Hydrometallurgy, 14 (1985) 47---65 47

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

S O L V E N T E L U T I O N O F G O L D F R O M C.I.P. C A R B O N

D.M. MUIR, W. HINCHLIFFE, N. TSUCHIDA and M. RUANE

Mineral Chemistry Research Unit, Murdoch University, Perth, W.A. 6150 (Australia)
(Received September 12, 1984; accepted November 9, 1984)

ABSTRACT

Muir, D.M., Hinchliffe, W., Tsuchida, N. and Ruane, M., 1985. Solvent elution of gold
from C.I.P. carbon. Hydrornetallurgy, 14: 47---65.

The effectiveness of the solvents in promoting gold desorption from activated carbon
is in the order acetonitrile > methyl ethyl ketone >/ acetone ~ dimethylformamide >
ethanol. Aqueous acetonitrile and aqueous acetone strip gold in < 8 h using 2--3 bed
volumes at temperatures between 25 and 70°C. These organic solvents in particular are
strongly adsorbed onto carbon and significantly increase the activity of CN- relative to
Au(CN)~. Acetonitrile is quantitatively steam stripped from carbon and has little effect
on the kinetic activity of carbon and on the electrowinning or cementation of gold. How-
ever, acetone is not so readily recovered from carbon and causes a significant loss of
carbon activity.
The concentrated gold eluates are readily electrowon in a batch or continuous mode
using a simple diaphragm cell to give gold bullion foil. Preliminary cost analysis indicates
that this procedure is cheaper than the Zadra elution procedure and comparable to the
Anglo elution procedure.

INTRODUCTION

R e c e n t t r e n d s in the c a r b o n - i n - p u l p process t o w a r d s faster t h r o u g h p u t o f

c a r b o n a n d l o w e r loadings o f gold o n t o activated c a r b o n have placed a great-
er emphasis o n the gold e l u t i o n p r o c e d u r e a d o p t e d , a n d created a n e e d f o r
a m o r e rapid r e c y c l i n g o f t h e c a r b o n .
The Z a d r a e l u t i o n p r o c e d u r e , w i d e l y used in Australia and America,
(Zadra, 1 9 5 0 ; Zadra et al., 1 9 5 2 ) recycles h o t s o l u t i o n s o f 1% w / v N a O H ,
0.2% w / v NaCN t h r o u g h a gold c y a n i d e l o a d e d c a r b o n bed for up t o 72 h
at 9 5 - - 1 0 0 ° C to d e s o r b Au(CN)~. S o m e plants, t h e r e f o r e , have 'recently
a d o p t e d a m o d i f i e d h i g h - t e m p e r a t u r e pressurised Zadra p r o c e d u r e o p e r a t i n g
at 1 4 0 ° C and 6 0 0 kPa in o r d e r t o r e d u c e e l u t i o n times t o 1 0 - - 1 2 h. A p r o b -
lem is t h a t t h e eluates have to be c o o l e d b e f o r e depressurising a n d electro-
winning. Also the c o s t a n d m a i n t e n a n c e o f t h e s y s t e m s are n o t a t t r a c t i v e t o
small o p e r a t o r s .
The A n g l o e l u t i o n p r o c e d u r e (Davidson and D u n c a n s o n , 1 9 7 7 ; D a v i d s o n
a n d Veronese, 1 9 7 9 ) is an alternative a p p r o a c h r e c e n t l y d e v e l o p e d and

0304-386X/85]$03.30 © 1985 Elsevier Science Publishers B.V.

48

adopted by South Africa, which elutes gold in 8--12 h using deionised water
at 100--120°C. In this procedure, the carbon is previously presoaked with
5% w/v NaCN, 1% w/v NaOH solution. The main difference, compared with
the Zadra procedure, is that it is a batch operation which requires 20--30
bed volumes of eluant to be stored and subsequently electrowon. Further-
more, it is sensitive to the quality of water used. As demonstrated by Ruane
(1982), even 100 mg 1-1 Mg2÷ in the water can seriously inhibit the elution of
gold. Thus this procedure is not attractive to operators in locations where
only poor quality water exists.
Recent efforts have been directed towards the development of solvent
elution procedures which offer efficient gold elution in less than 8 h at am-
bient or moderate temperatures. Initial work by the Duval Corporation
(Heinen et al., 1976) showed that the addition of 10--20% v/v ethanol or
ethylene glycol to the Zadra system, reduced the elution time to around 8--
10 h. However, much of the solvent was adsorbed onto carbon and lost,
whilst that remaining in the eluate posed a fire hazard during electrowinning
in open cells on a large scale. Meanwhile, investigators at the Anglo American
Laboratories found that organic solvents also enhanced gold stripping rates
in the Anglo procedure (Martin et al., 1976). After presoaking the carbon,
pure azeotropic acetone and isopropanol eluted 95% of the gold in only 3
bed volumes at 50 ° C. These two solvents proved to be more effective than
methanol and ethanol, but no further optimisation or development was car-
ried out, nor was it understood why various solvents exhibited such differ-
ences in their ability to desorb gold.
Since 1981, research at Murdoch University into the solvent elution of
gold has led to an understanding of the mechanism and to a new improved
solvent system. Acetonitrile was found to strip the gold from carbon in less
than 2 bed volumes at 25°C (Parker and Muir, 1983; Tsuchida, 1984). This
provided a concentrated gold solution which was readily electrowon in a
simple diaphragm cell to provide gold bullion foil rather than a gold-impreg-
nated steel wool which has to be further processed and fluxed.
This paper reports the results of this investigation using various solvents
and various loaded carbons from local operating plants. It is shown that
aqueous acetonitrile is the most effective eluant and that there are funda-
mental reasons for its superior performance. Tests on the kinetic activity of
the stripped carbon, the solvent recovery from carbon, and gold recovery
from aqueous organic eluants are also reported. In all these tests acetonitrile
was consistently better than acetone. Preliminary cost estimates indicate that
the solvent elution procedure is competitive with the Zadra and Anglo pro-
cedures. Although reagent or solvent costs are higher, the shorter elution
times and smaller volumes permit significant energy savings.
In a subsequent paper (Muir et al., 1984) we shall show t h a t acetonitrile
is also the most effective solvent in the recently developed Micron Distilla-
tion procedure, (Griffin and Costello, 1982) in which gold is stripped in less
 49

than 4 h from presoaked carbon by refluxing and recycling hot solvent

vapours and condensates through a bed of carbon acting as a fractionating
column.

EXPERIMENTAL

Synthetic gold solutions were prepared from KAu(CN)2 (Johnson Mat-

they) and A.R. grade NaCN and NaOH. All solvents used were A.R. grade
and used w i t h o u t further treatment.
Pure coconut shell carbon (Kintal 6 X 16 mesh) was supplied by I.C.I. and
pure extruded peat carbon (R2020 2 mm pellets) was supplied by Norit Co.
Fresh carbons were washed with 5% w/v concentrated HC1 and water, then
attritioned in a jar roller for 12 h prior to use. Samples of gold-loaded car-
bons were kindly supplied by Whim Creek Consolidated (Meekathara), West-
ern Mining Corporation (Kambalda) and North Kalgurli Mines (Kalgoorlie),
and used directly.
Column elution tests were performed using a Masterflex peristaltic pump,
Kenley columns (Wright Scientific Ltd., Stonehouse, U.K.) and an ISCO
Model 1850 Fraction Collector. Gold and silver were analysed by atomic
absorption spectroscopy with a Varian Model 1200 AAS. Solvent concentra-
tions were determined by gas chromatography (GC) using a Pye Unicam
GCV chromatograph fitted with a Polar Pack T (0.2 p) column, and by
density using an Anton--Paar Precision densitometer.
Kinetic activity tests were run using magnetically stirred solutions of
10 mg 1-' Au (CN)~, 100 mg 1-' CN- and 1 g 1-' carbon, which were main-
tained at 25°C and a constant stirring rate of 600 min-' to achieve suspen-
sion of the carbon particles. Electrowinning was carried out in a flow-
through diaphragm cell purchased from H.B. Thompson Ltd., Newcastle,
U.K., using a Hewlett Packard Model 6226 B constant current power supply
and a Keithly multimeter.

RESULTS AND DISCUSSION

Comparison of organic solvents and optimisation of eluate composition

Organic solvents by themselves or mixed with water do not desorb gold

from carbon unless NaCN is added, or the carbon is previously soaked with
a strong NaCN solution. But when equilibrated with loaded carbon in the
presence of CN-, m a n y organic solvents effect gold desorption even at room
temperature. Preliminary tests aimed at identifying the most effective or-
ganic solvent and extending the previous work of Martin et al. (1976) estab-
lished that both the functional group and the carbon chain length were im-
p o r t a n t parameters. In general it was found that the desorption of gold in-
creased in the order water ~ simple alcohols < dipolar aprotics < higher al-
cohols < ketones < nitriles.
50

For practical purposes many solvents were eliminated because of their

limited solubility in water or high boiling points. Tests were then carried out
on selected solvents to compare the rates of gold desorption and to establish
the effects of organic solvent concentration, CN- concentration, and temper-
ature, using extruded peat and coconut shell carbon. As shown in Table
1, the most effective solvent proved to be 40% v/v aqueous acetonitrile (AN)
containing 50 g 1-1 NaCN, with up to 95% desorption of gold in 24 h at
25 ° C.
Acetone and methyl ethyl ketone are good alternative solvents b u t alco-
hols performed poorly at ambient temperatures.
It is of interest that both the rate and equilibrium of desorption of gold
are significantly affected by the concentrations of solvent and CN- but not
by the increase in temperature. This small temperature effect is in contrast
to that observed using aqueous CN- and suggests a different mechanism for
gold desorption using organic solvents.
In order to optimise the solvent elution conditions, further measurements
were made on the effect of AN and CN- on the rate of gold stripping at 70°C

TABLE 1

D e s o r p t i o n o f gold f r o m N o r i t ( e x t r u d e d p e a t ) a n d K i n t a l ( c o c o n u t shell) l o a d e d c a r b o n s
in e q u i l i b r i u m w i t h a q u e o u s organic s o l v e n t m i x t u r e s c o n t a i n i n g NaCN ( t e m p e r a t u r e =
25 ° C unless o t h e r w i s e s t a t e d ; 5 g c a r b o n / 2 5 ml s o l v e n t m i x t u r e )

Solvent mixture NaCN Carbon A u loading % Au desorbed

(% v/v) (g 1-1) type ( m g 1-1 )
lh 6h 24h

40% EtOH 10 Norit 5500 <5 8 12

40% DMF 10 Norit 5500 5 12 28
40% Ac 10 Norit 5500 25 60 70
40% AN 10 Norit 5500 25 65 75
40% AN 25 Norit 5500 40 70 88
40% AN* 50 Norit 5500 50 80 95
20% AN 50 Norit 5500 12 35 50
20% MEK* 50 Norit 5500 30 70 80
20% AcN*/AN 50 Norit 5500 17 35 50

10% AN 10 Kintal 5000 <5 5 12

20% AN 10 Kintal 5000 5 10 25
30% AN 10 Kintal 5000 10 30 60
40% AN 10 Kintal 5000 20 55 80
40% AN* 50 Kintal 5000 50 85 90
40% AN (50°C) 50 Kintal 5000 60 90 92
40% AN (70°C) 50 Kintal 5000 70 95 >95

Key: E t O H = e t h a n o l ; D M F = d i m e t h y l f o r m a m i d e ; A c = a c e t o n e ; A N = a c e t o n i t r i l e ; M E K
= methyl ethyl ketone; AcN = acrylonitrile.
* D e n o t e s s a t u r a t e d s o l u b i l i t y o f organic in a q u e o u s phase.
 51

from an extruded peat carbon. Figure 1 shows t h a t at this elevated temper-

ature much the same a m o u n t of gold was desorbed from carbon after 7 h
using 20--60% v/v AN/H20 containing 5--20 g 1-1 NaCN, but the rates of
desorption differed. Significantly lower rates of gold desorption were ob-
served using 20% v/v AN/H20, whilst slightly lower rates were observed us-
ing 5 g 1-1 NaCN. In comparison, an aqueous NaCN solution, in the absence
of AN, hardly desorbed any gold under the same conditions (Fig. 1). Other
tests established that an 80% methanol solution desorbed gold at a,rate be-
tween those for water and 20% AN/H20.

100" o?

80"
/D 0

c 60 ,/,,,'/ / ~ oo ~o 2¢-'
o_
7/ / • 40 ~o 2gL-:
0 /o / • ,.o ~o ,.gL-'
~ 4o
C3 / / l o ~.o ~ ~gL-I
• 0 5 lO gt -~

0
° 20

01 ~) ¼ rD
Time (hours)
Fig. 1. Elution of gold from extruded peat (Norit) carbon soaked in AN/H20 solution
containing NaCN and NaOH at 70 °C. Effect of concentration of AN, CN- and OH- on
rate and extent o f gold desorption. (Au on carbon = 3800 g t -1, equilibrated at 60 g C 1-1
solution).

We conclude that the best solvent system for gold elution is 40% v/v AN/
H20 containing 10 g 1-1 NaCN. Whilst elution can be performed satisfactorily
at ambient temperatures, the use of this solvent system at elevated tempera-
tures around 50--70°C offers faster and more efficient gold desorption.

Equilibrium isotherms

Based upon the carbon:solvent ratio used in the equilibrium studies we

calculate the equilibrium constant K for desorption (i.e., [Au]solution/
[ A U ] c a r b o n ) to be about 5 at 25°C for aqueous acetonitrile. This compares
with a value of about 0.0001 for water at 25°C under gold adsorption con-
ditions and a value of 0.02 for a dilute NaCN solution at 100 ° C under Zadra
elution conditions.
52

Stripping isotherms for gold on carbon were then established from equili-
brium measurements with 40% v/v aqueous acetonitrile containing 10 g 1-1
NaCN. These are shown in Fig. 2 compared with the stripping isotherms
from aqueous elution at 90 and 110°C. All the isotherms follow a linear
log--log relationship and show that the concentration of gold in the eluate
is directly related to the concentration of gold on the carbon. In the Zadra
elution procedure, the concentration of gold in the recirculating eluate
steadily falls as the gold is electrowon until a practical limit of about 5 mg
1-1 Au is reached when the carbon contains about 100--200 g t -1 Au. With
40% v/v aqueous acetonitrile at 25°C, the eluate is 100--200 times more
concentrated for the same gold loading on carbon, and allows more efficient
gold stripping when electrowon to low gold concentrations.
STRIPPING I S O T H E R M S
AQIJEOUSICN- vs. A Q U E O U S ANICN-

././
oooo
LOADED ,. /~/___

z
• • ] • ' 'o

1ooo //L
o

100 STRIPPED__,.
c AR oN < ' "

1C-- ' ' ' ' L

0.10 1-0 10-0 100 1000 10000 mg 1-1
GOLD IN SOLUTION
Fig. 2. Adsorption isotherms for gold on carbon relative to gold in solution using aqueous
NaCN and aqueous AN/NaCN stripping solutions at various temperatures (10 g 1-1 NaCN).

Stripping profiles of various loaded carbon columns using organic eluants

The performance of several aqueous organic solutions was compared

under practical conditions by slowly passing the eluant through columns of
loaded coconut shell and extruded peat carbon and comparing their gold elu-
tion profiles. Typically, little gold was eluted in the first bed volume and
most of the organic solvent was adsorbed onto carbon. Thereafter the gold
desorbed rapidly with more than 90% stripped in 1--2 bed volumes depend-
ing on flow rate, solvent, and temperature. When the carbon was presoaked
with pure aqueous solvent solution, gold elution t o o k place immediately on
contact with eluant containing NaCN, thus giving a more concentrated
eluate.
 53

Figure 3 compares the gold and silver stripping profiles from a loaded
c o c o n u t shell carbon (4810 g t -1 Au, 514 g t -1 Ag) which was slowly eluted
at 25°C at a rate of 0.25 bed volumes/h with 40% v/v aqueous acetone, 40%
v/v aqueous acetonitrile and 20% v/v aqueous m e t h y l ethyl ketone, each con-
taining 10 g 1-1 NaCN. These profiles confirm the results of the equilibrium
studies in demonstrating the superiority of the acetonitrile solvent over ke-
tone solvents. However, all three solvent systems eluted about 90% of the
gold and silver within 1--2 bed volumes with silver appearing slightly before
gold. This gave bulk eluates containing 3000--4000 mg 1-1 Au and 300--400
mg 1-1 Ag. At ambient temperatures, however, the kinetics of gold desorp-
tion were rather slow and attempts to desorb gold more quickly by increas-
ing the flow rate led to a broader peak and a less concentrated eluate
(Fig. 3a).
(o) 40% AN/H20/CN- (b)40% Ac/H20/CN- (c) 20% MEK/H20/CN-
[ 050 BV/h ]]0.25BV/h 0,3 BV/D 025 BV/h
f h
(12,9000)

6000' 1

~D Au ~Au Au
LI 400C
.c
O~

<~ 200C

C~
E
)j , • ,~
0' i ~ ~ o' i ~ ~ ~
Bed Volumes Eiuote Bed Volumes Bed Volumes
Fig. 3. E l u t i o n profiles o f N o r t h Kalgurli l o a d e d c o c o n u t shell c a r b o n ( 4 8 1 0 g t -~ Au,
4 1 5 g t -1 Ag) w i t h a q u e o u s a c e t o n i t r i l e (a), a q u e o u s a c e t o n e (b), a n d a q u e o u s m e t h y l
e t h y l k e t o n e (c) e l u a n t s a t 25°C e a c h c o n t a i n i n g 10 g t -1 NaCN.

A series of tests established t h a t the best stripping performance was

achieved either by presoaking the carbon with the solvent mixture for about
1 h prior to elution or by raising the temperature to 50--70 ° C. Eluants con-
taining 40 g 1-1 NaCN gave sharper elution peaks with less tailing compared
to eluants containing only 5 g 1-1 NaCN. It was also found that, as with aque-
ous elution procedures, gold was eluted more slowly from extruded peat
carbon than from coconut shell carbon.
Figure 4 compares the gold stripping performance of the Murdoch, Anglo,
and Zadra elution procedures on samples of loaded coconut shell and ex-
truded peat carbon. With both carbons, the Zadra procedure gave very low
54

concentrations of gold in the eluate and t o o k days to completely strip the

gold. The Anglo procedure stripped gold more efficiently and gave a peak
gold concentration after about 1--1.5 h or 2--3 bed volumes. Nevertheless,
10--20 bed volumes of deionised water were still required to desorb 95% of
the gold. Extruded peat carbon gave lower gold concentrations and t o o k
longer to eluate than coconut shell. With the Murdoch procedure using 40%
v/v A N / H 2 0 / N a C N as the eluant, c o c o n u t shell carbon was completely
stripped of gold in 2--3 bed volumes even at 25 ° C. However, extruded peat
was slow to elute gold at 25 ° C. It was found necessary to raise the tempera-
ture to 70 ° C and to increase the concentration of NaCN from 5 g 1-1 to 40 g
1-1 to achieve comparable stripping efficiency.
Attempts to further improve the solvent elution performance by presoak-
ing the carbon with a strong NaCN solution followed by elution at 70°C
with pure azeotropic A N / H 2 0 (80% v/v AN), as in the Anglo procedure,
proved to be unsuccessful. Although this approach worked satisfactorily it
seems that the solvent works best in the presence of CN-.

(o) Coconut She[I. (b) Extruded Peat

6000-

4 O00- Murdoch 25 °

i
m
hl

Murdoch 70 °

"7
~ 2000"

I f ~ _ . Ang 98 °

1 3 5 o' i 5
Bed Volumes Eluate Bed Volumes Eluate
Fig. 4. Comparison of Murdoch Anglo and Zadra elution procedures using North Kalgurli
loaded coconut shell (6800 g t-' Au) and Whim Creek extruded peat (3650 g t-' Au).
Conditions:
M u r d o c h 2 5 ° C: Eluted with 40% v/v AN/H20 containing 5 g 1-' NaCN (coconut shell)
or 40 g l-' NaCN (extruded peat) at 0.5 BV/h flow rate after 1 h presoak.
M u r d o c h 70°C: Eluted with 40% v/v AN/H~O containing 10 g 1-1 NaCN at 0.25 BV/h
after 1 h presoak.
A n g l o 98°C: Eluted with water at 2 BV/h after 1 h presoak with 50 g 1-' NaCN and
10 g 1-1 NaOH.
Zadra 98°C: Eluted with 2 g l-' NaCN, 10 g 1-' NaOH at 2 BV/h.
 55

Adsorption and recovery o f organic solvents on carbon

The use of activated carbon to adsorb trace organics, particularly colour-

ing and flotation agents, is well established, but little is known or reported
about the adsorption of low molecular weight organic solvents. Tsuchida
(1984), therefore established the adsorption isotherms for aqueous ethanol,
acetone and acetonitrile over the whole solvent composition range. He also
measured the uptake of solvent onto carbon at 25°C under typical elution
conditions, by carrying out accurate GC and precision densitometer readings
on the aqueous organic solutions before and after contact with carbon.
The adsorption isotherms of these solvents onto carbon (Fig. 5) show that
acetonitrile is more strongly adsorbed onto carbon from dilute aqueous solu-
tions than either acetone or ethanol, but that there is little difference in ad-
sorption using more concentrated solutions (>6 M organic). Over 300 g AN
are adsorbed onto each kg of carbon within 5 min of contact, whilst acetone,
ethanol, and MEK adsorption is only slightly less. In general the adsorption
follows a Freundlich isotherm with a linear log--log relationship between the
solvent on carbon and in solution.

13-

~" 12-
C-
O
..O
~- I.I- i A
O
~D
c
1.0- AcetonilriLe

~ 0.9-
Acetone / /

08" C H 3 ~ ~ m Ethano t CH3CH20H

07 o'~0:3 0% o'7 0'9 ~'~ ~3

log Organic in Solution M
Fig. 5. Adsorption isotherms for acetone, acetonitrile, and ethanol on carbon at 25 °C.

Although the a m o u n t of solvent adsorbed onto carbon during solvent elu-

tion with 20--40% v/v aqueous organic eluants proved to be very significant,
we followed on from this study by measuring the recovery of solvent from
the carbon by steaming or boiling the carbon in water and analysing the
distillate. We found t h a t most of the solvent is recovered by distillation or
steam stripping of the carbon (Table 2).
Tests showed that there was little difference in the solvent yield when the
carbon was either boiled or steamed at 100°C, but the recoveries varied de-
56

p e n d i n g o n t h e s o l v e n t . Whilst t h e r e was n e a r q u a n t i t a t i v e r e c o v e r y o f A N
and EtOH, m u c h lower recoveries of acetone and MEK were obtained. These
s o l v e n t r e c o v e r i e s w e r e c o n f i r m e d b y a t h e r m a l g r a v i m e t r i c analysis [ T G A )
o f s o l v e n t - s a t u r a t e d c a r b o n (Fig. 6). T h e T G A curves s h o w t h a t w a t e r and
A N are r e a d i l y r e m o v e d b y h e a t i n g t h e c a r b o n to a r o u n d 100 ° C; t h e c a r b o n
w e i g h t t h e n m a i n t a i n s a s t e a d y value until c a r b o n starts to oxidise a r o u n d
3 5 0 ° C . H o w e v e r , n o s t e a d y w e i g h t was o b s e r v e d w i t h a c e t o n e a n d M E K
s a t u r a t e d c a r b o n . T h e s e c a r b o n s c o n t i n u o u s l y d e c r e a s e d in w e i g h t as t h e
t e m p e r a t u r e was raised a b o v e 100 ° C. T h u s , it a p p e a r s t h a t k e t o n e s are m o r e
s t r o n g l y r e t a i n e d on c a r b o n a n d m a y u n d e r g o s o m e c h e m i c a l r e a c t i o n like
o x i d a t i o n t o c a r b o x y l i c acids or f o r m a t i o n o f c y a n o h y d r i n s in t h e p r e s e n c e
o f CN-.

TABLE 2

Adsorption and recovery of organic solvents from carbon

Solvent

AN Ac MEK EtOH

Initial solution (% v/v) 40 40 20 28

Solvent adsorbed at 25°C (g/kg C) 305 210 250 210
% Solvent recovered at 100°C >95 76--89 55--71 >95

tD 20 H2~'~
.L~D

40

160 200 460 660

TemperQture °C
Fig. 6. Weight losses of solvent-loaded carbon upon heating determined by thermal
gravimetric analysis. Key: after soaking in (a) water; (b) 40% v/v AN/H20; (c) 40% v/v
Ac/H20; (d) 20% v/v MEK/H20.
 57

Kinetic activity o f carbon before and after solvent recovery

Since the kinetic activity of carbon is an important parameter in the per-

formance of any C.I.P. operation it was feared that the adsorption of only
trace amounts of organic solvents, left after steam stripping, might signifi-
cantly affect the ability of carbon to be recycled directly into the adsorption
circuit, and necessitate the removal of organic in a reactivation kiln. How-
ever, these fears proved ungrounded and carbon exhibited remarkably good
activity even when fully saturated with organic solvent directly after gold
stripping.
Figure 7a shows the rate of uptake of gold from a solution containing
10 mg 1-1 Au(CN)~, 100 mg 1-1 CN- at pH 10.5 onto c o c o n u t shell which had
previously been soaked in 40% v/v AN/H20, 40% v/v Ac/H20 or 20% v/v
MEK/H20 each containing 10 g 1-1 NaCN. After contact with AN, the kinetic
activity of carbon was about 80% compared with fresh, untreated carbon,
but after contact with Ac and MEK, it was only 40%, presumably due to
chemical reaction of the ketones on the carbon surface. Repeated adsorp-
tion--stripping cycles caused a gradual decrease in the activity of carbon with
all three solvents. After 5 cycles with acetonitrile, the relative activity of car-
bon had d r o p p e d to a b o u t 50%, whilst with acetone the activity had

- 8000 a A*erOrgan t b A**rANS°ventRem°

D Fresh •

6000 ~ • Bo~l<
U~ • AN

. 2 000

O' ~ 2 4 6

Time (hours) Time(hours)

Fig. 7. (a) K i n e t i c activity o f c a r b o n for loading gold a f t e r e l u t i o n w i t h a q u e o u s organic
solvents, and (b) a f t e r r e m o v a l o f A N solvent b y boiling in water. G o l d u p t a k e m e a s u r e d
using 1 g C/l o f s o l u t i o n c o n t a i n i n g 10 mg 1-2 Au(CN)~ and 100 mg t -2 CN- at 25°C. Key:
(a) • - - f r e s h c a r b o n ; o, • - - a f t e r e l u t i o n w i t h 40% v/v A N / H ; O ( t w o s e p a r a t e runs);
• - - a f t e r e l u t i o n w i t h 40% v/v A c / H 2 0 ; ~ - - a f t e r e l u t i o n w i t h 20% v/v M E K / H 2 0 ; (b)
• - - a f t e r t r e a t m e n t w i t h 5% v/v HC1 and boiling w i t h w a t e r for 5 min; ~ - - as above b u t
b o i l e d b e f o r e acid t r e a t m e n t .
58

d r o p p e d to 20%. However, conventional Anglo and Zadra stripping of car-

bon produced a similar loss in activity upon each cycle to that observed with
A N / H 2 0 elution.
After solvent stripping with steam, the activity of the solvent-saturated
carbons improved, but not to the same level as fresh, untreated carbon (Fig.
7b). The relative carbon activity was 90% after removal of acetonitrile but
only 60% after removal of acetone. However, some further activation was
achieved by acid washing the carbon, as also shown in Fig. 7b. Acid washing
is particularly important for plant carbons heavily fouled with inorganics like
CaCOs (Ruane et al., 1983). It is of practical interest that clean carbon
showed an improved activity when acid washed before boiling to remove
acetonitrile. Presumably this reflects the greater chemical stability of ace-
tonitrile towards hydrolysis under acid rather than alkaline conditions.
We conclude that gold stripping with aqueous acetonitrile does not impair
the kinetic activity of carbon. On the other hand, aqueous acetone appears
to deactivate carbon and, together with its poor recovery from carbon, this
solvent elution system cannot be recommended.

Mechanism of gold elution using organic solvents

The fact that organic solvents adsorb strongly onto carbon, yet by them-
selves do n o t bring a b o u t gold desorption or loss of kinetic activity, suggests
that the role of the solvent is to affect the activity of ions and in particular
the exchange of CN- for Au(CN)~ at the active sites. The equilibrium con-
stant for gold desorption, K, is directly related to the activity ratio of CN-
and Au(CN)~, as can be seen from the reaction equation:
K
C ... A u ( C N ) 2 - a d s + CN-o ~ ~- C ... C N a d s + Au(CN)~so~
As discussed by Muir and Parker (1982) and Parker {1981), the main ef-
fect of organic solvents is to substantially increase the activity of small
anions like CN-. An increase in activity of up to 106 has been measured for
small anions, whilst large complex anions like Au(CN)~ are relatively unaf-
fected. Dipolar aprotic solvents like acetonitrile have a far greater effect on
anion activity than protic solvents like ethanol and water.
Detailed measurement of the single-ion activities of CN- and Au(CN)~
in aqueous acetonitrile and aqueous ethanol have been made by Tsuchida
(1984) and Muir et al. (1985), and are presented in Fig. 8. The results con-
firm that the activity of CN- increases very much more than that of Au(CN)~2
as the solvent concentration increases. The increase in activity is particularly
large with acetonitrile as compared with ethanol solutions. In the acetoni-
trile-rich environment (as present on the carbon surface) we predict the ac-
tivity of CN- to be 104--10 s times higher than it is in water whilst the activi-
ty of Au(CN)~ is only 102 times higher. Thus the equilibrium constant for
desorption of gold would change by ~102--103 in favour of Au(CN)~ being
displaced by CN- and entering the solution. On the other hand, ethanol
 59

. .
(a) E t O H - H 2 0 (b) A N - H z O

log 7 log I

. 4

ON-J

• • Au(CN) 2

oo o 0
Mole F r a c t i o n EtOH Mole F r a c t i o n AN
Fig. 8. Single-ion activities of CN- and Au(CN)~ in aqueous ethanol (a), and aqueous
acetonitrile (b).
would cause a change in K of ~<10. The effect of organic solvents in stripping
gold f r o m carbon t h e r e f o r e depends on the presence of a reasonable concen-
tration o f CN- as well as on the strong adsorption o f organic on the carbon.
The relative efficiency depends on the relative solvation and interaction of
th e solvent with CN- and Au(CN)~.

Recovery of gold from aqueous acetonitrile eluates

Three m e t h o d s may be considered for the recovery of gold from the rela-
tively c o n c e n t r a t e d gold eluates p r o d u c e d using aqueous acetonitrile. These
are (a) zinc cementation; (b) electrowinning in a conventional cell with a
steel wool ca t hode , followed by HC1 pickling and fluxing o f the steel wool;
or (c) electrowinning gold foil directly o n t o s m o o t h cathodes in a simple
flow-through diaphragm cell. There is a furt her opt i on of electrowinning in
a batch operation, or c o n t i n u o u s l y electrowinning and recycling the spent
eluant th r o u gh a loaded carbon column as in the Zadra Procedure. What
was n o t clear was w he t he r the presence o f high concentrations o f AN would
interfere with any o f these processes and thus require a solvent recovery step
before gold was recovered.

(a) Zinc cementation

C emen tati on tests using zinc p o w d e r on eluates containing 1300 mg 1-1 Au
showed no obvious effect of organic solvent, and precipitated gold rapidly in
60

5 min at 25°C leaving solution levels around 1 mg 1-1 Au(CN)]. There was no
need to add lead nitrate, as in the conventional zinc box, and the zinc slime
could be processed in the normal way. Although there is a problem when
using zinc, due to the build-up of Zn(CN)~- in solution which prevents ex-
tensive recycling, this m e t h o d does provide a useful rapid m e t h o d of gold
recovery.

(b) Electrowinning of bulk eluates

The presence of 40% v/v acetonitrile likewise did not significantly affect
the electrowinning of gold except for increasing the ohmic resistance of the
electrolyte. In a laboratory Mintek or Homestake cell (Fig. 9a) (Filmer,
1982; Paul et al., 1982) an eluate containing 1150 mg 1-1 Au was reduced to
2 mg 1-1 Au in 4 h, giving a clean powdery gold deposit on the cathode and
02 evolution at the stainless steel anode. The operating conditions are sum-
marised in Table 3. However, due to potential solvent losses and fire hazards
associated with this cell, further work was focused on the direct electro-
plating of gold using a sealed diaphragm cell (Fig. 9b) consisting of a tita-
nium plate cathode (50 cm2), a glassy carbon anode (50 cm 2) and an Ionac
MC 3470 cation-exchange membrane. A membrane was chosen rather than a
simple porous diaphragm, to prevent migration of solvent to the anode, and

a) Mintek Ceil
+ + + 4-
I

,, iI I I
m
I J IO I I
I i I i I
II

f I
j I I0
II i i

S t a i n l e s s steel a n o d e / Steel wool c a t h o d e

b) Diaphragm Celt

~1~ '~l n

Anolyte

Catholyte

Fig. 9. Electrolytic cells used for gold electrowinning studies. (a) Mintek cell; (b) dia-
phragm cell.
 61

dissolved O: to the cathode -- thus isolating the anolyte and catholyte. Semi-
permeable separators however, worked satisfactorily in practice.
In general it was f o u n d that the cell was ideally suited for recovering gold
from bulk eluates containing > 1 0 0 0 mg 1-1 Au. Fine-grained adherent gold
foil could be plated and subsequently peeled o f f the titanium cathode. Gold
was similarly plated onto aluminium or copper sheet cathodes which could be
subsequently etched away from the gold with NaOH or HNO3, respectively.
However, temperature, current density, and gold concentration were critical
factors in determining the gold morphology. Low temperatures, high current
densities, and low gold concentrations caused a nodular, less adherent gold foil.
Typically, smooth gold deposits were obtained at 50°C and current densities
of 5 mA cm -2 until the gold concentration decreased to around 500 mg 1-1.
At this point, typical current efficiencies exceeded 50%. Thereafter the de-
posit became more nodular, but nevertheless adherent, as co-evolution of
H2 became significant. In practice, gold was readily won to concentrations
< 1 0 mg 1-1 in 5 h, Table 3 compares the operating conditions and perfor-
mance of this cell compared to one operating under continuous elution--
electowinning recirculation, and a steel wool cell.

TABLE 3

Typical electrowinning cell operations using 40% (v/v) aqueous acetonitrile eluants

Condition Steel wool cell Titanium plate cella

strip solutionb synthetic stripping--electro-

(total eluate) solution winningb
(Zadra procedure)

Catholyte (ml) 1000 300 800

Au (rag 1-1) 1150 2280 --
NaCN (g 1-~) 40 10 10
NaOH (g 1-1) 0 10 10
Temperature (° C) 25 50 50
Recovery Au (%) 100 98 97
Time (h) 4 5 21
Solution flow (1 h -~) 4.0 2.5 0.42 c
Cell voltage (V) 4.6 5 5
Cathode area (cm :) unknown 50.3 50.3
Current density ( m A c m -2) - 10 d 5 5
Current efficiency (%) 2.9 8.0 3.3
Electro-deposition description powdery fine-grained adherent sheet
adherent sheet
Assay Au (%) -- 100 90.1
Ag (%) -- -- 8.7
aAnolyte 40% (v/v AN, 10 g 1-1 NaCN, 10 g 1-1 NaOH, 300--400 ml).
b F r o m 200 g Kintal carbon column, Au 6800 g t -I, Ag 600 g t -1.
CRecirculating through the carbon column.
dmA/cm3 steel wool.
62

(c ) Continuous electrowinning--elution
To test a continuous elution--electowinning operation, a column of coco-
n u t shell carbon containing 6800 g t -1 Au (North Kalgurli Ltd.) was eluted
at 50°C with 40% v/v AN, 10 g 1-1 NaCN and 10 g 1-~ NaOH and continuous-
ly recycled at 1 bed volume h -~ through the electrowinning cell and back to
the column. Figure 10 plots the gold concentration of the recycled solution
as it enters and leaves the column and passes through the cell. It shows that
the rapid and efficient stripping of gold from carbon provides much more
concentrated elutates than the Zadra process. Most of the gold was recovered
after 10 h with 96% recovered over 22 h when the concentration of gold in
the cell was < 1 0 mg 1-~. The gold deposited as an adherent foil which ap-
peared dark and somewhat brittle but readily peeled from the cathode and
assayed 90% Au and 8.7% Ag (Table 3).

1000

Z 6 8 i0 I'2
Time (hours)
Fig. 10. Gold concentration profile of recycled eluate upon continuous elution--electro-
winning o f loaded North Kalgurli coconut shell (6800 g t -1 Au) using Zadra-type proce-
dure. Conditions: eluate is 40% v/v AN/H~O containing 10 g 1-~ NaCN, 10 g 1-1 NaOH re-
cycled at 1 BV/h and 50 ° C; gold electrowon in diaphragm cell with cathode current den-
sity 5 mA cm -~.

We conclude that acetonitrile presents no intrinsic problems to cementa-

tion and electrowinning and need not be recovered from the eluate prior to
the recovery of gold, provided proper attention is given to cell design and
ventilation. The more concentrated gold electrolytes allow simple cells to
be used and offer direct electrolytic gold bullion recovery. Thus the eluate
can be largely recycled to strip further carbon, and only that which is bled
to maintain an impurity balance need to be distilled to recover the solvent.
Typically this would represent ~<33% of the total volume.

Reagent and energy costs o f the Murdoch solvent elution procedure

Assuming a 33% bleed of the eluate for solvent recovery, and 10% loss of
acetonitrile per cycle, estimated reagent and heating costs were determined
 63

f o r s t r i p p i n g 0 . 5 t o n n e o f c a r b o n u s i n g t h e M u r d o c h p r o c e d u r e . T h i s is
shown in Table 4 compared with the estimated costs associated with the
Zadra and Anglo procedures.
T h e m a i n c o s t o f t h e Z a d r a p r o c e d u r e lies i n m a i n t a i n i n g t h e t e m p e r a t u r e
of the recycled eluate over the extended times required for gold stripping,
w h i l s t t h e m a i n c o s t o f t h e A n g l o p r o c e d u r e lies in h e a t i n g t h e m u c h l a r g e r
v o l u m e s of e l u a n t r e q u i r e d . However, h e a t i n g costs of the A n g l o p r o c e d u r e
are e s t i m a t e d t o b e h a l f t h o s e o f t h e Z a d r a p r o c e d u r e . A l t h o u g h t h e e n e r g y
s a v i n g i n t h e A n g l o p r o c e d u r e is p a r t l y o f f s e t b y t h e h i g h e r c o s t s o f r e a g e n t s ,
w e e s t i m a t e t h a t t h e c o s t o f t h e A n g l o p r o c e d u r e is t w o - t h i r d s t h a t o f Z a d r a
procedure.

TABLE4

Estimated reagent and heating costs for stripping 500 kg carbon (1 m 3 volume) by the
Zadra, Anglo and Murdoch solvent elution procedures

Units Zadra Anglo Murdoch

Operating conditions
Temperature °C 98 110 70
Time h 48 10 6
Flow eluant BV h -1 2 2 0.5
Total volume eluant m3 3a 20 b 3b
Eluant bleed m3 1c -- 1 d

Reagent consumption (make-up)

NaOH ($0.6/kg) kg 12 2e 2
NaCN ($1.6/kg) kg 3 13 e 10
Acetonitrile ($1.5/1) 1 -- -- 50 f
D.I. water ($0.5/m 3) m3 1 20 0.5
HC1 wash ($0.2/kg) kg 100 100 100

Heating requirement
Eluant heating MJ 900 g 3000 g,i 400 h
Acetonitrile recovery MJ -- -- 1200 j
Heat losses MJ 6800 900 300
Total heat input MJ 7700 3900 1900

Reagent costs $ 33 54 112

Heating costs $ 193 88 48
Total cost of stripping $ 226 142 160

aRecycled eluate.
bBatch elution.
c Discarded to prevent build-up of impurities.
d Distilled to recover solvent, then discarded.
eAssuming 50% presoak solution is recycled.
fAssuming 10% loss/cycle from distillation and carbon recovery.
gAssume 70°C heat rise and energy requirement of 300 MJ/m 3 water.
hAssume 40°C heat rise and energy requirement of 100 MJ/m 3 water.
iAssuming 50% recycle of hot water or 50% heat recovery in heat exchanger.
JEstimated for distillation of 1 BV eluant and steam stripping carbon.
64

In t h e s o l v e n t e x t r a c t i o n p r o c e d u r e , r e a g e n t c o s t s are h i g h e r d u e t o t h e
a s s u m e d s o l v e n t losses, b u t h e a t i n g c o s t s a r e m u c h l o w e r since t h e v o l u m e
a n d t e m p e r a t u r e o f t h e e l u a n t is less. M o s t o f t h e e n e r g y is r e q u i r e d t o re-
c o v e r l o w b o i l i n g a c e t o n i t r i l e f r o m t h e b l e e d a n d t h e c a r b o n . Overall, t h e
c o s t o f t h e M u r d o c h p r o c e d u r e is e s t i m a t e d t o be c o m p a r a b l e t o t h a t o f t h e
A n g l o p r o c e d u r e . H o w e v e r , t h e a d v a n t a g e s it o f f e r s o v e r t h e A n g l o p r o c e -
d u r e are t h e s h o r t e r e l u t i o n t i m e s , t h e l o w e r c a p i t a l c o s t , a n d m o r e c o n c e n -
t r a t e d e l u a t e s f r o m w h i c h g o l d is m o r e e a s i l y r e c o v e r e d .

REFERENCES

Davidson, R.J. and Duncanson, E., 1977. Desorption of gold from activated carbon with
deionised water. J. South Afr. Inst. Min. Metall., 77 (12): 254.
Davidson, R.J. and Veronese, V., 1979. Further studies on the elution of gold from acti-
vated carbon using water as the eluant. J. South Afr. Inst. Min. Metall., 79 (19): 437--
495.
Filmer, A.O., 1982. The electrowinning of gold from carbon-in-pulp eluates. Proc. Symp.
on C.I.P. Technology for the Extraction of Gold, Aus. I.M.M., Melbourne, Vic., pp.
49--71.
Griffin, A.F. and Costello, M.C., 1982. Carbon desorption process development at Micron
Research (W.A.). Proc. Syrup. C.I.P. Technology for the Extraction of Gold, Aust.
I.M.M., Melbourne, Vic., pp. 140--156.
Heinen, H.J., Peterson, D.G. and Lindstrom, R.E., 1976. In: Weiss, A. (Ed.), World Min-
ing and Metals Technology. A.I.M.E., New York, N.Y., pp. 551--564.
Hussey, S.J., Salisbury, H.B. and Potter, G.M., 1979. C.I.P. gold adsorption from cyanide
leach slurries. U.S. Bur. Mines, Rep. Invest. No. 8368.
Martin, J.P., Davidson, R.J., Duncanson, E. and Nikosi, N., 1976. The elution of gold and
silver from activated carbon using organic solvents and the reactivation of the eluted
carbon. Report No. 6, Anglo--American Research Laboratories, Johannesburg, S.
Africa.
Muir, D.M. and Hinchliffe, W., 1981. The recovery of gold from cyanide leach solutions
by adsorption on carbon, stripping with aqueous solvents and electrowinning. Mineral
Chemistry Research Unit Report, Murdoch University, Perth, W.A.
Muir, D.M., Hinchcliffe, W. and Griffin, A.F., 1984. Research and developments in the
Micron Research (W.A.) solvent procedure for gold elution from carbon. Proc. Symp.
on Gold-Geology, Mining, and Extractive Metallurgy, Kalgoorlie, Oct. 1984.
Muir, D.M. and Parker, A.J., 1982. Applications of non-aqueous and mixed aqueous
organic solvents to chloride hydrometallurgy. In: Osseo-Asare, K. and Miller, J.D.
(Eds.), Hydrometallurgy: Research, Development and Plant Practice. A.I.M.E., New
York, N.Y., pp. 341--356.
Muir, D.M., Singh, P., Kenna, C., Tsuchida, N. and Benari, M., 1985. Hydrometallurgical
thermodynamics. II. Solvent effects on the activity and free energies of transfer of
CN , Ag(CN)~- and Au{CN)~ in ethanol--water and acetonitrile--water mixtures. Aust.
J. Chem., in press.
Parker, A.J., 1981. Solvation of ions. Applications to minerals and energy. Pure Appl.
Chem., 53: 1437--1445.
Parker, A.J. and Muir, D.M., 1983. Stripping gold or silver from particulate materials.
S. African Patent 81/7908; Australian Patent No. 527451; U.S. Patent 323558;
Canadian Patent 1,180,315.
 65

Paul, R.L., Filmer, A.O. and Nicol, M.J., 1982. The recovery of gold from concentrated
aurocyanide solutions. In: Osseo-Asare, K. and Miller, J.D. (Eds.), Hydrometallurgy:
Research, Development and Plant Practice, A.I.M.E., New York, N.Y., pp. 689--704.
Ruane, M., 1982. Comparison of the Zadra, Anglo-American and organic procedure
for desorption of gold from activated carbon. Proc. Symposium on C.I.P. Technology,
Aust. I.M.M., Melbourne, Vic., pp. 377--396.
Ruane, M., Hinchliffe, W., Hosking, J.W. and Muir, D.M., 1983. Carbon-in-pulp gold pro-
cessing technology. Report No. 2. Western Australian Mining and Petroleum Research
Institute (W.A.M.P.R.I.), Perth, W.A.
Smith, I., Hinchliffe, W., Hosking, J.W. and Muir, D.M., 1984. Fouling studies on C.I.P.
carbons and prospects for gold recovery using ion exchange resins. Report Project 35,
W.A.M.P.R.I., Perth, W.A.
Tsuchida, N., 1984. Studies on the mechanism of gold adsorption and elution in the
carbon-in-pulp process. Ph.D. Thesis, Murdoch University, Perth, W.A., submitted.
Zadra, J.B., 1950. A process for recovery of gold from activated carbon by leaching and
electrolysis. U.S. Bur. Mines, Rep. Invest. No. 4672.
Zadra, J.B., Engel, A.K. and Heinen, H.J., 1952. A process for recovery of gold from acti-
vated carbon by leaching and hydrolysis. U.S. Bur. Mines, Rep. Invest. No. 4843.