HydrometaUurgy, 20 {1988) 179-202 179

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

Leaching of Gold from a Chalcopyrite Concentrate

by Thiourea

G. DESCHENES
Energy, Mines and Resources Canada, CANMET, Ottawa, Ontario KIA OG1 (Canada)
and E. GHALI
Mining and Metallurgical Department, Laval University, Ste-Foy, Qudbec GOJ 1 YO (Canada)
(Received September 10, 1987; accepted October 2, 1987)

ABSTRACT

Desch~nes, G. and Ghali, E., 1988. Leaching of gold from a chalcopyrite concentrate by thiourea.
Hydrometallurgy, 20: 179-202.

A gold containing chalcopyrite concentrate has been treated with thiourea using H2S04. The
effects of some leach parameters such as thiourea concentration, oxidizing agents, redox potential,
pH, temperature, pulp density, acid pretreatment and S02 addition have been investigated. Max-
imum gold and silver extractions are respectively 95.5% and 85.4%. Hydrogen peroxide was found
to be an appropriate oxidant and successive leaches were performed to handle a 60% S/L pulp.
The consumption of thiourea is estimated to be 5-7 kg/t of concentrate. The value of the redox
potential is an important factor that influences thiourea consumption and gold extraction. Acid
pretreatment and S02 addition were useful in lowering thiourea consumption. Pretreatment also
reduces the S02 requirement of the system and improves silver extraction.

INTRODUCTION

Hydrometallurgical and electrometallurgical processes like Great Central

Mines [ 1 ], Duval [ 2 ], Dextec [ 3 ], Electroslurry TM [ 4 ], BHAS [ 5 ], Elkem
ICI [6] and Cymet [7] deal with the extraction of copper metal from chalco-
pyrite concentrate. Sulfur dioxide evolution is avoided by these metallurgical
techniques. Their non-polluting character and low capital investment are the
major reasons for research and development of such processes. To be compet-
itive with well established pyrometallurgical processes, these hydrometallurg-
ical techniques should deal with the complete treatment of the concentrate
especially for the precious metals recovery.
Some work has been done in extractive hydrometallurgy to recover precious
metals like gold and silver from copper concentrates or chalcopyrite residues
after copper extraction. These types of materials could be leached by conven-

0304-386X/88/$03.50 © 1988 Elsevier Science Publishers B.V.

180

tional methods but with high consumption of reagents. Several chemicals have
been tried on residues [8-10] but thiourea leaching appears to be most prom-
ising to extract gold economically. Soviet researchers [ 11] have reported that
thiourea is very effective in the recovery of noble metals from copper concen-
trates which are especially refractory to cyanidation.
Thiourea leaching has been done in hydrochloric, sulfuric and nitric acid
media. Dissolution of gold up to 97%, was reported in a solution containing 20
g/1 HC1, 0.20 g/1 HeO2 and 100 g/1 thiourea [12]. Many papers have been
published on leaching in sulfuric acid medium. Several types of ores have been
tested by Lodeischikov [ 13 ]. He found that acid pretreatment was required to
have maximum gold recovery. Gold recoveries from 92% to 98% were reported
after an 8 hours' leach in a solution containing 4 g/1 thiourea, 5 g/1 H2SO4 and
3 g/1 Fe2 (SO4) 3. Block-Bolten et al. [ 14 ] also found that preleaching results
in a higher extraction yield of precious metals.
The effect of various oxidants on the gold dissolution has been examined
[ 15-17] and possible mechanisms were investigated. Ferric ion produced the
fastest initial rate of gold dissolution [ 15 ]. Diffusion controlled reactions were
reported. Oxidation by ozone gas has been employed [17,18] and gave high
dissolution rate. However, thiourea consumption was very large. Hydrogen
peroxide was found to be better than air [ 17,19] and comparable to dissolved
oxygen as the oxidant.
Preroasted material, (pyrite and arsenopyrite) were leached in thiourea re-
sulting in gold extraction of up to 99% [ 20-23 ]. The thiourea concentration
used was 2% to 4% with a leaching time as short as 30 minutes [22]. Tests for
in-situ leaching have been reported in Australia in 1981 [24]. A mixture of
thiourea, thiosulfate and ferrocyanide was used in a "push-pull" test to recover
gold.
Recovery of up to 95% gold has been attained on a pyrite concentrate [ 17].
The solution contained thiourea (1.5%) and HzSO4 (0.35 N). Better results
were obtained with thiourea than with cyanide on a copper concentrate [ 24,25 ].
Low copper dissolution was reported. Chalcopyrite concentrate leached with a
thiourea solution (2%) and ozone (36 mg/1) gave 95% extraction of gold.
However, high thiourea decomposition was reported resulting in precipitation
of gold [ 16]. Carbonaceous material leached with thiourea has given 90-95%
gold extraction [ 25,26 ].
An industrial application of thiourea leaching has been reported in New South
Wales [ 27 ]. Leaching is done on antimony concentrate in less than 15 minutes
and gold is recovered with activated carbon. Thiourea consumption as low as
2 kg/t is mentioned and the total recovery of gold is approximately 85%. CSIRO
[28] carried out thiourea leaching on an oxidized gold ore (6.1 g/t Au, 5.2 g/t
Ag), controlling the pH, the redox potential and the thiourea concentration.
They found that raising either the thiourea concentration or the redox poten-
tial increased the rate of gold and silver extraction but also increased its thi-
 181

TABLE 1

Chemical and mineralogical analysis of chalcopyrite concentrate

Chemical analysis Mineralogical analysis

Au (g/t) 36-40 chalcopyrite, pyrite,

Ag (g/t) 80-85 small amount of pyrrhotite
Cu (%) 21 quartz, arsenopyrite,
Fe (%) 34 carbonates, galena, sphalerite,
S (%) 36 silicates, goethite, cobaltite,
SiO2 ( % ) 6.0 pentlandite.
Ca (%) 1.0
A; (%) 0.63
Zn ( % ) 0.57
Mg (%) 0.18
Co ( % ) 0.16
Ni (%) 0.10
Pb ( % ) 0.06
Mn (%) 0.02

ourea consumption. The use of SOe to reduce thiourea consumption has been
applied with success [ 20,29,30 ]. Sulphur dioxide helps to control the potential.
It is the way to prevent excessive oxidation of thiourea.
The objectives of this work are to investigate thiourea leaching of a gold
chalcopyrite concentrate, to optimize gold recovery, and to minimize thiourea
consumption. Effect of leach parameters such as thiourea concentration, tem-
perature, nature of the oxidizing agents, level of the redox potential, acid pre-
treatment and SO2 addition are considered. Silver recovery and acid
consumption are also studied.

EXPERIMENTAL

Material

A chalcopyrite concentrate was used in the leaching tests. The chalcopyrite

concentrate was supplied by Camchib Co., Chibougamau, Quebec.
Table 1 gives the chemical and mineralogical analysis of the sample.
The mineralogical analysis shows about 44% chalcopyrite and 35% pyrite in
the concentrate. Smaller amounts ofpyrrhotite and gangue minerals with traces
of arsenopyrite, galena, sphalerite, goethite, cobaltite and pentlandite occur.
Gold occurs only as electrum. Almost all gold was free in the feed crushed to
100% minus 45 z m while about 60% is free in the feed crushed to 80% minus
74 zm. Therefore, gold was liberated by grinding. Gold is attached (Fig. la) or
included (Fig. lb) in pyrite, partly enclosed or adjoined in chalcopyrite and
182

Fig. 1. Fig. 1 (a). Gold particle attached to pyrite grain. Gold vein between pyrite and chalcopyrite
grains.
Fig. 1 (b). Gold particle included in pyrite grain.
 183

Fig. 1 (c). Gold particle formed in a chalcopyrite vein localized in the middle of a pyrite grain.

arsenopyrite. Figure lc shows two small gold particles in a vein of chalcopyrite

formed in a pyrite particle. Gold that is free or attached to other minerals is
leachable but the included gold will not be leached.

Equipment and procedure

Sulphuric acid, thiourea, hydrogen peroxide and ferric sulphate were all
chemical reagents' grade and deionized water was used.
The glass leaching cell had a 1 litre capacity and an outer jacket. A Braun
Model Thermomix 1480 constant temperature bath was used to control the
temperature by circulating constant temperature water through the outer jacket.
A Fisher Ag, AgC1/KC1 (4 M) redox electrode was connected to a Fisher mil-
livoltmeter recorded to indicate the potential value of the leaching system.
Mixing was provided by a stirrer with an adjustable speed electrical motor. A
reflux condenser mounted on the top of the cell minimizes aqueous loss when
the system is heated.
Most of the tests were conducted in pulps at a solid/liquid ratio of 10%,
initial pH of 1.0 and 8 h leaching time. For each test a 100 g sample of chalco-
pyrite concentrate and 1.0 1 of leaching solution were used. Thiourea and the
oxidizing agent were added and stirred for about two minutes and then the gold
184

containing concentrate was introduced. Agitation was kept at the same value
( 800 m i n - 1). A volume of 15 ml of pulp was pipetted out after 0.5 h, 2.0 h and
at the end. For repeated tests, samples were taken at different times.
After determination of optimum conditions, leaching time was set to 4.0 h
using H202 and 7.0 h with Fe 3+ to study the effect of SO2 on thiourea con-
sumption. Pulp samples were then taken after 0.25 h, 0.5 h, 2.0 h and at the
end. Changes in volume due to sampling, addition of acid, NazSQ or H202
were considered in our calculations. SO2 was created in-situ by addition of
Na2SO3 solution (1.97 g/ml) using a micropump. The filter cake was washed
with distilled water and sent for fire assay analysis of precious metals content
using standard techniques [31-32]. The pregnant solution and the wash so-
lution were analysed for thiourea, gold and occasionally base metals (Fe, Cu)
by atomic absorption spectroscopy.
In some tests the pH control was performed manually by adding concen-
trated sulphuric acid to keep the system at the same value. Measurement of
pH was made with a pH meter using a combined electrode (glass/calomel
electrode).
Thiourea concentration in samples was determined by potentiometric titra-
tion with potassium iodate using an iodine selective electrode ( Orion 9453 ) in
conjunction with a double junction silver-silver chloride reference electrode
(Orion 900200) [33]. Because of the iodate consumed by SOz, a correction
factor derived from the ratio iodate/SOe was used when this gas was present
in the solution. Thiourea concentration was also determined by spectropho-
tometric method in the ultraviolet region and an indirect spectrophotometric
determination with sodium nitrite to compare the results. Thiourea consump-
tion was calculated by the difference in thiourea concentration after regener-
ation by reducing the formamidine disulfide. A practical and fast laboratory
method to regenerate thiourea is to contact the solution with zinc or iron pow-
der. However, the SO2 created in-situ by addition of Na2SO3 to the solution
will regenerate almost the same quantity of thiourea but with slower kinetics.
Thiourea adsorbed onto chalcopyrite was also considered as part of the total
thiourea consumption by analyzing thiourea in the filter cake wash water.

RESULTS AND DISCUSSION

(1) Influence of oxidizing agents

( A ) Ferric ion
The influence of the ferric ion as an oxidizing agent is illustrated in Fig. 2 at
three different concentrations. Without any oxidizing agent, the thiourea so-
lution provides an extraction of gold of 80% in 8 h. An addition of 2.0 g/1 of
this oxidant slightly improves the initial leaching kinetics but results in no real
improvement in gold extraction. Increasing the concentration of the oxidant
 185

90

~ 75
z
0
F- 6O

~- 4 5
x
bJ

I I I I_ I
0 2 4 6 8 I0
TIME (h)

Fig. 2. Influence ofFe ~+ concentration on gold extraction from chalcopyrite concentrate. Thiourea
10 g/l, pH 1.0, S/L 10%, 25°C, 800 min -1. O =0, A =2, • = 5 and [] = 8 g/l Fe :~+.

to 5.0 g/1 increases the leaching kinetics and also increases the extraction of
gold to 93.4% in 7 h. The figure shows that the rate of gold dissolution is very
rapid in the first thirty minutes of leaching. For the 5.0 g/1 concentration of
the oxidant, 80% of gold was leached in this period. Adding 8.0 g/1 of Fe :~+ in
solution caused a significant decrease in gold leaching. When the amount of
oxidant is too large, there is oxidation of thiourea and the remaining amount
of leachant is less powerful to extract gold. Several researchers have observed
a fast rate of gold dissolution in the initial leaching period when using ferric
ion.
Table 2 gives the evolution of the redox potential of the leach system under
different conditions. Without any oxidizing agent, the potential rises to the
point where there is oxidation of thiourea to formamidine disulfide. In fact,
this oxidation occurs at about 160 mV ( S.C.E. ) according to Groenewald [ 15 ],
corresponding to 204 mV with our reference electrode which is - 4 4 mV vs
S.C.E.

(B) Air
Sparging air (2.5 1/min) into a solution containing 10.0 g/1 thiourea did
provide better leaching kinetics than a solution without any addition of oxi-
dizing agent or with 2.0 g/1 of Fe 3+ but this regime reaches only 83.5% extrac-
tion of gold after 8 h. The gas flow has an influence on the dissolution of gold
for the first 4 h of leaching but it appears that both systems result in about the
same cumulative gold extraction which is quite comparable to a leaching so t
lution without any oxidizing agent (Fig. 2).

( C) Hydrogen peroxide
The effect of varying hydrogen peroxide concentration from 0.05% to 0.50%
was studied in leaches containing thiourea concentrations of 10.0 g/1. Higher
186

45I
,,,~30
L5

I I I I
2 4 6 8
TIME ( h )

Fig. 3. Influence of initial hydrogen peroxide concentration on gold extraction from chalcopyrite
concentrate. Thiourea 10 g/l, pH 1.0, S/L 10%, 25°C, 800 min -1. O =0.5, • =0.25, A =0.1 and
[] =0.05% H202.

concentrations of hydrogen peroxide were not considered because they pro-

duced an oxidation potential too high and resulted in a drop in gold recovery.
This decrease in the extraction of gold was already observed for the gold chal-
copyrite concentrate when the addition of H202 reached 1% [17]. Hydrogen
peroxide was added to thiourea solution before the introduction of the gold
concentrate.
Figure 3 shows the dissolution plots using 10.0 g/1 of thiourea with different
quantities of H202 added i.e. 0.05, 0.10, 0.25 and 0.50%, respectively. The ex-
traction rate of gold decreases with increasing H202 concentration. This be-
haviour was also observed by Gabra [ 16 ] and Soviet researchers [ 34 ] and they
related it to the decrease in available thiourea due to its oxidation with H202
to formamidine disulfide. The maximum extraction of gold was realized with
the lowest concentration of H202, namely, 89% extraction at 0.05% H202
leaching for 8 h. Table 2 shows the redox potential of each system.
The potential increases with the H202 addition or the formamidine disulfide
concentration. The higher H202 concentration result in about the same final
gold recovery (80-81%) that is comparable to the system without any oxidiz-
ing agent added. A small addition of H202 (0.05%) oxidizes only a small amount
of thiourea and then increases the recovery of gold by almost 10% compared
to the leaching without any oxidizing agent.

(2) Influence of thiourea concentration

(A) Ferric ion

The effect of thiourea concentration using 5.0 g/1 ferric ion as oxidant is
illustrated in Fig. 4. Four thiourea concentrations were studied, i.e. 5.0, 10.0,
20.0 and 30.0 g/1.
 187

TABLE 2

Change in solution potential during thiourea leaching, 8 hours, 10% S/L, 25 °C

Thiourea Oxidizing agent Range of redox potential Gold extraction

(g/l) (mV vs Ag, AgC1/KC1 (%)
(4M))

10.0 -- 120-205 80.5

10.0 2.0 g/l Fe 3+ 230-245 81.1
10.0 5.0 g/1 Fe 3+ 240-280 93.4
10.0 8.0 g/1 Fe 3+ 345-365 63.7
10.0 1.51/min air 107-241 81.8
10.0 2.5 1/min air 119-252 83.5
10.0 0.50% H202 380-350 80.5
10.0 0.25% H202 270-240 80.7
10.0 0.10% H202 225-250 81.8
10.0 0.05% H202 218-244 89.0
5.0 0.10% H202 254-306 81.6
5.0 0.05% H202 247-302 83.2
5.0 0.025% H202 245-272 85.9

About 50% Au was leached using 5 g/1 thiourea ( Fig. 4 ). The optimum leach-
ing is obtained with 10 g/1 thiourea resulting in 93.4% Au recovered. Respec-
tively 91.8% and 88.0% Au was recovered with 20 g/1 and 30 g/1 thiourea after
4 h leaching. Extending the leaching time of these two systems up to 8 h or
more, resulted in a precipitation of gold.
Increasing the thiourea concentration, particularly up to 10 g/l, produces an

90 - ~ ~ e •

75
Z
0
i.--
¢.,) 6 0

x 45 ___x3_.___---- - - - - - 0 " - - - - - ~ \x

50 \ \\
"o
15

0 2 4 6 S VZ4
TIME ( h )

Fig. 4. Influence of thiourea concentration using Fe 3+. Fe 3+ 5 g/l, pH 1.0, S/L 10%, 25°C, 800
m i n - 1. O = 5, • = 10, A = 20 and [] = 30 g/1 of thiourea.
188

,Q f O ~ O ~ 0 ~
90

75

z6o ~
I--

45
X
W

15

I ] I I
2 4 6 8
TIME ( h )

Fig. 5. Influence of initial thiourea concentration on gold extraction from chalcopyrite concen-
trate. H202 0.25%, pH 1.0, S / L 10%, 25°C, 800 min 1. © = 10, • = 15 and A =25 g/1 thiourea.

increase in the dissolution rate of gold especially in the initial leaching period
( 0.5 h). The same behaviour was previously observed by Groenewald and also
by Gabra [15,16]. There is however, a decrease in gold dissolution rate with
thiourea concentration above 20 g/1 (Fig. 4 ).
Thiourea is less stable at high concentrations and decomposes. Production
of elemental sulphur by decomposition of thiourea explains the decrease in
gold recovery [13,15,34,35]. The sulphur creates a stable film on gold and in
that way inhibits its dissolution.

( B ) Hydrogen peroxide
The influence of thiourea concentrations i.e. 10, 15, 25 g/1 on leaching was
studied in solutions containing 0.25% H202. Figure 5 shows that the initial
leaching rate increases with increasing thiourea concentration up to 15 g/1
thiourea and decreases when thiourea concentration reaches 25 g/1. The high-
est extraction of gold is obtained with 15 g/1 thiourea for the concentrations
examined.
By adding 0.25% H202 a maximum of gold extraction (93.2%) occurred in
a very short period of time, i.e. ] h. There is however, precipitation of gold
when the leaching time exceeds this 60 minutes period of time. The potential
of the system shows a drop from 250 mV to 230 mV (Ag, AgC1/KC1 (4 M))
which indicates the decomposition of formamidine disulfide to create thiourea
and elemental sulphur. In fact, the elemental sulphur produced from this re-
action may be responsible for precipitation of gold from the solution. It could
be gold adsorption of sulphur particles.
 189

z I00
0
I-
o
~90
i-
x
Ld
= 80 O

I I i I
70
I 2 3 4
Initial pH

Fig. 6. Influenceof pH on gold extraction from chalcopyriteconcentrate. Thiourea 10 g/l, Fe:~+ 5

g/l, 25 °C, 800 min- 1.

(3) Influence of pH

The influence of pH was investigated using 10.0 g/1 thiourea, 5.0 g/1 Fe :~+,
10% S / L at 25°C and 800 min -1. A leaching time of 7 h was used. The inves-
tigation was limited between pH 1 to 4 because of the stability of the thiourea
system. Figure 6 shows the decrease in gold recovery when the pH increases.
The best gold recovery obtained is with an initial pH of 1.0 and represents
93.2%. At pH 2.0, the gold extraction decreases to 86.8% and falls to 80.0% at
pH 4.0. Measurement of the final pH shows t h a t chalcopyrite concentrate is
an acid consumer. We will further evaluate the acid consumption of this
concentrate.

(4) Influence of temperature

Table 3a illustrates the effect of temperature using 10 g/1 thiourea and 5.0
g/1 ferric ion. Extraction of over 90% was obtained both at 40 and 60 ° C in 30
minutes. The gold leaching rate is thus improved with an increase of temper-
ature to 40 ° C. A total of 94.0% gold extraction was obtained at 60 ° C. Perform-
ance at 40°C is 93.5% extraction after 4 h. The same gold extraction took
almost 8 h to reach the same value at 25 °C. The difference from results re-
ported in the literature is t h a t no decrease of leaching efficiency was observed
at temperatures over 40 ° C. There is however, some gold precipitation at 60 ° C
but only after 4 hours leach.
Table 3b shows the influence of temperature on a hydrogen peroxide system
(5.0 g/1 thiourea and 0.05% H202). It was specifically selected to see how suc-
cessful the gold extraction could be with a low oxidizing agent concentration.
The highest extraction of gold (90%) is obtained at 40 ° C in 8 h. This result
represents an improvement of 7% over the gold extraction obtained at 25 ° C.
The gold recovery decreases to 88.0% at 60°C. This could be related to the
degradation of the gold thiourea complex itself and also to a loss of thiourea-
190

T A B L E 3a

Effect of temperature on gold recovery ( S/l = 10%, thiourea = 10 g/l, Fe 3+ = 5 g/l, pH = 1.0 )

Temperature Gold recovery ( % )

(°c)
30 min 4h 8h

25 80.4 87.3 93.4

40 90.7 93.5 93.4
60 92.2 94.0 92.5

/formamidine disulfide available. In fact, thiourea is reported to be unstable

at temperatures over 45 °C producing a drop in the recovery [ 17,26,36].

(5) Thiourea consumption

(A ) Choice of the oxidizing agent

The thiourea consumption was studied on two optimum systems, i.e. 10.0
g/1 thiourea with 5.0 g/1 Fe 3+ and 15.0 g/1 thiourea with 0.25% H202 at 25 °C.
The specific leaching time for each system was established according to the
kinetic plot.
Table 4 gives the conditions and the results of gold extraction and thiourea
consumption as a function of SO2 addition in the form of Na2SO3.
Without SO2, both Fe 3+ and H202 gave almost the same gold extraction of
93.4-93.2% (tests 1 and 3) in 7 h for the former and only 4 h for the latter.
However, thiourea consumption was about twice as high with H202 giving 55.0
kg/t compared to 20.6 kg/t with ferric ion. The lowest thiourea consumption
using ferric ion is related to the formation of a metal ligand complex:
Fe (III) -thiourea. The Fe (III) thiourea complex is not stable enough to have
an industrial application. It starts to decompose after about 2 days. We there-
fore agree with the previous studies which recommend against the use of ferric
ion for thiourea leaching [ 15,37 ]. There is also another problem with the use

T A B L E 3b

Effect of temperature on gold recovery ( S / L = 10%, thiourea=5.0 g/l, H202=0.05%, p H = 1.0,

leach time 8 h)

Temperature Gold recovery

(°c) (%)
25 83
40 90
60 88
 191

TABLE 4

Comparison of effect of ferric a n d hydrogen peroxide systems on gold recovery and thiourea con-
sumption. S / L = 10%, room temperature, p H 1.0

Test Thiourea Oxidant Leaching SO2 Au Tu cons.*

(g/l) (h) (kg/t) (%) {kg/t)

1 10.0 5.0 g/1 Fe :~+ 7.0 - 93.4 20.6

2 10.0 5.0 g/l Fe a+ 7.0 65.1 89.7 12.8
3 15.0 0.25% H202 4.0 - 93.2 55.0
4 15.0 0.25% H202 4.0 41.2 93.8 14.7

*Thiourea consumption.

of this oxidant. To be economical, thiourea leaching needs a recycle of the leach

liquor. Addition of ferric ion will create a more important build-up of impuri-
ties. This build-up will require a purification step and additional costs for the
treatment.
Tests 2 and 4 show gold extraction and thiourea consumption with the use
of SO2. This consumption was reduced by about 4 times with the H202 system
(from 55.0 kg/t to 14.7 kg/t) while the gold recovery was essentially unaf-
fected. For the Fe 3+ system, thiourea consumption decreased to 12.8 kg/t but
with a drop in gold extraction to 89.7%. It was thus decided to study the H202
system and to optimize gold leaching and thiourea consumption.

(B) Influence of S02 and acidpretreatment

The effect of SO2 and the pretreatment of gold concentrate with sulfuric
acid 1.0 M on thiourea consumption and gold recovery was studied (Table 5 ).
Acid pretreatment was carried out during 4 h at 400 rain-1 with a S/L 50%.
The pulp was filtered and washed with one volume of water.
For the non-treated chalcopyrite (tests 3, 4 and 5), we see that the SO2
addition reduces thiourea consumption. Gold extraction is 93.8% with 41.2

TABLE5

Effect of SO~ a n d acid p r e t r e a t m e n t on gold extraction a n d thiourea consumption. Thiourea 15.0

g/l, H202 0.25%, S/L= 10%, room temperature, p H 1.0, 4 hours

Test Pretreatment SO2 Au T u cons.

(kg/t) (%) (kg/t)

3 - - 93.2 55.0
4 - 41.2 93.8 14.7
5 - 20.7 95.5 22.6
6 H2SO4 1.0 M 24.3 91.0 13.2
7 H~SO4 1.0 M 41.2 88.5 5.3
192

kg/t S02 (test 4) and reaches 95.5% extraction if this amount is reduced to
20.7 kg/t (test 5) while thiourea consumption increases rapidly.
Pretreatment with sulfuric acid decreases thiourea consumption as shown
in the results of tests 6 and 7. Thiourea consumption is lowered to 13.2 kg/t by
adding 24.3 kg/t SO2 and decreases to 5.7 kg/t if the SO2 added is increased to
41.2 kg/t, while extraction of gold decreases from 91.0% to 88.5% respectively.
There are two reasons explaining this fall of gold recovery: the removal of
base metal ions such as copper and iron that improve gold leaching and the
loss of some leachable gold during the pretreatment step. It is possible that
copper from chalcopyrite is mainly responsible for this improvement in gold
extraction.
Figure 7 shows the dissolution of the gold chalcopyrite concentrate con-
tacted with H2SO4 1.0 M. Most of the soluble gold and copper are extracted in
the first fifteen minutes and most of the acid consumption also takes place in
this period. About 2.5-3% gold and 2% copper are extracted in four hours con-
tact. Most of the acid consumed after 15 minutes is required to dissolve iron
minerals according to this figure.
Thiourea consumption is substantially reduced from 14.7 kg/t to 5.3 kg/t for
tests 4 and 7 where leach conditions are the same except that the feed was acid
pretreated for test 7. Figure 8 shows the dissolution of gold, iron and copper
during the thiourea leach as a function of time for both these tests. The data
suggest that thiourea is a selective agent for gold, leaching about 90% Au and
only 1% copper and 5% iron. The pretreatment reduces the quantity of iron
and base metals going into solution and it has a side effect on gold leaching.
There is about 45 mg/kg difference in the cumulative copper but 500 mg/kg
difference in iron when the pretreatment is applied. Both metals influence gold
leaching and thiourea consumption but we have not quantified the contribu-
tion of each. The cupric ion will improve gold dissolution by oxidizing thiourea
to create formamidine disulfide. Thus the gold extraction is higher at 93.8%
with more iron and copper in solution compared to 88.5% with the pretreated
feed. For this difference of 6% Au recovered, 3% can be ascribed to the quantity
of leachable gold extracted during the pretreatment step (Fig. 7) and then the
real difference in the efficiency of the leach is 3%.

( C) Influence o[ the pulp density

Table 6 presents thiourea leaching on a system with a more industrially rel-
evant S/L ratio. These tests were performed with control of the pH because
the increased solid content raises the pH considerably because of the higher
concentration of acid consumers and this would depress gold recovery as dem-
onstrated in Fig. 7.
The increase of the S/L ratio from 10% to 60% creates a decrease in S02
requirement. With the same thiourea consumption (13 kg/t), the non-pre-
treated feed requires only about half of the SO2 (i.e. 13.8 kg/t vs 24.3 kg/t)
 193

I00,
--J

o s0 ~ 8 ~ A

o
~

<[
60

40
/ 6 E

t.iJ
,,,
n"
20
L~_
f
I 2 3 4
TIME (h)

Fig. 7. P r e t r e a t m e n t of gold chalcopyrite concentrate with H~S04 1.0 M, room temperature, S/L
50%, 400 m i n - 1. • Au, [] Cu, • Fe and A Free acid.

2so I
_____~ 2 5 0 ~ ~ r e t r e o t e d feed (
22op . . . . . . . . . . . .

z5 6.0g
o
r- 5
60

uJ 45

-J
~ 30
~___~ 2.0 '
15

I I I
O I 2 3 4
TIME {h)
Fig. 8. Effect of acidic pretreatmenton the leachingof gold chalcopyrite concentrateusing thi-
ourea. Thiourea 15 g/I, H202 0.25%, pH 1.0, S/L 10%, SO2 41 kg/t, room temperature. Open
symbols are non-pretreated,dosedare pretreated. V • Au, DIm Fe and O • Cu.

when the S/L ratio goes from 10% (test 6) to 60% (test 8). This reduction is
more important for the pretreated feed, i.e. 41.2 kg/t SO2 (test 7) to 5.8 kg/t
SOo (test 11) with a thiourea consumption of 5-6 kg/t. The larger reduction
in the SO2 requirement is another advantage of feed pretreatment.
On the same leaching time basis, gold extraction decreases from 91% to
71-72% with the increase in the S/L ratio (test 6 vs test 10 and 11 ). The main
194

TABLE 6

Effect of SOe and acid pretreatment on gold extraction and thiourea consumption. Thiourea 15.0
g/l, H20z 0.25%, S/L 60%, room temperature, pH control 1.0

Test Pretretment Leaching S02 Au Tu cons.

(h) (kg/t) (%) (kg/t)

8 - 4.0 13.8 74.0 13.1

9~ - 2.0 16.7 85.8 11.6
10 H2S04 1.0 M 4.0 10.8 70.8 4.3
11 H2S04 1.0 M 4.0 5.8 72.1 5.9
12 test 10 0.25 12.5 91.8 4.6
13b HeS04 1.0 M 1.0 5.2 94.8 6.2

a0.25% H202 added continuously during leach.

b4 leaches of 15 minutes.

reason for this fall in gold recovery is that initial thiourea concentration was
kept at the same level while the S/L ratio increased 6 times. Sulphur dioxide
affects not only thiourea consumption but also gold recovery in the absence of
this reductant. In fact an additional test performed without SO2 shows that
the gold recovered is not higher than 58%. We can reach 92% gold extraction
by repulping the residue of test 10 and leaching for only 15 minutes (see test
12 ). Total thiourea consumption is then 4.6 kg/t.
By adding HeO2 during the leach of non-pretreated feed (test 9), thiourea
consumption can be reduced with increased gold recovery. The average value
of the potential is lowered by raising the amount of SOz (Fig. 9). Comparing
test 8 and 9 shows that for an increase of 2.9 kg/t of SO2 and with double the
H202 used, there is a 25% increase in the cumulative gold extracted (85.8% vs
60.7%) after two hours leach (see Fig. 9). About 1.5 kg/t of thiourea can be
saved.
Test 13 represents the results of the pretreated material leached in four suc-
cessive and identical fifteen minute stages. A total of 6.2 kg/t thiourea and 5.2
kg/t SO2 are required to extract 94.8% gold. The redox potential decreases
from the first leach to the last one because of the decreasing supply of ions
from the mineral. This value drops from 280 mV to about 195 mV/calomel
electrode, Ag, AgC1/KC1 (4 M).

(6) Silver extraction and acid consumption

In general silver extraction increases with gold extraction for the same feed.
The comparison of tests 3 and 4, 6 and 7 or 10 and 11 presented in Table 6
indicates this behaviour. For the pulp with a S/L ratio of 10%, the highest
extraction of silver is 88.5%. However, silver recovery decreases more rapidly
than gold recovery with increasing S/L ratio. The acid pretreatment has a
beneficial effect on silver extraction. For a comparable gold extraction while
 195

F
-~" ................
z~
o :~ 2 0 0
I I I

90

75

Z
5
O
I.- 60

nr"
/I
I- 45
X
I..iJ
£9
O
J 50
O
¢,D
I
15 /x//

~-=-=-~--.----~----------LZ%e'------.-g - ....... 4 ........

0 0.5 1.0 1.5 2.0
TIME (h)

Fig. 9. Dissolution of gold and base metals for thiourea leaching of gold chalcopyrite concentrate
adding H20~ during the test. Thiourea 15 g/l, pH 1.0, S/L 60%, room temperature. - - - test 8, - -
test 9, A • Au, D I Fe and 0 0 Cu.

almost no silver is dissolved during the pretreatment ( <0.1 mg/kg), Ag re-

covery is almost doubled when the feed has been contacted previously with a
sulfuric acid solution (tests 4 and 6 or 8 and 11). Addition of SO2 improves
silver recovery (test 3 and 4). It is however, difficult to define the best system
for silver recovery because this parameter was not thoroughly examined.
Acid consumption during thiourea leaching was taken as the total quantity
of sulfuric acid needed to keep the pH constant. Results obtained show that
acid consumption varies with the quantity of base metals (mainly iron) dis-
solved during the leach which is proportional to the gold recovery.
Acid consumption was in the range of 28-37 kg/t for the treatment of the
crude feed but reached 46-50 kg/t when the feed was pretreated and leached
for about 4 hours. This total consumption for the pretreated material is based
on 15 minutes acid washing (32 kg/t) with the rest in the leach. Leaching the
pretreated feed in 4 stages of 15 minutes each did not reduce significantly acid
consumption which remained at a total of 44-48 kg/t.

INTERPRETATION

In an acidic solution of thiourea, the dissolution of gold proceeds according

to the following reaction:
Au+2CS(NH2)2 ~Au(CS(NH2)2) + +e (1)
196

TABLE 7

Extraction of gold a n d silver with thiourea from a gold chalcopyrite concentrate. Thiourea 15.0
g/l, H202 0.25%, room temperature, 4 hours

Test Au Ag S/L Pretreatment

(%) (%) (%)

3 93.2 30.4 10 -
4 93.8 49.1 10 -
6 91.0 85.4 10 H2SO4 1.0 M
7 88.5 71.7 10 H2SO4 1.0 M
8 74.0 33.2 60 -
10 70.8 43.4 60 H2SO4 1.0 M
11 72.1 51.5 60 H2SO4 1.0 M
12" 91.8 49.1 60 test 10
13" 94.8 39.7 60 H2SO4 1.0 M

*Test 1 2 - - T e s t 1 0 + 15 min a n d Test 1 3 - - 4 X 15 m i n leaching times.

This is a reversible reaction with an electrode potential of - 0 . 3 5 2 V at 25 °C

on a fresh gold surface and - 0 . 4 1 V on a passivated surface [15].
There is a leaching of gold without addition of Fe ~+ for a chalcopyrite con-
centrate. This can be attributed to the dissolution of iron and copper in pres-
ence of oxygen. Fe 3+ alone cannot leach gold [ 15 ]. Adding 5.0 g/1 of Fe 3+ raises
the potential and also forms the iron thiourea complex. It results in the opti-
m u m extraction of gold with 93% (Fig. 2).
The drop in extraction with 8.0 g/1 of Fe 3+ is caused by a lack of free thiourea
related to this high concentration of ferric ion and also to a very high redox
potential. The iron complexes with thiourea with formation of a metal-ligand
in a sulphate solution [ 15 ] :

Fe 3+ + C S ( N H 2 ) 2 + S O ~ - ~- (FeSO4(CS(NH2)2)) ÷ (2)
In contact with oxidants such as Fe 3+, thiourea may be oxidized in succes-
sive stages to form several products. The first is the formation of formamidine
disulphide [ 36 ] :

2CS (NH2) 2 ~ ((NH2) ( N H ) CSSC ( N H ) (NH~))

+2H ÷ +2e;E °=0.42V (3)

In a second irreversible reaction the formamidine disulphide yields thiourea

and an unidentified sulphinic compound which then decomposes to yield cy-
anamide and elemental sulphur. The elemental sulphur created at the end of
this decomposition has a detrimental effect by passivating the leachable gold
surface and precipitating some gold from solution.
The study of the effect of oxidizing agents shows that there is an equilibrium
 197

between thiourea and formamidine disulfide. The agressiveness and the leach-
ing efficiency of the solution depends on this equilibrium. We saw earlier that
the optimum extraction of gold was 93% using 10 g/1 thiourea and 5.0 g/1 Fe ~+
in one leach of 7 h. The potential of this system changed from 250 mV to 280
mV. The highest extraction rate is obtained with ferric ion. This is because
thiourea is not readily oxidized with this oxidant. However, this complex is not
stable enough for industrial use. An equivalent extraction of gold could be ob-
tained using a higher concentration of thiourea and some H202, i.e. 15 g/l thi-
ourea and 0.25% H202.
Gold extraction increases with an increase in thiourea concentration ( Figs.
4, 5 ) as has also been observed in previous investigations [ 15-18,26,29,37,38].
This behaviour does not seem to be related to a specific oxidizing agent but is
limited to a certain concentration of thiourea. When the initial thiourea con-
centration exceeds 2%, there is a fall in the dissolution rate of gold and also in
the cumulative extraction because of the decomposition of this product to el-
emental sulphur. Other workers have found a linear increase of gold dissolu-
tion with thiourea concentration up to 2% [ 26 ] while some [ 34-38 ] found this
limit as high as 9%.
The variation of gold extraction with pH (Fig. 6) is the same as reported in
the literature [ 15,16,23,26,28,34 ]. Acid consumers such as carbonates and py-
rite are responsible for raising the pH. However, the drop in gold extraction
reported by Bilston et al. [28] in an H202 system is greater than the one ob-
tained in this work using Fe 3+ as oxidant. Bilston explains his large decrease
in extraction (90% Au at pH 1.5 to 37% at pH 3.6) by the dependance of gold
dissolution on the pH in presence of hydrogen peroxide such as illustrated by
reaction (4) :
2 A u + 4 CS(NH2)2 + H 2 0 2 + 2 H+ ~ 2 A u ( C S ( N H 2 ) z ) ~ + 2 H20 (4)
We see that the effect of temperature on gold leaching with thiourea is a
function of the system used (Tables 3a and b). Temperatures above 40 ° C do
not adversely affect gold extraction in the Fe 3+ system but decreases extrac-
tion in the HeO2 system, even when comparing a ferric system with a high
thiourea concentration (where a greater sensitivity is expected) with a per-
oxide system at a lower thiourea level. Plaksin et al. [ 37 ] and Bunn [ 38 ] found
that liberation of elemental sulphur could be delayed and restricted using Fe :~+.
This may be one of the reasons explaining the difference in the effect of tem-
perature on the two systems. There is also the decomposition of HzO2 which
has to be considered at high temperatures.
The high performance at 60 ° C is related to the limited stability of the iron-
thiourea complex that temporarily avoids decomposition of the leaching agent
and formation of elemental sulphur which reduces the solubility of gold in
198

solution. A leaching temperature of 40 °C would be a better choice than 60 °C

because of the similar leaching kinetics and cumulative gold extractions with
lower energy requirements and better thiourea stability at the lower
temperature.
The better leaching kinetics provided with the increase of temperature up
to 40 ° C represents an advantage. It could reduce the leaching time by one half.
The final temperature selection must be based on consideration of gold ex-
traction, thiourea consumption and energy requirements.
The increase of copper and iron concentrations in solution affects thiourea
decomposition and the oxidizing power of these ionic species. The potential of
the system is a good indication of the concentration of oxidizing agents. The
non-pretreated feed has the higher starting potential of 272 mV which de-
creases to 201 mV (Fig. 8) by the end of the leach. This emf value always
remains above that of the pretreated feed which drops from 257 mV to 189 mV
during the leaching. The gap is about 15 mV. The highest value of the potential
produces the highest thiourea consumption as mentioned in the literature [ 28].
Acid pretreatment was expected to have a beneficial affect on thiourea con-
sumption. Soluble species such as copper and iron can have a negative influ-
ence on thiourea leaching but copper is the worst as reported by Pesic [39].
Its influence is on two fronts: copper complexes the available thiourea used to
leach gold and it also oxidizes a part of this thiourea to formamidine disulfide
according to the following reaction [ 40 ] :

Cu 2+ + ( n ) T u ~ ( C u ( T u ( n ) ) ) + +0.5 FD 2+ (5)

where Tu = thiourea, FD = formamidine disulfide.

When copper goes into solution, the potential rises probably because of pro-
duction of formamidine disulfide which is an oxidant. The non-pretreated
chalcopyrite produces more of this oxidant because of the greater supply of
copper in solution compared with the pretreatment case. Formamidine disul-
fide is less stable than thiourea and decomposes to cyanamide and elemental
sulphur consequently increasing thiourea consumption.
It remains unexplained why gold dissolved during the acidic pretreatment
of the gold concentrate with H z S O 4 (Fig. 7). Washing with water does not
remove any gold and the presence of gold in the acid washing could not be
related to the extraction of colloidal gold. Gold seems to complex during the
pretreatment with some unknown chemical compound leading to the loss.
The difficulty in lowering the thiourea consumption could be related to some
extent to the quantity of iron and base metals going into solution. It is difficult
to decrease thiourea consumption below 14 kg/t when the feed is leached as is
( Table 6, S/L 60% ). We can lower this consumption to 4.6 kg/t by adding 12.5
kg/t SO2 to the leach and pretreating the feed with sulfuric acid (test 12 ). Gold
extraction obtained is 92%. The recovery of gold could be raised to about 95%
 199

with the same pulp density but thiourea consumption also increases to 6.2 kg/
t (test 13 ). The total leaching time is as short as 60 minutes.
More ions are dissolved when the leach slurry is more concentrated. For the
non-pretreated chalcopyrite, the iron going into solution is proportional to the
S/L ratio while copper is unaffected. We saw occasional precipitation of copper
after going through a maximum (tests 5, 8-10) this copper concentration grad-
ually increases up to around 300 mg/L maximum while iron concentration
rises over 10 g/1. The increase of the S/L ratio without any significant increase
in dissolved copper suggests that copper precipitates from the solution. It does
not seem difficult to lower thiourea consumption when the S/L ratio is
increased.
Addition of hydrogen peroxide during the leach changes the evolution of the
potential (Fig. 9). The starting potential of test 9 is lower because 20% of the
total S02 is initially added to lower this value. The potential is increasing be-
cause of the continuous addition of HeOe while it rises initially for test 8 ( H2Oe
added initially) and decreases after about 20 minutes.
It is obvious that the value of the potential affects the dissolution rate of
gold if we study the initial or mean potentials of each system. The total amount
of the base metals (iron and copper) dissolved indicates the extent of gold
extraction. The greater the cumulative amount of these ions the higher the
gold extraction (Fig. 9). Sandberg et al. [41] found that Cu 2+ does improve
gold extraction using thiourea. The potential plot of test 9 is generally lower
than test 8 and the thiourea consumption is higher for the latter. We can con-
clude that the average value of the emf during gold leaching and the concen-
tration of oxidizing agents will determine the thiourea consumption and gold
extraction.
Silver and gold react differently in a thiourea leaching system. Gold extrac-
tion of about 95% results in silver extraction of 85% for a light pulp (10% S/
L) but silver drops to about 40-50% recovery when the pulp density is raised
to 60% S/L. This may be related to silver adsorption on solids. The leaching
conditions giving the optimum extraction of gold do not always produce the
maximum extraction of silver. Acid pretreatment enhances silver recovery but
consequently raises the total acid requirement of the process. Without pre-
treatment, acid consumption is about 35 kg/t but increases by 10 kg/t if the
pretreatment is applied.
Thiourea leaching shows a good potential application to treat sulphide con-
centrates, such as those of chalcopyrite and pyrite, to recover gold and silver.
The low toxicity of thiourea compared to cyanide is always mentioned as one
of the motivations for developing the research in this field. There is however,
a certain level of toxicity in the effluent streams from thiourea solutions after
prior neutralization. This has been noted in the literature [42] but the study
did not identify the source of the biological toxicity. In spite of the lower tox-
200

icity of thiourea versus cyanide compounds, precautions have to be considered

in the treatment of the waste streams of such solutions.

CONCLUSIONS

Thiourea leaching of a gold chalcopyrite concentrate is possible without ad-

dition of any oxidant but gold extraction is only about 80% in an 8 hours leach.
Addition of hydrogen peroxide and ferric sulphate result in the same gold ex-
traction, but the former system is faster. Lower recovery of precious metals is
obtained using air as an oxidant. The use of H202 is better than Fe 3+, leading
to a lower thiourea consumption and less impurity build-up.
A high leaching potential ( > 185 mV vs SCE ) is required to obtain high gold
recovery and good leaching kinetics at the same time. The base metals concen-
tration in the leach liquor parallels the gold recovery showing that thiourea
leaching liberates gold attached to minerals.
The high value of the emf, however, increases thiourea consumption. The
use of S02 reduces thiourea consumption by controlling the emf of the leach.
Acidic pretreatment of the feed with H z S O 4 is advantageous in reducing thi-
ourea consumption, lowering the SO2 requirement and obtaining better silver
extraction. However, this additional step is a potential source of gold loss and
raises the overall acid requirement. Leaching temperatures over 40°C and pH
above 2 are not beneficial to gold extraction.
The increase of the pulp density results in a drop in gold extraction but with
the use of four successive short leaches a recovery of 95% Au can be attained
in 60 minutes and S02 requirements are reduced. The remaining gold is prob-
ably locked in the minerals. Optimum thiourea consumption and silver recov-
ery are obtained with a pretreated feed. The choice of the optimum system
would be a compromise between gold recovery and reagent consumption. It
would require the selection of an appropriate leaching potential and other con-
ditions to achieve the highest precious metals extraction.

ACKNOWLEDGEMENTS

The authors would like to gratefully thank G.M. Ritcey (CANMET), M.

Nagamori (CRM), and G. Gabra (CRM) for their advice and interest in this
work. The authors would also like to acknowledge the Centre de Recherches
Minerales du Quebec and Canada Center for Mineral and Energy Technology
for encouragement and financial support. Special thanks are due to the Min-
eralogy Section of CANMET for the mineralogical work performed.

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