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~::'t .

The elution of gold from activated


'I~
",~'
. .
~
.
carbon at room temperature using
sulphide solutions
by M.D. Adams*

Synopsis Introduction Early work by Feldtman7 and Gross and


one qfthe main bottle- Scott8 indicated the potential of using sodium
The carbon-in-pulp (CIP) process is the most
necks in the carbon-in- sulphide for desorbing gold. In 1950, Zadra9, in
pulp process for the widely used method for the recovery of gold in
a pilot-plant study, demonstrated the technical
recovery qf gold is the new plants. However, despite the commercial
and commercial viability of sodium sulphide
eludon procedure, which success of the process as a whole, there remains
typicallY requires the solutions for the elution of gold at ambient
much scope for improvement. One such area is
headng qf causdc temperatures. He showed the carbon to be eluted
the elution of gold cyanide from loaded carbon. In
cyanide eluants to high efficiently in 4 hours at 25°C, and both the
temperatures for 16 to the Zadra process!, a hot solution of caustic
carbon and the eluate were found to be re-
24 hours. The present cyanide (typically comprising about 0,5 per cent
work demonstrates that
usable. There are several reasons why this
NaCN and 1,0 to 2,0 per cent NaOH) is
sodium sulphide soludon process is not in use today. One is that adsorbed
recirculated through an elution column and
as an alternadve eluant silver and base metals are not eluted, being
can dfect complete several electrowinning cells in, series. More recent
immobilized as insoluble silver and base-metal
eludon in about 4 hours modifications to this processz employ pressurized
sulphides. However, this may not be a great
at ambient temperatures. vessels or steam heat-exchangers to produce the
Eludon dfidendes qf problem, since an equilibrium situation may be
higher column temperatures (about 130°C)
around 100 per cent reached. The other problem is that the eluted
were obtained in 4 hours required for more efficient elution. Between 16
gold is sometimes re-adsorbed onto the carbon,
with a single pass qf and 24 hours are typically required before an
and it is this aspect in particular that this paper
eluant containing acceptable degree of elution is attained, and this
0,2 M Na2S and addresses.
not only represents a bottleneck in the CIP
0,4 NaOH~ut 10
bed-volumes qf eluant process, but also involves a large consumption of
energy and chemicals (cyanide has been shown Experimental Procedure
The inidal rate was slow
over thejirst hour qf to decompose rapidly under these conditions3). It
eludon, probablY because Approximately 1,1 kg of activated carbon (Le
is for these reasons that the recent trend towards
the acdvated carbon Carbone G210 AS) was screened to a particle
low-cyanide elution has arisen.
catalYsed the oxidadon size of +1,16-2,07 mm and thoroughly washed
qf sulphide to A popular alternative to the Zadra process
with de-ionized water to remove fines and
polYsulphide. Eludon was developed by the Anglo American Research
dfidendes qf around
soluble impurities. It was then contacted
Laboratories (AARL)4, in which pre-treatment of
100 per cent were also overnight with 1,44 g of KAu(CN)z in approxi-
the carbon with a hot solution of caustic cyanide
obtained in less than mately 1 litre of de-ionized water to achieve the
4 hours during the batch is followed by elution with hot de-ionized water.
required gold loading.
eludon qf carbon at However, the total time required for an
liquid-to-solid rados qf acceptable degree of elution is similar to that for
about 100. Lowerliquid-
the Zadra process.
to-solid rados resulted in
the re-adsorpdon qfgold, Recent efforts5 have been directed towards Batch Elution Experiments
probablY owing to the the development of elution procedures that
In each experiment, sulphide eluant was freshly
oxidadon qf sulphide to employ organic solvents such as acetonitrile or
polYsulphide, with the made up by the use of NazS'9HzO. Typically,S g
ethanol. which have been shown to result in
resultantfonnadon qf of loaded carbon was contacted with the
gold complexes that were efficient elution in about 8 hours at temperatures
appropriate volume of solution in a round-
eluted less readilY. 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
. Mintek,PrivateBag
X3015, Randhurg
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
2125. from the disadvantage that the solvent vapours
@ the experiment by X-ray fluorescence (XRF)
The South 4frican are invariably toxic, and may also represent a
analysis.
Institute qf Mining and fire hazard. The mining community is therefore
Metallurgy, 1994. SA
reluctant to employ these procedures on a large
ISSN 0038-223X/3.00
scale.
+ 0.00. Paper received,
Sep. 1993; revised paper
received, Mar. 1994.

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

~ 194 AUGUST 1994 The Joumal of The South African Institute of Mining and Metallurgy
Elution of gold using sulphide solutions
The results in Figure 15 show that the ionic
100 /
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
/
80 /
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
>-
u has little affinity for carbon23,24.
C 60
41
'u Effect of Temperature
!E
41 The results in Figure 16 show that the initial rate
C -- 8\ \
0 of elution is enhanced at higher temperatures.
\
.~ However, increasing amounts of adsorbed gold
40 \
\
w \
\ 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
20 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
0 enhanced rates of elution, as shown in
0 2 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~-
Figure 11-Effect of polysulphides on the batch elution of gold from activated carbon at conditions used in the species distribution
high liquid-to-solid ratios diagram in Figure 2. At pH 13, there are
substantial concentrations of polysulphides
(comparable with the concentration of S2-),
14. INGffi,N., KAKOLOWlcz,W., SILLEN, Effect of NaOH Concentration which would result in a depression of the elution
LG., and WARNQVlST,B. High-speed
computers as a supplement to
kinetics. This would also be affected by the
The pH value of a 0,2 M Na2S solution is approx-
graphical methods. V. Haltafall, a adsorption of polysulphides via reaction [2].
general program for calculating the imately 13. The addition of NaOH causes a shift
composition of equilibrium mix-
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
tures. Talanta, vo1. 14. 1967.
pp. 1261-1286. species is higher. This results in a concomitantly
the species distribution diagram in Figure 3. In
15. REMv, H., and ANDERSON,).5. higher elution rate, as shown in Figure 14.
Treatise on inorganic chemistry.
that case, the concentrations of polysulphides
Amsterdam, Elsevier, 1956. vo1. 1, Effect of NaC! Concentration were very much larger than the concentration of
p.738. S2-ions, and the solution remained yellow-
16. MORI, T., TAKEUCH',5., and MATSUDA, The ionic strength has a marked effect on the
S. Oxidation of sulphide ion by orange in colour throughout the experiment. The
elution of gold from activated carbon with
molecular oxygen in the presenCe of ratio of AuS~-to AuSi species was presumably
a water -repeDent catalyst. Nippon cyanide or caustic solutions because of the effect
Kugaku Kaishi, 1989. pp. 204-208.
very low, as evidenced by the negligible elution
of the Mn+ cation on the equilibrium:
(ChemAbstr., no. 110, 199893m). rate.
17. HAVA, S. and ONO,T. The hnproved Mn+ [Au(CN);]n (ads) H
white liquor oxidation process with
the new catalyst. Kami Fa Gikyosh(
Mn+ (aq) + Au(CN)2 (aq). [15]
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 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 Table V
for gold-the stimulus needed for
Stripping of silver from sulphide-eluted carbon by various methods
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. Stripping solution
pp. 339-346.

21. SEWARD,T.M. The hydrothennal 5M NH4CI


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

~ 198 AUGUST 1994 The Joumal of The South African Institute of Mining and Metallurgy

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