~::'t .
The elution of gold from activated
'I~
",~'
. .
~
Synopsis
one qfthe main bottle-
necks in the carbon-in-
pulp process for the
recovery qf gold is the
eludon procedure, which
typicallY requires the
headng qf causdc
cyanide eluants to high
temperatures for 16 to
24 hours. The present
work demonstrates that
sodium sulphide soludon
as an alternadve eluant
can dfect complete
eludon in about 4 hours
at ambient temperatures.
Eludon dfidendes qf
around 100 per cent
were obtained in 4 hours
with a single pass qf
eluant containing
0,2 M Na2S and
0,4 NaOH~ut 10
bed-volumes qf eluant
The inidal rate was slow
over thejirst hour qf
eludon, probablY because
the acdvated carbon
catalYsed the oxidadon
qf sulphide to
polYsulphide. Eludon
dfidendes qf around
100 per cent were also
obtained in less than
4 hours during the batch
eludon qf carbon at
liquid-to-solid rados qf
about 100. Lowerliquid-
to-solid rados resulted in
the re-adsorpdon qfgold,
probablY owing to the
oxidadon qf sulphide to
polYsulphide, with the
resultantfonnadon qf
gold complexes that were
eluted less readilY.
. Mintek,PrivateBag
X3015, Randhurg
2125.
@ the experiment by X-ray fluorescence (XRF)
The South 4frican
Institute qf Mining and
Metallurgy, 1994. SA
ISSN 0038-223X/3.00
+ 0.00. Paper received,
Sep. 1993; revised paper
received, Mar. 1994.
The Joumal of The South African Institute of Mining and Metallurgy
.
carbon at room temperature using
sulphide solutions
by M.D. Adams*
Introduction Early work by Feldtman7 and Gross and
Scott8 indicated the potential of using sodium
The carbon-in-pulp (CIP) process is the most
sulphide for desorbing gold. In 1950, Zadra9, in
widely used method for the recovery of gold in
a pilot-plant study, demonstrated the technical
new plants. However, despite the commercial
and commercial viability of sodium sulphide
success of the process as a whole, there remains
solutions for the elution of gold at ambient
much scope for improvement. One such area is
temperatures. He showed the carbon to be eluted
the elution of gold cyanide from loaded carbon. In
efficiently in 4 hours at 25°C, and both the
the Zadra process!, a hot solution of caustic
carbon and the eluate were found to be re-
cyanide (typically comprising about 0,5 per cent
usable. There are several reasons why this
NaCN and 1,0 to 2,0 per cent NaOH) is
process is not in use today. One is that adsorbed
recirculated through an elution column and
silver and base metals are not eluted, being
several electrowinning cells in, series. More recent
immobilized as insoluble silver and base-metal
modifications to this processz employ pressurized
sulphides. However, this may not be a great
vessels or steam heat-exchangers to produce the
problem, since an equilibrium situation may be
higher column temperatures (about 130°C)
reached. The other problem is that the eluted
required for more efficient elution. Between 16
gold is sometimes re-adsorbed onto the carbon,
and 24 hours are typically required before an
and it is this aspect in particular that this paper
acceptable degree of elution is attained, and this
addresses.
not only represents a bottleneck in the CIP
process, but also involves a large consumption of
energy and chemicals (cyanide has been shown Experimental Procedure
to decompose rapidly under these conditions3). It
Approximately 1,1 kg of activated carbon (Le
is for these reasons that the recent trend towards
Carbone G210 AS) was screened to a particle
low-cyanide elution has arisen.
size of +1,16-2,07 mm and thoroughly washed
A popular alternative to the Zadra process
with de-ionized water to remove fines and
was developed by the Anglo American Research
soluble impurities. It was then contacted
Laboratories (AARL)4, in which pre-treatment of
overnight with 1,44 g of KAu(CN)z in approxi-
the carbon with a hot solution of caustic cyanide
mately 1 litre of de-ionized water to achieve the
is followed by elution with hot de-ionized water.
required gold loading.
However, the total time required for an
acceptable degree of elution is similar to that for
the Zadra process.
Recent efforts5 have been directed towards Batch Elution Experiments
the development of elution procedures that
In each experiment, sulphide eluant was freshly
employ organic solvents such as acetonitrile or
made up by the use of NazS'9HzO. Typically,S g
ethanol. which have been shown to result in
of loaded carbon was contacted with the
efficient elution in about 8 hours at temperatures
appropriate volume of solution in a round-
between 25 and 70°C. The Micron distillation
bottomed magnetically stirred flask with reflux
procedure6 involves the refluxing and recycling
condenser for 48 hours. The solution was
of hot solvent vapours and condensates through
a bed of carbon that acts as a fractionating
column. The solvent elution procedures suffer
sampled periodically and analysed for gold by
atomic-absorption spectrophotometry (AAS).
The carbon was assayed for gold at the end of
from the disadvantage that the solvent vapours
are invariably toxic, and may also represent a
analysis.
fire hazard. The mining community is therefore
reluctant to employ these procedures on a large
scale.
AUGUST 1994 187 ....
Elution of gold using sulphide solutions
Improved rates Q/ Single-pass Elution Experiments Distribution diagrams for the species were
elution were obtained at prepared fromcalculationsgenerated by the
higher sulphide concen- The procedure was identical to that described by
HALTAFALL programme14. The species distri-
trations and pH values Adams and Nicopo in a study of the elution of
greater than about 13. bution for a 0,1 M Na2S solution is shown in
gold from activated carbon using cyanide and
Higher temperatures Figure 1. The predominant species are H,S (aq)
increased the initial hydroxide solutions. Fresh eluant was pumped
at pH valuesbelow7 and HS- (aq) at pH values
elution rate, but lowered into a reactor similar to that used for the batch
above 7. It is only at pH values greater than 13
the overall extraction experiments, which contained a fIXed mass of
~dency, probablY that a small fraction of S'- (aq) becomes evident.
carbon and volume of solutions. The eluate was
because Q/the The situation is somewhat similar in the case
deposition Q/ elemental removed by pumping from the top of the solution
of a 0,1 M Na,S2 solution, as shown in Figure 2.
gold on the carbon. at the same rate. The eluate fractions were
Smallfractions of S~- (aq) species become
Variation Q/the ionic collected and analysed for gold by MS. In some
strength by the addition evident only at pH values greater than 13. It is
instances, the DV-VIS spectra of eluate fractions
Q/ NaCl had no dfect on interesting to note that, at pH 14, the fractions of
were measured with a Beckman MIV DV-visible
the elution, which S~-speciesincrease in the order
co'lfirms that the elution
spectrophotometer. Unless specified otherwise,
mechanism in the case the conditions for the elution were as follows: S2-
< S;- < S~-< S~-< S~-« HS-.
Q/ sulphide is different Temperature 25 :!: 3°C
from that when cyanide The protonated HS4, H2S4'HSs, and H2Ss
Mass of carbon 26,7 g (75 ml wet-settled)
or I1)1droxide is used as speciesare present to only a negligible extent.
the eluant. Flowrate 200 mllh
When the solution under consideration
It is proposed that ~~~ ~2~
the elution Q/gold by
contains 0,2 M Na2Swith 0,6 M S, Le.with a
sulphide solutions Silver-stripping Experiments stoichiometry equivalent to Na2S4'the S~-species
proceeds by means Q/ an begin to play a more predominant role, as shown
initial step that involves A batch of activated carbon was loaded to in Figure3. Above a pH valueof 12, these
the reaction Q/ 1000 g/t of gold and 200 g/t of silver by a species are present in significant amounts, with
polYsulphide ions with
the adsorbed
method similar to that already described. The fractions increasing in the order
aurocyanide spedes, carbon then underwent a batch elution by the
S2- < S~-< S~- < S~- < S;- < HS-.
forming AuCN on the use of 0,2 M Na2S at 25°C. After 6 hours, the
carbon and thiocyanate carbon was filtered off and analysed for silver by At a pH value of 14, the S~-species constitute
in solution. This step is
followed by the
XRFanalysis. about half of the total sulphide species in
formation Q/poorlY solution.
adsorbed complexes Results and Discussion
with sulphide ions, such
as AUS32- The presence Batch Elution with Sulphide Solutions
Speciation Calculations for Po/ysulphide
Q/polY sulphides,
whether generated in Solutions Effect of Polysulphides at Low Liquid-to-
situ by the catalYtic solid Ratios
oxidation dfect Q/ The relevant reactions and stability constants for
activated carbon or by sulphides and polysulphides in aqueous solution Zadra9 has reported that, during an elutionwith
the addition Q/ are listed in Table I. These 'best' values were sodium sulphide, gold was initially re-adsorbed,
elemental sulphur, selected from the most recent literature on the followedby a slow release of gold from the
reduces the elution rate subject1H3. No stability constants for the S~- and
and ~dency drama- carbon. No explanation for this behaviour was
ticallY. This is probablY higher species were available, and these are given. In the present work, batch elution
due to theformation Q/ therefore not included. experiments were performed with
complexes such as AUS"
and AUS:;, which have a (a) a fresh solution of sodium sulphide made
high adsorption qlJlnity. up from Na2S.9H2O
(b) a polysulphidesolution of average Na2S2
composition, made up with a stoichio-
metric mixture of Na2S.9Hp and
Stability constants for polysulphides in aqueous solution elemental sulphur.
Figure 4 shows that a trend similar to that
Reaction reported by Zadra occurred in the batch elution
of 5 g of carbon loaded to 12 800 g/t of gold
2W (aq) + S2- (aq) H H2S (aq) using 50 ml of solution. The effect waseven
W (aq) + S2- (aq) H HS-(aq)
more enhanced when a polysulphide solution of
S2- (aq) + S H s~- (aq)
S2- (aq) + 2S H s;- (aq)
average 0,1 M Na2S2 compositionwas used.
S2- (aq) + 3S H s~- (aq)
S2- (aq) + 4S H s;- (aq)
W (aq) + s~- (aq) H HS~ (aq)
W (aq) + HS:; (aq) H H2S4 (aq)
W (aq) + s;- (aq) H HSs (aq)
W (aq) + HSs (aq) H H2S5 (aq)
W (aq) +OW(aq) H H2O

~ 188 AUGUST 1 994 The Joumal of The South African Institute of Mining and Metallurgy
Elution of gold using sulphide solutions
Fraction of total soluble sulphide Effect of Liquid-ta-solid Ratio
1
Further light may be shed on the re-adsorption
phenomenon by consideration of the effect of the
liquid-to-solid ratio on the batch elution of gold
from activated carbon using fresh sulphide
0,8 solutions. The results in Figures 5 and 6 show
that re-adsorption occurs when the liquid-to-
0,01 solid ratio is low, and not when the solution
volume exceeds about 200 ml for a 5 g batch of
0,008
0,6 loaded carbon.
0,006
Effect of Na2S Concentration
0,004
The effect of Na2S concentration on the batch
elution of gold from activated carbon at high
0,4 2- liquid-to-solid ratios is shown in Figure 7.
qo 11 12 13 14 Complete elution was achieved in about 1 hour
pH from a 1,0 M Na2S solution, and in 36 hours
from a 0,1 M Na2S solution. No re-adsorption
0,2 effect was evident under these conditions.
Figure 7 shows that re-adsorption occurred
after 36 hours when 0,01 Na2Swas used, which
52- suggests that the re-adsorption phenomenon is
0
\ related to the ratio of activated carbon to
0 2 4 6 8 10 12 14 sulphide concentration in the solution, as well as
pH to the liquid-to-solid ratio. The fact that the pH
shifts slightly is probably also a factor. It is
Figure 1-Distribution of sulphide species in the S2- -H2O system with variation in pH value
evident that re-adsorption is associated with
(0,1 MS" small amounts of sulphide present in relation to
the amount of gold in the system. No elution
was obtained in the case of 0,001 M Na2S
solution. Possibly a greater degree of oxidation
of sulphide to polysulphide occurs when the
initial sulphide concentration is low:
Fraction of total soluble sulphide
1 2 HS- (aq) + 1/2O2H H2O+ S~-(aq). [1]
15
This type of reaction occurs slowly when
H5 alkali sulphide solution stands in air. Activated
carbon is known16,17to catalyse the reaction,
0,8 with the ultimate formation of products such as
elemental sulphur and S20;~ This is in direct
0,01 agreement with the observations made during
5'. the present experiments: that the initially
0,008
0,6 S'; colourless Na2S solutions rapidly turned yellow
0,008 in colour owing to the formation of intermediate
polysulphides18 (S~-to S~- are yellow in colour,
0,004
S~- to S~- are orange, and S~- to S~- are red). The
0,4
0,002 yellow colour tended to disappear after about 1
to 2 hours of reaction, which suggests that either
~o 11 12 the carbon eventually reduces the polysulphide
pH
back to sulphide, or that elemental sulphur was
deposited on the carbon surface in a secondary
0,2
reaction, e.g.
Activated
5~- S~- H Sads + S2- (aq). [2]
\ carbon
° 2 4 6 8 10 12 14
° pH

Figure 2-Distribution of polysulphide species in the s-s2--H2O system with variation in pH

value (0,1 M S~-)

The Journal of The South African Institute of Mining and Metallurgy AUGUST 1994 189 ~
Elution of gold using sulphide solutions
Fraction of total soluble sulphide These reactions are substantiated by
1 measurements of the visible spectra of various
solutions. Giggenbach19 measured such spectra
and assigned bands to individual polysulphides,
as detailed in Table Il.
0,8
Table 11
Visible absorbance bands due to
polysulphide ions in aqueous solution
0,6 (after Giggenbach 19)

Wavelength, Ilm

229
0,4 250
358
417; 303
368; 303
0,2 375; 299

The peak maxima of the various solutions

measured in the present study are shown in
° 2 4 6 8 10 12
° pH Table Ill. Large amounts of polysulphides were
found to be present in Na2S + S mixtures, partic-
ularly after being boiled. No evidence for
Figure 3-Distribution of polysulphide species in the S- S2--H2O system with variation in pH
polysulphide species was found in fresh 0,1 M
value (0,2 M S;-J
Na2S solution; however, some polysulphides,
mainly S~~were detected in the solution after it
had been exposed to the atmosphere for 1 week.
400
Polysulphides were detected in 0,1 M Na2S
INB~1M NB~1MI solutions that had been contacted with activated
carbon for periods of up to 24 hours. However,
no polysulphides were found to be present after
96 hours.
300 In the eluates of batch sulphide elutions with
and without gold present, polysulphides were
0::: detected after 2 hours, but not at 24 hours and
~
E 48 hours, which is consistent with reactions [1]
15 and [2].
'5200 Despite the re-adsorption that occurs under
~ certain conditions, a 95 per cent elution of gold
.5
"Cl from carbon at room temperature in less than
"0
Cl 1 hour in a batch system is a significant
improvement on that achieved under comparable
conditions with the conventional caustic cyanide
100
\ /
eluant.
. //
\ /
/
\
\ ... //
0
0 10 20 30 40 50
rlmB, h

Figure 4-Effect of polysulphides on the batch elution of gold from activated carbon at Iow
liquid-to-solid ratios

~ 190 AUGUST 1994 The Joumal of The South Afncan Institute of Mining and Metallurgy
Elution of gold using sulphide solutions
60 [Na~J
.
L:S 40
100
-- -, --- -- - - - "~:" ;
1,0 M
(pH 13,51
L:S 10
. ,
,.;' .
50 0,1 M
L:S 5 ,
... ;
(pH 13,01
.
80 ,
,,
40
. 0,01 M
(pH12.51
'#. '#.
. ...
>.
u 0,001 M
c ~ 60 (pH 11,01
ell ell
'u 30 0
'u
=CII
c
!i
0
'S ~. .~
iii ..~- ----- IiJ
40
20 /
;'
I
/
_/-~
/ "" --~- \
\
20 \
10 \
\
\
\
\
,
\
\

0 ------- 0
0 2 4 24 48
0 2 4 24 48
Time,h Time, h

Figure 5-Effect of liquid-ta-solid ratio on the batch elution of gold from Figure 7-Effect of Na2S concentration on the batch elution of gold from
activated carbon at high initial gold loading activated carbon

60
.
L:S 40
Effect of pH Value
,, " L:S 10
.
60 / The form in which the sulphide is present

.'
/
,/ L:S £> depends on the pH value of the solution, as
...
I shown in Figure 1. The free S2-species is present
I
I to any significant extent only at values above
I
40 I 13; the HS- species predominates between pH
I
~ I values of 6 and 13; and the H2Sspecies predom-
~ I
I
inates at pH values below 6. The effect of eluant
i I
'u 30 I pH on the efficiency of gold elution is shown in
~c I
I
I
Figure 8. A high degree of elution is achieved
I
only at pH values above 13, which suggests that
~
iD I
I
I

it is the free S2-ion that reacts most readily with

20 the adsorbed aurocyanide species. This result is
in contrast to those obtained by Green et al. 20 on
a different system-the elution using thiourea of
10 gold that had been adsorbed as aurocyanide onto
strong-base ion-exchange resins. In that work2O,
it was found that acidic solutions were necessary
to achieve acceptable elution efficiencies. In that
0 ------
0 2 4 24 48 instance, acid destabilization of the Au(Cn);
Tlme,h complex is necessary in order to replace the
strongly held cyanide ligand (log ~2 Au(Cn); =
39,7) with the less strongly held thiourea ligand
(log ~2 Au(SC(NH2Jzn = 23,3):

Figure 6-Effect of liquid-ta-solid ratio on the batch elution of gold from activated carbon
at Iow initial gold loading

The Journal of The South African Institute of Mining and Metallurgy AUGUST 1994 191 ~
 Elution of gold using sulphide solutions

Table 11/
Visible spectral data for sulphide and polysulphide solutions

vw

.v-very strong, s-strong, w-weak, vw-very weak

~---. Au(CN)2 + W + H AuCN + HCN [3]

pH 14
100
~fr
I~"--'" . AuCn + SC (NH2h H NCAuSC(NH2h [4]
-~--- / pH 13 2NCAuSC(NH2h H Au(CN)2 + AU(SC(NH2h);. [5]
-~-
-~
//
/
/
. The stability constants for gold complexes
I with several sulphide ligands were measured,
/
I pH 9
80 .I
.I A and these complexes were found to have a much
.I
I higher degree of stability than the gold thiourea
/
/
pH 5 complex21 (Table IV), which is consistent with
.I
0 the notion that gold sulphides may form in
*'.;. sulphide eluate solutions.
u Seward21 and Renders and Seward22 have
c 60
GI demonstrated the predominance of the Au(SH);
'u complex between pH 4 and 10, and the
!E increasing predominance of species such as
GI
C Au2S;at pH values greater than 10 (Figure 9
0
and Table IV). However, this is not the only
'5 40 possible species present in the alkaline region
W
since the data were scattered and somewhat
ambiguous in that region21. Other complexes that
may be present under alkaline conditions21
include Au2S~~ AU2SHS32-,AUS32-,Au2(SHjzS2-,
20 AuSHS2-, AU2(SH-3, AU2SHS-. and AuS-. The
presence of multi-charged gold complexes such
as AuS~- in alkaline sulphide solutions is
therefore consistent with the present experi-
_A ,
---- -- - - - - - - 0" ,.A. mental results.
---;:,--- It is proposed that the elution of gold by
0
0 2 4 24 48 sulphide solutions proceeds by means of an
Time, h initial step that involves the polysulphide ion,
expressed as S~- for clarity:

Au(CN); + S~- H AuCN + SCW + S2-. [6]

Figure 8-Effect of pH on the batch elution of gold from activated carbon

~ 192 AUGUST 1994 The Journal of The South African Institute of Mining and Metallurgy
Elution of gold using sulphide solutions
Acknowledgements
Table IV
This paper is published by
permission of Mintek. The Stability constants for several Au(l) complexes at 25°C (after Seward2')
excellent technical assistance
of Mr C. Tolken, Mrs O.L. Complex log ~
Wellington, and Ms K.T.
Wintle is gratefully 41,1
AU2S~-
acknowledged. 30,1
Au(HS)2
AuHSo 24.5
References AU(S20:J~- 26,0
AuCH2N(SNH2)~ 22.2
1. ZADRA, J.B.. ENGEl,A.L., and HEINEN,
H.J. A process for recovering gold
and silver from activated carbon by

leaching and electrolysis.

Washington, US Bureau of Mines,
R/4843.1952.32pp.

log mAu, t The type of re-arrangement reaction,

-3 represented by [7] and [8], between gold
cyanide and another ligand has been
I demonstrated previously for thiosulphate23:
I
-4
AuCN + S205- H NCAuS205- [9]
ms,t = 0.01 2 NCAuS205- H AU(S203)~- + Au(CN)z [10]
-5 25 °C
and for thiols (RS-)24:

Au(CN)z + RSH H RSAuCW [11]

-6
2 RSAuCN- H Au(RS)z + Au(CN)z. [12]

-7 Effect of Initial Gold Loading on Carbon

The initial gold loading on carbon does not have
-8 a great effect on the elution efficiency, as shown
in Figure 10. However, high gold loadings of
about 10 000 to 50 000 g/t depress the elution
-9 slightly when compared with an initial loading of
2 4 6
1000 g/t. This is consistent with the results
pH shown in Figures 5 and 6, and confirms that
high molar ratios of gold to sulphide depress the
Figure 9- The solubility of Au2S at 25'C as a function of pH (after Renders and Seward22)
elution of gold.
Effect of Polysulphides at High Liquid-ta-solid
2. BAILEY,
P.R. Application of activated This mechanism is substantiated by evidence Ratios
carbon of gold recovery. The
from current work for the presence of AuCN on
extractive metallurgy 91 gold in The effect of polysulphides on the elution
South Africa. Stanley, G.G. (ed.). carbons that have been eluted by sulphide efficiency at high gold loadings (12800 g/t) and
johannesburg, South African
solutions, and by the presence of SCNin the
Institute of Mining and Metaliurgy, relatively low liquid-to-solid ratios (about 10)
1978. pp. 379-614. eluates as measured by ion chromatography.
are shown in Figure 4. A comparison of these
3. ADAMS,M.D. The chemistry of The elution behaviour of gold depends on
cyanide in the extraction of gold. H. results with those obtained at low gold loadings
the relative concentrations of sulphide and
Mechanisms of cyanide loss in the (1245 g/t) and high liquid-to-solid ratios (about
carbon-in-pulp process.;'5.IJ'r. polysulphide ions in solution. In the presence of
ll1$t.MinMetall.,vo!.90.1990. 100) is interesting, as shown in Figure 11. There
pp. 67-73. a small amount of polysulphide, it is postulated
is now no evidence of re-adsorption from
4. DAVIDSON, R.J., and DUNcANsoN, D. that gold is converted into a multi-charged anion 0,1 M Na2S solution with no added polysul-
The elution of gold from activated that has little affinity for activated carbon, and is
carbon using deionized water. Ibid., phides. The re-adsorption effect in the presence
vo!. 77. 1977. pp. 254-261.
eluted:
of polysulphides is still evident at high liquid-to-
5. MulR,D.M. HINCHUfF<, W.D.,
TSUCHIDA,N., and RUANE,M. SOlvent
2 AuCN + 2 S2- H AuS~- + Au(CN)z. [7] solid ratios but is much less marked, with the re-
elution of gold from CIP carbon. adsorption equilibrium predominating only after
Hydrometallurgy, vo!. 14, no. 1. When a large amount polysulphide is
48 hours, as compared with 1 hour in the low
1985. pp. 47-65. present, the gold is proposed to be converted into
6. MUlR, D.M. HINCHUffE, W.D., and
liquid-to-solid experiment.
GIDfAN, A. Elution of gold from car-
a singly charged anion that has a relatively high
bon by the Micron solvent distil- affinity for activated carbon, and is re-adsorbed:
lation procedure. Hydrometallurgy,
vo!. 14.1985. pp. 151-169. AuCN+ 2 S~- H AuSz + SCW + S2-. [8]
7. FELDTMAN,W.R. The precipitating
action of carbon in contact with
auriferous cyanide solutions. TriJllS.
ll1$m. Min. Metal/., vo!. 24.1914.
pp. 329-371.

The Journal of The South African Institute of Mining and Metallurgy AUGUST 1994 193 ....
Elution of gold using sulphide solutions

Initial Au on Effect of Na~ Concentration

carbon, g/t
As observed previously, the rate of elution is
,..---. 49000
100 ,, . enhanced at higher sulphide concentrations. At
lower sulphide concentrations, the elution is very
,,~ 9400
,
,, , /',...
-8
I
. slow, as shown in Figure 12. After a time that is
approximately inversely proportional to the Na2S
, " /M
" / 1300 concentration, there is a sudden and dramatic
80 A increase in the elution rate. For example, with
",~~/~ ,/
, 0,05 M Na2S, this increase occurs after 2,3
A , ~~
~
hours; with 0,1 M Na2S, after 1,2 hours; and
~ ,
,/ " with 0,2 M Na2S, after 0,5 hours. The batch
elution experiments showed that, at Iow
u>- 60 ---8'
c sulphide-to-gold ratios, there is a predominance
.1 of polysulphide in solution, and the re-
u
i adsorption equilibrium [9] predominates. When

s
'5
40
iD
20
0 are associated with re-adsorption effects. Eluants
0 2
Figure 10-Effect of initial gold loading
8. GROSS,J., and Scorr, j.W. Precipita-
tion of gold and silver from cyanide
soiution on charcoal. Washington,
US Bureau of Miues, Terhnica/
Paper 378. 1927. 78 pp.
9. ZADRA, j.B. A process for the
recovery of goid from activated
carbon by ieaching and eiectrolysis.
Washiugton, US Bureau of Mines,
R14fJ72.1950.47pp.
10. ADAMS, M.D., and NICOl, M.J. The
kinetics of elution of goid from acti-
vatedcarbon. Gdd100. Proceedings
0/ the International (()1J/erence on
Go/d. Johannesburg, South African
iustitute of Miniug and Metallurgy,
1986. vol. 2, pp. 111-121.
11. RAMACHANDRA,RAO, S., and HEPlER,
C.G. Equilibrium constants and
thermodynamics of ionization
aqueous hydrogen suiphide.
/(ydrometa//urgy, vol. 2. 1978.
pp. 293-299.
12. LICHT,S., FOROUZAN,F., and LoNGO,
K. Differential densometric analysis
of equilibria in highiy concentrated
media: determination of the
aqueous second acid dissociation
constant ofH,S. Anal. chem., vol.
62.1990. pp. 1356-1360.
13. SIllEN, LG., and MARTEIL, A.E.
(eds.).StabiliryronstanlS. London,
The Chemical Society, 1964.
4 24 48
Time, h
on the batch elution of gold from activated
There is very little information available
regarding the complexes that are formed
between gold and polysulphide in aqueous
solution, although polysulphides have been
shown25 to leach gold from the arsenical stibnite
concentrate. Mellor26 states that the solubility of
gold in polysulphide solution is due to the
formation of AuS;3and AuS2 species. The
predominance of species like these in the early
stages of elution, where the S~- polysulphide
species were found to be present, would account
for the re-adsorption phenomenon mentioned
earlier, since these singly negatively charged
of
complexes are likely to have a high affinity for
activated carbon27.
Single-pass Elution of Gold Cyanide with
Sodium Sulphides
The batch experiments that were discussed in
the previous section may be useful in the
interpretation of some of the effects that were
observed in the single-pass elution experiments.
the polysulphide concentration has been
sufficiently lowered by adsorption onto the
activated carbon, reaction [2], there is a
significant amount of sulphide ion in solution,
and the elution equilibrium, reactions [7] and
[8], predominates. The application ofuv-visible
spectrophotometry to the eluates revealed the
presence of polysulphides (absorbance at
295 nm) in regions of high elution rate. These
results are consistent with the batch results, and
corroborate the hypothesis that polysulphides
containing 0,4 M Na2S or higher were found to
result in the elution of about 98 per cent of the
gold from the carbon in about 4 hours at these
flowrates.
Adams and Nicopo, using an identical experi-
mental arrangement with cyanide and hydroxide
solutions, found the kinetics of elution to be first
carbon
order and to be described by the rate equation
-dcldt=k(C-K5), [13]
where C and S are the concentrations of gold on
the carbon and in solution, respectively, and k
and K are constants. The incorporation of this
equation in the mass balance yields the relation
InC=lnCo-k't, [14]
where Cois the initial concentration of gold on
the carbon, t is the time from the start of elution,
and k' depends on the experimental conditions
and diffusion coefficients.
Whereas data from the equivalent cyanide
and hydroxide elutions yielded linear relations
when In Cwas plotted against t, this was not the
case for the sulphide elutions, as shown in
Figure 13. The initial region with the slower rate
corresponds to the region where polysulphides
were detected in the eluates. This results in a
delayed onset of elution.

~ 194 AUGUST 1994 The Joumal of The South African Institute of Mining and Metallurgy
Elution of gold using sulphide solutions
100
80
'#.
>-
u has little affinity for carbon23,24.
C 60
41
'u
!E
41
C --
0 of elution is enhanced at higher temperatures.
.~
40
w \
20
0 enhanced rates of elution, as shown in
0 2
Figure 11-Effect of polysulphides
high liquid-to-solid ratios
14. INGffi,N., KAKOLOWlcz,W., SILLEN,
LG., and WARNQVlST,B. High-speed
computers as a supplement to
graphical methods. V. Haltafall, a
general program for calculating
composition of equilibrium mix-
tures. Talanta, vo1. 14. 1967.
pp. 1261-1286.
15. REMv, H., and ANDERSON,).5.
Treatise on inorganic chemistry.
Amsterdam, Elsevier, 1956. vo1. 1,
p.738.
16. MORI, T., TAKEUCH',5., and MATSUDA,
S. Oxidation of sulphide ion by
molecular oxygen in the presenCe of
a water -repeDent catalyst. Nippon
Kugaku Kaishi, 1989. pp. 204-208.
(ChemAbstr., no. 110, 199893m).
17. HAVA, S. and ONO,T. The hnproved
white liquor oxidation process with
the new catalyst. Kami Fa Gikyosh(
vo1. 42, no. 1. 1988. pp. 46-51.
(ChemAbstr, no. 108, 152387t).
18. THORNE,D.L.c., and RoBERTS,E.R.
Inorganic chemistry. Edinburgh,
Oliver and Boyd, 1954. p. 565.
19. GIGGENBACH,W.Opticalspectraand
equilibrium distribution of polysul-
phide ions in aqueous solution at
2'.lnorg. Chem., vo1.11, no. 6.
1972. pp. 1201-1207.
The Journal of The South African Institute of Mining and Metaliurgy
The results in Figure 15 show that the ionic
/
JI- - --e
~ strength had a negligible effect on the elution
~
/
/
with sulphide solution; so, the simple equation
/
fI [15] does not hold in this case. Owing to the
/
/'
very stable gold sulphide complexes that form in
/
/ aqueous solution (Table I), and the tendency22 of
/
/
thiolligands for the displacement of cyanide
. /
/
/
/
from Au(CN)2 , it is suggested that the
mechanism of sulphide elution involves a similar
. type of ligand displacement reaction, with the
formation of a multi-charged gold complex that
Effect of Temperature
The results in Figure 16 show that the initial rate
8\ \
\
However, increasing amounts of adsorbed gold
\
\
\ are presumably deposited as an insoluble form,
\
\ such as Auo, resulting in the plateau effect in the
\
\ high-temperature curves in Figure 16. This
'8 premise could not be confirmed by XRD analysis
owing to the low gold loading that was present.
Effect of Other Anions
The addition of sulphite and, to a greater extent,
thiosulphate ions to the eluant results in
4 24 48 Figure 17. These ions may assist by reducing
Time,h any polysulphides back to sulphide ion.
Figure 17 also shows the slight depressing effect
of 0,2 M S, and the dramatic effect when 0,6 M S
is added to the eluant, which virtually completely
eliminated the elution. The 0,2 M Na2S
conditions are equivalent to the 0,1 M S~-
on the batch elution of gold from activated carbon at conditions used in the species distribution
diagram in Figure 2. At pH 13, there are
substantial concentrations of polysulphides
(comparable with the concentration of S2-),
Effect of NaOH Concentration which would result in a depression of the elution
kinetics. This would also be affected by the
The pH value of a 0,2 M Na2S solution is approx-
adsorption of polysulphides via reaction [2].
the imately 13. The addition of NaOH causes a shift
In the case of 0,6 M S, the conditions are
to a higher pH region, where the fraction of S2- equivalent to the 0,2 M S~-conditions used in
species is higher. This results in a concomitantly
the species distribution diagram in Figure 3. In
higher elution rate, as shown in Figure 14.
that case, the concentrations of polysulphides
Effect of NaC! Concentration were very much larger than the concentration of
S2-ions, and the solution remained yellow-
The ionic strength has a marked effect on the
orange in colour throughout the experiment. The
elution of gold from activated carbon with
ratio of AuS~-to AuSi species was presumably
cyanide or caustic solutions because of the effect
very low, as evidenced by the negligible elution
of the Mn+ cation on the equilibrium:
rate.
Mn+ [Au(CN);]n (ads) H
Mn+ (aq) + Au(CN)2 (aq). [15]
AUGUST 1994 195 ....
 Elution of gold using sulphide solutions
[Na;zSJ (NaOHI
0.005M 0,0 molll
100 -+- 100 --.-
0.05M 0,4 molll
-- -+-
0.1 M
- A-
80 0.2M
80
~
0.4M
-B- ~
#.
0.6M >-
~
c
.
60 -A - ~
QI
60

'u 1.0M U
==
. -- !E
GI
c 2.0M C
0 0
~
iD 40 "5 40
iii

20 20
.8
....----
-- 0
0
0 2 3 4 0 2 3 4
Tlme.h Time, h

Figure 12-Effect of Na~ concentration on the single-pass elution of Figure 14-Effect of NaOH concentration on the single-pass elution of
gold cyanide from activated carbon gold cyanide from activated carbon

[Nal>1 (NaCI]
7
0.05 M 0,0 molll
-+- 100 --.-
0.1 M 0,4 mol/l
--
6,8
=
_....~ ---

80
0,6 mol/l
- .-
0,8 molll
~
~
6,6 u>- 60
C
-t:: QI
ca
'u
c.i !E
QI
..E
C
0
6,4 +I
:I 40
iii

6,2 20

6 0
0 2 3 4 0 2 3 4
Tlme,h Time, h

Figure 13-Plot of In C versus t for the elution of gold from activated Figure 1~Effect of NaCI concentration on the single-pass elution of
carbon at different sulphide concentrations gold cyanide from activated carbon

~ 196 AUGUST 1994 The Journal of The South African Institute of Mining and Metallurgy
 Elution of gold using sulphide solutions
Temp.
100
100 22"C
--+-
30.C
----
.e-T"°~"" 40"C 80
80 ~...~.:e - ..-
I? ~~.---- SO.C 'I.
-B-
#.
u>. 60
U
c
.
'I
p,

rifl ,~~
/J{.JI--
~. ~8'
'O.C
-EJ-
9S.C
g>.
.
'13
!E
60

Si
~.l'
-8 -
.
c0
c0
-g 40
m
f ~iiJ
~40

r;J
20 20

0 0
0 2 3 4 0 2 3 4
Time. h Time.h

Figure 16-Effect of temperature on the single-pass elution of gold Figure 18-Effect of pretreatment on the single-pass elution of gold
cyanide from activated carbon cyanide from activated carbon

Eluant Effect of SulphidePretreatmentFollowedby

Elution with De-ionized Water
Na:; 0.2 M
100
Na:;p:s0.2 M In an attempt to extend the concept of sulphide
~
elution to the AARL method, loaded carbon was
Na:; 0.2 M pretreated with 0,2 M Na2S for 4 hours. before
80
NaJ)~~2 M being drained and eluted with de-ionized water.
The experiment was unsuccessful, as shown in
NaJ) 0.2 M
'# - A- Figure 18. This is attributable to the fact that
>. Na:; 0.2 M alkaline solution is necessary21 for the stabiliza-
~ 60 SO.2M tion of gold in the elutable AU2S~-form. Figure
.!!
u -e- 15 shows that Au(HS)"2is the predominant form
'ic Na~ 0,2 M
SO.6M
between pH 4 and 10, and this singly negatively
charged species would probably27,28be strongly
0 -I-
~ 40 adsorbed by activated carbon.
iii
Stripping of Silver from Sulphide-eluted
Carbons
20 Several experiments were carried out on the
feasibility of stripping the silver, in particular,
from the carbon in a step subsequent to sulphide
BJDB-O-O elution. Gold was first eluted batchwise from
0
0 1 2 3 4 carbon containing 1000 g/t of gold and 200 g/t
Time. h of silver with a 0,2 M Na2S solution. The results
obtained by several different stripping methods
are shown in Table V, and indicate that it is
possible to remove most of the silver from
sulphide-eluted carbon. These procedures could
Figure 17-Effect of other anions on the single-pass elution of gold cyanide from activated undoubtedly be optimized further.
carbon

The Journal of The South Afncan Institute of Mining and Metallurgy AUGUST 1994 197 ...
Elution of gold using sulphide solutions
20. GREEN, B.K, ASHURST, K.G., and
CHANTSaN, T.E. A dedicated resin
for gold-the stimulus needed for
universal acceptance of a resin-in-
pulp process. Bhappu, R.B., and
Harden, R.J. (eds.). Gold Forum on
Ted1nology and Praca'ces-World
Gold '89. SME, Colorado, 1989.
pp. 339-346.
21. SEWARD,T.M. The hydrothennal
geochemistry of gold. Gold metal-
lurgy and exploradon. Foster, R.P.
led.). Glasgow, Blackie, 1991.
pp. 37-62.
22. RENDERS,
P.J" and SEWARD,T.M. The
stability of hydrosulphido- and
sulphido-complexes of Aull) and
Ag(l) at 25'(, Geochim. Casmochim.
Acta, vol. 53. 1989.
pp. 245-253.
23. El-HINNAWI, M., PETER,lo, and
MmR, B. Raman spectra of
copper(l), silver(!) and gold (I)
cyanides in aqueous solutions of
sodium thiosulphate.! Raman
Spectrosc., vol. 16, no. 4.1985.
pp. 272-279.
24. LEWlS, G., and SHAW, C.F. Compe-
tition of thiols and cyanide for
gold(l)./norg. Chem., vol. 25.
1986. pp. 58-62.
25. LDuw, N.J., EDWARDS,A.M" and
GUSSMAA,H.W. A new process to
extract gold and stibnite from
arsenical concentrates. Chem.SA,
vol. 3,1977. pp. 135-136.
26. MEllOR, J. Comprehensive treatise
on inorganic and thearedcal
chemistry. London, Longmans
Green, 1923. vol. 3, p. 613.
27. GAlLAGHER,N.P., HENDRIX,I.lo,
MllOSAVLIEVlC,E.B., NElSON, I.H.,
and SoWIIC, lo Affinity of activated
carbon towards some gold(l)
complexes. Hydrometallurgy,
25.1990. pp. 305-316.
28. ADAMS, M.D. The chemistry of the
carbon-in-pulp process.
Johannesburg, University of the
Witwatersrand, Ph.D. thesis, 1989.
29. HEPEl, T., HEPEl, M., LES'KO, M.,
SEWERYNSKI, B., WOjTOWlCZ, J.,
MYCZKDWSKI, Z., GOTFRVD, lo,
SZOlOMICKI, Z., CAIS, A.,
KoUROVOWSKl, aGU'A, A., and
J"
BIESZCZAD,T. Hydrometailurgical
processing of materials containing
silver, lead and their compounds
resulting from leaching of copper
from sulphide concentrates. Pol.
Patent97320. 31 Jul., 1978.3 pp.
(ChemAbstr. 90: 15514OC: NIM-
TR-995).
30. SAND'URG, KG. and HUlATT, J.lo
Recovery of silver, gold, and lead
from a complex sulphide ore using
ferric chloride, thiourea, and btine
leach solutions. Washington,
Bureau of Mines, R/9022.
14 pp.
31. GAlLAGHER,N.P., and LEI, K.P.V.
Recovery of lead and silver from
plumbojarosite by hydrothermal
sulfidation and chloride leaching.
Washington, US Bureau of Mines,
R/9277.1989.9pp.
~ 198
Table V
Stripping of silver from sulphide-eluted carbon by various methods
Stripping solution
5M NH4CI
90°C
pH 7,0
(HCI/NHa)
S:L40
6h
0,5M Na2S20a 30;
25°C this work
pH 7,0
S:L40
6h
0,5M Na2S0a 30;
25°C this work
pH 6,0
S:L40
6h
50 9/1 NaCI 30; 31
90°C
pH 7,0
S:L40
6h
Zadra9 has shown that carbon can be Increasing temperature raised the initial
elution rate, but lowered the overall extraction
recycled between loading and stripping many
times without a loss in efficiency. It is conceiv- efficiency, probably owing to the deposition of
able that the form of the silver and base-metal elemental gold on the carbon.
vol.
sulphides that are produced inside the carbon Increased ionic strength, by means of NaCI
during sulphide elution and subsequent regener- addition, had no effect on the elution, which
ation is such that some cyanide leaching of these confirms that the elution mechanism in the case
species occurs during the subsequent adsorption of sulphide is different from that when cyanide
step. This could result in equilibrium loadings of or hydroxide is used as the eluant.
these elements eventually being reached, with no The elution of gold by sulphide solutions is
further detrimental effect on gold recovery. proposed to proceed by means of an initial step
that involves the reaction of polysulphide ions
with the adsorbed aurocyanide species, forming
Conclusions
AuCN on the carbon and thiocyanate in solution,
This is followed by the formation of poorly
Elution efficiencies of around 96 per cent were
adsorbed complexes with sulphide ions, such as
obtained with a single pass of eluant containing
0,2 M Na2S and 0,4 M NaOH in 4 hours-about AuS~~The presence of polysulphides, whether
generated in situ by the catalytic oxidation effect
10 bed-volumes of eluant. The initial rate was
of activated carbon or by the addition of
slow over the first hour of elution, probably
elemental sulphur, serves to reduce the elution
because the activated carbon catalysed the
rate and efficiency dramatically. This is probably
oxidation of sulphide to polysulphide.
due to the formation of complexes such as AuS-
US
Elution efficiencies of around 100 per cent
were also obtained in batch elutions of carbon in and AuSi, which have a high adsorption affinity.
1986.
Sodium sulphide solutions are rapid and
less than 4 hours at liquid-to-solid ratios of
effective for the elution of gold from activated
about 100. Lower liquid-to-solid ratios resulted
carbon at room temperature. As silver and base
in re-adsorption of the gold, probably owing to
metals are not eluted, the technique is suitable
the oxidation of sulphide to polysulphide with
for applications where the carbon is not intended
the resultant formation ofless elutable gold
complexes. for re-use, for example, in the elution of gold
from carbon fines. .
No attempt was made to fully optimize the
elution conditions, but several trends were
evident. Improved rates of elution were obtained
at higher sulphide concentrations and pH values
greater than about 13,
AUGUST 1994 The Joumal of The South African Institute of Mining and Metallurgy
- ~-- -- -