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
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
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
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
~ 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
The Journal of The South African Institute of Mining and Metallurgy AUGUST 1994 193 ....
Elution of gold using sulphide solutions
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
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.
~ 198 AUGUST 1994 The Joumal of The South African Institute of Mining and Metallurgy
- ~-- -- -