Separation and Purification Technology 230 (2020) 115834

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

The use of new modified activated carbon in thiosulfate solution: A green T

gold recovery technology
⁎ ⁎
Yunlong Chena, Futing Zib, , Xianzhi Hub, , Peng Yanga, Yongping Mab, Huiling Chengb,
Qiang Wanga, Xuecong Qina, Yang Liua, Shuliang Chena, Chaowu Wangb
a
Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093, China
b
Faculty of Science, Kunming University of Science and Technology, Kunming 650500, China

A R T I C LE I N FO A B S T R A C T

Keywords: A clean and effective activated carbon modification method aimed at the cleaner production of gold using
Thiosulfate activated carbon was investigated in this paper. Activated carbon rich in nitrogen and sulfur (H-AC) was syn-
Gold thesized by a clean and simple method. The gold adsorption performance of H-AC was investigated by ad-
Activated carbon sorption experiment, in which a gold adsorption capacity of 25.8 kg/t was achieved on H-AC. The materials were
Adsorption
characterized by FT-IR, SEM, EDS and XPS, the results identified that the activated carbon’s modification and the
Ligand exchange
gold adsorption on H-AC were successful. Furthermore, the adsorption of Au(S2O3)23− on H-AC may be a ligand
interchange mechanism. Last, it was found that about 87.6% of gold could be stripped from H-AC-Au containing
gold 2.0 kg/t via elution. This study reported a new effective activated carbon related gold recovery method in
non-cyanide clean thiosulfate system, which is of great significance to the cleaner production of gold.

1. Introduction According to literature, thiosulfate has been used to leach gold and
satisfactory results have been achieved [9–12]. However, there is no a
Cyanide is an extremely toxic substance, whose use can cause death suitable process for gold recovery in thiosulfate system due to the fact
to humans, wild or domestic animals, and fishes, as well as environ- that activated carbon’s very poor adsorption ability to Au(S2O3)23− ion
mental damage [1]. However, it is known that there is a large amount [7,13].
of sodium cyanide used for gold extraction every year in the world [2], Among other alternative technologies such as sedimentation by
whose mechanism is shown in Eq. (1). Therefore, it is meaningful to metals [14,15], adsorption [13,16–21], and solvent extraction [22,23],
study a new non-toxic alternative reagent to cyanide in gold produc- sorption is acceptable from the perspective of cost savings and en-
tion. vironmental protection [24–28]. For sorbents, resin’s usage in thio-
sulfate and cyanide system has been broadly reported in literature
4Au + 8CN− + O2 + 2H2 O = 4Au(CN)2− + 4OH− (1)
[11,25–30], and silicon’s usage in thiosulfate system has also been
In previous studies, researchers have investigated some alternative studied by some researchers [31,32], while modified activated carbon
gold leaching methods (including biological oxidation, halogens, is though as the more competitive one to be used in ore pulp because its
thiourea, thiocyanate, ammonia and thiosulfate) [1,3–6]. Among these higher hardness compared to resin and large particle size compared to
methods, thiosulfate, once used as fertilizer [3], is regarded as the most silica beads [7,17]. And the technology of gold adsorption using acti-
clean reagent, whose mechanism is shown in Eq. (2). Compared with vated carbon in cyanidation is mature [33,34], which could be directly
other methods, leaching gold with thiosulfate has advantages such as employed in the thiosulfate system.
lower price (thiosulfate per unit weight is cheaper than that of cyanide), It is known that modification (such as impregnation, chemical
less influence from other cations, faster leaching rate (in copper-am- treatment, physical treatment) [35,36] on activated carbon can boost
monia system), and more effective leaching of carbonaceous ores its adsorption ability. In our previous study, it was found that activated
[3,5–8]. carbon’s gold adsorption ability could be improved by treating with
4Au + 8S2 O32 − + O2 + 2H2 O → 4Au(S2 O3)32− + 4OH− cupric ferrocyanide [17], or silver ferrocyanide [18], or MBT [37].
(2)
Although progress has been achieved, the gold adsorption capacity

⁎
Corresponding authors.
E-mail addresses: 345992103@qq.com (F. Zi), xianzhihu2@sina.com (X. Hu).

https://doi.org/10.1016/j.seppur.2019.115834
Received 22 March 2019; Received in revised form 16 July 2019; Accepted 19 July 2019
Available online 27 July 2019
1383-5866/ © 2019 Published by Elsevier B.V.
Y. Chen, et al. Separation and Purification Technology 230 (2020) 115834

needs to be improved. Cuprous cyanide has also been employed to study [37]. It was needed to be highlighted that the gold concentration
improve activated carbon’s gold affinity, while whose preparation was fixed at 100 mg/L except it was specifically stated.
process required relatively more procedures and strict treatment con-
ditions [38].
2.2.3. Adsorption experiment
Literature show that the adsorption ability of activated carbon
Before the adsorption experiments were conducted, a fixed 0.5 g
mainly depends on the large surface area [39], surface functional
adsorbent was placed into 100 mL prepared gold adsorption solution in
groups containing heteroatoms such as oxygen, nitrogen, and sulfur
an Erlenmeyer flask. Besides, the mechanical stirrer (speed:
[40,41]. Besides, adsorption ability can also be influenced by hydro-
180–200 rpm) was placed above the Erlenmeyer flask to strengthen the
phobicity [42] and π-π interaction between aromatic organic materials
adsorption process, and a temperature-controlled water reservoir was
and π electrons on activated carbon’s graphene crystallite [43,44].
placed under the Erlenmeyer bottle to control the temperature of ad-
Based on the rules above, 1-phenyl-5-mercaptotetrazole (PMT), char-
sorption surrounding. For the purpose of testing the adsorption effect of
acterized with (a) poor solubility in water, (b) aromaticity, and (c) rich
sorbent, the aqueous sample was partly taken out at fixed time and
heteroatoms [45,46], is employed to improve activated carbon’s ad-
subjected to AAS for gold concentration determination.
sorption ability to gold in thiosulfate solutions in this study.
The level of gold adsorption, as one index to measure the gold ad-
Moreover, gold desorption or elution after gold adsorption, which is
sorption ability of adsorbent, was calculated by the Eq. (3), in which the
vital for this technology, has not been reported up until now. Of course,
level of gold adsorption of sorbent was represented by R1 (%), the in-
literature shows that gold can be taken out from activated carbon by
itial gold concentration and gold concentration at certain time t were
incineration [30], but this technology is expensive and extremely
described by C0 (mg/L) and Ct (mg/L), respectively.
harmful to atmospheric environment. So, it is vital to find new methods
to enhance the gold adsorption ability and to strip gold from activated C 0 − Ct
R1 = × 100%
carbon. C0 (3)
In this paper, activated carbon rich in nitrogen and sulfur (H-AC)
was prepared in the laboratory. Fourier Transform Infrared The gold capacity of activated carbon, as another index to measure
Spectroscopy (FT-IR), N2 adsorption isotherms, Scanning electron mi- the gold adsorption ability of adsorbent, was calculated from Eq. (4). In
croscope (SEM) and X-ray Photoelectron Spectroscopy (XPS) were used Eq. (4), the gold capacity of sorbent was represented by q (kg/t), the
to characterize the adsorbents. The gold adsorption ability of H-AC was amount of sorbent used in adsorption process was present by M (g), and
studied through adsorption experiment, and the possible gold adsorp- V (L) was the volume of adsorption solution.
tion mechanism was discussed. Importantly, a method to separate gold R1 × C0 × V × 1000
from activated carbon is also reported. q=
M × 1000 (4)

2. Materials and methods Freundlich equation, as shown in Eq. (5), was used to study the
adsorption process. In this equation, ce represented the gold con-
2.1. Materials centration in solution at equilibrium, qe was used to represent the gold
capacity on carbon at equilibrium. The item n was constant.
2.1.1. Reagents
q e = kce1/n (5)
The main raw materials were coconut shell-derived activated
carbon with diameter of 2–5 mm and gold powder (99.9% purity). The Pseudo-first-order and pseudo-second-order kinetic equations, as
reagents including PMT, NaOH, hydrochloric acid (HCl), N,N-di- shown in Eqs. (6) and (7), respectively, were employed to study the
methylformamide (DMF), and ethanol (EtOH) were all analytically gold adsorption process from the perspective of kinetics. In Eqs. (6) and
pure, and used as received. (7), qe and qt were used to represent the gold adsorbed on adsorbent at
equilibrium and time t, and k1 and k2 are used to represent the rate
2.1.2. Instruments constants.
FT-IR (Nicolet iS10, Thermo Fisher, Waltham, MA, USA) were em-
ployed to investigate the spectral information of samples. SEM (Phenom k1
log(q e − qt) = logq e − t
Prox, FEI Co., USA) attached with EDS was adopted to characterize the 2.303 (6)
materials’ element composition, morphology and structure. XPS ana-
1 1 1
lysis was performed to characterize the chemical environment of = + t
qt k2q 2e qe (7)
needful element in materials through PHI 5000 Versa Probe (FULVAC-
PHI, Inc., Japan/USA). AAS (AAS-300, PerkinElmer, USA) was em-
ployed to detect the remaining gold amount in adsorption solution.
Autosorb I (Quantachrome Corporation, USA) was employed to study 2.2.4. Exploration experiment for gold stripping from H-AC-Au
the Brunauer–Emmett–Teller (BET) surface area, total pore volume and In this part, 0.5 g H-AC-Au with a fixed gold capacity of 2 kg/t was
pore size of the materials by N2 adsorption at 77 K. placed into 20 mL different organic solvent under 40 °C in constant
temperature water bath oscillation shaker to explore the gold stripping
2.2. Methods ability of organic solvent. After a period of time, the activated carbon
was incinerated under 800 °C in muffle furnace for 8 h. Then, the ash
2.2.1. Preparation of H-AC content was dissolved by 1:1 aqua regia and kept boiling for 30 min on
A solution used for activated carbon modification was prepared by electric hot plate. Last, the dissolved ash was subjected to AAS to de-
mixing 0.6 g PMT with 20 mL EtOH. After that, the 2.0 g original acti- termine the gold concentration. The gold stripping ability was calcu-
vated carbon was added into the prepared solution. After 12 h, acti- lated by gold capacity according to the equation below:
vated carbon particles were washed and dried. Hereto, the target ma- Q0 − Qt
terial H-AC was prepared, which was used as adsorbent in the following R2 = × 100
Q0 (8)
experiment.
where Q0 (kg/t) and Qt (kg/t) are the gold capacity of activated carbon
2.2.2. Preparation of adsorption solution before and after dealing with organic solvent, R2 (%) represents the
[Au(S2O3)2]3− solution was prepared according to our previous gold stripping ability.

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Y. Chen, et al. Separation and Purification Technology 230 (2020) 115834

gold (H-AC-Au) were listed. Totally, the surface area, pore volume and
pore diameter of H-AC were decreased compared with original acti-
vated carbon’s. Among them, micropore volume of H-AC is changed
remarkably, decreased more than 50% of original one’s, which means
that PMT may mainly be adsorbed in the micropore region of activated
carbon. After gold adsorption, its surface area and volume decreased
further, whereas its average pore diameter was bigger than the average
pore diameter of H-AC. The reason may be that some micropore was
blocked during the gold adsorption process, so, the pore volume and
surface area decreased but the pore diameter decreased.
Moreover, from the results that the values of both pore volume and
surface are decreased gradually from original activated carbon to H-AC
to H-AC-Au, it verified that PMT’s hydrophobicity on modification is an
important role, or else the surface and volume may be increase after
gold adsorption because that gold adsorption process is carried out in
aqueous solution. Furthermore, it has been reported that activated
carbon has aromatic graphite crystallite structure containing many sp2
C atoms [43], therefore another reason of PMT’s adsorption may be the
Fig. 1. FT-IR spectra of AC, PMT and H-AC.
aromaticity of PMT itself and activated carbon, which can produce a
weak interaction (eg., π-π stacking) between aromatic structures.
3. Results and discussion
3.1.3. SEM results
3.1. Characterization SEM was employed to analyze the microscopic morphology of ac-
tivated carbon, and EDS attached to SEM was used to analyze the
3.1.1. FTIR results change in elemental composition of activated carbon. The results were
The IR spectra in Fig. 1 illustrate the changes in functional groups in shown in Fig. 2. In this image, A, B, and C represented the original
the region from 400 to 3000 cm−1 on AC, PMT and H-AC. Compared activated carbon, activated carbon rich in heteroatom (H-AC), and ac-
with the spectra of activated carbon, some new peaks (1570 cm−1, tivated carbon after adsorption of gold (H-AC-Au), respectively. As
1355 cm−1, 1190 cm−1, 1141 cm−1, 906 cm−1, 833 cm−1, 752 cm−1, shown in Fig. 2, there was much pore structure including pores in
680 cm−1, 609 cm−1, and 499 cm−1) appeared on the spectra of H-AC. perpendicular and parallel orientation to surface of activated carbon on
When compared the spectra of H-AC and that of PMT, it was found that the three kinds of activated carbon. Moreover, a white substance was
some of the new peaks, including 1500 cm−1, 1355 cm−1, 1190 cm−1, also observed on the surface. According to the mechanism, these white
906 cm−1, 752 cm−1, 680 cm−1, were appeared on that of H-AC could substances may belong to some metal element, because heavier atoms
also be found on that of PMT. would appear brighter in the pattern of backscatter imaging [48].
According literatures [46,47], these peaks verified the presence of From the EDS results of activated carbon, it was found that the
C]S group (1190 cm−1) in thioamide, and CeNeH group (1500 cm−1) white substance on its surface mainly included C, O, K, Si, Mg, Ca, and P
in aromatic amines, and benzene ring with five adjacent free H atoms element. Among them, C was activated carbon’s inherent element, and
(752 and 680 cm−1) on H-AC. Besides, the simultaneous presence of O may be from metal oxides or non-metal oxides produced during the
stretching vibration peaks of SH group at 2536 cm−1 and C]S group preparation of fresh activated carbon [49].
(1200 cm−1) on the spectra of PMT is because that PMT could exist in After treating with PMT, the peaks of S and N from PMT appeared in
the form of both ketone and thiol. the energy spectrum, which confirmed that heteroatoms were in-
Therefore, it could verify that PMT was adsorbed physically on corporated in activated carbon. For H-AC-Au, the peak of Au was found
activated carbon because the almost the same peaks (no more than in the spectrum, which indicated that the gold in the thiosulfate solu-
10 cm−1) were found on PMT and H-AC, and that PMT on H-AC may be tion was successfully adsorbed on H-AC
present as form ketone. It can also be attained from the spectra that
some PMT was dimerized because the S-S group (499 cm−1) was also 3.1.4. XPS results
found on H-AC, Which was from one oxidation product of thiol [45]. Elements present in the adsorbents including C, N, S, and Au were
Thus, the above IR results confirm the incorporation of heteroatom- investigated using XPS. Additionally, the valence states of elements S
containing functional groups on the activated carbon. and Au on activated carbon were analyzed via S2p and Au4f orbit,
respectively, with the help of Multipak software. The results were
3.1.2. BET results shown in Fig. 3.
The pore and surface properties were analyzed using BET method In Fig. 3(A), the change in elemental constituents of the original
with N2 adsorption apparatus, as shown in Table 1, in which the ob- activated carbon, H-AC, and H-AC-Au was illustrated. As shown in
tained results of surface area, pore volume and pore diameter of ori- Fig. 3(A), the original activated carbon mainly consisted of carbon and
ginal activated carbon, H-AC, and activated carbon after adsorption of trace amounts of oxygen. However, nitrogen and sulfur were observed
as new elements in the spectrum of H-AC. Thus, it was demonstrated
Table 1 that heteroatom nitrogen and sulfur were inserted into activated carbon
Summarized results of N2 adsorption measurements. successfully. Furthermore, gold as a new element was observed in the
spectrum of H-AC-Au in addition to the C, N, S, and O elements, which
Items AC H-AC H-AC-Au
proved the presence of gold on H-AC-Au. From the three spectra, the
2
Surface area (m /g) 1189.439 482.394 293.983 roles of nitrogen and sulfur were obvious in enhancing the activated
Micropore area (m2/g) 893.681 364.194 200.500 carbon’s affinity towards gold in thiosulfate solution.
External surface area (m2/g) 295.757 118.200 93.483 In Fig. 3(B), the results of binding energy of S2p3/2 were exhibited.
Total pore volume (m3/g) 0.739 0.244 0.163
It can be seen from this figure that the S2p3/2 peaks were mainly lo-
Micropore volume (m3/g) 0.364 0.147 0.082
Average pore Diameter (nm) 2.577 2.174 2.234 cated at the binding energies of 182.21, 164.10, 167.52, and 168.19 eV,
which were attributed to the binding energy of sulfur in thiol, disulfide

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Y. Chen, et al. Separation and Purification Technology 230 (2020) 115834

Fig. 2. The morphology and elemental components from SEM-EDS analysis.

linkage, sulfinic acid, and sulfonic acid respectively [50]. According to S# 2p3/2 at 161.92 and 167.78 eV, respectively, which is consistent
the reported literature [51], this substances may be produced following with the values reported in the literature [50]. However, none of these
the reaction shown in Eqs. (9) and (10). This indicates that oxidization two peaks were founded in Fig. 3(C), which demonstrated that thio-
reaction occurred with different degrees on thiol of PMT during the sulfate was not presented on H-AC-Au. Therefore, this result also fur-
preparation of H-AC, because the binding energy usually increases with ther proves that gold on activated carbon was not present with thio-
the increase in chemical valence state of element in XPS [50]. sulfate ion.
[O]
2R − SH → R − S − S − R (9)
3.2. Gold adsorption
[O] [O] [O]
R − SH → R − SOH → R − SO2 H → R − SO3 H (10) 3.2.1. The influence of Na2S2O3 concentration in adsorption solution
In Fig. 3(C), the XPS results of S2p3/2 in H-AC-Au were demon- As shown in Fig. 4A, the gold recovery behaviors for 100 mL of
strated. The peaks of S2p3/2 were at the binding energies of 162.9, 100 mg/L gold solutions with pH of 9.0 were investigated with 0.05,
164.8, 168.28, and 168.9 eV, respectively, which means that the sulfur 0.1, 0.2, 0.3, and 0.4 mol/L S2O32−. Relatively high level of adsorption
herein was in four markedly different chemical environments. The peak of about 65% was achieved when the thiosulfate concentration was
at binding energy of 162.9 eV may be due to the unoxidized exocyclic 0.05 mol/L. However, the adsorption level of adsorption decreased
sulfur in PMT. The peak at 168.9 eV was attributed to the binding en- slightly as the thiosulfate concentration increased from 0.1 to 0.4 mol/L
ergy of sulfur in sulfuric ion [50]. However, the peak at 184.8 eV was after 48 h. The lower thiosulfate concentration seems to be more
attributed to the binding energy of disulfide linkage, which may be available for gold adsorption. The reason for this may be that thio-
from the potential oxidization product of thiol on PMT in the presence sulfate ions was one product produced in this process.
of O2 or other oxidizing agent [51].
In Fig. 3(D), the results of binding energy for Au 4f of gold on H-AC- 3.2.2. The influence of pH value in adsorption solution
Au were displayed. This figure told that Au4f7/2 had only one peak at Adsorption experiments were carried out using 0.5 g H-AC and
binding energy of 84.61 eV, which was the energy of Au4f7/2 in gold 100 mL solutions containing gold 100 mg/L, with the pH of 6.0, 7.0,
(I) in accordance with previous reports where gold(I)-thiolate com- 8.0, 9.0 and 10.0, respectively, to study the influence of pH value. The
pound or complex was studied by XPS [52,53]. More precisely, it may level of adsorption after 24 h and 48 h were plotted in Fig. 4B. It can be
be that gold(I)-thiolate compound or complex contains PMT related seen that gold was concentrated by H-AC at all of the tested pH values,
ligand because Au(S2O3)23− is difficult to be adsorbed on activated but the lower pH values showed better adsorption results with a rela-
carbon in previous studies [3,13]. tively small difference about 10% between the biggest and smallest
In Fig. 3(E), the results of binding energy values for S2p3/2 of pure values. The reason may be that the higher alkalinity lowered the
thiosulfate reagent were displayed. It can be clearly seen from Fig. 3(E) amount of adsorption sites on the H-AC because -SH may be more easily
that Na2S*S#O3 simultaneously have binding energies of S* 2p3/2 and oxidized into sulfonic acid or other acid containing oxygen and sulfur

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Y. Chen, et al. Separation and Purification Technology 230 (2020) 115834

Fig. 3. XPS results of activated carbon, H-AC, H-AC-Au, and pure Na2S2O3 reagent.

under the higher alkaline condition, which was not favorable for re- were shown in Fig. 4C. It can be seen that when the solution tem-
acting with gold ions. However, a pH of 9.0 was chosen for the sub- perature increased from 25 to 55 °C, the level of adsorption of gold
sequent experiments because it has been reported that pH is around 9.0 increased too. At the temperature of 55 °C, the level of adsorption
in practical leaching liquid [17]. reached the best value of about 82%. Although lower level values of
adsorption were observed at 25, 35, and 45 °C, the level of adsorption
was still greater than 60% after 48 h. Over all, the adsorption of gold by
3.2.3. The influence of temperature in adsorption solution
activated carbon was more favorable at higher temperature. The reason
The adsorption of 0.5 g H-AC at four different temperatures (25, 35,
may be that increasing temperature facilitated the adsorption of gold in
45, and 55 °C) were studied using 100 mL of 100 mg/L gold solution
solution adsorption on H-AC.
with pH of 9.0 and thiosulfate concentration of 0.1 mol/L, the results

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Y. Chen, et al. Separation and Purification Technology 230 (2020) 115834

Fig. 4A. The effect of Na2S2O3 concentration on Au(S2O3)2− recovery (CAu: Fig. 4D. The effect of initial gold concentration on gold recovery (C(Na2S2O3):
100 mg/L; pH: 7.0; m(H-AC): 0.5 g). 0.1 mol/L; pH: 9.0; m(H-AC): 0.5 g).

process may be a reversible because there were some gold residue in

thiosulfate solution (for initial gold concentration of 20, 40 80 and
100 mg/l). Moreover, the consequence that the quantity of gold on
activated carbon increased with the increase in initial gold concentra-
tion was indicated.
Besides, for adsorption from the same 10 mg/L gold thiosulfate so-
lution at the same temperature and within the adsorption time (24 h),
using 0.5 g H-AC prepared in this work could reached a gold recovery
percentage nearly 100%, while 1.0 g MBT-AC prepared in previous
study only reached a value about 70% [37], which demonstrated that
the adsorption ability of H-AC is better than the activated carbon
treated with MBT.

3.2.5. Multi-stage gold adsorption

Fig. 4B. The effect of pH on gold recovery (CAu: 100 mg/L; C(Na2S2O3): 0.1 mol/
Multi-stage adsorption was carried out using 0.5 g H-AC and 100 mL
L; m(H-AC): 0.5 g). of solution containing Au(S2O3)23− 100 mg/L and S2O32− 0.1 mol/L,
with pH value of 9.0 at the temperature of 25 °C. After 48 h, H-AC was
transferred into another 100 mL of the same solution. Five stages ad-
sorption were carried out, the results were shown in Fig. 5.
As seen from Fig. 5, activated carbon showed outstanding gold re-
covery ability (more than 70%) in the initial stage. Then, the recovery
ability weakened, but was still good even at the fifth stage where a
recovery of 10% was reached. A total gold loading amount of 25.85 kg/
t was gained on activated carbon, which is relatively better than the
value of 18.402 kg/t attained using activated carbon treated with MBT

Fig. 4C. The effect of temperature on gold recovery (CAu: 100 mg/L;
C(Na2S2O3):0.1 mol/L; pH: 9.0; m(H-AC): 0.5 g).

3.2.4. The influence of initial gold concentration in solution

The adsorption from solutions with initial gold concentrations of 10,
20, 40, 80, and 100 mg/L were researched, and the results were shown
in Fig. 4D. As shown in Fig. 4D, when the initial concentration was
10 mg/L, the gold was almost removed completely by 0.5 g H-AC after
24 h. When the initial concentration was 20 mg/L, the gold was re-
moved entirely at 48 h. At initial concentration of 100 mg/L, the lowest
recovery rate of 65% (13.14 kg/t) was achieved, at the time of 48 h.
Fig. 5. The results of multi-stage adsorption on activated carbon (CAu: 100 mg/
According to the above results, it can be concluded that the adsorption
L; C(Na2S2O3): 0.1 mol/L; pH: 9.0; m(H-AC): 0.5 g.)

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Fig. 6. Results of Freundlich adsorption isotherm model. Fig. 7. Results of Pseudo-first order kinetic model.

[37]. This adsorption capacity is relatively satisfactory and the success

of cycling adsorption is also of some significance for practical produc-
tion.

3.2.6. Adsorption isotherm

Based on the Freundlich model, the adsorption results at three
temperatures were fitted, as shown in Fig. 6. The curve was obtained by
plotting log(ce) versus log(qe). The related factors were obtained from
the slope and intercept of the curve at 35, 45 and 55 °C, and are shown
in Table 2. The results showed that the linear correlation parameters of
Freundlich adsorption isotherm model at temperatures of 35, 45 and
55 °C were 0.9965, 0.9971, and 0.9956, respectively. Langmuir model
was also tried, but the linear correlation was not good, so the results
were not shown in here.
The results attained above indicated that the adsorption behavior
could be described using Freundlich adsorption isotherm model on
some extent. According to literature [17], the conformity to Freundlich
adsorption isotherm model indicates that multi-molecular chemical Fig. 8. Results of Pseudo-second order kinetic model.
adsorption may be involved in the process of gold adsorption on H-AC.
However, the values obtained from pseudo-first order kinetic model
3.2.7. Adsorption kinetics deviated significantly from the experimental values. Moreover, the high
The results of pseudo-first order kinetic model and pseudo-second gold absorptive capacity on H-AC indicated that H-AC owns relatively
order kinetic model for the adsorption of gold on H-AC with gold better gold adsorption performance than original activated carbon,
concentrations of 20, 40, 80, and 100 mg/L in thiosulfate solution at the which is of some significance for the applications of activated carbon in
temperature of 55 °C were shown in Figs. 7 and 8, respectively. For thiosulfate system.
conveniently comparing their suitability to this adsorption process, the
parameters of both models are listed together in Table 3. As seen from
this table, larger R2 values were attained via the fitting of pseudo- 3.2.8. Adsorption mechanism
second order kinetic model. This indicates that the adsorption kinetics As attained in section 3.1.4, the binding energy of R-S− increased
of gold on H-AC was more likely to be pseudo-second order kinetic from 162.21 to 162.9 eV after gold adsorption, and the binding energy
reaction. of disulfide linkage on increased from164.1 to 164.8 eV, which means
For initial gold concentrations of 20, 40, 80 and 100 mg/L, the that chemical surroundings of both R-S− and disulfide linkage were
obtained values for gold absorption capacity of H-AC from pseudo- changed after gold adsorption. It was reported that R-S2− and disulfide
second order kinetic model were 4.141, 8.013, 14.577 and 18.08 kg/t, linkage can compete with thiolate ligand in gold (I) thiolate complex
respectively. These calculated values were very close to the experi- [54–57], while Au(S2O3)23− ion is very structurally similar with thio-
mental values of 3.94, 7.57, 13.88 and 17.15 kg/t, respectively. late. Besides, when binding with gold (I), the negative charge of PMT
may be preferably dispersed due to the presence of large conjugated
Table 2 system on PMT, which would cause the gold (I) thiolate complex con-
Summarized parameters of Freundlich model. taining PMT ion more stable than Au(S2O3)23− ion [58,59]. Therefore,
Intermediate product: [R-S-Au-S2O3]2− and final product: [R-S-Au-S-
Temperature (°C) Freundlich parameters
R]− may be produced from two different reaction route (A to B and 1 to
R2 k n 3) may be present on H-AC after the adsorption of Au(S2O3)23−. [R-S-
Au-S2O3]2− on carbon was not found by XPS may be that it was just an
35 0.9965 5.752 2.349
intermediate product. Therefore, according to the results of XPS and
45 0.9971 7.124 2.549
55 0.9956 9.264 2.392 adsorption experiments, the adsorption process may be involved a li-
gand exchange between the substitution by PMT ion or R-S radical in

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Table 3
Summarized parameters of two kinetic models.
Kinetic model The Concentration of gold (mg/L) R2 K1(h−1)/K2(L·mg−1 h−1) qe (mg/g)

Calculated Experiment

Pseudo-first order kinetic model 20 0.9827 0.070 2.100 3.94

40 0.9877 0.065 4.435 7.57
80 0.9801 0.058 8.327 13.88
100 0.9855 0.055 10.760 17.15

Pseudo-second order kinetic model 20 0.9982 0.064 4.141 3.94

40 0.9967 0.027 8.013 7.57
80 0.9973 0.013 14.577 13.88
100 0.9913 0.010 18.083 17.15

Fig. 9. The mechanism of preparation of H-AC and adsorption of Au(S2O3)23− on H-AC.

disulfide of PMT and thiosulfate ion, as shown in Fig. 9.

3.3. Exploration experiment results for gold stripping from H-AC-Au

3.3.1. The gold stripping results using different solvents

The stripping of gold from H-AC-Au was tested with methanol,
ethanol, acetone, chloroform and dimethyl acrylamide (DMF) the re-
sults were shown in Fig. 10. The stripping percentage increased from
left to right, DMF can stipe gold from H-AC-Au, reached a stripping
percentage about 79.2%. It can be clearly seen that the gold stripping
ability is positively correlated to the polarity of solvent: DMF >
methanol > ethanol > acetone > chloroform, which demonstrated
that solvent with strong polarity may be in favor of gold stripping.

3.3.2. The gold stripping results of different time

Then, the effect of treatment time to stripping efficiency was also
Fig. 10. The results of gold stripping using different solvent at elution time of
investigated, whose results were shown in Fig. 11. As shown in Fig. 11,
12 h.
when time increased from 4 to 24 h, the stripping percentage boosted
from 63.4 to 87.6%, which indicated that the increase of time can
improve the gold stripping percentage on some extent. Although this 4. Conclusions
work did report the gold stripping work in activated carbon related
thiosulfate system for the first time, it was undeniable that other work Activated carbon rich-in heteroatoms, mainly including nitrogen
was needed to improve the stripping efficiency because present out- and sulfur atoms, was prepared. H-AC showed relatively adaptability to
come still could not compete with that of resin [29,60]. a wide range of thiosulfate concentration (0.05–0.4 mol/L) and a wide

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Y. Chen, et al. Separation and Purification Technology 230 (2020) 115834

solutions with ammonia and thiosulfate using activated carbon, Revista De

Metalurgia 42 (2006) 222–233.
[14] H. Arima, T. Fujita, W.T. Yen, Gold cementation from ammonium thiosulfate so-
lution by zinc, copper and aluminium powders, Mater. Trans. 43 (2002) 485–493.
[15] P. Navarro, R. Alvarez, C. Vargas, F.J. Alguacil, On the use of zinc for gold ce-
mentation from ammoniacal–thiosulphate solutions, Miner. Eng. 17 (2004)
825–831.
[16] M.J. Nicol, G. O'Malley, Recovering gold from thiosulfate leach pulps via ion ex-
change, JOM-J. Miner. Met. Mater. Soc. 54 (2002) 44–46.
[17] H. Yu, F. Zi, X. Hu, Y. Nie, P. Xiang, J. Xu, H. Chi, Adsorption of the gold–thiosulfate
complex ion onto cupric ferrocyanide (CuFC)-impregnated activated carbon in
aqueous solutions, Hydrometallurgy 154 (2015) 111–117.
[18] H. Yu, F.T. Zi, X.Z. Hu, Y.H. Nie, Y.L. Chen, H.L. Cheng, Adsorption of gold from
thiosulfate solutions with chemically modified activated carbon, Adsorpt. Sci.
Technol. 36 (2018) 408–428.
[19] B. Fotoohi, L. Mercier, Recovery of precious metals from ammoniacal thiosulfate
solutions by hybrid mesoporous silica: 3-Effect of contaminants, Sep. Purif. Technol.
139 (2015) 14–24.
[20] B. Fotoohi, L. Mercier, Recovery of precious metals from ammoniacal thiosulfate
solutions by hybrid mesoporous silica: 2-A prospect of PGM adsorption, Sep. Purif.
Technol. 149 (2015) 82–91.
[21] B. Fotoohi, L. Mercier, Recovery of precious metals from ammoniacal thiosulfate
solutions by hybrid mesoporous silica: 1-Factors affecting gold adsorption, Sep.
Fig. 11. The results of gold stripping using DMF at different treatment time. Purif. Technol. 127 (2014) 84–96.
[22] W.U. Zhichun, Separation of gold from other metals in thiosulfate solutions by
solvent extraction, Sep. Sci. Technol. 34 (10) (1999) 2061–2068.
pH range (6.0–10.0). H-AC had strong affinity for gold in thiosulfate [23] J. Zhao, Z. Wu, J. Chen, Solvent extraction of gold in thiosulfate solutions with
solution, whose gold adsorption capacity reached about 25.85 kg/t. amines, Solvent Extr. Ion Exch. 16 (1998) 527–543.
[24] L. Cermakova, I. Kopecka, M. Pivokonsky, L. Pivokonska, V. Janda, Removal of
It was found that Freundlich adsorption isotherm model and cyanobacterial amino acids in water treatment by activated carbon adsorption, Sep.
pseudo-second order model could describe the adsorption process well. Purif. Technol. 173 (2017) 330–338.
With the help of SEM, FT-IR, N2 adsorption, and XPS, it was found that [25] G.C. Lukey, J.S.J. Van Deventer, D.C. Shallcross, Equilibrium model for the sorption
of gold cyanide and copper cyanide on trimethylamine ion exchange resin in saline
the adsorption of gold on H-AC may be happened through a partial or solutions, Hydrometallurgy 59 (2001) 101–113.
complete ligand exchange reaction. Furthermore, a simple, cost-effec- [26] X. Dai, P.L. Breuer, M.I. Jeffrey, Comparison of activated carbon and ion-exchange
tive, green and efficient stripping method was developed to achieve a resins in recovering copper from cyanide leach solutions, Hydrometallurgy 101
(2010) 48–57.
gold stripping percentage of 87.6%. [27] M.I. Jeffrey, S.D. Brunt, The quantification of thiosulfate and polythionates in gold
In total, a work including gold adsorption and stripping was in- leach solutions and on anion exchange resins, Hydrometallurgy 89 (2007) 52–60.
vestigated using activated carbon as adsorbent in thiosulfate solution [28] M.I. Jeffrey, D.M. Hewitt, X. Dai, S.D. Brunt, Ion exchange adsorption and elution
for recovering gold thiosulfate from leach solutions, Hydrometallurgy 100 (2010)
for the first time, which is important to the development of cleaner 136–143.
production of gold. Of course, (a) what gold adsorption results would be [29] A.C. Grosse, Gold recovery from thiosulfate leach liquors using ion exchange resins,
in the presence of Cu2+ and other ions and (b) how to control the Aust. J. Chem. 55 (2002) 547.
[30] I.S. Kwak, M.A. Bae, S.W. Won, J. Mao, K. Sneha, J. Park, M. Sathishkumar,
potential influence of these ions would be studied in the future work.
Y.S. Yun, Sequential process of sorption and incineration for recovery of gold from
cyanide solutions: comparison of ion exchange resin, activated carbon and biosor-
Acknowledgements bent, Chem. Eng. J. 165 (2010) 440–446.
[31] B. Fotoohi, L. Mercier, Some insights into the chemistry of gold adsorption by thiol
and amine functionalized mesoporous silica in simulated thiosulfate system,
This work was financially supported by the Natural Science Hydrometallurgy 156 (2015) 28–39.
Foundation of China (51674128; 21764008). [32] B. Fotoohi, L. Mercier, Modification of pore structure and functionalization in MSU-
X silica and application in adsorption of gold thiosulfate, Micropor. Mesopor. Mater.
190 (2014) 255–266.
References [33] P.J. Tauetsile, E.A. Oraby, J.J. Eksteen, Activated carbon adsorption of gold from
cyanide-starved glycine solutions containing copper. Part 1: Isotherms, Sep. Purif.
[1] G. Hilson, A.J. Monhemius, Alternatives to cyanide in the gold mining industry: Technol. 211 (2019) 594–601.
what prospects for the future, J. Cleaner Prod. 14 (2006) 1158–1167. [34] P.J. Tauetsile, E.A. Oraby, J.J. Eksteen, Activated carbon adsorption of gold from
[2] A. Akcil, Managing cyanide: health, safety and risk management practices at cyanide-starved glycine solutions containing copper. Part 2: Kinetics, Sep. Purif.
Turkey's Ovacik gold-silver mine, J. Cleaner Prod. 14 (2006) 727–735. Technol. 211 (2019) 290–297.
[3] M.G. Aylmore, D.M. Muir, Thiosulfate leaching of gold—a review, Miner. Eng. 14 [35] C.Y. Yin, M.K. Aroua, M.A.W.D. Wan, Review of modifications of activated carbon
(2001) 135–174. for enhancing contaminant uptakes from aqueous solutions, Sep. Purif. Technol. 52
[4] G. Senanayake, Gold leaching in non-cyanide lixiviant systems: critical issues on (2007) 403–415.
fundamentals and applications, Miner. Eng. 17 (2004) 785–801. [36] C. Young, N. Gow, M. Melashvili, Impregnated activated carbon for gold extraction
[5] M.I. Jeffrey, P.L. Breuer, W.L. Choo, A kinetic study that compares the leaching of from thiosulfate solutions, Sep. Technol. Miner., Coal, Earth Resourc. (2012)
gold in the cyanide, thiosulfate, and chloride systems, Metall. Mater. Trans. B – 391–404.
Proc. Metall. Mater. Proc. Sci. 32 (2001) 979–986. [37] Y. Chen, F. Zi, X. Hu, H. Yu, Y. Nie, P. Yang, H. Cheng, Q. Wang, X. Qin, S. Chen,
[6] P.L. Breuer, M.I. Jeffrey, An electrochemical study of gold leaching in thiosulphate Y. Zhang, Grafting of organic sulfur-containing functional groups on activated
solutions containing copper and ammonia, Hydrometallurgy 65 (2002) 145–157. carbon for gold(I) adsorption from thiosulfate solution, Hydrometallurgy 185
[7] D.M. Muir, M.G. Aylmore, Thiosulphate as an alternative to cyanide for gold pro- (2019) 102–110.
cessing – issues and impediments, Miner. Process. Extractive Metall. 113 (2004) [38] C. Young, N. Gow, M. Melashvili, M. LeVier, Impregnated activated carbon for gold
2–12. extraction from thiosulfate solutions, Sep. Technol. Miner., Coal, Earth Resourc.
[8] P.L. Breuer, M.I. Jeffrey, Thiosulfate leaching kinetics of gold in the presence of (2012) 391–404.
copper and ammonia, Miner. Eng. 13 (2000) 1071–1081. [39] L. Nielsen, M.J. Biggs, W. Skinner, T.J. Bandosz, The effects of activated carbon
[9] J. Cui, L. Zhang, Metallurgical recovery of metals from electronic waste: a review, J. surface features on the reactive adsorption of carbamazepine and sulfamethoxazole,
Hazard. Mater. 158 (2008) 228–256. Carbon 80 (2014) 419–432.
[10] V.H. Ha, J.C. Lee, J. Jeong, H.T. Hai, M.K. Jha, Thiosulfate leaching of gold from [40] S. Biniak, G. Szymański, J. Siedlewski, A.Ś.J.M. Tkowski, The characterization of
waste mobile phones, J. Hazard. Mater. 178 (2010) 1115. activated carbons with oxygen and nitrogen surface groups, Carbon 35 (1997)
[11] B. Xu, K. Li, Q. Li, Y.B. Yang, X.L. Liu, T. Jiang, Kinetic studies of gold leaching from 1799–1810.
a gold concentrate calcine by thiosulfate with cobalt-ammonia catalysis and gold [41] A. Macías-García, C. Valenzuela-Calahorro, V. Gómez-Serrano, A. Espínosa-
recovery by resin adsorption from its pregnant solution, Sep. Purif. Technol. 213 Mansilla, Adsorption of Pb 2+ by heat-treated and sulfurized activated carbon,
(2019) 368–377. Carbon 31 (1993) 1249–1255.
[12] Q. Wang, X.Z. Hu, F.T. Zi, P. Yang, Y.L. Chen, S.L. Chen, Environmentally friendly [42] S.H. Wu, P. Pendleton, Adsorption of anionic surfactant by activated carbon: effect
extraction of gold from refractory concentrate using a copper – ethylenediamine – of surface chemistry, ionic strength, and hydrophobicity, J. Colloid Interf. Sci. 243
thiosulfate solution, J. Cleaner Prod. 214 (2019) 860–872. (2001) 306–315.
[13] C. Vargas, P.N. Donoso, E. Araya, F. Pávez, F.J. Alguacil, Recovery of gold from [43] P.J.F. Harris, Z. Liu, K. Suenaga, Imaging the atomic structure of activated carbon,

9
Y. Chen, et al. Separation and Purification Technology 230 (2020) 115834

J. Phys.: Condens. Matter 20 (2008) 3931–3939. assembled monolayers: XPS characterization, J. Phys. Chem. B 104 (2000)
[44] Z. Zhang, H. Huang, X. Yang, L. Zang, Tailoring electronic properties of graphene by 6562–6567.
π–π stacking with aromatic molecules, J. Phys. Chem. Lett. 2 (2011). [54] O. Foss, A. Jonsson, L.G. Sillén, A. Linnasalmi, P. Laukkanen, Kationoid reactivity of
[45] U. Agarwala, B. Singh, Complexes of 1-substituted tetrazoline-5-thiones with Cu sulphur, Sulphenyl Compd. (1947).
(1), Ag (1), Au (1), and Hg (1), Indian J. Chem. 7 (1969) 726–728. [55] A.J. Parker, N. Kharasch, The scission of the sulfur-sulfur bond, Chem. Rev. 59
[46] B. Pergolese, A. Bigotto, Vibrational assignments and theoretical calculations of 1- (1959) 583–628.
phenyl-5-mercaptotetrazole and 1-phenyl-5-mercaptotetrazolate, J. Mol. Struct. [56] S.M. Bachrach, J.T. Woody, D.C. Mulhearn, Effect of ring strain on the thiolate-
655 (2003) 479–489. disulfide exchange. A computational study, J. Org. Chem. 67 (2002) 8983–8990.
[47] D. Lin-Vien, N.B. Colthup, W.G. Fateley, J.G. Grasselli, The Handbook of Infrared [57] M. Dilorenzo, S. Ganesh, L. Tadayon, J. Chen, M.R.M. Bruce, A.E. Bruce, Reactions
and Raman Characteristic Frequencies of Organic Molecules, Academic Press, of organic disulfides and gold(I) complexes, Met. Based Drugs 6 (1999) 247–253.
London Sydney Tokyo Toronto, 1991. [58] R.A. Bryce, J.M. Charnock, R.A.D. Pattrick, A.R. Lennie, EXAFS and density func-
[48] G.E. Lloyd, Atomic number and crystallographic contrast images with the SEM: a tional study of gold(I) thiosulfate complex in aqueous solution, J. Phys. Chem. A
review of backscattered electron techniques, Mineral. Mag. 51 (1987) 3–19. 107 (2003) 2516–2523.
[49] M. Smisek, S. Cerny, New books – active carbon: manufacture, properties, and [59] J.A. Shelnutt, Correlation between metal stability, charge transfer, and Raman
applications, Anal. Chem. 42 (1970). frequencies in metalloporphyrins and their π-π complexes, J. Am. Chem. Soc. 105
[50] J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, Handbook of XPS, 1995. (1983) 774–778.
[51] Saul Patai, The Chemistry of the Thiol Group Part 2, John Wiley & Sons, 1974. [60] H. Zhang, D.B. Dreisinger, The recovery of gold from ammoniacal thiosulfate so-
[52] C. Battistoni, G. Mattogno, F. Cariati, L. Naldini, A. Sgamellotti, XPS photoelectron lutions containing copper using ion exchange resin columns, Hydrometallurgy 72
spectra of cluster compounds of gold, Inorg. Chim. Acta 24 (1977) 207–210. (2004) 225–234.
[53] M.C. Bourg, A. Badia, R.B. Lennox, Gold-sulfur bonding in 2D and 3D self-

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