Minerals Engineering, Vol. 7, No. I, pp. 71-86, 1994 0892-.-6875/94 $6.00+0.

00
Printed in Great Britain © 1993 Pergamon Press Lid

FACTORS AFFECTING THE ELUTION OF GOLD CYANIDE

FROM ACTIVATED CARBON

J.S.J. van DEVENTER and P.F. van der MERWE

Department of Metallurgical Engineering, University of Stellenbosch,

Private Bag X5018, Stellenbosch, 7600, South Africa
(Received 16 June 1993; accepted 17 August 1993)

ABSTRACT

Functional relationships were detetTnined between the effects of pH, tetnperature, and the
concentrations of cyanide and cations on the gold cyanide equilibrium during elution from
activated carbon in cohlmns and in batch reactors. Although the parameters in these
functional relationships will differ for different types of activated carbon and for different
conditions of pre-treatrnent, the form of the relatiouships wouM remain unchanged. Such
a multi-parameter equilibrium expression can be incorporated hzto a dynamic model
describing a continuous shifi in the adsorption/desorption equilibrium as elution proceeds.

The elution of gem cyanide is suppressed by the presence of cations (Mn+) through the
formation of M n+ (Au(CN)e')n on the carbon. The horizontal position of the goM peak in
an AARL elution profile was found to be a function of the elution of the cations from the
carbon bed. High temperatures and intense cyanide pre-treatment, i.e. conditions
favourable for desorption, decreased the sensitivity of geM elution to flow rate and the
radial distribution of the gem through the carbon particles. This implies that the
resistance to mass transfer was less profound under strong elution conditions.

Keywords
Activated carbon, gold cyanide, elution, cyanide, adsorption

~TRODUCTION

The carbon-in-pulp (CIP) process is used world-wide as the main method for recovering gold from
leached pulps. In an earlier paper it was shown that the adsorption of gold cyanide onto activated carbon
has been researched thoroughly, while the elution of gold from the loaded carbon has not been analysed
methodically to the same extent [1]. Moreover, the mechanism ofelution has never been studied in detail
before [2]. Therefore, many opportunities exist for research on factors affecting the desorption process.

Mainly three methods of elution are used in industry, i.e.: (a) The Zadra process in which warm cyanide
solution is circulated through an elution column and electrowinning cell (a U.S. Bureau of Mines
invention); (b) The Anglo American Research Laboratory (AARL) method consisting of a pre-treatment
step with hot caustic cyanide solution followed by elution with hot deionized water (a South African
invention); (c) The use of organic solvents, which involves variations of (a) and Co) (an Australian
invention).
71
72 J.S.J. VAN DEVENTER and P. F. VAN DER MERWE

Cyanide and hydroxide salts are added during both the AARL and Zadra elution procedures to enhance
the elution of the gold cyanide. The equilibrium between the adsorbed gold and the gold cyanide in
solution is affected by the concentrations of these additives, which change continuously during a run [3].
Both the equilibrium of adsorption/desorption as well as the degradation of the cyanide are affected
significantly by temperature. Adams and Nicol [4] listed the most significant influences on elution, in
order of decreasing importance, as follows : temperature, cyanide and hydroxide concentrations, and the
ionic strength of the eluant. Likewise, Davidson [5] considered the temperature and reagent cyanide
addition to be the most important factors affecting gold elution. In cases where the loaded carbon
contained large amounts of calcium carbonate, the temperature and acid washing of the carbon were
considered to be most important for efficient elution [6].

Davidson [5] stated that the effects of temperature, reagent cyanide addition and ionic strength are
confounded to such extent that it is "not possible to quantify each parameter in isolation". Although simple
models [7,8] have been proposed for the Zadra process, few attempts [3,9,10] have been made to model
the more complex AARL process, in which the equilibrium curve shifts as the spectator cations are
displaced from the column. Whereas previous models could be applied only to specific conditions, a
modelling approach which takes all the sub-processes into account will be of general use in Zadra, AARL,
organic solvent as well as continuous elution processes [3]. No previous study has provided a thorough
quantification of the effects of the many variables involved in the elution process.

An important factor which has been overlooked by most researchers is the effect of adsorption on the
desorption process. The adsorption process will determine the form in which the gold is adsorbed, and
the radial distribution thereof through the carbon particles. The depth to which the gold has penetrated
into the porous structure of the carbon might determine the ease with which it will desorb [11].

It is the objective of this paper to quantify the effects of the following important variables on gold elution:
temperature, pH, the concentrations of cyanide and cations, the conditions of pretreatment, the nature of
the adsorbed gold, acid washing, dimensions of the column, and flow rate. The interrelationship between
some of these variables will be explained in terms of their effects on the equilibrium expression, which
is an essential component of any dynamic elution model.

EXPERIMENTAL

Powder of KAu(CN) 2 dissolved in distilled water was used as adsorbate. The pH was adjusted by the
addition of small amounts of HCI or KOH. Unless specified otherwise, the pH was 8.5 in all experiments.
All chemicals were of AR grade. Eluted activated carbon from the Beatrix mine in South Africa was acid
washed and rinsed with deionised water to remove as many impurities as possible prior to use. Unless
otherwise specified, the carbon was dried at 120°C tbr 3 days before being weighed, soaked in water and
used in the experiments. It was tbund that no AuCN was formed on the carbon during adsorption from
alkaline solutions at room temperature. The mean particle size was 1.42 mm and provided a void fraction
of 0.292 in a packed colunm, the apparent density was 839 kg.m "3 and the BET surface area was
determined as 792 m2.g -1. The pore volume of the carbon was determined as 6.34x10 4 m3.kg -1 by
measuring the mass loss upon oven drying of a sample of carbon saturated with water.

Equilibrium isotherms were determined by contacting weighed, oven dried samples of carbon with 1.0
litre solutions of gold cyanide with known initial concentrations lbr 21 days at different pH's,
temperatures, and concentrations of cations and cyanide.

The aim of this study was to investigate the fundamentals of elution and not to obtain the highest possible
elution efficiencies. Therefore, a convenient temperature of 70°C was selected for most of the elution
runs. These investigative runs were conducted in a glass column with a temperature controlled water
jacket. The downward flow of eluant through the column was controlled. A bed volume (BV) is defined
here as the empty volume of the reactor that is occupied by the packed bed of carbon, i.e. 17.16 cm3.
The bed height used was 14.3 cm, the h/d ratio was 11.57 and the flow area was 1.2 cm 2. One bed
volume of the glass column contained 9.4 g of dry carbon.
 Elution of gold cyanide from activated carbon 73

Unless otherwise specified, the pre-treatment step was conducted outside the column in glass beakers for
30 min. in 20 ml of a 20 g KCN/I solution at room temperature. After the pre-treatment, the carbon was
separated from the solution with a strainer, and excessive solution removed by blotting with filter paper.
The carbon was then dropped into the glass column containing half a bed volume of eluant at the elution
temperature. The high concentration of cyanide in the pre-treatment ensured sufficiently high pH values
in the pre-treatment step as well as the subsequent elutions. The starting time for the elution was taken
as the moment when flow of eluant was introduced. Some experiments were conducted at a room
temperature of 20°C, unless a different temperature is specified.

SUB-PROCESSES

The continuous change in conditions during an AARL elution is the result of mainly three important
sub-processes occurring simultaneously. Desorption of gold is the most obvious of these, followed by the
diffusion thereof out of the carbon into the interparticle solution. The other two sub-processes involve the
removal of the pre-treatment reagents from the carbon bed, i.e. firstly, the diffusion of cations from the
pores of the carbon, and, secondly, the decomposition and diffusion of the cyanide from the carbon pores.

Figure 1 shows a typical elution profile obtained at 70°C. The concentrations of the gold, cyanide and
potassium have been normalised tbr comparative reasons. Note the sharp decline in the cyanide and
potassium concentrations within the first two bed volumes. The tailing effect is because of the reagents
being trapped in the pores of the carbon. The peak in the gold profile only appears once the bulk of the
pre-treatment reagents have been removed. The pH remains high for the whole duration of the run, even
though the pH of the water supply has not been adjusted.

1.0 , i v

t.

0 8
•
.',i ....)' ......................... pH

• I!
>--

0.4

J \il
0.@
0 4 8 12 16
Bed Uolumes
Fig. 1 Normalised AARL elution profiles at 70°C tbr carbon
containing 4.83 gAu/kg after 72 h of loading.
[Au] = 140.Y p.p.m.; [K +] = 3500.Y p.p.m.; [CN-] = 1500.Y p.p.m.; pH = 14.Y

All the above-mentioned factors affect the gold cyanide equilibrium [3,10], so that the latter will also
change continuously throughout an elution run. It is therefore important to know the equilibrium isotherm
at all possible combinations of these factors. Furthermore, it will only be possible to model the elution
of the gold cyanide once models have been developed to describe the changes in the concentrations of the
cyanide and the spectator cations. Very little has been published on the incorporation of factors affecting
74 J.S.J. VAN DEVENTER and P. F. VAN DER MERWE

the equilibrium of adsorption/desorption [12] in the isotherm expression, so that a detailed quantitative
study in this regard is justified.

MODIFIED FREUNDLICH ISOTHERM

At each possible combination of factors, such as pH, temperature and cyanide concentration, a unique
Freundlich isotherm (q = AC n) can be measured for the equilibrium adsorption of aurocyanide onto a
specific activated carbon. In order to determine the two parameters, "A" and "n", in this isotherm, at least
three to four combinations of equilibrium gold loading and concentrations would be required. It is clear
that it is impractical to establish the gold cyanide equilibrium at enough combinations of conditions to
enable extrapolation to other combinations.

In an attempt to minimise the parameters in the Freundlich isotherm, a possible relationship between A
and n was investigated. From the work of Cho and Pitt [13] it seemed that lowering of the equilibrium
constant, "A", is usually accompanied by an increase in the value of the exponent. If the values of "A"
and "n" determined by Van Deventer [14] for more than ten different carbons under different adsorption
conditions were plotted [3], a linear relationship was found which yields:

Qe = A CebA+B (1)

where b and B are constants that can be determined by measuring the Freundlich isotherms for a specific
carbon at different conditions. With only the one unknown, A, in the isotherm expression, it was now
possible to describe the equilibrium at a certain combination of factors with only one set of values of Qe
and C e. By keeping all factors constant and changing only one factor at a time it was thus possible to
quantify the effect of each factor on the value of A, and therefore its effect on the gold cyanide
equilibrium.

FACTORS AFFECTING THE ELUTION OF AUROCYANIDE

Temperature

The adsorption of gold onto activated carbon is an exothermic process [15], and an increase in
temperature will shift the equilibrium to favour desorption. Figure 2 presents equilibrium isotherms
determined for gold cyanide adsorption onto carbon at temperatures of 22°C, 30°C, 40°C and 60°C. With
no pre-treatment the adsorption and desorption isotherms for this carbon were found to be identical [ 16].
Higher temperatures would have necessitated the addition of cyanide to prevent the formation of AuCN.
As cyanide is readily hydrolysed at high temperatures, it would have been impossible to determine all
equilibria at the same cyanide concentration. A least squares regression on the data in Figure 2 provided
the following correlation between A and n in the equilibrium expression for the carbon:

Qe = A'Ce-O'002688'A + 0.2902 (2)

The curves in Figure 2 were calculated using Eq. (2). (All curves in other figures merely represent trends
in the data and are not model predictions.) In order to test the validity of an Arrhenius relationship
between temperature and the equilibrium gold loading, the logarithm of A was plotted against the
reciprocal of the absolute temperature in Kelvin. The resulting straight line through the data gives:

A = 0.019 exp(2190/T) (3)

This constitutes an isosteric heat of adsorption of 18.2 kJ/mol., which is significantly lower than the 42
kJ/mol, measured by McDougall et al. [15]. Such large differences are possible due to the wide variation
in properties between activated carbons. A cyanide pre-treatment which modifies the surface of the carbon
decreases the isosteric heat of adsorption even further [ 16].
 Elution of gold cyanide from activated carbon 75

70.
60
r-'1
[2 50
2~
\
<E

Cn 30
20 * 22
(:3
[] 3 0
I0 ~0
o 60
I i I I I
0
0 5 i0 15 20 25 30
Ce [g u/rn3]

Fig.2 Equilibrium isotherms for the adsorption of gold cyanide onto activated carbon
at different temperatures. Curves calculated from average A values with Eqs. (2) and (3).

pH of solution

Davidson [17] related the effect of pH on the adsorption of metal cyanide complexes to the strong
adsorption of both hydroxide and hydronium ions, whereas Adams et al. [18] and Adams and Fleming
[2] favoured a mechanism in which OH- reacts with the functional groups on the surface of the carbon.
Van der Merwe [16] found that log-log plots of the equilibrium metal loading versus the pH for four sets
of published data resulted in straight lines in all cases.

The In(A) values for gold cyanide in contact with activated carbon at different pH values yielded a straight
line:

A = 113 exp(-0.16 pH) (4)

Room temperature and a constant [K +] = 1100 g/m 3 were used. When the experiment was repeated at
40°C and [K +] = 1500 g/m 3, the constants in Eq. (5) at 40°C differed from those determined at room
temperature, but the functional form remained the same:

A = 138 exp(-0.21 pH) (5)

Cyanide concentration

Adams and Nicol [19] found that the rate of desorption in a Zadra type of elution reached a maximum
at a cyanide concentration of 0.2 M. The decrease in elution rate at higher concentrations was ascribed
to the opposing effect of cyanide and ionic strength. It was illustrated that, at a constant ionic strength
(maintained by the addition of NaCI), an increase in cyanide and hydroxide concentrations resulted in
faster desorption kinetics. In the present study the effect of cyanide on the equilibrium adsorption of gold
cyanide on activated carbon was determined at a constant [K +] by the addition of KCI at room
temperature. Despite the variation in pH values, a log-log plot of A vs. (C N + 1) produced a straight line,
i.e. (The value of unity was added to the cyanide concentration to prevent taking the log of zero in the
absence of cyanide.):

A = 32 (C N + 1)-°A55 with Ct~ in p.p.m. CN" (6)

76 J.S.J. VAN DEVENTERand P. F. VAN DER MERWE

Cation concentration

The beneficial effect of cations on the adsorption of gold on activated carbon has been reported to be in
the order Ca 2+ > Mg 2+ > H + > N a + > K + [15]. Thus, a low ionic strength and the absence of
Ca 2+ and Mg 2+ will favour desorption. Van der Merwe [16] showed that a log-log plot of some
published loading capacities versus ionic strength at a fixed solution phase concentration yielded a straight
line.

The equilibrium capacity under elution conditions will not only be a function of the concentration of
cations in the liquid phase, but also of the cations adsorbed on the carbon [17]. During an acid wash most
of the contaminant elements are removed from the carbon. Moreover, it was shown [17] that during the
pretreatment step in the elution cycle the aurocyanide complex will be linked preferably to the spectator
cation introduced with the pretreatment reagents. From these observations it can safely be assumed that
after an acid wash and a cyanide or hydroxide pretreatment the main cation to be considered in the elution
step will be the cation introduced with the pretreatment reagents.

Because different cations, even with the same charge, have different effects on the adsorption and
desorption of Au(CN)2-, each cation was considered separately in the present study so that the ionic
strength was not studied as such. Furthermore, it is unlikely that an ion such as CN', which has a positive
effect on desorption, will contribute to the negative effect of the ionic strength. As mentioned earlier,
mainly potassium was studied here. Although other cations will affect the adsorption of gold to different
degrees, the trends will be similar to that observed tbr potassium. A plot of In(A) as a function of the
concentration of potassium (CK) or calcium (Cca) at room temperature gives:

A = 2 4 ( C K + 1)0.069 (7)

A = 26 (Cca + 1)0'127 (8)

The stronger dependence of equilibrium on the calcium concentration than the potassium concentration
is obvious. Although inconceivable, a zero cation concentration was provided for in the (tea t + 1) term.
Little or no difference could be observed in the resulting gold elution profiles when NaCN was used as
pretreatment reagent instead of KCN [16]. The H + cation was not treated here as another cation, because
it was already accounted for in the effect of the solution pH.

Cyanide pretreatment in an AARL elution

It was shown that almost all the gold loaded onto activated carbon could be recovered with deionized
water after a pretreatment with potassium carbonate [20]. The carbonate pretreatment, however, led to
poor elution of silver and other base metals as well as the build-up of calcium carbonate on the carbon.
The poor elution of the metals, other than gold, was blamed on the instability of these complexes under
high pH pretreatment conditions [20]. Therefore, sodium cyanide is usually added in order to stabilise the
metal cyanide complexes.

Van der Merwe [16] showed that equimolar solutions of sodium cyanide and potassium cyanide produced
identical elution curves, which indicates that the effect of cyanide blinds any difference that could result
from the different cations. The relative insignificance of hydroxide compared to cyanide in the
pretreatment is illustrated in Figure 3. Identical elutions were carried out with identical samples of gold
loaded carbon. The only difference was that the one sample was pretreated with a KCN solution and the
other with a KOH solution with the same pH and potassium concentration. In the case of the cyanide
pretreatment the maximum gold concentration in the elution was more than 10 times higher than for the
hydroxide pretreatment.

The effect of cyanide in the above experiment cannot be linked to the dissolution of an irreversibly
adsorbed gold species, because AuCN did not form on the carbon under normal conditions [16].
Furthermore, if CN" displaces Au(CN) 2" from loaded activated carbon by a mechanism of competitive
 Elution of gold cyanide from activated carbon 77

adsorption, it could have been expected that more desorption of gold would have occurred during the
pretreatment step. It is important to note that the peak in the gold elution profile appeared only after most
of the cyanide had been washed out of the carbon bed. An experiment was then devised to investigate the
necessity for cyanide in the eluant (Figure 4). To ensure the lowest possible carry over of cyanide from
the pretreatment to the elution stage, the carbon was boiled in the pretreatment reagent to decompose most
of the cyanide. At the end of the pretreatment the cyanide concentration was measured as 80 mgCN'/l
(compared to the initial concentration of 8000 mgCN'/l). The elution step of this experiment consisted of
two stages. During the first stage an eluant containing 2000 ppm potassium (as KCI) was pumped through
the carbon bed. The high cation concentration suppressed the elution of the gold and provided 4 bed
volumes of eluant to rinse the carbon of cyanide that was carried over from the pretreatment step. For
the second stage of the elution the potassium rich eluant was replaced with distilled water. Even though
the cyanide concentration in Iche solution was practically zero at this stage, Figure 4 reveals that a peak
in the gold concentration appeared almost instantaneously. Moreover, the maximum gold concentration
was more than 60 % higher than that measured in a similar elution without the initial high cation level.
This can be ascribed to the more intense pretreatment to which the carbon was subjected.

Pretre~tment
120 + KCN

CO I00
E
\
D 80
<E
C~ 60
L.J

20
I I I i
0
0 8 12 16 20
Bed Uolumes
Fig.3 Gold elution profiles in a column after pretreatment with either KCN or KOH solutions
at 70°C, pH = 12 and [K +] = 12 300 p.p.m. Carbon loaded for 24 hours up to 4.8 gAu/kg.

From the above experiment it follows that the free cyanide that is present during the elution step of the
AARL procedure is of secondary importance to that in the pretreatment. This means that it is the effect
of the cyanide that was present in the pretreatment step and not the carry-over of pretreatment reagents
to the eluant that enhances the elution of the gold. Because of the high ionic strength in the pretreatment
step, the bulk of the gold desorption occurs only during the elution stage once the cation concentration
is lowered. The horizontal position of the gold peak will therefore be a function of the kinetics of the
removal of the cations carried over from the pretreatment stage.

The deactivation of activated carbon by cyanide was investigated by comparing the gold adsorption ability
of fresh carbon to that of carbon that was pretreated in a strong cyanide solution. When this test was done
initially, the carbon that was treated with cyanide was boiled in distilled water before the adsorption test
to decompose all the free cyanide occluded in its pores. No difference could be detected in the subsequent
behaviour of the two samples of carbon towards gold cyanide. The test was then repeated, but instead of
boiling the cyanide treated carbon, the remaining cyanide was eluted with distilled water in a glass column
at room temperature. The carbon was then removed from the column and the adsorption of gold cyanide
78 J. S. J. VAN DEVENTER and P. F. VAN DERMERWE

onto the pretreated carbon (in a batch strirred tank reactor) was compared to the adsorption onto a similar
sample of fresh carbon in Figure 5. The lower adsorption capacity of the pretreated sample proves that
the surface of the carbon was changed in such a way that its affinity for the aurocyanide anion was
reduced. This deactivation, however, can be reversed by exposure of the carbon to high temperature.

1.0
l Gold
a Pot assi urn
0.8

0.6

0. 4

0.2

0.0
0 2 4 6 8 10 12 14 16
Bed Volumes
Fig.4 The prolonged effect of a cyanide pretreatment on the elution of gold cyanide at 7BC
in a column using activated carbon with an initial loading of 4.98 gAu/kg.
[Au] = 220.Y p.p.m.; [K+] = 2500.Y p.p.m.

1.0

0.8

0.6

0.4

0.2

0.0
0 5 10 15 20 25 30
Time Chrl
Fig.5 Illustration of the effect of the deactivation of activated carbon towards aurocyanide
caused by cyanide. Initial [Au] = 24 p.p.m.; pH = 9.5; Volume of batch reactor = 1 litre.

The effect of cyanide in solution and the effect of cyanide that was decomposed or adsorbed on the
carbon, will be referred to here as the effect of cyanide and the effect of cyanide-age respectively. The
cyanide-age of the carbon, QN, is defined as the amount of cyanide, in g CN-/kg carbon, that has been
 Elution of gold cyanide from activated carbon 79

adsorbed or oxidised on the carbon. In an experiment to quantify the effect of cyanide-age on the
desorption of gold cyanide, five samples of carbon were loaded with gold to the same level. These gold
loaded samples of carbon were then treated with solutions of different cyanide concentrations, before they
were transferred to distilled water and the gold concentrations monitored. The elution steps of the
experiments were conducted in small quantities of water at 70°C to resemble the high carbon
concentration in an elution column. Samples of the solutions were taken after 22, 52 and 94 hours. As
it was found that the gold concentration in solution declined with time, it was decided to take the
concentrations at 94 hours as being representative of the effect of the cyanide-age on the gold equilibrium.
To account for the different pH values measured for the five samples, the calculated A-values were
normalised for pH by dividing them by exp(-0.2 pH). These normalised A-values were plotted as a
function of the cyanide-age of the carbon and could be correlated as follows:

A = const/(0.06 QN + 1) (9)

The value of the constant in Equation 9 was determined as 10.2 at a solution pH of 10. The decline in
the concentration of gold in solution during the elutions in the aforesaid experiment can be attributed to
two possible factors:

(1) The carbon was loaded with gold over a period of less than 2 days. This would have resulted in
a concentration gradient of adsorbed gold through the carbon particles [ 11 ]. Further diffusion into
the finer pores of the carbon during the elution step could thus lead to the re-adsorption of gold
that was eluted from the surface of the particles during the initial stage of the experiment.

(2) As discussed earlier, the activity of the activated carbon towards gold cyanide can be restored
after a cyanide pretreatment if the carbon is exposed to higher temperatures. The elution
temperature of 70°C employed here could therefore be responsible for the gradual recovery of the
activity of the carbon. This could have resulted in the re-adsorption of the gold that was initially
desorbed.

The occurrence of re-activation of the carbon after a cyanide pretreatment was further investigated by
measuring the elution of gold from carbon that was loaded over a period of three weeks. Sufficient time
was thus allowed during the adsorption stage to ensure a homogeneous distribution of gold throughout the
carbon particles, and thereby eliminating factor (1) above. The elution profile determined in a batch
reactor, after a cyanide pretreatment in a separate container, is presented in Figure 6. Desorption occurred
for the initial 3 hours of the experiment, whereafter the concentration of gold in solution started to
decrease. In this case the re-adsorption of the gold could be ascribed only to the deterioration of the effect
of the cyanide pretreatment in the elution step. This re-activation of the carbon makes it difficult to
accurately quantify the effect of the cyanide pretreatment, or cyanide-age, on the gold cyanide
equilibrium. By the time that sufficient time has elapsed to reach equilibrium, the effect of the cyanide-age
has already been destroyed.

Presence of irreversibly adsorbed species

Davidson and Veronese [6] reported nearly identical gold elution profiles for loaded carbon that has been
air-dried, oven-dried at 110°C or used as is. However, all these samples of carbon have been acid washed
and pretreated with cyanide before elution, which would have transformed any irreversibly adsorbed
species to reversibly adsorbed AuCN. The oven drying of loaded carbon can lead to the formation of
AuCN or Au(0) and care should be taken in the cyanide pretreatment of such carbons to ensure the
transformation of any irreversibly adsorbed species before elution [16]. In Figure 7 irreversibly adsorbed
AuCN or Au was formed by drying the loaded carbon at 150°C for 18 hours.

From Figure 7 it becomes evident that the presence of AuCN or Au during the elution step at room
temperature will slow down the process and affect its efficiency. Although the experiments in Figure 7
were conducted in batch, the same detrimental effect of an irreversibly adsorbed species is expected for
the Zadra elution process in which no cyanide pretreatment is conducted. Under such circumstances the
ME 7/I--F
80 J.S. $. VAN DEVENTi~R and P. P. VAN DBR MEmWE

reaction of AuCN or Au with CN- can become rate controlling. The batch elution profiles presented in
Figure 8 are of acid washed carbon in cyanide solutions at room temperature. The one sample of carbon
was powdered before the elution and the other used as is. Although the same equilibrium seems to apply
in both cases, the rate of elution was much higher where contact between the cyanide and the gold species
was increased by reducing the particle size o f the carbon. It is thus expected that particle size will have
a significant effect on the rate of Zadra type elutions if the carbon contains irreversibly adsorbed species.

40

30
CO
E
\ • Qi : 16 g / k g
<K o Qi : 7 g/kg
20
E7~

I0 Q

I I I I I

0 5 10 15 20 25 30
Time [ h r ]
Fig.6 R~ctivation of ca~on towa~s aur~yanide a ~ r a c y ~ d e pretr~tment. Volume of wa~r
in batch reactor = 500 ~ ; Mass of carbon = 3.0 g; pH = 11; ~ m ~ r a m r e = 6 ~ C .

0.4
* Hith ~u or ~uCN

0.3
.,-I
(:3
\
/-x

c~ 0.2
I
(:3
x~

0.1

0.0 ' ' '

O 2 4 6 8
Time [ h r ]
Fig.7 The effect of an irreversibly adsorbed species on elution with cyanide, but without a cyanide
pretreatment. The carbon was loaded to 23 gAu/kg, dried for 18 hours at 150°C in the case of Au or
AuCN being formed, whereafter 1.0 g carbon was contacted with 1.0 litre of water containing lgKCN/I
at pH = 11 in a batch reactor.
 Elution of gold cyanide from activated carbon 81

0.25

0.20
.~--I
C~
A
\ 0,15 " "
c2i
I
.I.--t
(:3
0. I 0
V

o. o5 o

0,00 0 5 10 15 2O 25 313

Time Eh]
Fig. 8 Effect of particle size on elution in a batch reactor with irreversibly adsorbed AuCN
present on the carbon. Carbon was loaded to 18.7 gAu/kg, whereafter 1.0 g carbon
was contacted with 1.0 litre of water at pH = 11.

Ratio o f c o l u m n h e i g h t / d i a m e t e r (h/d)

Menne [21] presented elution profiles obtained from laboratory scale columns with h/d ratios ranging from
1.5:1 to 12:1. No apparent effect could be observed. Variations due to different hid ratios on large
columns were attributed mainly to deviations from plug flow. Davidson [5], on the other hand, supported
a chromatographic mechanism for the process and expected (more so than proved) the elution profile to
be strongly dependent on the hid ratio. Both workers, however, stated that care should be taken in the
design of proper distributors for large columns so as to avoid the eluant from bypassing portions of the
carbon bed.

The effect of the geometry of the elution column was investigated in Figure 9. The gold elution profiles
presented were obtained by performing identical elutions in the glass column and in a stainless steel
column which was 300 times larger by volume. These columns had h/d ratios of 11.3 and 7.5
respectively. The same flow rate of eluant, expressed as number of bed volumes per hour, was used. Very
similar elution profiles were measured for both cases, with only a slightly sharper profile for the glass
column, which had the higher h/d ratio. The relative insensitivity to column geometry, at the same
space-time, can be seen as an indication that little deviation occurred from plug flow.

Flow rate

Davidson [17] investigated the effect of flow rate on the elution of gold after a 3 % potassium carbonate
- 1% potassium hydroxide pretreatment and found that sharper elution profiles were obtained at lower
flow rates. However, Davids'on [5] subsequently reported that in a column with a h/d ratio of 10, the
elution of gold was independent of flow rate in the region of 1 to 5 bed volumes per hour. (A stronger
pretreatment solution of 2 % sodium cyanide and 2 % sodium hydroxide was used in the latter study.) The
insensitivity of elution towards flow rate was interpreted as an indication that the elution mechanism was
not intraparticle controlled under the specified conditions.
 82 J.S.J. VAN DEVENTER arid P. F. VAN DER MERWE

140
120
//• * Bed v o l . = 17 ml

100

8o
6o
40

2O

0 I I I i

0 4 8 12 16 20
Bed U o l u r n e s
Fig.9 Gold elution profiles from columns with different size and geometry at 80°C.
Initial carbon loading = 2.78 gAu/kg.

Figure 10 contains elution profiles obtained at identical conditions with pre-treatment at room temperature,
but with different flow rates of eluant. The measured elution profiles were similar at the start of a run,
but revealed some difference after two bed volumes, when the carbon starts to become reactive by losing
its cyanide-age. Van der Merwe [16] analysed breakthrough curves for the adsorption of silver cyanide
onto activated carbon in columns and found adsorption to be more sensitive to variations in flow rate than
is the case for elution. When the conditions are less favourable for adsorption, such as when a strong
pretreatment is used, the sensitivity towards flow rate decreases. This implies that although adsorption
onto activated carbon is widely accepted to be diffusion controlled, it is not necessarily the case for
desorption.

140
_~ * 2.3 BU/h
120 5, 9 B U / h

CO I00
2
\
3 80

60

0 40

20
I I I
0
0 5 I0 15 20
Bed Uolumes
Fig. 10 The column elution of aurocyanide from activated carbon
loaded initially at 4.85 gAu/kg at different flow rates and 70°C.
 Elution of gold cyanide from activated carbon 83

Distribution of adsorbed gold

The distribution of gold cyanide through loaded carbon particles will depend on the initial concentration
of gold in solution and the duration of contact between the solution and the carbon. The higher the initial
concentration and the shorter the time of adsorption, the more gold will be adsorbed closer to the particle
surface and in the macro pores. If more time for diffusion of the gold is allowed, it will be distributed
more evenly through the particle and more gold would have diffused from the maeropores to the
micropores. The effect of the distribution of adsorbed gold on the desorption thereof at room temperature
was investigated in Figure 11. It can be observed that the rate of elution was higher for carbons that were
loaded with gold over shorter periods of time, i.e. where steeper concentration gradients of adsorbed gold
were present on the carbon.

As with the effect of flow rate, it was found that the elution was less sensitive to the distribution of the
adsorbed gold under conditions that were more favourable for desorption, e.g. after a cyanide
pretreatment at room temperature. Again, this implies that the elution process is more diffusion controlled
under weaker desorption conditions, but becomes more equilibrium controlled under stronger desorption
conditions.

It 3 I I I !

(:3 0.2
\
A
(:3
I
(:3
V 0.1
° t(ad~) = 42 h
" t(ad~;) = 1'44 h

0,0 ' ' ' '

0 20 40 60 80 100
Time [h]
Fig. 11 Effect of radial distribution of adsorbed gold cyanide on the kinetics of elution
of 1.0 g carbon in a 1.0 litre batch reactor containing water. Initial gold loading = 9.5 gAu/kg.

Acid washing

The effect of an acid wash where no calcium was present, is illustrated in Figure 12. The carbon used
in the experiments was loaded from gold cyanide solutions and treated in acid and cyanide solutions
containing H + and K + as the only cations. Much lower gold elution was measured where the carbon was
acid washed prior to the cyanide pretreatment. This can be attributed to mainly two factors : (a) Although
the acid washed carbon was washed with distilled water before it was added to the cyanide solution,
enough acid was left on the carbon to destroy a large percentage of the cyanide that would have been
utilised for the desorption of the gold, and (b) the acid lowered the pH of the eluant from approximately
10 for the non-acid washed carbon to 9 for the acid washed carbon.
84 J.S.J. VAN DI~VENTER and P. F. VAN DEg MERWE

As discussed, it is presumed that a largo percentage of the cyanide requirement in the pretreatmont is for
the neutralisation of residual acid from the acid wash. It is anticipated that the hydroxide in the
pretreatmont step can be utilised better if the protreatment step is split into a separate hydroxide
pretreatment (to neutralise the acid), followed by a cyanide pretreatment (to solubilise the gold). The
carbon used in the elution experiments in this study was loaded from gold solutions containing no calcium.
No acid treatments were thus conducted and no hydroxide was added to the pretreatment solutions.

200
/,~ * No acid ua.sh

150
09
E
\
D
<E i00
[3'
t.--2

O 50

i i i
0
0 5 I0 15 20
Bed Uolumes

Fig. 12 The detrimental effect of an acid wash on the column elution of gold
adsorbed from solutions without calcium at 70°C. Initial gold loading = 5.1 gAu/kg.

I N T E R R E L A T I O N S H I P OF EFFECTS ON GOLD EQUILIBRIUM

If the effects of cyanide, temperature, cation concentration and pH on the equilibrium adsorption of gold
cyanide are independent of each other, it follows from the law of mass action that the value of A in the
Froundlich expression can be written as a product of functions (fl to fs) as follows:

A = A o. ft (QN)" ff(CN)" f3(PH) 'f4(CK) •I"5(T) (10)

A o is a constant if all other possible effects are kept constant. If all variables except one are kept constant
in Eq. (10), those constant effects can all be combined in the value of A o and the functional form of the
relationship between A and the one variable can be determined as was done earlier in this paper.
However, Eqs. (4) and (5) show that the dependency of A on the pH is a function of temperature.
Although the functional relationship between A and pH was the same at different temperatures, the
parameters had to be changed. It can thus be expected that more of the effects will be dependent on
temperature and that Eq. (10) cannot be used to extrapolate from one temperature to another, except if
all tbe other variables remain the same [16].

By combining Eqs. (4), (6) and (7) for a constant temperature and cyanide-age, Eq. (10) changes to:

A -- A o (C N + 1)f (CK+ I)P exp(pwpH) (11)

In Eq. (11) the value of Ao accounts for all the other effects that are kept constant. In order to investigate
the interrelationship between the concentration of cyanide, potassium and pH, equation Eq. (11) was fitted
to a wide range of data at room temperature [16], and yielded the following parameter values:

A o --87.66, f = - 0 . 1 0 4 , p = 0.0455, and Ph = - 0 . 1 6 3 6 .

 Elution of gold cyanide from activated carbon 85

When these parameters in Eq. (11) were used to predict the gold loedings for the individual effects of
CN', K + and pH, and the results were compared with those correlated by the individual expressions, the
average error was 3% and the maximum error was 7 ~ [16]. If the effects of CN', K + and pH were
totally independent of each other, the values of the parameters would have remained the same as those
determined previously. It therefore appears that interactions between the different effects exist indeed.
However, these interactions are sufficiently small to permit the use of Eq. (11) within acceptable limits
of error.

CONCLUSIONS

The throe most important sub-processes of the gold elution process are the changes in the concentrations
of cyanide, spectator cation and gold. As the changes in the concentrations of cyanide and spectator
cations affect the elution of the gold cyanide directly, a dynamic model for the elution of the gold and the
associated equilibrium expression also have to account for the other two sub-processes. The elution of
gold cyanide is suppressed by the presence of cations (Mn+) through the formation of Mn+(Au(CN)2")n
on the carbon. Also, the horizontal position of the gold peak in an AARL elution profile is a function of
the elution of the cations from the carbon bed.Therefore, the modelling of the AARL elution process is
complicated by the shifting equilibrium curve as reagents are rinsed from the column. The functional
relationships between the more important effects on elution and the gold cyanide equilibrium measured
in this study provide a useful basis for defining an equilibrium expression for each combination of carbon
and conditions of pretreatment. Although the parameters in these functionalities will differ for different
conditions, the nature of the relationships would remain unchanged.

High temperatures and cyanide pretreatments, i.e. conditions favourable for desorption, decreased the
sensitivity of the elution of gold cyanide to flow rate and the radial distribution of the gold through the
carbon particles. This implies that the resistance to mass transfer was less profound under strong elution
conditions, where the process is equilibrium controlled. The most important effect of cyanide is its
reaction with the functional groups on the carbon surface to passivate the surface for adsorption of gold
cyanide, and thereby cyanidepromotes the elution of gold cyanide. This passivating effect of cyanide is
reduced at higher temperatures, and also decreases with time as the carbon is reactivated. Free cyanide
in the rinsing step of an AARL elution is of lesser importance than the cyanide in the pretreatment step.

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