate the use of thiourea in leaching the gold
ore from the Agnico Eagle mine. The ore is currently processed by flotation to obtain a
copper concentrate. A fraction of the gold is also floated with the copper concentrate,
since it is partially associated with the copper-based minerals (chalcopyrite). The
flotation tailings are processed by cyanidation to extract the gold. Thus an alternative to
cyanidation would be useful, since the mine's copper concentrate contains a large
amount of gold. The approach used in this work consists of treating the ore directly.
Thiourea leaching of gold ores is presented as an alternative to cyanidation.
The dissolution of gold in a thiourea solution is an electrochemical process [3]. An
acidic medium must be used to ensure the stability of the thiourea and to prevent it from
degrading too rapidly. The Au-thiourea complex is formed as follows:

(I)
The Au-thiourea complex is cationic, while the Au-cyanide complex is anionic. A
number of reduction reactions can be involved in the electrochemical reaction, depend-
ing on the oxidizing agent used:
0z + 4H+ + 4e --+ 2HzO (2)
HzOz + 2e --+ 20H- (3)
(4)
It should be added that oxygen alone as an oxidant is not sufficient for thiourea in
practice. The overall reactions in the presence of oxidizing agents such as H202 and
ferric ions are as follows:

Au + H202 + 2SC(NHz)2 + H+ --+ Au(SC(NH2)2)z+ + H20 (5)

Au + Fe3+ + 2SC(NHz)2 --+ Au(SC(NH2)2); + Fez+ (6)


As it happens, thiourea in the presence of oxidizing agents reacts on its own to give
formamidine disulphide (FD).
2SC(NHz)2 --+ NHz(NH)CSSC(NH)NHz + 2H+ + 2e, Estct = -0.42 V (7)
2SC(NHZ)2 + H20z --+ NHz(NH)CSSC(NH)NHz + 2HzO (8)
2SC(NHz)2 + 2Fe3+ --+ NH2(NH)CSSC(NH)NH2 + 2Fe2+ + 2H+ (9)
P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) 189-203 191

The mechanisms by which thiourea is oxidized to FD are still obscure. Several


studies seem to give results that are in dispute. FD is itself a powerful oxidizing agent
and plays an important role in gold leaching [2]:

2Au + 2SC(NHz)2 + NHz(NH)CSSC(NH)NHz + 2H+~ 2Au(SC(NHz)z);


( 10)
The first thiourea oxidation step is to FD. The second step is the irreversible
degradation of FD to thiourea, elemental sulphur, cyanamide and several sulphur-con-
taining products, according to one of the following two reactions [3]:
NHiNH)CSSC(NH)NHz ~ 2[CN-NHz] + HzS + SO (11)
NH2(NH)CSSC(NH)NHz ~ SC(NHz)z + CN-NHz + SO ( 12)
The presence of elemental sulphur in solution could cause the passivation of gold
particles, inhibiting the leaching. It is known that the addition of S02 can regenerate
thiourea from FD. In fact, SOz is a selective reductant of FD [2,3].

2. Experimental approaches

With the aim of finding the optimum conditions for leaching gold with thiourea, a
partial factorial design was used. The matrices and statistical techniques applied were
developed by Taguchi [4]. The Fisher tables for the analysis of variance came from
Snedecor and Cochran [5]. The approach is to determine the important factors from a
preliminary experimental plan. The theoretical model is then elaborated and applied. A
confirming test or experience is carried out on the same mineral at the end. The main
steps followed are outlined below.
The elements to be optimized were gold recovery, thiourea consumption, acid
consumption and base consumption. The last three elements were analysed in terms of
cost. The factors and levels studied to characterize leaching of the ore were acid
pretreatment prior to leaching, pH, leaching duration, initial thiourea concentration,
continuous addition of thiourea and concentration of oxidizing agents such as ferric
sulphate and hydrogen peroxide. Only the pretreatment involved two levels, while the
other factors had three levels.
The gold ore, from the Val d'Or mine in the DJ. Laronde division of Agnico Eagle,
was received already ground. An initial amount of ore (20 kg) was homogenized to
obtain homogeneous samples and divided into batches of 500 g, which were used in the
tests. The particle-size analysis, performed in duplicate by wet screening, indicated that
82% of the material was under 74 JLm.

2.1. Pretreatment (acid washing)

Acid washing is an operation consisting of leaching the elements which consume


thiourea. The main thiourea-consuming elements in order of importance are iron, copper,
192 P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) /89-203

zinc, lead, antimony and arsenic. As a result of this pretreatment, gold extraction can be
increased and thiourea consumption decreased during thiourea leaching of the ore.
The ore was pretreated with a 0.5 M solution of sulphuric acid. The solid/liquid ratio
was 1:2. The leaching time was fixed at 4 h. Sampling of the solution was performed at
0.5, 1, 2 and 4 h to evaluate the iron and copper extraction kinetics and to determine
acid consumption.

2.2. Cyanidation

The potassium cyanide and calcium hydroxide were certified reagent grade and
distilled water was used. The leaching cell was made of acrylic plastic, with a capacity
of 6 I. The inside walls of the cell were provided with baffle plates to avoid vortex
formation. The bottom of the cell was designed to allow injection of a gas into the pulp.
The pH was measured with a combination pH electrode containing a reference electrode
(AgCljKCl 4 M).
At the start of each test, a 1000 g sample was mixed with 3 I of solution. Prior to
cyanidation, the pH was brought to its working value (pH 11.5) by adding lime. Enough
cyanide was added to obtain the concentration required to begin the test. Samples were
taken to monitor changes in the gold extraction kinetics and cyanide consumption. At
each sampling, the pH was readjusted and the free cyanide analysed quantitatively.
Determination of the free cyanide in solution was by titration with silver nitrate.
For each sampling, 50 ml of solution was taken. However, an equal volume of water
was added to maintain a constant solid/liquid ratio; accordingly, enough potassium
cyanide was also added to maintain a constant cyanide concentration. At the end of the
experiment, the solids were recovered by filtration, washed and dried. The solid residue
was analysed by fire assay to determine the amount of residual gold.

2.3. Thiourea leaching

The sulphuric acid, sodium hydroxide, thiourea, ferric sulphate and hydrogen perox-
ide were all certified reagent grade chemicals and distilled water was used. The leaching
cell and cover were made of acrylic plastic. This polymer is only very weakly attacked
by acid, so the chances of interference from this effect during leaching could be
disregarded. The reactor capacity was 2.5 1. The four openings in the cover allowed
insertion of the electrodes, the impeller and the acid and thiourea injection tubes. A
combination pH electrode connected to a pH monitor (Chemcadet) stabilized the pH at
the desired value. A variable-volume pump carried the acid into the reactor and another
pump (a low-volume Minipuls) did the same for the thiourea. A redox electrode
connected to a millivoltmeter recorded the potential of the system during leaching. A
multimeter was used to zero the potential relative to the standard hydrogen electrode.
Mixing was performed by a 5 em teflon impeller driven by a variable-speed electric
motor.
The tests were carried out on pulps with a solid/liquid ratio of 50% for leaching
periods of 24, 48 and 72 h. At the beginning of each test, a 500 g sample of ore and 1.0 I
of leaching solution were used. The gold ore was introduced into the reactor and stirred
P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) 189-203 193

for a few minutes, long enough to stabilize the pH at the desired level. Then the thiourea
was added. An initial amount was introduced into the system and the remainder was
added in the form of a concentrated solution. To avoid precipitation of the thiourea in
the graduated cylinder, the solution was acidified with sulphuric acid. A volume of 16
ml of pulp was removed with a pipette after 0.5, 2, 4, 6 and 24 h. These samples were
taken for use in atomic absorption analysis of the gold, iron and copper, quantitative
analysis of the thiourea and colorimetric determination of the ferrous ions in solution. At
the end of the experiment, the solids were recovered by filtration. The filter cake was
repulped for 30 min with the addition of 500 ml of acidified water. The tailings were
analysed for arsenic and gold with the gold being determined by fire assay. The sample
for these analyses was randomly prepared. Finally, the changes in volume caused by the
samplings and by the addition of acid, base and thiourea were taken into consideration.
The potassium dichromate method was used in the determination of thiourea (Cuthill
and Atkins [6] and CANMET I).

3. Results and interpretations

3.1. Chemical and mineralogical analysis

In this high-sulphide ore (18% S), the gold and silver grades are 5.65 glt and 23 glt
respectively. The major metallic elements are, in order of importance, Fe, AI, Ti, Mg,
Zn, Cu and Pb. The chemical analysis of the ore is given in Table 1. The large
concentrations of zinc, lead and copper suggest that high thiourea consumption levels
are to be expected. Interestingly, the copper, iron and zinc concentrations decreased after
acid washing, while the gold concentration increased. It should also be noted that arsenic
increased from 125 ppm to 188 ppm. It should be mentioned in passing that arsenic can
have an adverse effect on the titration of thiourea with K2Cr207.
The mineralogical analysis was performed by X-ray fluorescence, which showed that
the main mineralogical elements are quartz, pyrite (33.56%), chalcopyrite (1.29%),
sphalerite (1.04%), galena as inclusions in sphalerite (0.13%), bornite (trace) and
covellite (trace). It is interesting in this regard that bornite (CusFeS4) and covellite
(CuS) are cyanide-consuming minerals. The bornite particles were embedded in covel-
lite.

3.2. Pretreatment (acid washing)

Acid washing is a pretreatment that uses sulphuric acid to leach the elements which
consume thiourea, such as iron and copper. Fig. 1 illustrates the extraction of copper and
iron and indicates the sulphuric acid consumption.
It is apparent from these results that the levels of copper and iron extraction were
around 200 and 17000 ppm respectively. The consumption of sulphuric acid remained

I Titration Procedure, CANMET, Natural Resources Canada, internal document, 1991, 12 pp.
194 P. Lacoste-Bouchet et at. I Hydrometallurgy 47 (1998) 189-203

Table I
Chemical analysis (g/t) of the gold ore from the OJ. Laronde Division of Agnico Eagle, Val d'Or, before and
after acid washing
Element Before After
Au 5.65 6.65
Ag 22.9 19.1
Cu 3972 3824
Fe 15.97% 13.59%
Ca 0.22% 0.08%
Al 4.47% 1.31%
Mg 0.18% 0.09%
Na 0.51% 0.45%
Ti 0.07% 0.12%
K l.l6% 1.02%
Mn 289 230
Ni 10 10
V 17 20
Cr 14 15
As 125 188
Sr 54 30
Zn 708 885
Co 15 12
Sb 7 9
Ba 233 480
Sc 2 <I
Zr 133 135
Pb 826 809
Te < 25 < 25
Sn < 20 < 20
Ga <10 11
La 21 <5
W < 20 < 20
Li 25 22
Nb 5 17
Mo 6 2
Bi <5 <5
Ta 25 <5
Y 6 <5
Cd 19.5 17.9
S 18.6%

relatively low, at 13 kg/t. It should be noted that sulphuric acid consumption reached a
plateau after only 2 h of leaching.

3.3. Cyanidation

The shapes of the curves for gold extraction as a function of time were the same for
both tests. Fig. 2 shows the gold recovery for two concentrations of cyanide. Gold
P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) 189-203 195

1600 16~
-t:::
OJ
::-
'[ 1200
H2SO4 12
S
::l
aE
o 800 8 ::l
til
Q) c:
u, 0
0
"C
400 4 Ti
Gu <C
0
2 3 4
Time(h)
Fig. 1. Dissolution of iron and copper during the acid leach of a copper-gold are. H2S04, 0.5 M.

extraction reached 66.3% in 30 h of cyanidation with 1000 ppm KeN. The gold
extraction is reduced to 50% using 500 ppm KeN in 48 h of leaching.
Moreover, the cyanide consumption was very high in both cases. With 500 ppm
KeN, a consumption of 4.9 kg/t was reached, while for 1000 ppm KeN, the
consumption was as high as 7.3 kg/t. In the analyses of the final liquid samples, a
concentration of about 300 ppm copper was observed for both tests. On the other hand,
the iron did not seem to go into solution, since only 10 ppm was found in solution after
47 h for test 1, while the iron concentration was less than 0.5 ppm in test 2. The mild
refractory nature of the ore indicates that cyanidation requires a pretreatment step using
lead nitrate to oxidize the metallic sulphides. This pretreatment would also increase the
gold recovery and decrease the cyanide consumption. Extensive work on the cyanidation
of a copper-gold ore containing the same amount of copper indicated that it is possible
to recover up to 96% gold with 1.85 kg/t cyanide using oxygen and lead nitrate [7]. In

80 r-------------------------------------,
70
~ 60
~ 50
~
o 40
~
"C 30
"0
C9 20 .......500 ppm KeN
10 . -0- 1000 ppm KeN

O ~~-L~~~~~~~~~L-~~-L~~-J
o 8 16 24
32 40 48
Time(h)
Fig. 2. Effect of cyanide concentration on the leaching of a gold are. pH 11.5.
196 P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) 189-203

the scope of this work, we did not invest more effort to improve the cyanidation because
it was not the goal of the project.

3.4. Results of thiourea leaching

Table 2 combines the results and the factorial design of the study. Gold recovery and
the consumption levels of thiourea, acid and base were inserted into the last four
columns of the matrix. The average of each level was calculated for gold recovery,
consumption of thiourea, acid and base, and relative costs of reagents. The average of
each level was determined using the following equation:

y, + Yz + ... +Yn
x= (13)
n

Yn are the results of a level, n the number of results in a level (for example gold
recovery or relative costs of reagents).
To be independent of the increase in reagent costs, we used an index to give the
relative costs associated with the consumption of reagents. However, the costs of
reagents were necessarily assumed to remain constant among themselves. It should also
be mentioned that the cost of thiourea represents between 75% and 85% of the total

Table 2
Thiourea leaching results according to the factorial design
Test Pretreat- pH Dura- [Thiourea] [Thiourea] [Fe2(S04)3] [H202] Gold Thiourea Acid Base
ment (B) tion added solution (F) (G) recovery consump. consump. consump.
(A) (C) (D) (E) (g/I) (g/I) (%) (kgj/t) (kg/t) (kgyt)
(h) (g/I) (gil)
Al yes 24 2 2 0 0 80.7 3.0 31.4
A2 yes 48 4 6 20 0.05 59.5 13.8 31.4
A3 yes 72 6 10 10 0.1 82.3 10.0 47.1
A4 yes 2 24 2 6 20 0.1 61.2 4.6 2.3
AS yes 2 48 4 10 10 0 83.0 4.5 3.6
A6 yes 2 72 6 2 0 0.05 81.7 4.2 3.6 1.9
A7 yes 3 24 4 2 10 0.05 79.1 2.8 9.7 8.2
A8 yes 3 48 6 6 0 0.1 76.S 2.2 4.8 5.6
A9 yes 3 72 2 10 20 0 81.1 3.3 7.3 8.0
AIO no I 24 6 10 20 0.05 63.9 9.0 39.9
All no 48 2 6 10 0.1 75.0 6.7 21.8
Al2 no I 72 4 2 0 0 53.9 6.1 45.3
A!3 no 2 24 4 10 0 0.1 61.7 4.0 4.8
AI4 no 2 48 6 2 20 0 63.9 5.0 12.7
AIS no 2 72 2 6 10 0.05 72.2 3.8 1.8
AI6 no 3 24 6 6 10 0 57.7 5.8 8.5
AI7 no 3 48 2 10 0 0.05 64.6 8.9 7.3
AI8 no 3 72 4 2 20 0.1 68.0 4.2 1.2
P. Lacoste-Bouche! et at. / Hydrometallurgy 47 (1998) 189-203 197

reagent cost [8,9]. This index was thus a relatively good reflection of thiourea consump-
tion. The relative cost was determined as follows:
Ct($/kg) = TU + H2S04 + Ca(OH)z (14)
C = (ConsTU * CTU) + (Consacid * Cacid) + (ConsbaSe * Cbase)
(15)
r Ct
Ct is the total cost per unit weight of each product, TU the thiourea, Cons .r the
consumption of reagents, Cx the cost for I kg of reagent and x is the reagent.
The reagent costs considered were as follows:
Thiourea, $2.20/kg; H2S04, $O.085/kg; Ca(OH)2' $O.35/kg.
Figs. 3 and 4 are graphic representations of the tendency of each factor in turn for
gold recovery and the relative cost of reagents. The horizontal line cutting the graphs in
two is the total average of all gold recovery figures in Fig. 3 and the total average of all
relative costs in reagents in Fig. 4.
It is apparent from Fig. 3 that pretreatment plays an important role in gold recovery.
Thus it seems to be an essential preliminary stage in thiourea leaching. As expected,
gold recovery increases with time (Fig. 3). In the case of ferric sulphate, it appears that
optimum extraction is reached with 10 gil (2.4 gil FeH). Evidently, the addition of
20 gil ferric sulphate (4.8 gil FeH) results in a pronounced reduction in gold
recovery. This is caused by a lack of thiourea which is transformed into formamidine
disulphide by the action of the FeH ions, in accordance with reaction (9).
Hydrogen peroxide oxidizes thiourea in accordance with reaction (8). Unlike the
reaction with ferric sulphate, this reaction is not inhibited by any known mechanism.
Thus with ferric sulphate a complex is formed between the ferric ions and thiourea in a
sulphated medium, according to the following reaction:
SC(NH2)2 + FeH + SO}- - [Fe(III)S04SC(NH2)2] + (16)
The absence of any inhibitor of the reaction between thiourea and hydrogen peroxide
accentuates the decomposition of thiourea on the basis of reactions (II) and (12). This is

80
Pre pH Time Initial TU TU solution Ferric Peroxide
78 treatment (h) (giL) (giL) sulphate (%)
(gil)
76
e. 74
e-
Q) 72
>
0
o 70
l!?
"0 68
(5
o 66
64
62
60
yes no 1 13 24172 216 2 110 0120 o 1,1
2 48 4 6 10 .05
Level of factors
Fig. 3. Gold recovery variation as a function of the level of factors during leaching.
198 P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (/998) /89-203

10
Pre- pH Time Initial TU TU solution Ferric Peroxide
9 treatment (h) (giL) (giL) sulphate (%)
(giL)
8
7
~
iii
0
6
0
Q) 5
> 4
~
Q5
a: 3
2

0
yesno 1 13 24172 2 16 2 110 o 120 o 1 ,1
2 48 4 6 10 .05
Level of factors
Fig.4.The relativceostvariatioans a functionof thelevelof factorsduringleaching.

why the use of hydrogen peroxide does not significantly increase gold extraction and
results in high thiourea consumption. Nevertheless, a certain level of gold extraction is
achieved, since the FD decomposition kinetics are relatively slow compared to the gold
dissolution kinetics (Fig. 3). Moreover, it causes an increase in thiourea consumption
(Fig. 4). Its use was therefore rejected and ferric sulphate was chosen as the oxidizing
agent. Table 3 gives the initial and final potentials and the average potential for each

Table 3
Potentialasnd elementsleached,factoriadlesignexperiments
TestNo. Start Potential Average Elements(ppm)
(mV) end copper iron
Al 410 410 410 91 674
A2 565 470 518 105 3562
A3 445 345 395 136 2106
A4 610 400 505 98 4035
AS 505 385 445 162 2435
A6 470 465 468 178 700
A7 520 455 488 112 2420
A8 445 395 420 167 812
A9 670 455 563 134 3600
AIO 500 355 428 158 4960
All 450 300 375 110 3090
AI2 457 565 511 144 1170
AI3 505 450 478 132 1158
AI4 505 420 463 102 4100
AI5 545 445 495 142 3680
AI6 450 415 433 102 2716
AI7 545 465 505 106 1270
AI8 575 355 465 130 3820
P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) 189-203 199

~~ o<?
~() ~- - --
0.80 :;.- ~
c Au[SC(NH2)2b --
[SC(NH)(NH2)12
Au +
:::I: [SC(NH)(NH2)12
cr.i
-;;
W

-0.80 ..... .l...-_ _, --'-_---'-_--'-_--L----=-..... .


o 2 4 6 8 10 12 14
pH
Fig. 5. E-pH diagram of the Au-SC (NH2)2 -H20 system at 25C for different concentrations of thiourea
and formamidine disulphide [2]. [Au]: 2.54* 10-5 M, (a) [SC(NH2)2]: 0.197 M, [[SC(NH)(NH2)]z]: 1.010-4
M; (b) [SC(NH2)2]:0.152 M, [[SC(NH)(NH2)]zl: 0.122 M; (c) [SC(NH2)2]: 0.013 M, [[SC(NHXNH)]zl:
0.059 M.

experiment. In general, the initial potential was 500 mV (SHE) and the final potential
was around 425 mV/SHE. The average potential was 462 mV (SHE).
The Pourbaix diagram for the Au-thiourea-Hyu system (Fig. 5) allows a better
understanding of thiourea leaching of gold. The stability zone of the
Au(SC(NH2)2)i
complex fluctuates in potential between 200 mV and 650 mV/SHE and in pH between
o and 4 [2,10].
An increase in the concentration of gold in solution reduces the stability zone of the
Au(SC(NH2)2)i complex [2]. The stability zone of the Au(SC(NH2)2)i complex
shown in Fig. 5 varies as a function of the ratio of thiourea concentration to that of FD.
Accordingly, this zone passes through a maximum and subsequently decreases. There is
evidently a TV /FD ratio which will provide an optimum stability area and thus
maximum gold extraction for a given ore. This ratio is related to the redox potential [3].
Moreover, the second stage of thiourea oxidation can result in an excessive release of
elemental sulphur.
With regard to relative costs, Fig. 4 indicates that pretreatment has no significant
relationship to reagent cost. However, the pH seems to have an adverse effect on costs.
The small increase in costs between pH 3 and pH 2 is insignificant. It would therefore
be normal to preclude leaching at any pH below 2. As expected, an increase in thiourea
concentration in the solution increases its consumption. In addition, the presence of
ferric sulphate also increases thiourea consumption by oxidation.
200 P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) 189-203

80
78
76
e-
Q)
74 ~
>
0
72
0 70
~ 68
"'0 66
(5
~
C!J 64 o with pretreatment
62
600
*
without pretreatment
0.5 1.5 2 2.5 3 3.5 4
Acidity (pH)

Fig. 6. Influence of the acid pretreatment on pH and gold recovery.

The factorial design does not reveal any particular tendency in costs linked to
hydrogen peroxide or duration. However, we may assume that there is an increase to a
plateau in each case. Hydrogen peroxide can be definitively eliminated as an oxidizing
agent for the process, since it only increases costs without producing a significant
increase in gold extraction.
The analysis of variance (ANOVA) [8] shows that pretreatment contributes to
producing 37% of all the effects. Moreover, we find there is an interaction between
pretreatment and pH which accounts for 29%. Fig. 6 illustrates the interaction between
pH and pretreatment for gold recovery. In addition, ferric sulphate, total thiourea and
time contribute to gold recovery in proportions of 14%, 11% and 6% respectively. The
contribution of hydrogen peroxide to gold recovery appears to be negligible. Clearly,
pretreatment and a high pH during leaching are recommended.
In terms of the relative cost of reagents, the interaction between pretreatment and pH
accounts for the greatest contribution, at 45%. Fig. 7 shows the interaction between pH
and pretreatment for the relative reagent costs. Total thiourea, duration and ferric
sulphate influence relative reagent costs in proportions of about 8% for the first and 4%
for the other two, while the effect of hydrogen peroxide accounts for around 7%.

010r-----------------------------------~
'E 9
&8
_m 7
6

2 5
:g 4
o 3

Q)_> 2
o with pretreatment
iii 1 * wijhout pretreatment
~ 0 OL----'----L-- JL----'---.....J..-----l3----.J.._--_J
0.5 1.5 2 2.5 3.5 4
Acidity (pH)

Fig. 7. Influence of the pretreatment on the acidity and relative cost of reagents.
P. Lacoste-Bouchet et al.j Hydrometallurgy 47 (1998) 189-203 201

4. Discussion

This work has adopted a factorial design approach to the assessment of thiourea
leaching of the copper-gold ore. Eighteen experiments were used to create a model
which describes the leaching of gold on the basis of selected factors. The study showed
that acid washing is essential prior to thiourea leaching (Fig. 6). Moreover, the
contribution of acid pretreatment to gold recovery is 37%. Yet such pretreatment was
found to be inexpensive, with costs in acid of about $1.04/t (13 kglt consumed acid).
The results of the cyanidation tests showed that this ore is refractory to cyanide,
creating a low gold recovery and a high cyanide consumption.
It was shown that, for all pH levels, thiourea leaching without pretreatment is less
effective in terms of gold extraction than with pretreatment. Furthermore, it seems that
the adjustment of the solution pH, after pretreatment, to a value of 3 favours gold
extraction. Accordingly, it is recommended that gold extraction be performed at pH 3
with pretreatment. Generally speaking, gold extraction increases with pH reduction,
since thiourea is stable at low pH levels. However, the pH behaviour can be explained
by the fact that a more aggressive medium releases greater amounts of thiourea-consum-
ing elements. An initial quantity of 2 gil thiourea, followed by the addition of 10 gil
thiourea over 72 h of leaching, provides optimum gold extraction. Table 2 shows that
the combined effect of these three factors on gold recovery is 12.2%.
Ferric sulphate was preferred to hydrogen peroxide, since, unlike the latter, it
increases gold extraction significantly (a 14% effect, Table 2). However, it does increase
thiourea consumption (reagent cost, Fig. 4). Yet the effect on reagent consumption is
only 4.3% for ferric sulphate, compared to 7.4% for hydrogen peroxide [8]. It should
also be noted that too much ferric sulphate does not favour gold leaching, which falls off
rapidly. Fig. 3 indicates that gold extraction without ferric sulphate is near the total
average, at 70.0%. The use of 10 gil ferric sulphate (4.8 gil FeH) contributes to a 5%
increase in gold extraction. If we continue to increase the ferric sulphate concentration to
20 gil (9.6 gil FeH), gold extraction drops to nearly 4% below the average recovery
level.
The optimum conditions for achieving high gold extraction can be summarized as
follows:
pretreatment, leaching at pH 3, 72 h duration, 2 gil initial thiourea, 10 gil added
thiourea and 5 gil ferric sulphate.
The potential at the start of the experiment was highly oxidizing (500 mV SHE)
because of the addition of ferric sulphate. The potential fell rapidly to 440 mV (SHE)
after 24 h. This drop in potential was related to the reduction of ferric ions and the
addition of thiourea. The system became less oxidizing. After 72 h, the potential was
around 425 mY. This potential is just above the stability zone of gold with thiourea. It
should be mentioned that this departure from theory derives from the fact that the pH at
the interface with the gold may be different from the overall pH of the solution (which is
measured) and that there are also many overvoltages which can cause the experimental
values to deviate from thermodynamic equilibrium [9,10].
The average redox potential of experiment Al was 410 mV (SHE), while that of the
confirming experiment was 467 mV (SHE). The confirming test was carried out on a
202 P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) 189-203

Table 4
Gross profits from thiourea leaching of gold, experiments Al to AI8
Experiment No. Gross profit ($/t) Experiment No. Gross profit ($ It)
Al 69.83 AIO 10.97
A2 -3.36 All 36.61
A3 34.53 A12 35.25
A4 16.71 AI3 43.02
A5 58.86 AI4 25.81
A6 65.97 AI5 45.87
A7 52.80 AI6 30.56
A8 60.60 AI7 38.76
A9 45.61 AI8 24.56

Price: gold = 15 $/g; thiourea = 2.20 $/kg; H2S04 = 0.085 $/kg; Ca(OH)2 = 0.35 $/kg; Fe2(S04)3 = 0.61
$/kg.

sample of the same zone 5 of the D.J. Laronde division. A more oxidizing medium thus
favours gold extraction. For experiment AI, however, thiourea consumption was 3.0
kg/t, while that of the confirming experiment was 3.9 kg/t. This consumption is
relatively low for the second case, as the concentration of added thiourea was 12 gil,
compared to 4 gil for the first case.
The gross profits associated with leach tests Al to A18 are given in Table 4.
Cyanidation of the ore resulted in a gross profit of $30.61/t for test 1 and $42.61/t for
test 2 (Table 5). For thiourea, the profits achieved in the confirming experiments were
$62.39/t (details in Ref. [8]). The use of thiourea increased the gross profit margin by
about $20/t. According to the model, gross profits could reach $67.87/t, for an
increase in value of $25.00 over test 2.
When we analyse the gross costs in Table 4, we find that test Al showed a better
performance than the theoretical model and the confirming experiment. This is because
this test did not use ferric sulphate, which sells for $O.I/kg and costs $12.20/t of
treated ore. The optimum gold recovery level is limited by the high price of ferric
sulphate. However, it is evident that ferric sulphate is recommended for gold extraction
by thiourea. It can be added then, that care is required in the interpretation of a factorial
approach.

Table 5
Gross costs and profits from cyanide and thiourea leaching of gold
Experiment Profit Consumption Acid Gross profit
($/t) of reagents wash without
($/t) ($/t) Fe2(S04)3 ($/t)
Cyanidation test 1 42.92 12.31 30.61
Cyanidation test 2 56.69 17.38 42.61
Confirmation 85.63 10.00 1.04 74.59
Model 89.00 7.89 1.04 80.07

Price: gold = 15 $/g; thiourea = 2.20 $/kg; H2S04 = 0.085 $/kg; Ca(OH)2 = 0.35 $/kg; Fe2(S04)3 = 0.61
$/kg; NaCN = 2.20 $/kg.
P. Lacoste-Bouchet et al. / Hydrometallurgy 47 (1998) 189-203 203

5. Conclusions

Using thiourea, the system producing maximum profit requires an acid wash. An
initial concentration of 2 gil thiourea is sufficient to begin with, and an addition of 10
gil ensures gold extraction of 89%. A leaching time of 72 h is recommended, and
thiourea consumption is 3.9 kg/t. It is thus possible to achieve a gross profit of $70 It of
leached ore. The redox potential of such a system is between 410 mV and 450 mY.
It should be mentioned that the application of the factorial experiment systems for
test programs with complex chemistry and interdependent variables has the merits to
limit the experiments and evaluate the parameters, but the results should be interpreted
carefully.

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