The Adsorption of Introduction

Hydrometallurgical processing can be effectively used for the

Gold on Activated treatment of gold-bearing raw materials. Cyanidation is
currently the main choice for the extraction of gold from

Carbon from ores. However, the toxicity of cyanide and the failure of this
complexant to extract gold from the so-called difficult to
treat raw materials (e.g. carbonaceous and copper-gold ores)

Thiosulfate- led to the investigation of alternatives for gold extraction

from various resources.
Chloride, thiosulfate, sulphide, ammonia and sulfite have
Ammoniacal been identified as low cost alternatives, the first two being
more beneficial in terms of health and safety issues and low

Solutions environmental impact. Among the above complexing

agents, thiosulfate is of considerable interest, because it can
be used for leaching of gold from carbonaceous gold ores as
gold-thiosulfate complex which is not preg-robbed by the
P Navarroa, C Vargasa, M Alonsob, carbonaceous component of the ores [1,2]. The gold
FJ Alguacilb leaching reaction with thiosulfate can be described, in its
a Departamento de Ingeniería Metalúrgica, simplified form, by the following reaction:
Universidad de Santiago de Chile, Avda. L. B. O’Higgins
1
3363, Casilla 10233, Santiago, Chile. 2Au+4S2O32- + – O2 + H2O
2
2Au(S2O3)3-
2 + 2OH
- (1)
E-mail: pnavarro@lauca.usach.cl
b Centro Nacional de Investigaciones Metalúrgicas To accelerate this reaction, catalytically, ammonium
(CSIC), Avda. Gregorio del Amo 8, Ciudad Universitaria, hydroxide and copper (II) are commonly added:
28040 Madrid, Spain. E-mail: fjalgua@cenim.csic.es
Au + 5S2O32- + Cu(NH3)42+ Au(S2O3)3- 5-
2 + 4NH3 + Cu(S2O3)3
(2)
Abstract The formation of cuprous thiosulfate complex in the above
The adsorption of gold on activated carbon in reaction consumes the thiosulfate and retards the gold
ammoniacal thiosulfate solution was studied. The leaching. Thus, the cuprous complex should be oxidized back
variables affecting the adsorption of gold on the to cupric ammine complex as much as possible:
carbon included, among others, temperature,
concentrations of ammonium hydroxide and 4Cu(S2O3)35- + 16NH3 + O2 + 2H2O
thiosulfate, and those of accompanying cations and
anions. The apparent activation energy for the 4Cu(NH3)42+ + 12S2O32- +4OH- (3)
adsorption process was estimated to be 19.4 kJ/mol,
and this value indicates that the gold adsorption is Combining Eqs. (2) and (3) results in the overall gold
film diffusion-controlled. It was also found that the dissolution reaction in thiosulfate solution (Eq.(1)).
rate of initial adsorption rate was fast, when Once gold is dissolved, the recovery of gold from the
compared to that of the overall adsorption process. pregnant thiosulfate solutions can be carried out by different
procedures e.g. adsorption, solvent extraction, etc. [1,3-7].
Though adsorption on activated carbon is one of the
Keywords common procedures used in the recovery of gold from
thiosulfate, ammonia, activated carbon, gold cyanide solutions [8], it has not been used widely for the
processing of gold-thiosulfate solutions, several reasons for
this situation are described in the literature [9].
In this paper, the results of an investigation on the
application of this technology to the adsorption of gold from
ammoniacal thiosulfate solutions are reported.

Experimental

The gold thiosulfate complex used in this investigation was

obtained from Alfaaesar, a stock gold solution was prepared

Gold Bulletin 2006 • 39/3 93

Table 1 Table 3
Characteristics of the activated carbon Influence of pH on gold adsorption
Length (cylinder) 5.6mm pH Gold Gold
Diameter (cylinder) 3mm adsorption (1 h) adsorption (8 h)
Surface area 925 m2/g 8.5 11.3% 26.0%
Micropores 96% 9.5 18.5% 29.5%
10.5 31.2% 55.4%
11.0 4.4% 23.3%
by dissolution of the reagent in distilled water. Each working
Aqueous solution: 10 mg/l Au, 1.02x10-4 M thiosulfate, 1 M NH4OH.
gold solution was prepared by mixing a known quantity of the
Temperature: 20°C. Added activated carbon: 0.3g
stock solution with an appropriate amount of ammonium
hydroxide solution. All other chemicals were of reagent grade.
The activated coconut-shell carbon, obtained from Anglo 100
40°C
Chilena SA, was washed with deionized water, dried at 60°C 90 20°C
for 48 h and stored in a desiccator under vaccum. Table 1
lists main physical characteristics of the activated carbon. 80 5°C

% gold adsorption
Gold adsorption tests were carried out in a 1000 ml glass 70
reactor equipped with a stirring device. The reactor was 60
placed in a constant temperature water bath. Experiments
50
were run at a stirring speed of 500 min-1 with 500 ml of the
gold solution. When the pH of the solution was properly 40
adjusted and the desired temperature was reached, the 30
experiments were initiated by placing a weighed amount of
20
the activated carbon into the reactor. Samples were
periodically taken for chemical analysis by AAS. The 10
effectiveness of the adsorption process was estimated from 0
the percentage of gold adsorption, which was calculated by 0 2 4 6 8
using the following equation: Time, hours

(C0– Ct) . Figure 1

A= 100 (4)
C0 The percentage of gold adsorbed on activated carbon at various
temperatures
where C 0 is the initial gold concentration and C t is the
concentration at an elapsed time, t, after the addition of while the effect of ammonium hydroxide concentration
active carbon. was less significant at longer reaction times, at which the
percentage of gold adsorbed onto the carbon is practically
the same at the three different ammonium hydroxide
Results and discussion concentrations used.
Though not shown in this paper, a further increase in
Effect of ammonium hydroxide ammonium hydroxide concentration led to a decrease in
Experiments were carried out at three different the adsorption of gold on the carbon. This result may be
concentrations of ammonium hydroxide, namely 0.3, 0.6 attributed to the competitive adsorption of ammonium
and 1 mol/l. The aqueous solution had the initial ion with gold ion on the carbon surface, i.e., an increase in
concentrations of 10 mg/l for gold and 1.02x10-4 M for ammonium hydroxide concentration results in a decrease
thiosulfate. The results of these experiments (Table 2) in activity and diffusivity of gold ion, leading to a decrease
show that at shorter times, the adsorption of gold on the in gold adsorption [10].
carbon increased with increasing ammonium hydroxide
concentration up to 0.6 mol/l and then remained constant, Effect of pH
Previous investigations on gold leaching confirmed that a
Table 2 pH value of near 9.5 was optimal for gold extraction
The adsorption of gold on activated carbon as a function of various [1,2,11]; therefore, the effect of pH on gold adsorption was
NH4OH concentrations studied in this range. As can be seen from the results
NH4OH, mol/l Gold Gold shown in Table 3, the pH variation did affect the gold
adsorption (1 h) adsorption (8 h) adsorption, i.e., it was severely retarded at the lower and
0.3 23.6% 53.8% higher pH values, with an optimum gold adsorption taking
0.6 32.8% 55.4% place at the pH of 10.5.
1.0 32.5% 55.5% Generally speaking the adsorption rate of gold on
pH 9.5. Temperature: 20°C. Added activated carbon: 0.3g activated carbon is relatively fast during the initial stage if

Gold Bulletin 2006 • 39/3 94

Table 4
Effect of different anions on the adsorption of gold on carbon 100
Gold
Anion % Gold adsorptiona 90
10 mg/L
S2O3 2-(1.02x10-4M) 55.4 80 25 mg/L

% gold adsorption
S2O3 2-(0.2M) 13.2 35 mg/L
70
Cl-(0.5M) 41.0
60
ClO4-(0.5M) 46.5
a After 8 h. Other experimental conditions were the same as for Figure 2 50

40
100
S2O32- 30
90
1.02x10-4M 20
80 0.05M
0.2M 10
% gold adsorption

70
0
60 0 2 4 6 8
50 Time, hours

40 Figure 3
The percentage of gold absorbed on activated carbon as a function of
30 initial gold concentration in solution. Aqueous phase: various gold
concentrations and 0.8M NH4OH at pH 10.5. Added activated carbon:
20
0.3g. Temperature: 20°C
10

0 the aqueous solution influences the adsorption of gold onto the

0 1 2 3 4 5 6 7 8
activated carbon. Two effects can be seen: first, the adsorption
Time, hours rate increases with increasing initial thiosulfate concentration,
Figure 2 and second, the percentage of gold adsorbed during a given
The percentage of gold adsorbed on activated carbon at various length of time decreases with increasing thiosulfate
thiosulfate concentrations. Aqueous phase: 10mg/l gold, 0.8M NH4OH concentration. This is a serious drawback because practical
and various thiosulfate concentrations at pH 10.5. Added activated leachings are expected to contain an excess of thiosulfate.
carbon: 0.3g. Temperature: 20°C
The decrease in gold adsorption is probably caused by
compared to that of the overall adsorption process. This is side reactions which affect the overall gold adsorption
attributable to the quick adsorption of gold on macropores process, e.g., excess thiosulfate ions can undergo the
of activated carbon and the slow diffusion of gold into following disproportionation reactions [4,5]:
micropores, which comprises a large percentage (96%) of
the total pore volume of the carbon. S2O3
2
<==> S0 + SO32- (4)

Effect of temperature
2-
3S2O3 + H2O <==> 2SO42- + 4S0 + 2OH- (5)
To investigate the influence of temperature on the The precipitated sulphur may decrease the surface area
adsorption of gold on activated carbon, experiments were available for gold adsorption. In addition, the probable
carried out at 5, 20 and 40°C. The initial concentration of decomposition of thiosulfate into tetrathionate (S4O62-) and
gold was 10 mg/l, the thiosulfate concentration was trithionate (S3O62-) and the detrimental effect of these species
1.02x10-4 M and the ammonium hydroxide concentration may also result in a decrease in gold adsorption.
was 0.8 M. The pH of the aqueous phase was 10.5, and Furthermore, the influence of various anions on the
0.3 g of activated carbon was added to the gold solution. adsorption of gold was investigated by adding individually
Figure 1 shows the effect of temperature on the adsorption those anions into the gold solution as the corresponding
of gold. It is seen that, within the range of temperature sodium salt. Table 4 summarizes the observed effects of
investigated, the adsorption of gold on activated carbon thiosulfate, chloride and perchlorate ions on the adsorption of
increased with increasing temperature. The activation gold on the carbon. It can be seen that the presence of these
energy was estimated as 19.4 kJ/mol. This value supports the anions caused a decrease in gold recovery. The decrease in
contention that the gold adsorption proceeds via a film gold adsorption in the presence of these anions is also
diffusion-controlled mechanism [6, 12-14]. attributable to a decreased diffusivity of gold species caused
by the anions [15].
Effect of thiosulfate and different anions Though not investigated in the present work, it is known that
Figure 2 plots the percentage of gold adsorption vs time for the addition of cyanide ions in the system has a positive
experiments performed with various initial thiosulfate influence, increasing the adsorption of gold onto the
concentrations. It can be seen that the presence of this anion in carbon [1].

Gold Bulletin 2006 • 39/3 95

 100 100
Cu(II)
90 nil 90
80 0.1 g/L 80
1 g/L
% gold adsorption

% gold adsorption
70 70
60 60
50 50

40 40
mL solution/g
30 30
carbon relationship
20 20 1600
800
10 10
480
0 0
0 2 4 6 8 0 2 4 6 8
Time, hours Time, hours

Figure 4 Figure 5
The percentage of gold adsorbed on activated carbon in the presence The percentage of gold adsorbed on activated carbon with various
of copper (II) in the solution. Aqueous phase: 10mg/l gold, 1.02x10-4 M amounts of activated carbon. Aqueous phase: 10mg/L gold, 1.02x10-4
thiosulfate, 0.8M NH4OH and copper (II) at pH 10.5. Added activated M thiosulfate, 0.8 M NH4OH at pH 10.5. Temperature: 20°C
carbon: 0.3g. Temperature: 20°C

Effect of gold concentration adsorption was also investigated. The presence of zinc in the
gold solution, though full data are not presented in this paper,
As can be seen from Figure 3, the initial gold concentration showed an effect similar to that of copper; e.g., the percentage
has a significant influence on the adsorption of gold. It is gold recovery found in the absence of zinc was equal to 54.0%,
clear that the higher the initial concentration of gold, the while in the presence of 0.1 and 1 g/l zinc, the recovery
lower the adsorption rate. Moreover, the percentage of gold percentages were 48.7% and 34.8%, respectively after 6 h of
adsorbed onto the carbon increased as the initial gold adsorption time. All other experimental conditions were
concentration was decreased. This result can be understood identical to those for Figure 4.
by assuming that the available active sites are insufficient to
increase gold loading proportionately to the increase of gold
in the initial aqueous solution, and thus decreasing the Effect of the amount of
percentage of gold adsorption onto the carbon. activated carbon

Experiments were carried out using various amounts of

Influence of copper (and zinc) carbon to examine its effect on both the percentage of gold
adsorbed and on the adsorption rate. Experimental results
As described already, the role of copper in the dissolution obtained by varying the ratio of the volume of solution to the
of gold in ammoniacal thiosulfate solutions is very important. amount of added carbon from 1600 to 480 ml of solution/g
Thus, it seemed appropriate to determine the influence of this of carbon are shown in Figure 5. It is seen that the recovery
metal, normally present as Cu(NH3)42+ complex, on the of gold increases with a decrease in the above ratio, while the
adsorption of gold. This was determined at various adsorption rate is only slightly affected by the variation of the
concentrations of copper (0-1 g/l). amount of carbon added to the solution. It can be deduced
As can be seen from Figure 4, the presence of copper in that the surface area of the carbon plays an important role in
solution in the form of the above complex affects the the adsorption, because the more carbon used, the greater
adsorption of gold onto the carbon. As the concentration of the surface area. Typical metal loadings of the carbon after
copper was increased, the percentage of the gold recovered the reaction time of 8 h were found to be 7.0, 4.6 and 3.4
became less. One probable explanation for this behaviour is the g/kg carbon, respectively for the solution volume to weight of
co-adsorption of copper with gold (e.g. at the initial Cu(II) carbon ratios of 1600, 800 and 480 (ml solution/g carbon),
concentration of 0.1 g/l, 10.7% of this metal was adsorbed respectively.
onto the carbon after 8 h). The authors wish to acknowledge CONICYT (Chile) for
Zinc can also be present in the raw material, and thus, it can project FONDECYT 7040009 and also wish to thank CSIC
be found in the gold leaching solution. Its influence on gold (Spain) and USACH (Chile) for project 2003CL0001.

Gold Bulletin 2006 • 39/3 96

About the authors 3 H. Zhang, D. Dreisinger, Hydrometallurgy, 2002, 66, 67 and
references therein
P Navarro (Professor) and C Vargas (Adjuntant Professor) are 4 A.C. Grosse, G.W. Dicinoski, M.J. Shaw, P.R. Haddad,
within the staff of the Department of Metallurgical Hydrometallurgy, 2003, 69, 1 and references therein
Engineering of the Universidad of Santiago de Chile, their 5 J.B. Hiskey, J. Lee, Hydrometallurgy, 2003, 69, 45
investigations include the hydrometallurgical processing of 6 P. Navarro, R. Alvarez, C. Vargas, F.J. Alguacil, Min. Eng., 2004,
raw materials. M Alonso (Scientific Tenure) and FJ Alguacil 17, 825
(Professor) are within the staff of the High Council of 7 H. Zhang, D.B. Dreisinger, Hydrometallurgy, 2004, 72, 225
Scientific Research (CSIC) of the Spanish Government, their 8 J. Marsden, I. House, The Chemistry of Gold Extraction, Ellis
investigations include, besides aerosol sciences and Horwood, Chichester, 1992
environmental sciences, the hydrometallurgical processing of 9 N.P. Gallagher, J.L. Hendrix, E.B. Milosavljevic, J.H. Nelson, L.
raw materials. Solujic, Hydrometallurgy, 1990, 305
10 Q. Xu, X. Meng, K.N. Han, Min. & Met. Proc., 1996, November,
141
References 11 H. Arima, T. Fujita, W.T. Yen, Min. & Metal. Proc., 2003, 20, 81
12 R.H. Perry, D. Green, Perry’s Chemical Engineers’ Handbook,
1 M.G. Aylmore, D.M. Muir, Min. Eng., 2001, 14, 135 and references McGraw-Hill, New York, 1984
therein 13 F.J. Alguacil, M. Alonso, L.J. Lozano, Chemosphere, 2004, 57, 789
2 P. Navarro, C. Vargas, A. Villarroel, F.J. Alguacil, Hydrometallurgy, 14 P. Navarro, C. Vargas, F.J. Alguacil, Rev. Metal. Madrid, 2005, 41, 107
2002, 65, 37 15 T. Rubcumintara, K.N. Han, Met. Trans. B, 21B, 429

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