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-

THE carbon-in-pulp (CIP) process is the preferred
method used internationally for extracting gold from
leached pulps. Although the kinetics and mechanism of
adsorption of gold cyanide onto activated carbon have
been studied thoroughly, the elution of gold from the
carbon has not been researched methodically to the same
extent. In two recent articles, we have made first at-
tempts to quantify the complex inter-relationship be-
tween variables affecting the equilibrium of desorption t~]
and to model the dynamic behavior of the elution process
on a general basis, lz} However, little research has been
conducted on the mechanism of the elution process, aside
from the brief discussion presented by Adams and
Fleming. t3] The ongoing debate in industry whether or
not cyanide is required in elution is mainly the result of
a lack of understanding the mechanism of elution of
aurocyanide. In neither of the existing articles on the elu-
tion process has any attempt been made to isolate some
of the complex phenomena affecting elution. Some vari-
ables, such as the concentrations of cyanide and cations,
can have opposing effectstq but are usually difficult to
decouple in a normal elution run.
Consequently, there is a need for a systematic study
on the mechanism of elution, which will require the de-
sign of special experiments. It is the objective of this
article to formulate such a mechanism of elution from
J.S.J. VAN DEVENTER, Professor, and P.F. VAN DER MERWE,
Ph.D. Graduate, axe with the Department of Chemical Engineering,
University of Stellenbosch, Stellenbosch, 7600, Republic of South
Africa.
Manuscript submitted November 29, 1993.
sorbed on the surface of the carbon.
Two main techniques of elution are used in industry:t4]
(1) The Zadra process, in which warm cyanide solution
is circulated through an elution column and electro-
winning cell (a United States Bureau of Mines inven-
tion); and (2) The Anglo American Research Laboratory
(AARL) method, consisting of a pretreatment step with
hot caustic cyanide solution, followed by elution with
hot deionized water (a South African invention). An
Australian invention, t5,6} which involves the use of or-
ganic solvents, is also used in a few industrial applica-
tions. In general, the AARL method is preferred because
of lower operating costs, especially with the develop-
ment of continuous elution. Therefore, the AARL pro-
cedure was used as a basis for the present investigation.
According to Adams and Nicol, tT] temperature, cya-
nide and hydroxide concentrations, and the ionic strength
of the eluant constitute the most significant effects on
elution. In cases where the loaded carbon contains high
levels of calcium carbonate, the temperature and acid
washing of the carbon are considered to be most im-
portant for efficient elution.[8] Cyanide and hydroxide salts
are added during both the AARL and Zadra elution pro-
cesses to promote the elution of the gold cyanide. The
equilibrium between the adsorbed gold and the gold cy-
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-
position of the cyanide are affected significantly by
temperature, tz~ High temperatures and intense cyanide
pretreatment (i.e., conditions favorable for elution) de-
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
particles, c~]This implies that the resistance to mass trans-
fer is less profound under strong elution conditions. An
elution model, which assumes equilibrium of auro-
cyanide between the solution and carbon phases at any
point in an elution column, can then be formulated, tzl It
has been shown that such a model simulates AARL elu-
tion runs at different temperatures and pretreatment con-
ditions using the same set of parameters, tal
Adams and Nicol [TJ surmised that the desorption of gold
involves the competitive adsorption of cyanide and auro-
cyanide on activated carbon. Likewise, Tsuchida tul as-
sumed that the desorption of gold from carbon can be
expressed by the following equilibria:
{AuCN}r + CN- r {Au(CN)2-}~o,,,,~on
{Au(CN)2}ca~n + CN- 4:> { C N - } ~
+ {Au(CN)~}solution
The ratio of occurrence of AuCN to Au(CN)~- on the
carbon in the elution column is dependent on the type
of activated carbon and the conditions of acid wash-
ing. I12] It is important to know this ratio and hence the
reversibility of adsorption, because it will determine the
need for cyanide in the elution step. If the conditions of
acid washing are not too severe, most of the gold will
be present as Au(CN)~-, so that elution without cyanide
is sometimes possible in practice.
Measuremenfl ul of the activity coefficients of CN- and
Au(CN)~- revealed that in an organic-rich environment,
the activities of CN- and Au(CN)~ were, respectively,
102 to 104 and 20 times higher than in water. It was
claimed that in organic solvent~water mixtures, the much
higher increase in activity of the C N - than the
Au(CN)~- will shift the preceding equilibria to favor the
desorption of the gold. Tsuchida et al. I~3I attributed
the decreased kinetic activity of eluted carbon to - C N
being a poor leaving group, as well as to the deactivation
of the active sites by the oxidation of cyanide by chemi-
sorbed oxygen to CO~- and NH~. In testing the effect
o f various anions on the elution o f gold, it was found
that anions with higher nucleophilicities were more ca-
pable of desorbing gold. This was interpreted as an in-
dication that the active sites are able to undergo
nucleophilic substitution reactions.
Adams et al. U4] and Adams and Fleming TM explained
the desorption of Au(CN); from activated carbon at high
pH on a similar basis as a result of the elution from a
polymeric adsorbent with phenolic hydroxyl functional
groups. They proposed that the weakly acidic functional
groups, such as phenolic hydroxyl, are deprotonated by
OH-, leaving the surface more negatively charged and
hydrophilic:
R-OH + NaOH ~ R-O-Na + + H20
Such a surface will be less compatible with the auro-
cyanide ion pair, thus favoring desorption. This mech-
anism is supported by the observation of Cho and Pitt t~51
that an increase in pH results in a more negative zeta
potential of the activated carbon.
The preceding findings indicate that cyanide can pro-
mote the elution of gold by three different mechanisms:
8 3 0 - - V O L U M E 25B, DECEMBER 1994
(1) reaction with the adsorbed gold cyanide species,
(2) competitive adsorption (which is regarded here as being
similar to ion exchange), and (3) reaction with the car-
bon functional groups. It is the objective of this article
to investigate the relative importance of mechanisms (2)
and (3) and to distinguish between the depressing effect
of spectator cations [~] and the enhancing effect of cya-
nide on the elution of aurocyanide.
II. EXPERIMENTAL
The main adsorbate used in experiments was pow-
dered potassium aurocyanide KAu(CN)2 dissolved in
distilled water. Small amounts of HC1 or KOH were added
to the process solution in order to control the pH. Eluted
[1] coconut-shell-based activated carbon from the Beatrix
gold mine near Virginia in South Africa was acid washed
and rinsed with deionized water to remove as many im-
[2] purities as possible prior to use. The carbon was dried
at 120 ~ for 3 days before being weighed, soaked in
distilled water, and used in the experiments. By con-
ducting a series of tests as described elsewhere, ~12]it was
found 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 column; the apparent den-
sity was 840 kg" m-a; and the Brunauer-Emmett-Teller
(BET) surface area was determined as 790 m 2. g-l. The
pore volume of the carbon was determined as 6.35 x
1 0 - 4 m 3 - kg -1 by measuring the mass loss upon oven
drying of a sample of carbon that was saturated with
water.
The objective of this study was to investigate the
mechanism of elution and not to obtain the highest pos-
sible elution efficiencies. Hence, a convenient temper-
ature of 70 ~ was selected for most of the elution runs.
Besides some batch elution tests conducted in 1.0-L so-
lution (or less) at a stirring speed of 700 rpm, all elution
runs were conducted in a glass column with a temperature-
controlled water jacket. The downward flow of eluant
through the column was controlled manually. A bed vol-
ume (BV) is defined here as the empty volume of the
column that is occupied by the packed bed of carbon
(i.e., 17.16 cm3). The bed height used was 14.3 cm, the
height/diameter ratio was 11.57, and the flow area was
1.20 cm 2. One bed volume of the glass column con-
tained approximately 9.4 g of dry carbon.
The pretreatrnent step was conducted outside the col-
umn in glass beakers. Unless otherwise specified, pre-
treatment was conducted for 30 minutes in 20 mL of a
20 g K C N / L solution at 20 ~ After the pretreatment,
the carbon was separated from the solution with a strainer
and excessive solution was removed by blotting with fil-
ter paper. The carbon was then dropped into the glass
[3] column containing half a bed volume of eluant at the
elution temperature. The high concentration of cyanide
in the pretreatment ensured sufficiently high pH values
in the pretreatment step, as well as during the subsequent
elutions. The starting time for the elution was taken as
the moment when flow of eluant was introduced. Al-
though distilled water was used for elution in most cases,
some experiments required the addition of potassium
chloride to the eluant.
METALLURGICAL AND MATERIALS TRANSACTIONS B