The Mechanism of Elution

of Gold Cyanide from Activated Carbon

J.S.J. VAN DEVENTER and P.F. VAN DER MERWE

Numerous articles have appeared on the mechanism of the adsorption of gold cyanide onto
activated carbon. In contrast, little information is available on the mechanism of elution of the
adsorbed gold. It is the objective of this article to formulate such a mechanism on the basis of
batch and column elution tests without analyzing adsorbed species on the carbon directly. The
presence of spectator cations (M"+) enhances the formation of M"+{Au(CN)~}, ion pairs on the
carbon, which in turn suppress the elution of gold cyanide. The dynamics of removal of these
cations determine the horizontal position of the gold peak in an elution profile. When the con-
centration of cations in the eluant is high and no cyanide is present in the solution or on the
carbon, very little desorption of gold is observed. The quantitative effect of the concentration
of spectator cations on the equilibrium for desorption of aurocyanide can be estimated from the
elution profiles for gold and cations. Free cyanide in the eluant, which causes some competitive
adsorption of cyanide with aurocyanide, therefore plays a minor role at the elevated temperatures
used in industry. A more important effect of cyanide is its reaction with functional groups on
the carbon, the products of which passivate the surface for adsorption of aurocyanide, and thereby
cyanide promotes the elution of aurocyanide. The degree of passivation, which is determined
to a large extent by the temperature of pretreatment, also affects the elution of cations and the
degradation/adsorption of cyanide itself. Reactivation of the carbon surface occurs when the
adsorbed/decomposed cyanide is removed by the eluant. At high temperatures of pretreatment,
such as used in practice, it is not necessary to include a reactivation term in the mathematical
model for elution.

I. INTRODUCTION experiments, without directly analyzing the species ad-

sorbed on the surface of the carbon.
THE carbon-in-pulp (CIP) process is the preferred Two main techniques of elution are used in industry:t4]
method used internationally for extracting gold from
leached pulps. Although the kinetics and mechanism of (1) The Zadra process, in which warm cyanide solution
adsorption of gold cyanide onto activated carbon have is circulated through an elution column and electro-
been studied thoroughly, the elution of gold from the winning cell (a United States Bureau of Mines inven-
carbon has not been researched methodically to the same tion); and (2) The Anglo American Research Laboratory
extent. In two recent articles, we have made first at- (AARL) method, consisting of a pretreatment step with
tempts to quantify the complex inter-relationship be- hot caustic cyanide solution, followed by elution with
tween variables affecting the equilibrium of desorption t~] hot deionized water (a South African invention). An
and to model the dynamic behavior of the elution process Australian invention, t5,6} which involves the use of or-
on a general basis, lz} However, little research has been ganic solvents, is also used in a few industrial applica-
conducted on the mechanism of the elution process, aside tions. In general, the AARL method is preferred because
from the brief discussion presented by Adams and of lower operating costs, especially with the develop-
Fleming. t3] The ongoing debate in industry whether or ment of continuous elution. Therefore, the AARL pro-
not cyanide is required in elution is mainly the result of cedure was used as a basis for the present investigation.
a lack of understanding the mechanism of elution of According to Adams and Nicol, tT] temperature, cya-
aurocyanide. In neither of the existing articles on the elu- nide and hydroxide concentrations, and the ionic strength
tion process has any attempt been made to isolate some of the eluant constitute the most significant effects on
of the complex phenomena affecting elution. Some vari- elution. In cases where the loaded carbon contains high
ables, such as the concentrations of cyanide and cations, levels of calcium carbonate, the temperature and acid
can have opposing effectstq but are usually difficult to washing of the carbon are considered to be most im-
decouple in a normal elution run. portant for efficient elution.[8] Cyanide and hydroxide salts
Consequently, there is a need for a systematic study are added during both the AARL and Zadra elution pro-
on the mechanism of elution, which will require the de- cesses to promote the elution of the gold cyanide. The
sign of special experiments. It is the objective of this equilibrium between the adsorbed gold and the gold cy-
article to formulate such a mechanism of elution from anide in solution is affected by the concentrations of these
additives, which change continuously.[9} Both the equi-
librium of adsorption/desorption as well as the decom-
J.S.J. VAN DEVENTER, Professor, and P.F. VAN DER MERWE, position of the cyanide are affected significantly by
Ph.D. Graduate, axe with the Department of Chemical Engineering,
University of Stellenbosch, Stellenbosch, 7600, Republic of South temperature, tz~ High temperatures and intense cyanide
Africa. pretreatment (i.e., conditions favorable for elution) de-
Manuscript submitted November 29, 1993. crease the sensitivity of aurocyanide elution to flow rate

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 25B, DECEMBER 1994--829

and the radial distribution of the gold through the carbon (1) reaction with the adsorbed gold cyanide species,
particles, c~]This implies that the resistance to mass trans- (2) competitive adsorption (which is regarded here as being
fer is less profound under strong elution conditions. An similar to ion exchange), and (3) reaction with the car-
elution model, which assumes equilibrium of auro- bon functional groups. It is the objective of this article
cyanide between the solution and carbon phases at any to investigate the relative importance of mechanisms (2)
point in an elution column, can then be formulated, tzl It and (3) and to distinguish between the depressing effect
has been shown that such a model simulates AARL elu- of spectator cations [~] and the enhancing effect of cya-
tion runs at different temperatures and pretreatment con- nide on the elution of aurocyanide.
ditions using the same set of parameters, tal
Adams and Nicol [TJ surmised that the desorption of gold
II. EXPERIMENTAL
involves the competitive adsorption of cyanide and auro-
cyanide on activated carbon. Likewise, Tsuchida tul as- The main adsorbate used in experiments was pow-
sumed that the desorption of gold from carbon can be dered potassium aurocyanide KAu(CN)2 dissolved in
expressed by the following equilibria: distilled water. Small amounts of HC1 or KOH were added
to the process solution in order to control the pH. Eluted
{AuCN}r + CN- r {Au(CN)2-}~o,,,,~on [1] coconut-shell-based activated carbon from the Beatrix
{Au(CN)2}ca~n + CN- 4:> { C N - } ~ gold mine near Virginia in South Africa was acid washed
and rinsed with deionized water to remove as many im-
+ {Au(CN)~}solution [2] purities as possible prior to use. The carbon was dried
at 120 ~ for 3 days before being weighed, soaked in
The ratio of occurrence of AuCN to Au(CN)~- on the
distilled water, and used in the experiments. By con-
carbon in the elution column is dependent on the type
ducting a series of tests as described elsewhere, ~12]it was
of activated carbon and the conditions of acid wash-
found that no AuCN was formed on the carbon during
ing. I12] It is important to know this ratio and hence the
adsorption from alkaline solutions at room temperature.
reversibility of adsorption, because it will determine the The mean particle size was 1.42 mm and provided a void
need for cyanide in the elution step. If the conditions of fraction of 0.292 in a packed column; the apparent den-
acid washing are not too severe, most of the gold will
sity was 840 kg" m-a; and the Brunauer-Emmett-Teller
be present as Au(CN)~-, so that elution without cyanide (BET) surface area was determined as 790 m 2. g-l. The
is sometimes possible in practice.
pore volume of the carbon was determined as 6.35 x
Measuremenfl ul of the activity coefficients of CN- and 1 0 - 4 m 3 - kg -1 by measuring the mass loss upon oven
Au(CN)~- revealed that in an organic-rich environment, drying of a sample of carbon that was saturated with
the activities of CN- and Au(CN)~ were, respectively,
water.
102 to 104 and 20 times higher than in water. It was
The objective of this study was to investigate the
claimed that in organic solvent~water mixtures, the much
mechanism of elution and not to obtain the highest pos-
higher increase in activity of the C N - than the
sible elution efficiencies. Hence, a convenient temper-
Au(CN)~- will shift the preceding equilibria to favor the
ature of 70 ~ was selected for most of the elution runs.
desorption of the gold. Tsuchida et al. I~3I attributed
Besides some batch elution tests conducted in 1.0-L so-
the decreased kinetic activity of eluted carbon to - C N
lution (or less) at a stirring speed of 700 rpm, all elution
being a poor leaving group, as well as to the deactivation runs were conducted in a glass column with a temperature-
of the active sites by the oxidation of cyanide by chemi- controlled water jacket. The downward flow of eluant
sorbed oxygen to CO~- and NH~. In testing the effect through the column was controlled manually. A bed vol-
o f various anions on the elution o f gold, it was found
ume (BV) is defined here as the empty volume of the
that anions with higher nucleophilicities were more ca-
column that is occupied by the packed bed of carbon
pable of desorbing gold. This was interpreted as an in- (i.e., 17.16 cm3). The bed height used was 14.3 cm, the
dication that the active sites are able to undergo height/diameter ratio was 11.57, and the flow area was
nucleophilic substitution reactions. 1.20 cm 2. One bed volume of the glass column con-
Adams et al. U4] and Adams and Fleming TM explained
tained approximately 9.4 g of dry carbon.
the desorption of Au(CN); from activated carbon at high The pretreatrnent step was conducted outside the col-
pH on a similar basis as a result of the elution from a umn in glass beakers. Unless otherwise specified, pre-
polymeric adsorbent with phenolic hydroxyl functional treatment was conducted for 30 minutes in 20 mL of a
groups. They proposed that the weakly acidic functional 20 g K C N / L solution at 20 ~ After the pretreatment,
groups, such as phenolic hydroxyl, are deprotonated by the carbon was separated from the solution with a strainer
OH-, leaving the surface more negatively charged and and excessive solution was removed by blotting with fil-
hydrophilic: ter paper. The carbon was then dropped into the glass
R-OH + NaOH ~ R-O-Na + + H20 [3] column containing half a bed volume of eluant at the
elution temperature. The high concentration of cyanide
Such a surface will be less compatible with the auro- in the pretreatment ensured sufficiently high pH values
cyanide ion pair, thus favoring desorption. This mech- in the pretreatment step, as well as during the subsequent
anism is supported by the observation of Cho and Pitt t~51 elutions. The starting time for the elution was taken as
that an increase in pH results in a more negative zeta the moment when flow of eluant was introduced. Al-
potential of the activated carbon. though distilled water was used for elution in most cases,
The preceding findings indicate that cyanide can pro- some experiments required the addition of potassium
mote the elution of gold by three different mechanisms: chloride to the eluant.

8 3 0 - - V O L U M E 25B, DECEMBER 1994 METALLURGICAL AND MATERIALS TRANSACTIONS B

 III. SUBPROCESSES OF ELUTION the elution of gold. Nevertheless, most desorption of gold
Mainly, three important subprocesses that occur si- (Figure 1) occurred when most of the free cyanide had
multaneously govern the continuous change in condi- already been washed out of the carbon bed. No AuCN
tions during an AARL elution cycle. The removal of the was formed on this specific carbon, so that the effect of
pretreatment reagents from the carbon bed constitutes, cyanide could not be linked to the dissolution of an ir-
reversibly adsorbed gold species, tul Furthermore, if CN-
first, the diffusion of cations from the pores of the car-
bon and, second, the decomposition and diffusion of the had displaced Au(CN)2 from loaded activated carbon by
cyanide from the carbon pores. These subprocesses cause a mechanism of competitive adsorption, it could have
been expected that more desorption of gold would have
the desorption of gold, followed by the diffusion of gold
occurred during the pretreatment step. In fact, almost no
cyanide out of the carbon into the interparticle solution.
A typical set of elution profiles obtained at 70 ~ is gold desorbed during the pretreatment step in any of the
depicted in Figure 1. The elution profiles of gold, cya- experiments. This indicates that the relative effects of
spectator cations and cyanide are not clear and require
nide, and potassium, as well as the pH, are normalized
for comparative purposes. A sharp decline in the cyanide further investigation.
and potassium concentrations occurred within the first
two bed volumes, followed by an elongated tail as a re-
sult of the slow removal of reagents being trapped in the IV. E L U T I O N O F S P E C T A T O R CATIONS
pores of the carbon. The peak in the gold profile only
appeared once the bulk of the pretreatment reagents (i.e., The concentration of potassium in the pretreatment so-
lution for the elution run depicted in Figure 1 decreased
the cyanide and spectator cations) had been removed.
Despite the fact that the pH of the water supply was not from 12,300 to 7380 mg K + / L after it was added to the
gold-loaded carbon. The carbon was only blotted with
adjusted, the pH remained high for the whole duration
of the run. It was shown in a previous article TM that all filter paper after it was removed from the adsorption so-
lution, so that the residual water in the pores could have
these factors affect the gold-cyanide equilibrium, which
been responsible for the dilution of the pretreatment re-
consequently changes continuously throughout an elu-
agents. An experiment was then devised to determine the
tion run. A mathematical model for this shifting iso-
effect of the type of anion on the possible adsorption of
therm is required in order to simulate a complete elution
cations.
profile. Whereas Banini and Stange t161 considered only
A sample of dry carbon was added to a KCI solution
the concentration of hydroxyl ions in this isotherm (by
eliminating the effects of cyanide pretreatment), it is clear with the same initial potassium concentration as de-
scribed previously. This led to a slight increase in the
that both cyanide and spectator cations should be taken
into account. 1],2] concentration of potassium in the solution, which was
attributed to the fact that the carbon must have contained
From the profiles in Figure 1, it is evident that the
some adsorbed potassium that was desorbed when it was
presence of potassium as the spectator cation depresses
brought into contact with water. When the pretreatment
the elution of gold because of the strong adsorption of
step prior to the elution run of Figure 1 was repeated
ion pairs. However, the role of cyanide is not apparent
from these profiles. It is well known 17,nA3! that the pres- with dry carbon (so that dilution was eliminated), it was
found that the potassium concentration still decreased from
ence of cyanide depresses the adsorption of gold, and it
12,300 to 10,200 mg K + / L and the cyanide concentra-
is known from industrial practice that cyanide enhances
tion from 7435 to 5841 mg C N - / L .
The observation that more potassium is adsorbed from
a KCN than a KC1 solution indicates that K § is co-
1 adsorbed with cyanide and does not adsorb on its own,
because carbon does not have a high affinity for chlo-
0.8 ride. tln The molar ratio of potassium to cyanide con-
-~ -~1(- -X- -
sumed in the elution run with dry carbon at 20 ~
described previously was calculated as 1 : 1.03, which is
0.6
almost stoichiometric. When the pretreatment was con-
ducted at 70 ~ this ratio decreased to 1:1:37, which
0.4 agrees with the finding that more decomposition and less
I I adsorption of cyanide occurs at higher temperatures) 4~
0.2 I-~- pH I Van der Merwe t4~ showed that the elution of potassium
is independent of temperature and flow rates up to
37 bed volumes per hour. However, the elution of po-
O-
tassium is affected by the nature of the anion in the pre-
2 4 6 8 10 12 14 16 18 treatment reagents. This is supported by the results of
Bed volumes Figure 2, where the elution profiles of K + after a KC1
and KCN pretreatment were compared. The concentra-
Fig. 1 - - N o r m a l i z e d AARL elution profiles in a column at 70 ~ and tion of K + in the eluate was higher for KCN than for
a flow rate of distilled water as eluant of 49.2 m L / h . [Au] =
KCI for most of the run, as a result of the significantly
130- Y mg A u / L ; [K*] = 4000- Y mg K+/L; [CN-I = 2200. Y mg
C N - / L ; pH = 15- Y. The 9.41 g of carbon contained 4.85 g A u / k g lower adsorption of K + from KCl than KCN solutions.
after 22 h of loading and was pretreated for 30 rain in 20 mL solution Although the preceding experiment indicated that
of 20 g K C N / L at 20 ~ spectator cations, such as potassium, adsorb mainly in

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 25B, DECEMBER 1994--831

 elution step of this experiment consisted of two stages.
During the first stage, an eluant containing 1972 mg K+/L
as KCI was pumped through the carbon bed. The high
cation concentration suppressed the elution of the gold
and provided four bed volumes of eluant to rinse the car-
bon of cyanide that was carried over from the pre-
treatment step. For the second stage of the elution, the
__~ 100 potassium-rich eluant was replaced with distilled water.
r Although the cyanide concentration in the solution was
practically zero at that stage, a peak in the gold concen-
10 tration appeared almost instantaneously. Moreover, the
maximum gold concentration was more than 60 pct higher
than that measured in a similar elution without the initial
high cation stage, as depicted in Figure 1. This can be
1
ascribed, however, to the more ~intense" pretreatment
0 2 4 6 8 10 12 14 that was carried out here. The latter effect will be in-
vestigated in Section V.
Bed volumes
From the preceding experiment, it follows that the free
Fig. 2 - - T h e relative effects o f pretreatment with K C N and KCI on cyanide that is present during the elution step of the AARL
the elution o f potassium in a column at 20 ~ and a flow rate of procedure is of secondary importance to that in the pre-
distilled water as cluant of 39.8 m L / h . The 9.41 g of carbon was
treatment. This means that it is the effect of the cyanide
pretrcated for 30 min at 20 ~ in 20 m L of solution initially containing
[K § = 12,300 m g K + / L as K C N or KCI. At the end of pretreatment, that is present in the pretreatment step and not the carry-
[K +] = 7380 m g K+/L for the K C N and [K+I = 12,240 m g K + / L over of pretreatment reagents to the eluant that enhances
for the KCI. the elution of the gold. Because of the high concentra-
tion of spectator cations in the pretreatment step, the bulk
of the gold desorption occurs only during the elution stage
association with cyanide, it is still necessary to investi- once the cation concentration is lowered. The horizontal
gate the relative importance of spectator cations v s cy- position of the gold peak will therefore be a function of
anide during elution. Figure 3, depicts an experiment to the dynamics of the removal of the cations carried over
determine the effect of potassium in the absence of cy- from the pretreatment stage.
anide. After pretreatment in a solution that contained ini-
tially 7886 mg C N - / L as free cyanide, the carbon was
boiled for 1 hour in the pretreatment reagent to decom- V. PASSIVATION OF THE CARBON SURFACE
pose most of the cyanide. This was done to ensure the
lowest possible carryover of cyanide from the pretreat- Davidson and Duncansont~yj showed that more than
ment to the elution stage, and resulted in a residual 99 pct of the gold loaded onto a coconut-shell-based car-
free-cyanide concentration of only 80 mg CN-/L. The bon could be recovered with deionized water after a pre-
treatment with potassium carbonate. A nearly identical
gold elution profile was obtained with an equimolar
2500 sodium-carbonate pretreatment. The carbonate pre-
treatment led, however, to poor elution of silver and other
base metals, as well as to the buildup of calcium car-
2000 .t IAul* I0 bonate 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. Fur-
~ 1500 ther tests indicated that it was the higher hydroxide con-
centration associated with the addition of carbonate, and
I.~ 1000 not the carbonate itself, that was responsible for the ef-
ficient elution of gold. The carbonate in the pretreatment
was then replaced with sodium hydroxide and sodium
51111 cyanide. The sodium cyanide was added in order to in-
crease the stability of the metal-cyanide complexes. Fur-
ther investigations revealed that the elution of all the
0 I I I metal-cyanide species could be improved by adding less
0 5 10 15 20 hydroxide to the pretreatment. In practice, hydroxide is
still added to the pretreatment, but mainly to stabilize
Bed volumes
the cyanide.
Fig. 3 - - A n A A R L column elution subsequent to a step change in The relative insignificance of hydroxide compared to
potassium concentration in the eluant at a flow rate of 49 m L / h and cyanide in the pretreatment is illustrated in Figure 4.
70 ~ The eluant initially contained 1972 m g K § as KCI and was
replaced by distilled water after 2.5 bed volumes. The 9.41 g o f car-
Identical samples of gold-loaded carbon were pretreated
bon initially contained 4.98 g A u / k g . It was pretreated at 35 ~ for at the same pH and the same initial concentration of po-
44 h in 20 m L of solution o f 20 g K C N / L and then boiled for 1 h, tassium. The only difference was that one sample was
which decreased the [CN-] to 80 mg C N - / L . pretreated with a KCN solution and the other with a KOH

832--VOLUME 25B, DECEMBER 1994 METALLURGICAL AND MATERIALS TRANSACTIONS B

solution. As in the case of Figure 2, more potassium carbon, which proves that the surface of the carbon was
adsorbed in the presence of cyanide, so that the residual modified in such a way that its affinity for the auro-
concentrations were 7380 and 8712 mg K+/L, respec- cyanide complex was reduced. However, this passiva-
tively, for the KCN and KOH solutions. Despite the higher tion can be reversed easily by exposure of the carbon to
loading of potassium in the case of cyanide pretreatment, high temperature in the absence of free cyanide.
the maximum gold concentration in the elution was more A further experiment was devised to determine the rel-
than 10 times higher than that for the hydroxide pre- ative importance of the competitive adsorption and the
treatment. It has been shown that the free cyanide in passivating effect of cyanide during pretreatment.
solution is not the dominant effect, so that this experi- Figure 6 depicts the gold elution profiles of two exper-
ment suggests that the presence of cyanide during pre- iments in which the carbon was pretreated at different
treatment causes passivation of the carbon surface, which temperatures, but with the same "loading" of cyanide of
enhances the elution of gold. 7.0 g CN-/kg after pretreatment. The loading is defined
This passivation of activated carbon by cyanide was as the amount of cyanide that is removed from the pre-
investigated by comparing the ability of fresh carbon to treatment solution as a result of either competitive ad-
adsorb gold to that of carbon that was pretreated in a sorption or decomposition on the carbon surface. The
strong cyanide solution. When this test was conducted
initially, the cyanide-treated carbon was boiled in dis-
tilled water before the adsorption test to decompose all
1
the free cyanide occluded in its pores. No difference could
be detected in the subsequent affinity of the two samples
toward gold cyanide, as determined by adsorption in a 0.8
batch-stirred tank reactor. Hence, any possible passi-
vating effect was eliminated by the boiling, which de- 0.6
stroyed all residual free cyanide. This is in contrast with
the experiment represented in Figure 3, which preserved 0.4
the passivating effect of pretreatment by leaving a resid-
ual 80 mg CN-/L as free cyanide. Although high tem-
peratures could convert Au(CN)2 to AuCN, this was not 0.2
the case here, otherwise the same adsorption profiles could
not have been obtained, t1'~21 0 i I I I I I I

Instead of boiling the cyanide-treated carbon, the test 0 5 10 15 20 25 30

was then repeated by eluting all the remaining cyanide
with 190 bed volumes of distilled water in a glass col- Time (h)
umn at room temperature. The carbon was then removed
Fig. 5 - - T h e deactivating effect of cyanide pretreatment on the batch
from the column, and the adsorption of gold cyanide onto adsorption of gold in a batch reactor. Initial [Au] = 24.5 m g A u / L ;
the pretreated carbon was compared to the adsorption pH = 9.5; volume of solution = 1.0 L; mass of carbon = 1.0 g; The
onto a similar sample of fresh carbon in a batch-stirred carbon was pretreated in 10 m L solution of 20 g K C N / L for 40 h at
tank reactor9 Figure 5 shows that the carbon pretreated 20 ~ and rinsed with 190 bed volumes of distilled water at a flow
in KCN had a significantly lower adsorptivity than fresh rate of 35 m L min. For untreated carbon, only distilled water was
used.

140 200

120 * 100 d e g C~

100 150
_l
:3
< 80
E 60
tO 40
20
0
0 ! . : : : : : l !
0 2 4 6 8 10 12 14 16 18 0 2 4 6 8 10 12 14 16 18

Bed volumes Bed volumes

Fig. 4 - - T h e relative effects of pretreatment with either K C N or K O H Fig. 6 - - The effect of the temperature of cyanide pretreatment on the
on gold-elution profiles in a column at 70 ~ and a flow rate of dis- elution of gold cyanide in a column at 70 ~ and a flow rate of dis-
tilled water as eluant of 49.5 m L / h . The 9.41 g of carbon initially tilled water as eluant of 48.5 m L / h . The 9.41 g of carbon initially
contained 4.9 g A u / k g and was pretreated in 20 m L of solution ini- contained 4.83 g A u / k g and was pretreated for 30 min in 20 m L (at
tially containing 12,300 m g K + / L (as either KCN, or K O H and KCl) 20 ~ or l0 m L (at 100 ~ solution of 20 g K C N / L . At both 20 ~
at a pH o f 12.3 and 20 ~ for 30 min. and 100 ~ the cyanide loading was 7.0 g C N - / k g after pretreatment.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 25B, DECEMBER 1994--833

extent of adsorption decreases with an increase in tem- In the AARL elution process, most of the adsorption
perature, so that the carbon pretreated at 100 oC could and reaction of cyanide occur in the pretreatment step,
be expected to have a significantly higher ratio of de- whereas in the Zadra process, the cyanide is decomposed
composed to adsorbed cyanide than that at 20 ~ 1~SlUn- simultaneously with the elution of the gold. Yet in both
fortunately, no analytical method exists whereby this ratio processes, the presence of cyanide in solution as well as
can be determined. the reactions of cyanide on the carbon surface enhance
Figure 6 reveals that significantly improved elution of the desorption of gold. Therefore, it is important to in-
gold was obtained after pretreatment at 100 ~ where vestigate the possible effect of cyanide loading on the
very little adsorption of cyanide would have occurred. decomposition of cyanide itself.
A mechanism of displacement of aurocyanide by cya- The oxidation reactions, Eqs. [9) and [10}, are cata-
nide during cyanide pretreatment at industrial elution lyzed by the presence of activated carbon and are more
temperatures can thus be ruled out to a large degree. As significant at low temperatures. However, the hydrolysis
it was proved that the cyanide in the pretreatment step reactions, Eqs. [6] through [8] dominate at high tem-
does not displace or modify the gold-cyanide species, t41 peratures and are the main cause for the loss of cyanide
it is postulated that the cyanide that is decomposed on during Zadra or AARL elution/2~ Measurement of the
the surface of the carbon during the pretreatment stage decomposition rate of cyanide revealed first-order ki-
changes the functional groups on the surface in such a netics for both the hydrolysis and oxidation reac-
way that the surface becomes less receptive for adsorp- tions. [4,t91 In the present study, no distinction is made
tion. Adams and Fleming TM presented the following ex- between adsorption, hydrolysis, or oxidation of cyanide
amples of possible reac.tions that can occur between during measurement of the kinetics of removal of cya-
cyanide and the functional groups present on the surface nide from solution. An experiment was conducted in
of the carbon: which one sample of carbon was repeatedly contacted
with fresh solutions of cyanide in a batch-stirred tank
O O- reactor for different periods of time. During such a batch
It K I test, small samples of solution were taken and analyzed
R - - C - - R + CN- r R--C--R [4] for free cyanide. The loading of cyanide on the carbon,
[ representing the removal of free cyanide from solution,
CN was then calculated from a mass balance at the end of
each period. The decrease in free-cyanide concentration
(K -~ 11,000)
during each period revealed first-order kinetics, as ex-
I pected. Figure 7 shows a plot of the firt-order rate con-
--C--C-- + CN- r --C=C-- + HCN stant k(CN) for each period of contact as a function of
I II ] [5] the calculated cyanide loading at the end of the preced-
H O O- ing period. Clearly, the rate of decomposition of the cy-
anide decreased with an increase in the cyanide loading
Under industrial alkaline conditions of gold elution, cy- of the carbon. This relationship appears to be strongly
anide is decomposed via several reactions, tl91 of which temperature dependent, laj Therefore, the passivation of
the following are considered to be the most important. the carbon surface caused by the decomposition of cy-
Hydrolysis anide inhibits not only the adsorption of gold cyanide,
CN- + 3H20 ~ {HCOONH4} + OH- [6]
1
{HCOONH4} + 202 ~ H C O ; + NH~" [7] 12

HCO3 + NH + + 2OH- ~ (pH 10.5) 10

NH3+CO~ +2H20 [8] 8

Oxidation
1
C N - + 2 02 ~ {CNO-} [9]

{CNO-} + 2H20 ~ CO~- + NH4 [10]

These reactions would increase the negative-charge den- 2
sity on the surface and render it less receptive for
Au(CN)~. Although this modification of the carbon sur- 0
face would occur already during the pretreatment step, 0 l 2 3 4 5 6
the high concentration of cations (M n+) would favor the Cyanide "loading" [gCN/kg]
formation of M"+{Au(CN)2}, ion pairs on the carbon sur-
face and thereby restrict the desorption of gold during Fig. 7--The decrease in the first-order rate constant for the decom-
position of cyanide with an increase in the cyanide loading. The
this stage. Once the concentration of cations is lowered carbon, with a mass of 21 g, was contacted repeatedly for different
during the elution stage, the Au(CN); will be desorbed periods with 350 mL of solution containing 0.525 g CN-/L at
from the deactivated carbon surface. 18 ~

834--VOLUME 25B, DECEMBER 1994 METALLURGICAL AND MATERIALS TRANSACTIONS B

but also most other reactions on the carbon surface. Van quantify the effect of the cyanide pretreatment, or the
der Merwe 14] confirmed this observation by showing that cyanide loading, on the gold cyanide equilibrium. When
the conversion of cyanide during a Zadra elution run de- sufficient time has elapsed to reach equilibrium, the ef-
clined with time as the carbon surface became passivated. fect of the passivation has already been destroyed through
reactivation.
It was shown in a previous article t~j that the parame-
VI. REACTIVATION OF THE ters in the functional relationships between elution con-
CARBON SURFACE ditions and adsorption/desorption isotherms are strongly
It is well known that elution under industrial condi- dependent on the conditions of pretreatment. Further-
tions restores the activity of the carbon completely if it more, because reactivation of the carbon surface pro-
is not fouled with undesirable organic and inorganic spe- ceeds with time, it is necessary to devise a method to
cies. This means that any passivation of the carbon sur- estimate the equilibrium curve after a cyanide pre-
face should also be reversed. The possible reactivation treatment, but during the subsequent elution stage. The
of the carbon surface after a cyanide pretreatment was method described subsequently was used to estimate the
investigated by monitoring the elution of gold from car- change in the equilibrium isotherm parameter A during
bon that had been loaded over a period of 3 weeks. Suf- an AARL elution in a packed bed of carbon if the mod-
ficient time thus was allowed during the adsorption stage ified Freundlich isotherm tlJ is defined as follows, with
to ensure a fairly homogeneous distribution of gold Qe and Ce being the equilibrium loading and solution
throughout the carbon particles. A short period of ad- concentration, respectively:
sorption would have resulted in a loading gradient of ad- Qe = A" Ce -0"002688"A+0"2902 [1 1]
sorbed gold through the carbon particles, t2~] Under these
circumstances, further diffusion into the finer pores of If it is assumed that resistance to mass transfer becomes
the carbon during the elution step could have led to the negligible after the pretreatment step, t2j equilibrium be-
readsorption of gold that had been eluted from the sur- tween the gold cyanide on the carbon surface and that
face of the particles during the initial stage of the in the interparticle solution will pertain during the elu-
experiment. tion step at every position in the column, including the
Figure 8 depicts the batch elution profiles for two outlet. As the concentration of gold in solution is mea-
samples of carbon loaded to different levels after a cy- sured at the outlet, the equilibrium at the outlet will be
anide pretreatment in a separate container. Desorption known if the loading on the carbon is known. The latter
occurred for the initial 3 hours of the experiment, where- can be estimated by assuming that at any stage, the load-
after the concentration of gold in solution started to de- ing at the outlet will be lower than or equal to the initial
crease gradually. In this case, the readsorption of gold gold loading and higher than the average loading in the
could be ascribed only to the deterioration of the effect column. The average loading at time t can be calculated
of the cyanide pretreatment during the elution step. This from a gold balance by integration of the area under the
reactivation of the carbon makes it difficult to accurately gold elution profile from t = 0 to t = t. With the maxi-
mum and minimum loadings at the outlet known, the
minimum and maximum values of A at the outlet thus
40 can be calculated from Eq. [11]
Figure 9 shows the result of applying the preceding
method to the elution data of Figure 1, with the values
of A varying between 0.8 and 2.1. While the initial gold
30 loading was a constant value, the average loading in the

<
E
20 I
-- 6.3 gAu/kg
7.0 gAu/kg
2.5

2
A (max.)]
~ A (min.) [
O

10 1.5
<

I I I I I I

0 5 10 15 20 25 30 0.5 I ! I I !

T i m e (h) 0 5 10 15 20
Fig. 8 - - R e a c t i v a t i o n of carbon during the batch elution of gold cy- Bed volumes
anide at 60 ~ in 500 m L of K O H solution at a pH of 10.7. The
3.0 g of carbon was loaded with gold for 21 days and then pretreated Fig. 9 - - E s t i m a t i o n of the m i n i m u m and m a x i m u m A values in the
for 30 min at 20 ~ in 5 m L solution of 7.3 g CN / L . shifting isotherm during the A A R L elution depicted in Fig. 1.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 25B, DECEMBER 1994--835

column decreased with an increase in the volume of eluant The observed reactivation is probably caused by the
that passed through the column. The difference between removal of the decomposition products of cyanide from
the maximum and minimum Qe values, and conse- the carbon surface as eluant flows through the carbon
quently the difference between the maximum and mini- pores. However, this postulated phenomenon would be
mum A values, increased with time (or bed volumes). very difficult, if not impossible, to quantify or to inves-
However, during the initial two to three bed volumes tigate as an isolated process. The volume of eluant with
when little gold had been eluted, the values of A were which the carbon has been rinsed thus can be taken as
more exact. The latter A values were plotted in Figure 10 being representative of the degree of reactivation of the
as a function of the potassium concentration. The power carbon surface. Hence, the reactivation in Figure 11 is
relationship between A and the potassium concentration accounted for empirically by expressing the value of A
in Figure 10 serves as further proof of the validity of an as a function of the number of bed volumes:
equilibrium approach, as it was shown previously t*~ that
such a relationship exists at true equilibrium. The ex- A = 2.16 (Vs + 1)~ [~2]
ponent in this relationship is 0.24, as determined from
the slope in Figure 10, which corresponds reasonably Figure 12 depicts the gold profile for the experiment
with the value of 0.20 determined for true equilibrium. 141 considered in Figure 11 and indeed shows some degree
Therefore, this is a new method to estimate the depen- of readsorption of gold at the constant level of potassium
dence of the equilibrium curve on the concentration of
spectator cations.
Consequently, if the concentration of spectator cations 3
is kept constant during an AARL elution, the value of 2.9
A should also be constant if all other factors remain the 2.8
same. This was examined in Figure 1 l, where the cal-
2.7
culated minimum and maximum A values were plotted
as a function of the number of bed volumes that passed 2.6
through the column with a constant level of potassium 2.5
in the eluant. As a result of the high potassium concen- < 2.4 --@-- A (max.)
tration, little elution of gold, if any, occurred, leading 2.3
to a very small difference between the minimum and 2.2
maximum estimates of A. However, Figure 11 shows
2.1
that the A values did not remain constant, but increased
2 1 ! t i
with time. The carbon had been loaded over a period of
3 days, so that a loading gradient of adsorbed gold 0 5 10 15
throughout the carbon particles was unlikely, t2~] There-
fore, this increase in A could not be ascribed to re- Bed volumes
adsorption caused by a favorable loading gradient. Fig. 11 - - E s t i m a t i o n of the m i n i m u m and m a x i m u m A values for a
Consequently, reactivation of the carbon surface toward constant concentration o f 12.0 g KC1/L in the eluant with a flow rate
gold cyanide after a cyanide pretreatment is the only other of 47.6 m L / h during an A A R L column elution at 70 ~ The 9.41 g
of carbon initially contained 4.81 g A u / k g and was pretreated for
mechanism responsible for this readsorption and pro- 30 min at 20 ~ in 20 m L of solution of 20 g K C N / L .
vides further support for the reactivation postulated in
Figure 8.

18 I
16 . . . . . . . . . . . . . . . . . . .

14
0.8
ill 9 Experimental
"~ 12 , Model with
"~1 reactivation
0.6 _,r lo

0.4 8

9 Exp
0.2
4 I t I I I I : : '

0 2 4 6 8 10 12 14 16 18
0
5 5.5 6 6.5 7 7.5 8 8.5 Bed volumes

In ( K + 5 0 ) Fig. 1 2 - - T h e use of an equilibrium model to simulate an A A R L col-

u m n elution at 70 ~ with a constant potassium concentration of
Fig_ 10--Quantification of the effect of potassium on the equilibrium 12.0 g K C I / L in the eluant at a flow rate of 47.6 m L / h . The 9.41 g
of gold elution after a cyanide pretreatment, based on the average A of carbon initially contained 4.81 g A u / k g and was pretreated at 20 ~
values in Fig. 9, for 30 min in 20 m L solution o f 20 g K C N / L

836--VOLUME 25B, DECEMBER 1994 METALLURGICAL AND MATERIALS TRANSACTIONS B

 in the eluant. When an equilibrium-based elution model, efficiencyof gold elution. At cyanide concentrations below
such as that proposed in a previous article, [21 is applied 3 pet, the gold-elution profile was much more sensitive
to the experimental results of Figure 12 without consid- to the addition of cyanide in the pretreatment step. The
ering reactivation, no desorption or adsorption is pre- carbon, therefore, had reached its maximum passivation
dicted because of the high level of potassium. However, at a cyanide concentration of 3 pct in the pretreatment
if a reactivation term, such as that in Eq. [12], is in- and was unaffected by higher cyanide concentrations. A
corporated in the model, a satisfactory fit of the experi- similar result was obtained by Laxen et al.,[23] who ob-
mental data is obtained. This provides further evidence served that a reduction in pretreatment time from 8 to
that reactivation of the carbon surface is one of the sub- 2 hours and a four times weaker pretreatment solution
processes constituting the elution of gold cyanide. had no detrimental effect on the elution.
Nevertheless, Van der Merwe [41 showed that the A new method is proposed in which the dependency
equilibrium-based elution model becomes less dependent of the adsorption/desorption isotherm for aurocyanide
on reactivation at temperatures of about 130 ~ on the concentration of spectator cations can be esti-
mated from the elution profiles for gold and cations.
Reactivation of the carbon surface occurs when the
adsorbed/decomposed cyanide is removed by the eluant.
VH. CONCLUSIONS AND SIGNIFICANCE
This reactivation can be observed more accurately when
The most important subprocesses constituting the elu- a high concentration of cations in the eluant depresses
tion of aurocyanide are the decomposition or adsorption the desorption of aurocyanide. At high temperatures of
of cyanide on the surface of the carbon and the elution pretreatment, such as those used in practice, it is not
of cyanide and the concomitant removal of spectator cat- necessary to include a reactivation term in the mathe-
ions, as well as the subsequent elution of aurocyanide. matical model for elution.
Spectator cations (M~§ depress the desorption of auro-
cyanide by the formation of the neutral M'§
species on the carbon. The formation of these species is
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- of the dynamics of removal of the cations present in the Morrison, and J.P.W. Van der Westhuysen: Miner. Eng., 1994,
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such carbon has been pretreated with cyanide and the 6. D.M. Muir, W.D. Hinchliffe, and A. Griffin: Hydrometallurgy,
1985, vol. 14, pp. 151-69.
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METALLURGICAL AND MATERIALSTRANSACTIONS B VOLUME 25B, DECEMBER 1994--837

20. D.M. Muir, A. Aziz, and W. Hoecker: Proc. 1st Int. 22. R.J. Davidson: in Carbon-In-Pulp School, South African Institute
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838--VOLUME 25B, DECEMBER 1994 METALLURGICAL AND MATERIALS TRANSACTIONS B