Hydrometallurgy, 24 (1990) 135-156

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

135

S t u d i e s on the S o l v e n t E x t r a c t i o n of Gold from

Cyanide Media
P.A. RIVEROS

Canada Centre for Mineral and Energy Technology (CANMET), Mineral Sciences
Laboratories, 555 Booth Street, Ottawa, Ont. KIA OG1 (Canada)
(Received January 17, 1989; revised and accepted August 17, 1989 )

ABSTRACT
Riveros, P.A.,1990. Studies on the solvent extraction of gold ~omcyanidemedia. Hydrometal-

lurgy, 24:135-156.
The recovery of gold from real cyanide solutions using commercial quaternary amines was studied. The quaternary amines exhibited good selectivity for gold over base metals, fast reaction
kinetics, high loading capacity and low water solubility. The use of an aromatic diluent, such as
Solvesso 150, was required to prevent the formation of emulsions. The feasibility of running a
continuous circuit was demonstrated with a pilot plant campaign. Gold can be eluted efficiently
with acidic thiourea and air sparging or recovered in metallic form by incinerating the organic
solvent. Solvent extraction appears to have a great potential for the recovery of gold from cyanide
solutions.

INTRODUCTION

A project is underway at the Canada Centre for Mineral and Energy Technology (CANMET) to develop a solvent-in-pulp (SIP) system for recovering
gold from leaching pulps. The long-term objective is to bypass the costly solid/
liquid separation step and, thus, to develop an advantageous alternative to the
currently used carbon-in-pulp technology. Some preliminary results about this
project have been recently reported [1,2]. Initially, several extractants, including some recently investigated organophosphorus extractants [ 3,4 ], were
tested to determine their potential and suitability for a SIP application. In the
course of this testwork, it was found that quaternary amines exhibited an excellent combination of chemical and physical properties. This result prompted
a more in-depth investigation into various aspects of the extraction of gold
with quaternary amines. This investigation revealed that commercial quaternary amines possess a good selectivity for gold over base metals, a high loading
0304-386X/90/$03.50

1990 Elsevier Science Publishers B.V.

136

P.A. RIVEROS

capacity and fast kinetics. It was further found that gold can be either stripped
with acidic thiourea and air sparging or recovered in metallic form by incinerating the organic solvent. A small pilot plant was run to demonstrate the
feasibility of a continuous extraction process. This paper reports the results
and discusses the potential of solvent extraction in the extractive metallurgy
of gold.
EXPERIMENTAL

The commercial extractant Aliquat 336 [tri- (Cs-Clo)alkyl methyl ammonium chloride] from Henkel Corporation was used in most experiments. In
addition, two new products supplied by Sherex Chemical Company Inc. and
designated as Adogen 481 (tri-octyl methyl ammonium chloride ) and Adogen
483 (tri-tridecyl methyl ammonium chloride) were also tested. The aromatic
diluent Solvesso 150 (Exxon Corporation) was used in all cases. The organic
solutions were washed several times with aqueous solutions of sodium chloride
before using.
The concentration of gold and other metals in aqueous solutions was determined by Inductively Coupled Plasma (ICP) spectrophotometry. The organic
solutions were analyzed by X-ray fluorescence methods.
QUATERNARY A M I N E S

The extraction of gold with quaternary amines has been the subject of previous studies [ 5 ]. It has been established that quaternary amines have a great
affinity for the gold cyanide complex and that the exchange reaction proceeds
as follows:
R4N+X - + A u ( C N ) ~ = R 4 N + A u ( C N ) ~ + X -

(1)

where R is a long hydrocarbon chain and X - is a common anion such as C1or H S 0 4 .

Previous attempts to apply quaternary amines to the recovery of gold have
been hampered by the formation of massive emulsions when the organic was
contacted with alkaline cyanide solutions [6,7]. This phenomenon is attributable to the surfactant properties of most organic amines in the hydroxide
form. Previous researchers have tested several modifiers with the purpose of
correcting the emulsification problem, but surprisingly only aliphatic diluents
have been used so far.
Shivrin et al. [6] established that the smaller the size of the hydrocarbon
chains bonded to the ammonium group, the higher the tendency to emulsification. This phenomenon was attributed to the relatively higher water solubility of the amines with shorter chains. Amines with long hydrocarbon chains
exhibited a smaller tendency to emulsification, but also a lower loading capac-

SOLVENT EXTRACTIONOF GOLDFROM CYANIDE

137

ity. Thus, the most appropriate chain lengths appear to be R = Cs for the amines
of the type R4N + X - and R = Cs-C lOfor the amines of the type R3 (CH3) N + X .
Groenewald [7] found that Di-Isobutyl ketone (DIBK) was fairly effective
in reducing the degree of emulsification. Although the use of DIBK enabled
Groenewald to gather important information on the properties of quaternary
amines, the relatively high water solubility of DIBK would preclude its use on
an industrial scale.
In the present work, it was confirmed that emulsions formed readily when
an aliphatic diluent, such as Varsol 140, was used. It was also found that the
aromatic diluent Solvesso 150 produced good phase disengagements provided
that some simple precautions were taken. Since fresh commercial quaternary
amines have a considerable amount of water-soluble impurities, the organic
solutions should be washed thoroughly with an aqueous solution of sodium
chloride before using. Washing with dilute sodium hydroxide produced a severe
emulsification. Slow phase disengagement and haziness were observed when
the organic was washed with pure water, probably due to the low ionic strength.
On the other hand, the phase separation is greatly improved once the organic
phase is partially loaded with cyano complexes. For this reason, the operation
of a continuous circuit was found to be practically emulsion-free. On a bench
scale, experiments using 20% vol/vol solutions of extractant in Solvesso 150
showed satisfactory phase disengagements. This represents a significant improvement over Groenewald's DIBK/Kerosene system which could not tolerate concentrations higher than 4% Aliquat 336 due to the formation of emulsions [7].
CYANIDE LEACH SOLUTIONS

Most experiments were done with a clarified cyanide solution from Campbell Red Lake Mines (Ontario). Since this solution had a high concentration
of gold and base metals (Table 1 ), it was particularly useful to study the selectivity trends of quaternary amines. However, since most gold operations produce solutions having lower concentrations of both gold and base metals, a
second solution was obtained from Teck-Corona Hemlo Mines (Ontario) to
compare the results. As shown in Table 2, this solution was more dilute and
less contaminated with base metals. Both solutions had a pH of 10.5 and were
used without modifications, except that NaCN was added as required to cornTABLE 1
Composition of the Campbell Red Lake solution (mg 1 1)
Au

Cu

Fe

Ni

Zn

Ag

Co

As

Sb

Ca

10

85

31

43

34

1.2

2.1

3.3

1.8

27

138

P.A. R1VEROS

TABLE 2
Composition of the Teck-Corona Hemlo solution (mg 1-1 )
Au

Cu

Fe

Ni

Zn

Ag

Co

As

Sb

Ca

14

'2

0.2

0.2

0.1

0.3

2.3

115

3500j

5~ Aliquat 3 3 6 / C a m p b e l l ~
oooao 10~ Aliquat 336/Campbelq
AAA~ 20~ Aliquat 336/Campbel~
~-~- 25~ Aliquat 336/Hemlo !
5~ Adogen 481/Campbell
***** 5~g Adogen 483/Campbell j
ooooo

1
i2500 l

W/

o 2000 1

~ 1500 -o

1000 -

~ 500
o

G,

2
Aqueous

Concentration

10

12

14

16

of Gold, m g / L

Fig. 1. (]old e x t r a c t i o n i s o t h e r m s .

pensate for the gradual loss of free cyanide over time. No speciation studies
were conducted as it is generally accepted that metals are present in their lower
oxidation states and forming cyanide complexes anions, e.g., Au(CN)~-,
C u ( C N ) ~ - , C u ( C N ) ~ - , Z n ( C N ) ~ - , N i ( C N ) ~ - and Fe(CN) 4- [8].
I,OADING CAPACITY
Figure 1 presents equilibrium isotherms for the extraction of gold under various conditions. The gold loadings vary widely with the compositions of both
the organic and aqueous phases. Aliquat 336 exhibited a higher loading capacity than both Adogen 481 and Adogen 483 at the same volume percent concentration. As expected, increasing the concentration of Aliquat 336 from 5% to
10% and 20% resulted in progressively higher gold loadings. The gold loadings
from the less contaminated Teck-Corona Hemlo were quite high and thus a
much lower concentration of Aliquat 336 (2.5%) was used to obtain comparable gold loadings. As will be discussed later, this is because the presence of
zinc cyanide and other base metals has some influence on the gold loading.

SOLVENT EXTRACTION OF GOLD FROM CYANIDE

139

'S
1000

__~

_ _ ~ _ ~

v
-4

L.)
lOO
0
,4

ooooo
aaaDD
~aaaa
~9999

5~ Aliquat 336/Campbell ]
10~ Aliquat 336/Campbelli
30s~ Aliquat 336/Campbell]
2.Ssg Aliquat 336/Hemlo
i
5~ Adogen 481/Campbell
***** 5~ Adogen 483/Campbell

,13

10

I000

Equilibrium

2000

Gold

Loading,

3000

mg/L

Fig. 2. Gold d i s t r i b u t i o n coefficients v e r s u s gold loading.

Figure 2 presents the gold distribution coefficients, DAu, as estimated from the
isotherms versus the equilibrium gold loadings. It can be seen that with an
adequate concentration of extractant the DAu can reach values close to 1000.
These gold loadings and distribution coefficients compare very favourably with
those reported for other liquid extractants. For example, the DAu values obtained with 100% tributyl phosphate (TBP) and a 1 : 1 mixture of TBP/Alamine 336 were 8.4 and 30.1 respectively with the Campbell Red Lake Solution
[9]. Miller et al. obtained DAu values ranging from 17 to 155 for di-butyl butyl
phosphonate (DBBP) and from 6 to 55 for TBP using synthetic gold cyanide
solutions [3 ]. Groenewald reported a maximum gold loading of only 0.52 g l- 1
for Aliquat 336 in kerosene/DIBK, also with a synthetic solution [ 7 ].
SEI,ECTIVITY

The selectivity of quaternary amines was studied by saturating a given volume of the organic phase with a cyanide solution in a series of successive stagewise contacts. The stagewise saturation procedure was as follows: One aliquot
of organic (initially 50 ml) was contacted for 10 min at room temperature with
a cyanide solution at an aqueous to organic (A: O ) ratio of 40:1. After complete
phase disengagement both the organic and the aqueous phases were sampled
and analyzed. This procedure was repeated several times using the same organic and fresh aqueous solution.
Figure 3 presents the stagewise saturation of 5% Aliquat 336 with the Campbell Red Lake solution. It was found that there are marked differences in the

140

P.A. RIVEROS

2500

~2ooo.
0

1500
ooooo
09

~I000
~D

~oo~
I~ . . . .

Gold
Nickel
Copper
Iron

I
I

I
j

500
0
0

Number

of S t a g e w i s e

Contacts

Fig. 3. Stagewise saturation of 5% Aliquat 336 in Solvesso 150 with the Campbell Red Lake solution. The aqueous to organic ratio was 40 : 1 at each stage.
1000

100"

10

ooooo Gold
A a a a a Zinc
O ~
Nickel

,.0

a-_~_~2

ooooo Copper
xxxxx Iron

0.1
0

Number

of S t a g e w i s e

1'0

Contacts

Fig. 4. Variation of the distribution coefficients during the stagewise saturation of 5% Aliquat 336
with the Campbell Red Lake solution.

extractability of each metal cyanide complex. While gold, zinc and nickel are
extracted to a large extent, copper and iron are practically not extracted. Among
the metals that are extracted, gold is the only one whose loading increased
constantly as the organic became saturated. A comparison between the relative
organic concentrations and the feed concentrations (Table 1 ) shows that gold
is being concentrated in the organic phase with respect to all the other metals.
Figure 4 presents the variation of the individual distribution coefficients
throughout the stagewise saturation. It can be seen that Aliquat 336 exhibits
the following order of affinity for the metal cyanide complexes:

S O L V E N T

E X T R A C T I O N

OF

GOLD

FROM

141

CYANIDE

(2)

Au > Zn > Ni > Cu,Fe

Figure 5 presents the separation factors of gold over each metal as a function
of the gold loading. The separation factors were calculated by dividing the
individual distribution coefficients. Thus the separation factor of metal A over
metal B is:

SA/~ =DA/DB

(3)

It can be seen that the selectivity of Aliquat 336 for gold over copper and
iron is very high. The selectivity for gold over nickel and zinc is less pronounced
but nonetheless significant. There is a slight tendency for the separation factors to increase as the gold loading increases, which suggests that a multistage
countercurrent process would enhance the degree of separation.
Similar results were obtained with other extractants. Figure 6 presents the
stagewise saturation of 5% Adogen 483. This extractant exhibited a slightly
higher selectivity for gold but lower capacity as compared with Aliquat 336.
Adogen 481 behaved similarly to Aliquat 336, except that a third phase formed
at high loadings, possibly due to its shorter hydrocarbon chains. The third
phase formation was readily cured, however, by using 2% isodecanol as a phase
modifier.
Figure 7 presents the stagewise saturation of 2.5% Aliquat 336 with the TeckCorona Hemlo solution. Gold is clearly extracted preferentially and in high

!000

r/?

_ 100=
O

e--4

Of
~

10-

SAu/Ni
SAu/Fe
SAu/Zn

0.1

1000

2000

Equilibrium Gold Loading, mg/L

Fig. 5. Variation of the separation factors during the stagewise saturation of 5 J%Aliquat 336 with
the Campbell Red Lake solution.

142

P.A. RIVEROS

2000

d
1500~

ooooo Gold
4~AA
Zinc
<~ 90 Nickel
o ~ a
Copper

~ ~x Iron

1000

0
o
.~

500

J
o
0

~
Number

of Stagewise

Contacts

Fig. 6. Stagewise saturation of 5% Adogen 483 in Solvesso 150 with the Campbell Red Lake solution. The aqueous to organic ratio was 40 : 1 at each stage.

.2000
oO

1500 -

ooooo Gold

!
~00
Nickel
]
m m o D o Copper
Iron

/p
/ ~

~1000 0

0
ro

.~

/
/

500
/

Number

of Stagewise

Contacts

Fig. 7. Stagewise saturation of 2.5% Aliquat 336 in Solvesso 150 with the Teck-Corona Hemlo
solution. The aqueous to organic ratio was 40 : 1 at each stage.

loadings from this dilute and less contaminated solution. This is attributable
to the absence of Zn (CN)~- ions, which also results in slighter higher extractions of nickel, copper and iron.
The separation of gold from copper and iron is particularly important. These
two metals, which are usually associated with gold in many ores, give rise to
several contamination problems in the refining of gold. Figure 8 summarizes
the gold/copper separation factors, SAu/Cu,obtained from various stagewise
saturation experiments. With the Campbell Red Lake solution, the SAu/Cuvalues ranged from 300 to 700 whereas with the Teck-Corona Hemlo solution a

SOLVENT

~o

1000

EXTRACTION

OF GOLD

FROM

143

CYANIDE

I00:
,

ESD

0
r..)

10
ooooo
ccc[]a
~AAA
00

*****

o
r~

5~ Aliquat
336/Campbell
10~ Aliquat
336/Campbell
20~ Aliquat
336/Campbell
2.5~
Aliquat
336/Hemlo
5~ Adogen
481~Campbell
5~ Adogen
483/Campbell

, , J , i i , , i i i , T r T J i i i i , , , , f f , , J

1 ooo

2000

5ooo

E q u i l i b r i u m Gold L o a d i n g , m g / L
Fig. 8. Separation factors of gold over copper.

o
r.,3

1000

u
*

o
I-,

0
x

100

I3,.,

cy]

o
ooooo
mODDm
aaaaa
00000

*****

"cJ
0

'

'

'

'

'

'

'

'

'

5~ Aliquat
336/Campbe[l
10~ Aliquat
336/Campbell
20~
Aliquat
336/Campbell
2.5~
Aliquat
336/Hemlo
5~ Adogen
481/Campbell
5~ Adogen
483/Campbell
i

1000

2000

( T

5000

Equilibrium. Gold Loading, mg/L

Fig. 9. Separation factors of gold over iron.

lower degree of selectivity was observed. Similarly, Fig. 9 shows the corresponding separation factors for gold over iron, SAu/Ye. In this case, the SAu/Ee
values ranged from 150 to 900 with the Campbell Red Lake and from 35 to 90
with the Teck-Corona Hemlo solution. The reason for the difference in the
degree of selectivity is probably related to the concentration of zinc and to the
ionic strength. Since the Campbell Red Lake solution contains more ions than

144

P.A. RIVEROS

the Teck-Corona Hemlo, its higher ionic strength appears to exert a relatively
stronger influence on the extraction of copper and iron than on the extraction
of gold.
Despite these fluctuations, it is apparent that quaternary amines exhibit a
marked selectivity for gold over copper and iron. This result agrees with previous work indicating that quaternary amines have a higher affinity for univalent ions, such as A u ( C N ) ~ , than for multivalent ions, such as Fe(CN) 4- ,
Cu (CN) 43-, and Cu (CN) ~- [ 10 ]. However, this trend contrasts strongly with
the behaviour of strong-base resins which, despite having a similar active group,
exhibit no selectivity for gold [11]. This suggests that the size of the hydrocarbon chains attached to the ammonium group bears a strong effect on the
selectivity exhibited by that group. A similar conclusion was stated by Shivrin
et al. [6] who found that quaternary amines of the type R4N+X - and
R~(CH3)N+X - exhibited a higher selectivity for gold than the quaternary
amines of the type R2(CH3)2N+X - or R(CH3)3N+X -. The fact that the
amines used in the present work belong to the first category of amines, i.e.,
R~ (CH3)N+X -, agrees with the above observation. Furthermore, most strongbase resins have the configuration R (CH3)3N + X - and are, therefore, related
to the less selective family of quaternary amines.
CONTINUOUS CIRCUIT

It has been recognized that running a continuous solvent extraction circuit

for gold presents a big difficulty because of the extremely high aqueous-toorganic ratio that is required [ 12 ]. Depending on the gold concentration in the
feed solution and the desired loading, the A: 0 ratio could be in the range of
100-1000: 1. This would exceed by far the typical ratios found in practice.
Moreover, such a high A: O ratio dictates that the phase mixing should be done
with an organic-continuous dispersion in order to minimize the losses of organic solvent.
After considering the alternatives, and bearing in mind that a small organic
inventory is required to keep the volume of the cyanide solution within reasonable limits, it was decided to use a series of agitated glass columns specially
designed and built for this experiment. A diagram of these columns is shown
in Fig. 10. During the operation, the aqueous solution flowed continuously
through a series of columns by gravity. Each column contained a given volume
of organic, which was pumped periodically into the next up-stream stage. The
columns were fitted with mechanical impellers of the p u m p / m i x type in order
to have the aqueous solution dispersed into the organic phase. By careful adjustment of the impeller speed, weir controls, and aqueous flow rate, it was
possible to operate the columns with a stable organic-continuous (water-inoil) dispersion. When this condition was attained, two liquid zones were clearly
discernible within the columns: Settled aqueous raffinate occupied the lower

145

SOLVENT EXTRACTION OF GOLD FROM CYANIDE

PHA5'E

I:.:I

AQUEOUS
PHASE

OUT

PUMP/MIX STIRRER
O 0RGANIC-CONTINUOUS DISPERSION

I@SETTLED AQUEOUSP~S~
CONTROL

Fig. 10. Extraction column for continuous countercurrent solvent e x t r a c t i o n of gold,

AQUEOUS, mg/L

ORGANIC, mg/L

Au

Cu

Fe

Ni

Zn

Au

Cu

Fe

Ni

Zn

10.0

85

31

43

34

2300

76

557

3820

7.0

84

32

44

36

755

62

482

3470

2.6

82

31

43

37 ~

252

62

O 480

3460

1.2

81

31

43

37 ~

90

60

507

3300

---....~._.. /
8.2

79

30

40

19 ~

Fig. 1l. Extraction profile for 10% Aliquat 336 and the Campbell Red Lake solution. Aqueous to
organic flow ratio = 200 : 1.

three quarters of the column while the top quarter was filled with the organiccontinuous dispersion.
The McCabe-Thiele procedure was applied to the distribution isotherms of
Fig. 1 to choose appropriate combinations of flow rates, number of stages, and
extractant concentration. The aqueous flow rate was set at about 1 Bed Volume/min (50-60 ml min-1), which gave a residence time of 2-3 min in each
column.
Figures 11 and 12 present extraction profiles at steady state for the Campbell

146

P.A. RIVEROS

AQUEOUS, mg/L

Au

ORGANIC, mg/L

Cu

Fe

Ni

Zn

Au

Cu

Fe

Ni

Zn

6.0

14

02

2580

82

733

9fl

2.6

14

0~

568

161

364

21

0.6

14

0~

94

232

70

0.3

14

0~

~ . ~ .....~

Fig. 12. Extraction profile for 5% Aliquat 336 and the Teck-Corona Hemlo solution. Aqueous to
organic flow ratio = 400:1.

Red Lake and the Teck-Corona Hemlo solutions, respectively. As expected

from the bench-scale data, gold was extracted with a good degree of selectivity,
especially over copper and iron. Gold recoveries were estimated at 98% with
the Campbell Red Lake solution and 95% with the Teck-Corona Hemlo solution. These values could be readily increased by adding more stages to the
circuit.
The loaded organic showed a 10-20% volume reduction with respect to the
fresh organic. Although it is possible that some organic was lost through adsorption on the walls and tubing, most of this volume reduction is believed to
be due to a shrinkage that takes place when a quaternary amine becomes loaded
with gold. As discussed below, the water solubility of quaternary amines is
quite low and could not account for the volume reduction. The amount of gold
collected in the organic fractions agrees closely with the amount of gold extracted from the feed solution. This fact gives support to the assumption that
the organic is not lost but it shrinks when it becomes loaded with gold.
X-ray fluorescence analyses of the loaded organic showed that the extraction
of minor metals was negligible. With the purpose of verifying this result, the
raffinate was periodically sampled throughout the campaign and analyzed for
silver, cobalt, arsenic, antimony, and calcium. The analyses, which are presented in Table 3, underline the high selectivity of Aliquat 336 for gold over
most elements. Apparently, solvent extraction, unlike activated carbon, provides an effective way to separate gold from many common impurities. In a
processing plant, this fact could reduce or eliminate the subsequent gold refining steps.
The concentrations of free cyanide, thiocyanate, and the solubility of the

147

SOl,VENTEXTRACTIONOF GOLDFROMCYANIDE
TABLE 3
Continuous circuit. Analysis of minor elements
Solution

Campbell feed
Campbell raffinate:
Sample 1
Sample 2
Sample 3
Sample 4
Hemlo feed
Hemlo raffinate:
Sample 1
Sample 2
Sample 3

Concentrations
(mg1-1)
Ag

Co

As

Sb

Ca

1.2

2.1

3.3

1.8

27

1.1
1.1
1.2
1.2

2.1
2.1
2.1
2.1

3.0
2.8
3.4
3.1

1.7
1.6
2.0
1.6

27
07
22
21

0.2

0.1

0.3

2.3

115

0.2
0.1
0.1

0.1
0.1
0.1

0.3
0.0
0.0

2.3
2.3
2.3

115
130
127

TABLE 4
Continuous circuit. Concentration of free cyanide, thiocyanate, and solubility of quaternary amines
Solution

Free C N (mgl 1)

SCN(mgl -~)

Dissolved quaternary
amine (mgl 1)

Campbell feed
Campbell raffinate:
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5

449

351

<1

426
390
386
385
380

321
396
304
302
289

12
9
11
4
3

270

52

260
280
270

50
51
50

8
8
8

Hemlo feed
Hemlo raffinate:
Sample 1
Sample 2
Sample 3

Aliquat 336 in the aqueous phase are important factors in a gold recovery process. Samples of the raffinate were taken periodically during the campaign and
the analyses are presented in Table 4. The extraction of both cyanide and thiocyanate ion was small. As expected from reported values [5], Aliquat 336
exhibited a remarkably low water solubility which represents an important
advantage from economical and environmental standpoints. In addition, the
phase separation was excellent throughout the campaign. Only minor amounts

148

P.A. RIVEROS

of crud were occasionally observed with highly loaded organics, but this did
not accumulate or interfere with the extraction. The physical characteristics
of quaternary amines appear to be more suitable for a large-scale application
as none of the problems associated with some organophosphorus extractants
[ 13,14 ] were encountered.
STRIPPING
Because of their high affinity for the gold cyanide complex, quaternary amines
are not readily stripped. Among the several procedures that were tested, only
two showed promise and were selected for a more detailed study: (1) stripping
with acidic thiourea solutions and air sparging, and (2) incineration of the
organic solvent.
Acidic thiourea

This reagent is reportedly used in the U.S.S.R. for the elution of gold from
strong-base resins [15]. In the presence of a mineral acid and thiourea, the
gold cyanide complex decomposes and a gold-thiourea complex, Au[CS
(NH2)2] + , forms. Since this complex is positively charged, it is not held by
ammonium groups.
R4N+Au(CN)~ + 2 H X + 2 C S ( N H 2 ) 2
= R 4 N + X - + A u [ C S ( N H 2 ) 2 ] 2 X - + 2HCN

(4)

where X - is usually C1- or H S 0 4 .

The attractive features of this procedure are: (1) the extractant is simultaneously stripped and regenerated, and (2) an important amount of free cyanide can be recovered and recycled. In the case of strong-base resins, some
operational problems have been reported, such as [ 15 ]: (1) breakage of the
resin beads due to osmotic shock, (2) precipitation of cobalti- and ferrocyanide
compounds in the resin matrix, and (3) decomposition of thiourea during the
gold electrowinning. In addition, the generation of the toxic gas hydrocyanic
acid during the stripping requires strict safety precautions.
Quaternary amines are free from most of the above problems. Since they do
not have a rigid matrix and extract little or no iron and cobalt, they are practically immune to both osmotic shock and the precipitation of cobalti- and
ferrocyanide compounds. More importantly, since quaternary amines exhibit
fast reaction kinetics and high loading capacity for gold, the inventory of loaded
organic in a processing plant would be relatively small. This fact would greatly
facilitate the safe handling of hydrocyanic acid.
Groenewald [ 7 ] reported that the stripping of Aliquat 336 with thiourea in
hydrochloric acid solutions was inefficient, producing a maximum concentra-

SO[NENTEXTRACTIONOFGOLDFROMCYANIDE

149

tion of only 0.68 g Au 1-1 in the strip liquor. The same researcher obtained
better efficiency with mixtures of thiourea and perchloric acid. However, no
information was given about the possible oxidation effect of the perchloric acid
on the quaternary amine or about the need to remove the perchlorate ion before
recycling the extractant.
In the present work it was confirmed that solutions of thiourea in hydrochloric or sulphuric acid produced poor strippings or gold. Further tests showed
that the presence of hydrocyanic acid (HCN), which is generated during the
stripping, has a strong influence on the stripping efficiency. Hydrocyanic acid
is a gas at room temperature, but it is evolved from aqueous solutions at a slow
rate because of its high solubility in water [ 16 ]. Unless it is removed at a fast
rate, hydrocyanic acid tends to concentrate in the aqueous phase where it affects negatively the efficiency of the gold stripping as shown by eq. 4.
It was found experimentally that air sparging is an effective way to remove
hydrocyanic acid from the strip liquors. The equipment used for the thiourea
stripping with air sparging is shown in Fig. 13. The sparging of air accomplishes both the continuous removal of HCN and the mixing of the two liquid
phases. On leaving the stripping chamber, the air stream is forced through two
traps filled with sodium hydroxide which capture the HCN and transform it
into NaCN for recycling.
Figure 14 shows the HCN evolution (measured with Draeger tubes) when a
sample of loaded organic was contacted with three different acid solutions by
means of air sparging. The air flow rate was set at about 0.5 Bed Volumes per
second. The results show that, despite the vigorous air sparging, HCN was
evolved slowly since it took between 1-2 h to eliminate it completely from the

AIR IN
AIR FLOW ~--~
~

-----~AIR OUT

O ORGANIC/AQUEOUS/AIRMIXTURE
O NaOH TRAPSFOR HCN
~VALVE
Fig. 13. Equipmentfor stripping goldwith acidic thiourea and air sparging.

150

P.A. RIVEROS

-~.200

i oooo 0.5
Hydrochloric Acid
~ n a ~ 1.0 NNSulphuric Acid
O G D D 1.0 N Sulphuric Acid +
0.5 M Thiourea

< 150
o
~ 100

o 50
z
0

60

120

180

TIME, m i n u t e s
Fig. 14. Concentration of hydrocyanic acid in the stripping chamber during the acid stripping.

~ 2000ooooo
: ~ - ~

Acid
washed
Organic
Untreated
Organic:

1500 I

lOO0

\\

500

-<
\

20

40

60

TIME, m i n u t e s
Fig. 15. The rate of gold stripping with acidic thiourea and air sparging.

stripping chamber. The elimination of HCN was much faster when thiourea
was added to the acid solution. This may be the result of a faster decomposition
of the cyanide complexes by the action of thiourea. In the absence of thiourea,
the evolution of HCN proceeds at a slower rate, regardless of the type and the
concentration of the acid.
It was found that, in the absence of thiourea, solutions of 0.5-2 N hydrochloric or sulphuric acid were inefficient for stripping gold, even when applying
air sparging. However, some of the less stable cyanide complexes were decomposed and this fact provided a practical way to remove selectively some of the

SOINENT EXTRACTIONOF GOLDFROM CYANIDE

151

impurities from the loaded organic. Washing with 1 N sulphuric acid was effective for removing nickel and zinc, but some small amounts of gold were also
stripped. On the other hand, washing with 1 N hydrochloric acid resulted in
the removal of nickel with no stripping of gold, but zinc also stayed in the
organic phase. The most satisfactory results were obtained with a mixture of
1 N H2SO4 and 0.05 N HC1, which removed most of the zinc and nickel without
stripping any gold.
As shown in Fig. 15, washing the organic solution with acid had an important
effect on the subsequent thiourea stripping of Aliquat 336. The stripping of
gold was much faster with the acid-washed organic than it was with the untreated organic. This is probably because a considerable amount of HCN is
evolved and removed during the acid wash. As a result, lesser amounts of HCN
are evolved during the stripping. This finding underlines the effect that the
concentration of aqueous HCN has on the efficiency of the gold stripping.
The stripping procedure was tested on several samples of loaded organic.
Two typical experiments are described below:

Experiment 1
A 50-ml sample of 10% Aliquat 336 solution, loaded with the Campbell Red
Lake solution in the continuous circuit, was put into the stripping chamber
(see Fig. 13 ). The air sparging was started and 25 ml of a mixture of I N H 2 S 0 4
and 0.05 N HC1 were added. After two hours, the HCN concentration in the
chamber, as measured with Draeger tubes, was within safe levels. The acid
solution was allowed to settle and removed from the stripping chamber. A solution containing 0.5 M thiourea and 1 N sulphuric acid was introduced into
TABLE 5
Stripping of 10% Aliquat 336 with 0.5 M thiourea and 1 N H2SO4
Solution

Initial
volume
(ml)

Concentrations
(mg l -~ )
Au

Acid wash
Strip liquor:
Fraction 1
Fraction 2
Fraction 3
Fraction 4
Fraction 5
Fraction 6
Loaded organic
Stripped organic

Cu

Zn

Ni

Fe

25

6297

578

20
20
20
20
20
20

3215
1783
575
215
68
22

110
5
0
0
0
0

418
265
180
140
99
74

858
363
6
0
0
0

0
0
0
0
0
0

50

2080
0

83
0

3860
218

578
0

0
0

152

P.A. RIVEROS

the chamber. After 10 min of mixing, the spent thiourea solution was removed
and a fresh aliquot of acid thiourea solution was added. The latter step was
repeated several times until no gold was left in the organic phase. The air
sparging was maintained constant during the experiment at a flow rate of 0.5
Bed Volumes per second. The analyses of the solutions are presented in Table
5.

Experiment 2
The stripping procedure was repeated with a 50-ml aliquot of 5% Aliquat
336, loaded with the Teck-Corona Hemlo solution in the continuous circuit.
The analysis of the solutions is presented in Table 6.
These results demonstrate that the stripping of gold from quaternary amines
with acidic thiourea and air sparging is quite effective. The organic solution
was completely depleted of gold after the stripping procedure. The acid wash
was effective in removing significant amounts of impurities such as zinc and
nickel. Therefore, the strip liquors, which on recycling could attain several
grams of gold per liter, are not excessively contaminated and should produce a
high-purity final product.
The recovery of gold from thiourea solutions has been studied before [17].
It is believed that gold could be readily recovered by electrowinning or precipitation. Due to the high concentrations of gold in the strip liquor the possible
losses of thiourea during the electrowinning or precipitation would be only a
minor factor on the overall economics of the process.
TABLE 6
Stripping of 5% Aliquat 336 with 0.5 M thiourea a n d 1 N H2SO4
Solution

Initial
volume
(ml)

Concentrations
(mg 1-1 )
Au

Cu

Zn

Ni

Fe

Acid wash
Strip liquor:
Fraction 1
Fraction 2
Fraction 3
Fraction 4
Fraction 5
Fraction 6

25

13

12

1615

20
20
20
20
20
20

5228
1192
160
24
4
2

110
5
0
0
0
0

6
8
6
7
6
7

17
1
0
0
0
0

0
0
0
0
0
0

Loaded organic
Stripped organic

50
-

2228
0

55
0

137
111

734
0

0
0

SOLVENT EXTRACTIONOF GOLDFROMCYANIDE

153

Incineration of the organic solvent

As shown above, gold loadings in the range of 2-3 g Au per liter of organic
solution can be readily obtained in a countercurrent operation. It is interesting
to note that the major component of the organic phase is the diluent, whose
volume concentration ranges from 80 to 97.5%. If this diluent was removed by
distillation, the residual extractant would have a high concentration of gold.
In Fig. 16 the isotherms of Fig. 1 have been modified to show the gold loadings
per volume of extractant. It can be seen that for the more dilute organic solutions, e.g. 2.5% and 5% Aliquat 336, the gold loading per volume of extractant
can reach very high values. The gold concentration in these cases suggests that
incineration may be a viable way to recover the contained gold.
Incineration is practiced occasionally to recover gold from activated carbon.
However, activated carbon burns slowly and at high temperatures, which requires the use of an additional fuel. Therefore, elution methods are preferred
for activated carbon. By contrast, quaternary amines, being liquid hydrocarbon compounds, burn readily at comparatively low temperatures. Since base
metals are unlikely to be reduced to the metallic state under these conditions,
the gold recovered by incineration would be of high purity.
Several samples of loaded organic were subjected to distillation and incineration to demonstrate the technical feasibility of the procedure. Solvesso 150
distilled readily below 100 C under vacuum and the separation from Aliquat
336 was complete. The liquid residue (loaded Aliquat 336 ) burned gently without the need for additional fuel. No losses of gold were detected during the
~60.
ooooo 5~ Aliquat 336/Campbell
ooooo
10~ Aliquat 336/Campbell
~ a
2 0 ~ Aliquat 336/Campbell
$0 2.5~ Aliquat 336//Hemlo
5~ Adogen 481/Campbell
*_**** 5~ Adogen 483/Carnpbel]

4o

~" 20

"tJ

2
o

4,

&

~'o

1~2

1'4

A q u e o u s C o n c e n t r a t i o n of Gold, m g / L
Fig. 16. Equilibrium isotherms modified to show the gold loading per volume of extractant.

154

P.A. RIVEROS

procedure. X-ray diffraction and scanning electron microscopy analyses of the

incineration solid residue indicated the presence of metallic gold, nickel oxide,
zinc oxide, and silica. Hot dilute nitric acid removed readily the zinc and the
nickel from the solid residue. The remainder was melted in a furnace at 1100 C
to produce clean round particles of high-purity gold.
Although replacing the burned extractant on a continuous basis may appear
expensive in principle, the estimated reagent cost would be within the acceptable limits established by a recent study [18]. Furthermore, the incineration
process offers additional advantages, such as: (1) elimination of electrowinning or precipitation, (2) faster gold output, leading to a reduction of the gold
inventory, (3) the production of high-purity gold, requiring no further refining
steps. One possible way to reduce the reagent costs would be to use quaternary
amines of a technical grade. Whether these technical grade quaternary amines
would exhibit the same chemical and physical characteristics would have to be
evaluated with additional testwork.

CONCLUSIONS

The solvent extraction of gold from cyanide media with quaternary amines,
such as Aliquat 336, is a feasible and advantageous process. Commercial quaternary amines present several favourable characteristics, including good selectivity for gold, fast kinetics, high loading capacity, low water solubility, and
good phase separation.
Compared to conventional technology, solvent extraction offers a significant
reduction of the gold inventory, elimination or simplication of the refining
steps, and simpler transportation requirements, all of which would lead to important economical savings. These attractive features should encourage the
current attempts to develop a solvent-in-pulp process, which would have a
great impact on the extractive metallurgy of gold.
In addition, solvent extraction could be used in those operations that produce clarified solutions, such as heap leaching. This increasingly popular technique would benefit from the reduction in solution volume resulting from the
faster kinetics of solvent extraction.
The stripping of gold from quaternary amines can be readily done with acidic
solutions of thiourea and air sparging. Because of their fast kinetics and high
capacity, the stripping of quaternary amines can done in a small circuit, which
facilitates the handling of the generated HCN.
In those cases where high loadings of gold are obtained, the recovery of gold
by distilling the diluent and incinerating the residue appears attractive. An
aspect that should be explored is the use of technical grade quaternary amines
with the purpose of lowering the reagent cost.

SOINENTEXTRACTIONOFGOLDFROMCYANIDE

155

ACKNOWLEDGEMENTS
T h e a u t h o r is grateful to the N a t u r a l Sciences a n d E n g i n e e r i n g R e s e a r c h
Council of C a n a d a for p r o v i d i n g financial support. T h a n k s are e x t e n d e d to
Mr. G. R i t c e y for m a n y valuable suggestions a n d c o m m e n t s . T h e help received
f r o m Dr. R. M o l n a r , Mr. X. G a o a n d Mr. P. P r u d ' h o m m e d u r i n g t h e developm e n t of the project is gratefully acknowledged. I w o u l d also like to t h a n k Dr.
D. M u i r for several useful discussions.

REFERENCES
1 Ritcey, G.M., Molnar, R., Riveros, P., Wong, E.W., He, P.J., Gao, X., Prud'homme, P. and
Koegler, C., 1988. Solvent extraction of gold from cyanide leach slurries. In: Int. Solvent
Extraction Conf. {ISEC'88), July 1988, Moscow.
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MSL 87-140 (TR), October 1987.
3 Miller, J.D., Wan, R.Y., Mooiman, M.B. and Sibrell, P.L., 1987. Selective solvation extraction of gold from alkaline cyanide solution by alkyl phosphorous esters. Sep. Sci. Technol.,
22(2,3): 487-502.
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solution using modified amines. Hydrometallurgy, 16: 245-261.
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from cyanide solutions with quaternary ammonium compounds. Tsvet. Metal., 39: 19-23.
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alkaline solutions. In: Proc. Int. Solvent Extraction Conf. (ISEC'74). Soc. Chem. Ind., London, pp. 2715-2732.
8 Osseo-Assare, K., Xue, T. and Ciminelli, S.T., 1984. Solution chemistry of cyanide systems.
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ion exchangers. Anal. Chim. Acta, 53: 267-275.
11 Fleming, C.A. and Cromberge, G., 1984. The extraction of gold from cyanide solutions by
strong- and weak-base resins. J.S. Afr. Inst. Min. Metall., 84(5): 125-137.
12 Mooiman, M.B., Miller, J.D., Hiskey, J.B. and Hendriksz, A.R., 1984. Comparison of process
alternatives for gold recovery from alkaline cyanide solutions, In: J.B. Hiskey (Editor), Heap
and Dump Leaching Practice. SME/AIME, Salt Lake City, Utah, pp. 93-108.
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Vol. II, Munich, 11-16 Sept., 1986.
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Thesis. Univ. Utah, Dep. Metall. Eng.
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16

P.A.R1VEROS

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