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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