Hydrometallurgy 146 (2014) 111–118

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Selective recovery of gold on functionalized resins

Magdalena Pilśniak-Rabiega a,⁎, Andrzej W. Trochimczuk b
a
Division of Chemical Metallurgy, Faculty of Chemistry, Wrocław University of Technology, Wyspiańskiego 27, 50-370 Wrocław, Poland
b
Division of Polymer and Carbon Materials, Faculty of Chemistry, Wrocław University of Technology, Wyspiańskiego 27, 50-370 Wrocław, Poland

a r t i c l e i n f o a b s t r a c t

Article history: The functional resins containing guanylthiourea, 1-methylimidazole, 2-mercapto-1-methylimidazole,

Received 24 June 2013 dipropylamine, 1,2-dimethylimidazole and 1-(3-aminopropyl)imidazole ligands were highly selective for
Received in revised form 7 February 2014 the gold(I) and silver(I) from ammonia solution and they did not sorb ammine complexes of copper(II). The ki-
Accepted 26 March 2014
netics of gold(I) sorption on these resins was improved by immobilization of N,N-dimethylethanolamine ligands,
Available online 5 April 2014
which were responsible for increasing the hydrophilicity of the polymeric material. 1-Methylimidazole resins
Keywords:
retained their capacity towards gold in five consecutive sorption/desorption cycles. All resins in cyanide form
Polymeric resins in cyanide form displayed high affinity towards gold(I) from ammoniacal solution (100 g/L NH3·H2O, 5.00 g/L (NH4)2SO4). The
Sorption of gold(I) sorption degrees of gold were 99.5%.
Silver(I) and copper(II) © 2014 Elsevier B.V. All rights reserved.
Selectivity

1. Introduction
Gold is very rare and scattered precious metal, recovered from poor
grade raw materials on an industrial scale by using hydrometallurgical
methods, which are the only guarantee of the effective extraction of
this metal. Hydrometallurgy of gold is mainly based on cyanide leaching
of easily leachable ores in the presence of oxygen or air (Breuer et al.,
2005; Catrho and Koch, 1964; Hedley and Tabachnik, 1968; Miltzarek
et al., 2002). This type of ores is exhausted, which is why gold is extract-
ed now from refractory gold ores, where the gold is trapped in the copper
sulfide minerals or other metals. Release of the gold grains from these
ores requires a pretreatment (roasting, pressure leaching, bioleaching)
before the actual cyanide leaching. An alternative solution, which does
not require pre-treatment, is ammonia leaching of refractory ores in hy-
drothermal conditions under oxygen atmosphere. Ammonia is less toxic
than cyanide, relatively inexpensive and easily regenerated by evapora-
tion techniques (Han and Fuerstenau, 2000; Meng and Han, 1996). The
use of ammonia leaching requires the development of selective and ef-
ficient methods for separation of gold complexes from ammoniacal
solutions.
For the gold recovery from leaching solutions sorption on activated
carbon (CIP method, called “carbon in pulp”) and sorption on polymeric
resins (RIP method, called “resin in pulp”) are applied. Gold-selective
resins have some distinct advantages over activated carbon for the
⁎ Corresponding author. Tel.: +48 71 320 38 24.
E-mail address: magdalena.pilsniak@pwr.wroc.pl (M. Pilśniak-Rabiega).
recovery of gold. Resins have potentially higher loading capacities and
higher loading rates are less likely to be poisoned by organics, and do
not require thermal regeneration. The main disadvantage of polymeric
resins is that they are more expensive than activated carbon (Green
et al., 2002).
Polymeric materials, ion-exchange resins, containing selective func-
tional groups, and chelating resins are widely used in hydrometallurgy,
especially for the separation of noble metal ions from various solutions
(Parodi et al., 2008). Chelating polymers are characterized by the pres-
ence of reactive functional groups containing O, N, S and P donor
atoms that are capable of forming complexes with metal ions. These
materials are used when the concentration of metal ions in the solutions
is small and the resins display preferential sorption towards chosen
ions. The efficiency of the removal process depends on the process
parameters (pH of the solution, ion concentration, contact time) and
on the properties of the ion exchange/coordination resin (swelling,
crosslinking degree, type and structure of immobilized ligand).
The gold-selective resins (MINIX and AURIX) were developed by
Mintek and were used for the recovery of gold from cyanide leaching so-
lutions. MINIX is a strong-base resin, which contains tributylamine as
the functional group, while AURIX is a medium-base resin. They are re-
ported to be styrene-divinylbenzene resin beads functionalized with
guanidine functional group (Green et al., 2002).
The recent research on the selective metal ion removal has been
widely carried out by using specific ligands in modified polymers in
order to pre-concentrate the precious metal ions. Noble metals, es-
pecially gold, were loaded and recovered using: poly[4-vinylbenzyl(2-
hydroxyethyl)sulfide] resin (Qu et al., 2006), guanidine resin

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0304-386X/© 2014 Elsevier B.V. All rights reserved.
112 M. Pilśniak-Rabiega, A.W. Trochimczuk / Hydrometallurgy 146 (2014) 111–118
(Jermakowicz-Bartkowiak, 2005; Kolarz et al., 2004), resin contain-
ing calixpyrroles (Kałędkowski and Trochimczuk, 2006), bis(2-
benzimidazolylmethyl)amine resin (Pramanik et al., 2004), resin
containing benzimidazolylazo groups (Das et al., 1999), thiourea-
based coordinating polymers (Zuo and Muhammed, 1995), resins
with amino, thio and amino/mercaptane functionalities (Donia
et al., 2005), resin containing 1,4-bis(imidazolylazo)benzene ligands
(Pramanik et al., 2006), phosphine sulfide chelating polymers
(Sanchez et al., 2001), resin containing carboxymethylphosphonate
and methylenediphosphonate ligands (Trochimczuk, 2001). Polymers
with functional groups containing sulfur atoms are very effective for
the sorption of gold. The resin with amino/mercaptane ligands has the
highest affinity towards Au(III) ions (439 mg Au/g of resin) (Donia
et al., 2005). The polymeric resins with “soft” electron pair donor
atoms in the macrocyclic calix[4]pyrrole[2]thiophene ligand also dis-
play extremely high sorptive ability towards gold (335 mg Au/g of
resin) (Kałędkowski and Trochimczuk, 2006). The polymer with phos-
phonate groups can effectively remove AuCl− 4 complexes from hydro-
chloric acid solutions (130–166 mg Au/g of resin) and from solutions
containing large quantities of Cu(II) (70 mg Au/g) (Trochimczuk,
2001).
Our group had obtained novel resins containing different
ligands: carboxyphosphonate, 1-methylpiperazine, ethylenediamine,
dipropylamine, 1-methylimidazole, 2-mercapto-1-methylimidazole,
1,2-dimethylimidazole, 1-(3-aminopropyl)imidazole and different
amino ligands, which were used for the gold recovery from ammonium
buffer solutions (Pilśniak and Trochimczuk, 2006; Pilśniak and
Trochimczuk, 2007; Pilśniak et al., 2009).
The aim of this work was to present the possibility of the gold sorp-
tion from a single and the multicomponent solutions on the vinylbenzyl
chloride-divinylbenzyl copolymer functionalized with the aliphatic and
aromatic amine. This paper was a continuation of our research that was
focusing on preparing the new resins in order to improve gold sorption
kinetics and increase the efficiency and selectivity of Au recovery.
2. Experimental
2.1. Chemical reagents
The chemicals were Sigma-Aldrich products. The solution of gold in
ammonium buffer was prepared by dissolving metallic gold in aqua
regia. The solution of [AuCl4]− was introduced into ammonium buffer
solution (50.0 g/L (NH4)2SO4, 100 g/L NH3·H2O). Experiment was car-
ried out in autoclave under oxygen atmosphere (10–15 atm) and high
temperature (120 °C). The preparation of gold solution could be de-
scribed using the following reactions:
0 − þ
Au þ HNO3 þ 4HCl→½AuCl4  þ H þ NO þ 2H2 O
(Łętowski, 1975; Trzebiatowski, 1979)
− þ − þ
2½AuCl4  þ 8NH3  H2 O ¼ 2AuðNH3 Þ2 þ O2 þ 8Cl þ 4NH4 þ 6H2 O ð6Þ
(Lazarev and Kharlamov, 1987; Wozniak and Apostoluk, 2008; Xu et al.,
1996)
3þ þ
Au ¼ Au −2e=·2
2−
2O ¼ O2 þ 4e:
The initial gold concentrations were 398.0 and 431.4 mg Au/L. These
solutions were diluted twenty times with ammonium buffer (100 g/L
NH3·H2O, 5.00 g/L (NH4)2SO4) in order to obtain the concentration of
19.90 or 21.57 mg Au/L and various concentrations of ammonia and am-
monium sulfate.
The solutions of Au(NH3)+ 2 containing 19.90 or 21.57 mg/L of gold
and 100 g/L NH3·H2O and 5.00 g/L (NH4)2SO4 were used in the sorption
experiments.
The solutions of gold(I), silver(I) and copper(II) were prepared by
dissolving a known amount of copper sulfate and silver nitrate in am-
monium solution of gold.
The polymeric resins used in this work were prepared from the
starting material: vinylbenzyl chloride/divinylbenzene (VBC/DVB) co-
polymer. The polymeric support was obtained by typical suspension
polymerization. The chloromethyl groups present in its structure served
as a reactive place for the immobilization of a ligand. In an attempt to
prepare resin with optimal properties, three staring materials with dif-
ferent morphologies (Table 1) (expanded gel, gel and porous) were
used.
2.2. Methods of analysis
Water regain was measured using centrifugation method in which
about 1 g of polymer swollen in water was placed in a column with
filled-glass bottom and centrifuged at 3000 rpm for 5 min, weighted
and dried at 80 °C for 24 h. After cooling in a desiccator, the polymer
was weighted again. The water regain was calculated as (mw − md) /
md, where mw is the weight of the swollen polymer after centrifugation,
md is the dry weight of polymer.
Nitrogen content was determined using the Kjeldahl method after
mineralization of the sample of resin (about 200 mg) in the concentrat-
ed sulfuric acid containing copper sulfate and potassium sulfate.
The chlorine content was measured by burning about 20 mg of dry
polymer sample in oxygen in a flask containing 25 mL of 3% hydrogen
peroxide solution. The content of Cl was determined using Volhard's
method.
The sulfur content was measured by burning about 20 mg of dry
polymer sample in an oxygen-filled flask. The products of burning
were adsorbed in 15 mL of 3% hydrogen peroxide solution. After 1 h
the flask was heated in a water bath for 30 min in order to evaporate
carbon dioxide. Then the content of the flask was titrated with 0.01 M
NaOH in the presence of bromothymol blue.
Quaternary ammonium group content was determined using Leikin
method. Resin sample in chloride form was placed in chromatographic
column. The resin bed was washed with 200 mL of 4% sodium sulfate so-
lution and the effluent was collected in a 250 mL volumetric flask. Then,
15 mL of effluent was taken and titrated by using 0.01 mol/L silver ni-
trate solution. In this manner, chlorides from the strongly alkaline
group were determined.
The sorption capacity of resins towards gold, silver and copper from
ammonium buffer solutions was determined by contacting the resin
ð5Þ samples with 10 mL of metal ion solution. Metal ion solutions contain-
ing Au(I) (19.90 or 21.57 mg/L), Ag(I) (11.44 or 12.20 mg/L) and
Cu(II) (6.76 or 22.44 mg/L) were used in the sorption experiments.
The ratio of ligands in the resin to metal ions in the solution was set to
10:1. After 24 h the polymers were separated by filtration and the con-
centration of Au was measured using atomic absorption method on a
Perkin-Elmer Analyst 100.
For the kinetics of sorption, the identical samples of resin were shak-
en with 10 mL of solution containing 19.90 or 21.57 mg/L of Au(I) in an
ð7Þ ammonium buffer (100 g/L NH3·H2O, 5.00 g/L (NH4)2SO4). Samples
were taken at different intervals of time, resin and solution separated
and the concentration of gold was determined by AAS.
ð8Þ The distribution coefficient (Kd) was calculated as the ratio of the
amount of metal taken by 1 g of resin and the amount of metal remain-
ing in 1 mL of solution after sorption.
The selectivity coefficient (αsel) was calculated as the quotient of
distribution coefficients for each metal.
FTIR spectra of resins in KBr pellets were recorded on a Perkin-Elmer
System 2000 spectrophotometer.
 M. Pilśniak-Rabiega, A.W. Trochimczuk / Hydrometallurgy 146 (2014) 111–118 113

Table 1
Characteristics of the VBC/DVB copolymers.
VBC/DVB Crosslinking Solvent using Chlorine content Copolymer
copolymer agent content during [mmol/g] structure
[%] polymerization
I 2 Toluene 5.30 Expanded gel
II 0.5 – 5.25 Gel
III 40 Heptane/toluene 2.37 Porous
(1:1)
3. Results and discussion
3.1. The influence of polymer carrier structure on yield of modifications and
gold(I) sorption
The 1-methylimidazole resins and 2-mercapto-1-methylimidazole
resins were prepared from the same three starting materials: vinylbenzyl
chloride/divinylbenzene copolymers, which are characterized in ex-
perimental part (Section 2.1). Resins with 1-methylimidazole ligands
were obtained by microwave method and resins with 2-mercapto-1-
methylimidazole groups by conventional method (modification at
room temperature). Detailed procedures of resins obtained are present-
ed in Pilśniak and Trochimczuk (2007). Basic properties of the obtained
resins are presented in Table 2.
In the case of resins with 1-methylimidazole groups, the results of
immobilization of functional groups on polymeric material character-
ized by expanded gel, gel and a porous structure were comparable
(Table 2). The yield calculated from the nitrogen content was 63, 68
and 69%, respectively. The resin of the porous structure was character-
ized by the lowest concentration of nitrogen, due to the high content
of crosslinking agent (40 wt.% of DVB), and thus lower content of
chloromethyl groups as reactive sites for the immobilization of ligands.
The absence of chlorine in 1-methylimidazole resins indicated complete
substitution of chlorine atoms by amine in the copolymer network. The
resins of the expanded gel and gel structure were characterized by sim-
ilar values of water regain (4.00 and 4.04 g of water/g of polymer).
Water present in the structure of these polymers swelled the bulk of
polymeric materials. Water regain of porous type resin — 1.75 g of
water/g of polymer came mainly from water filling pores of the poly-
meric material. This resin had small values of water regain because of
the high degree of crosslinking of the polymer carrier.
For 2-mercapto-1-methylimidazole resin, the best result of the in-
troduction of functional groups in the polymer matrix was obtained
using as a carrier copolymer VBC/DVB (I), expanded gel type, containing
2% of crosslinking agent. Elemental analysis gave 7.35 mmol of N/g,
which corresponds to 87% yield of chloromethyl group substitution.
The reactions of two other copolymers VBC/DVB (0.5 and 40% of DVB)
with 2-mercapto-1-methylimidazole were also effective what was con-
firmed by yield results (73 and 82%, respectively) and chlorine content.
The resin of the porous structure was the most hydrophilic, having
water regain equal to 1.39 g of water per 1 g of polymeric material. It
was caused by the large specific surface area of the polymer, associated
with a high degree of crosslinking the copolymer and its synthesis in the
presence of toluene and heptane. The polymer surface area was larger,
the copolymer had more mesopores and macropores, which could be
filled with water. Water regain of this resin was mainly due to the pres-
ence of water, which filled the pores of the polymer material.
Influence of the structure of the polymer carrier on the efficiency of
gold(I) sorption from solution containing 21.57 mg/L of Au(I) in ammo-
nium buffer (100 g/L NH3·H2O, 5.00 g/L (NH4)2SO4) was also studied.
These results are presented in Table 3.
For 1-methylimidazole resin of the expanded gel, gel and a porous
structure, sorption of gold(I) was 15.5, 11.25 and 4.62 mg of Au/g of
resin, respectively. When gold recovery was expressed in terms of
mmol of gold per mmol of the ligand, the sorption equaled 0.025,
0.017 and 0.013 mmol of Au/mmol of ligand, respectively. These values
indicated that 2.5, 1.7 and 1.3% of the ligands could be utilized in the re-
moval of gold. The best sorption capacity towards gold showed resin,
which had expanded gel structure, because 2.5% of the functional
groups were involved in the sorption of Au from ammonia solutions.
The resin with 1-methylimidazolium ligands (Fig. 1) was a medium
strength anion-exchanger, which means that the main polymeric back-
bone had a positive charge and was surrounded by the exchangeable
anions, such as OH− and SO2− 4 . The presence of hydroxyl and sulfate
ions on the surface of 1-methylimidazole resin was confirmed by XPS
analysis (Pilśniak et al., 2009). The gold was sorbed by this resin in the
form of Au(I) but definitely not as Au(NH3)+ 2 , as these cations could
not enter the resin phase due to the electrostatic repulsion. The XPS
spectrum for this resin indicated the presence of complexes of gold(I)
such as Au(NH3)(OH), Au(OH)− + −
2 , or ion pair Au(NH3)2 (OH) . The de-
tails of XPS analysis are presented in our work (Pilśniak et al., 2009).
In the case of 2-mercapto-1-methylimidazole resin with expanded
gel, gel and a porous structure, gold sorption equaled 1.07, 4.67 and
3.78 mg of Au/g of resin, respectively. These values corresponded to
0.002, 0.008 and 0.011 mmol of Au/mmol ligand, which means that
0.2, 0.8 and 1.1% of the ligands were used in the recovery of gold(I)
from ammonium buffer. These results showed that the best sorbent
was resin with porous structure. This fact could be explained as a better
access to the functional groups, which were located mainly on the inner
surface of the pores. For 2-mercapto-1-methylimidazole resin, the
structure was such that ion-exchange was not possible but sulfur
atoms could be involved in the coordination and formation of four-
member rings together with the neighbouring nitrogen atoms (Fig. 1).
For further research presented in this paper, polymeric resins with
expanded gel structure were used. VBC/DVB (2% of DVB) copolymer
was characterized by a low degree of crosslinking, which had a large in-
fluence on its swelling (swelling is a function of crosslinking density)
and increased segmental mobility. These factors determined the easier
access to the chloromethyl group as reactive sites for the immobilization
of ligands. Moreover, this polymer allowed diffusion of ions in the poly-
mer network, such as: gold(I) during the sorption of this metal on the
resin.
Synthesis and basic characteristics of these resins are presented in
our work (Pilśniak and Trochimczuk, 2007).

Table 2
Characteristics of the 1-methylimidazole resin and 2-mercapto-1-methylimidazole resin with different morphologies (expanded gel, gel and porous).

Resin type Modification type Resin structure Water regain Nitrogen content Sulfur content Chlorine content Yield of
[g/g] [mmol/g] [mmol/g] [mmol/g] modification [%]

1-MIMa Microwave Expanded gel 4.00 6.20 – 0.00 63

Microwave Gel 4.04 6.73 – 0.00 68
Microwave Porous 1.75 3.50 – 0.00 69
Conventional (modification at room temperature) Expanded gel 0.34 7.35 4.48 0.00 87
2-M-1-MIMb Conventional (modification at room temperature) Gel 0.43 6.26 3.54 0.00 73
Conventional (modification at room temperature) Porous 1.39 3.56 2.42 0.00 82
a
1-Methylimidazole resin.
b
2-Mercapto-1-methylimidazole resin.
114 M. Pilśniak-Rabiega, A.W. Trochimczuk / Hydrometallurgy 146 (2014) 111–118

Table 3
Sorption of gold(I) on 1-methylimidazole resin and 2-mercapto-1-methylimidazole resin with different morphologies (expanded gel, gel and porous).

Resin type Modification type Resin structure Ligand concentrationa [mmol/g] Sorption of Au [mg/g] Sorption of Au [mmol/g] log Kd

1-MIMb Microwave Expanded gel 3.10 15.5 0.079 2.94

Microwave Gel 3.37 11.25 0.057 2.78
Microwave Porous 1.75 4.62 0.023 2.36
2-M-1-MIMc Conventional (modification at room temperature) Expanded gel 3.68 1.07 0.005 1.70
Conventional (modification at room temperature) Gel 3.13 4.67 0.024 2.37
Conventional (modification at room temperature) Porous 1.78 3.78 0.019 2.28
a
Calculated from nitrogen content in functional groups.
b
1-Methylimidazole resin.
c
2-Mercapto-1-methylimidazole resin.

3.2. Kinetics of gold(I) sorption
The kinetics of gold uptake is presented in Fig. 2, where the sorption
of gold(I) was plotted vs. time. The maximum uptake of gold was
reached within 120 h. Gold(I) was sorbed faster at the beginning of
the process (50% of maximum uptake was reached after 25–48 h), but
later the rate of uptake decreased and 100% of uptake was reached with-
in 5 days.
Resins 1 and 3 showed similar retention behaviour but for resin 2
was different. It could be explained that resins 1 and 3 had free pair of
electrons on nitrogen and on sulfur atoms (Fig. 1). Such electron pairs
should be able to coordinate with the gold in ammine complexes,
what suggested that the main mechanism of Au(NH3)+ 2 uptake was co-
ordination of metal ions.
In the case of resin 2, the absence of free pair of electrons on nitrogen
atoms of imidazole rings suggested that coordination of Au(I) was not
the mechanism of gold sorption. This positively charged resin 2 had
negatively charged species e.g. OH− and SO2− 4 present as counterions.
These species could be exchanged for the anionic complexes of gold,
Au(OH)− −
2 . Complexes of Au(I) and Au(OH)2 , can exist in ammonium
buffer (Patai, 1999). Alternatively, gold(I) could be sorbed on this poly-
−
meric resin as a neutral ion pair, Au(NH3)+ 2 (OH) or as neutral com-
plex, Au(NH3)(OH). The sorption of ion pair on imidazole resins was
suggested by Green (1988) in the case of gold(I) uptake from cyanide
solutions. He also noticed that the sorption of Au(CN)− 2 Na
+
caused
poor elution of gold(I) with 0.1 M NaOH and that the aromatic structure
of ligands favoured the sorption of ion pairs.
It seemed probable that during the sorption of Au(NH3)+ 2 on resin 3,
the imidazole ligands, having in this case a free electron pair, formed
specific complexes of Au(I) by ligand exchange mechanism. Gold(I)
could be then coordinated to two nitrogen donor-ligands and had a lin-
ear coordination geometry.
In relation to activated carbon, adsorption rate of gold complexes on
this material was relatively fast during the initial stage (compared to the
entire adsorption period). The maximum gold adsorption (10 kg Au/t of
carbon) was obtained after 120 h, and the adsorption efficiency was 98%
(Xu et al., 1996). It could be stated that the kinetics of gold(I) adsorption
on activated carbon was similar to the sorption kinetics on polymeric
resins.
3.3. Improvement of kinetics
The kinetics of gold(I) sorption on resin was improved by immobili-
zation of two types of functional groups on polymeric carrier (VBC/DVB
expanded gel type, containing 2% w/w of the crosslinker). One group
was causing increase of material's hydrophilicity and made possible dif-
fusion of ions inside polymeric matrix. The second group was responsi-
ble for efficiency and selectivity of sorption of selected ions.
In order to improve sorption kinetics we synthesised resins with 1-
methylimidazole and N,N-dimethylethanolamine ligands (resins F1
and F2) using conventional method (modification at 50 °C for 24 h).
The structure of investigated resins is presented in Fig. 3. In order to
obtain resin F1, 1-methylimidazole and N,N-dimethylethanolamine in
molar ratio 3:1 were used, in the case of resin F2 the ratio was 6:1. On
the basis of nitrogen content or quaternary ammonium group content
(Table 4), yield of chloromethyl group substitution in vinylbenzyl
chloride/divinylbenzene (VBC/DVB) copolymer was calculated.
The \CH2Cl groups present in its structure served as a reactive place
for the immobilization of a ligand. The yield of 1-methylimidazole li-
gand immobilization, calculated from the nitrogen content, was 26
and 40% in resins F1 and F2, respectively. Resins F1 and F2 displayed
quaternary ammonium group contents of 2.44 and 1.33 mmol/g
(Table 4). This corresponded to 52 and 28% yield of VBC/DVB modifi-
cation with N,N-dimethylethanolamine.
The maximum gold sorption (8.23 and 9.66 mg/g, respectively) was
reached within 74 h on resins with 1-methylimidazole and N,N-
dimethylethanolamine ligands (resins F1 and F2). The yield of Au(I)
sorption was 34 and 43%, respectively. 1-Methylimidazole resin (2)

NH S
guanylthiourea resin (1)
CH2NHCH2CH2NHCNHCNH2

[A-]
+ 1-methylimidazole resin (2)
CH2 N
N CH3

CH3
2-mercapto-1-methylimidazole resin (3)
N
CH2 S
N

Fig. 1. Structure of investigated resins.

 M. Pilśniak-Rabiega, A.W. Trochimczuk / Hydrometallurgy 146 (2014) 111–118 115

100 Table 4
Characteristics of resins F1 and F2.
90
resin 2 Resin Water regain Chlorine content Nitrogen content Quaternary
80 resin 3 no. [g/g] [mmol/g] [mmol/g] ammonium groups
Au (I) sorption [mg/g]

70 resin 1 content [mmol/g]

F1 4.34 0.23 4.96 2.44

60
F2 4.28 0.36 5.25 1.33
50

40

30
methylimidazole resin (resin 2). It could be concluded from these results,
20 that the gold sorption ability increased, sorption efficiency was 31%
(5.61 mg/g) in the first cycle and in the case of 2–5 cycles was 93–98%
10
(16.8–17.1 mg/g). Desorption efficiency was 14–18%, meaning that
0 resin was not fully regenerated, nonetheless sorption of gold was
0 20 40 60 80 100 120 140 160
effective.
time [h]
In order to explain better gold sorption on resin 2 in the 2–5 cycles
than in the first cycle, FTIR studies of 1-methylimidazole resin (spec-
Fig. 2. Kinetics of gold(I) sorption on polymeric resins: guanylthiourea resin (1),
1-methylimidazole resin (2) and 2-mercapto-1-methylimidazole resin (3).
trum 1a) and this resin after fifth cycles of sorption/desorption (spec-
trum 1b) were performed (Fig. 4.)
reached the maximum uptake of gold within 120 h, the yield of gold(I) In spectrum 1b, appearance of the two strong valence bands at 2143
sorption was 88%. It was found that immobilization of two types of func- and 2028 cm−1, characteristic for CN− ions from the KCN solution used
tional groups on polymeric material had an effect on kinetics improve- for desorption, was observed (Silverstein and Bassler, 1970). It seemed
ment, but it had negative influence on yield of gold(I) uptake. Decrease probable that during the second sorption of Au(NH3)+ 2 on resin 2,

of gold(I) sorption efficiency could be caused by blocking of reactive
places in polymer by N,N-dimethylethanolamine ligands, which was in-
creasing resin hydrophilicity. Also, an increased content of positive
charge on the resin could result in repulsion of Au(NH3)2+.
Data from the kinetics of the gold(I) were recalculated as − ln
cyanide anions from desorption were present on the polymeric surface,
formed dicyanoaurate(I) complexes by ligand exchange mechanism.
[Au(CN)2]− complexes like [Au(NH3)2]+ have linear coordination
geometry.
The dicyanoaurate(I) ion, Au(CN)− 2 , is the most stable complex ion

(1 − s t / s k) vs. time, where st denotes sorption after given time and sf formed by gold(I), and the logarithm of stability constant, log β2, was es-
is sorption at equilibrium. The slope of thus obtained straight line gave timated to be 49.0, for Au(NH3)+2 the value of log β2 corresponds to 26.5

the sorption rate constant k. In the case of resins 2, F1 and F2 the sorption
rate constants were 5.39·10−6, 7.69·10−6 and 6.92·10−6, respectively. It
appeared that the sorption rate constants were comparable for resins
with 1-methylimidazole and N,N-dimethylethanolamine ligands (resins
F1 and F2) and 1-methylimidazole resin (2). The introduction of N,N-
dimethylethanolamine ligands into the polymer slightly improved kinet-
ics of gold(I) sorption, but strongly reduced the recovery of gold on resins.
(Högfeldt, 1982). The values of the log β2 for cyanide and ammine com-
plexes may suggest that electrically neutral ammine ligands, NH3, were
substituted for cyanide anions, CN−, in gold(I) complexes. The forma-
tion of dicyanoaurate(I) complexes was also confirmed by the results
of desorption efficiency (14–18%). Difficulty in gold elution could be
caused by preferential sorption of anionic complexes of gold(I) on 1-
methylimidazole resin, which is an anion-exchanger.

3.5. Selectivity studies in three-component mixture

3.4. Resin's stability in cycles of sorption/desorption
For further study three new resins: dipropylamine resin (4), 1,2-
In order to check the resin's stability, 5 cycles of gold(I) sorption from
dimethylimidazole resin (5) and 1-(3-aminopropyl)imidazole resin
ammonium buffer (100 g/L NH3·H2O, 5.00 g/L (NH4)2SO4, 21.57 mg/L of
(6) were also used. Synthesis and basic characteristics of these resins
Au(I)) and desorption with 1% KCN in 0.3% H2O2 were performed on 1-
are presented in our work (Pilśniak and Trochimczuk, 2007). Selectivity
complex formation

[A-]
+
CH N
N CH3

[A-] CH
3
+
CH NCH2CH2OH

CH3

hydrophilicity
Fig. 3. The structure of resin with 1-methylimidazole and N,N-dimethylethanolamine Fig. 4. FTIR spectra of 1-methylimidazole resin (2) before (spectrum 1a) and after (spectrum
ligands (resins F1 and F2). 1b) sorption/desorption cycles.
116 M. Pilśniak-Rabiega, A.W. Trochimczuk / Hydrometallurgy 146 (2014) 111–118

Table 5
Precious metal uptake (Au(I), Ag(I) and Cu(II)) from ammonium buffer.

Resin no Sorption of Aua–Agb–Cuc Sorption of Aua–Agb–xCuc log Kd αsel (Au/Ag)

from three-component from three-component
solution [mg/g] solution [%]

Au Ag Au Ag Au Ag

1 2.85 0.82 6.12 3.11 2.15 1.84 2.04

2 10.3 1.73 9.97 2.95 2.72 2.16 3.62
3 10.6 2.08 18.2 6.30 2.78 2.26 3.31
4 2.67 0.52 7.40 2.54 2.13 1.64 3.09
5 5.09 0.86 5.24 1.56 2.40 1.85 3.55
6 2.37 1.39 3.71 3.85 2.06 2.07 0.983

1. guanylthiourea resin.
2. 1-methylimidazole resin.
3. 2-mercapto-1-methylimidazole resin.
4. dipropylamine resin.
5. 1,2-dimethylimidazole resin.
6. 1-(3-aminopropyl)imidazole resin.
a
CAu = 21.57 mg/L (0.1090 mmol/L) xCu — copper is not sorbed.
b
CAg = 12.20 mg/L (0.1130 mmol/L).
c
CCu = 22.44 mg/L (0.3510 mmol/L).

studies were performed in three-component mixture of gold(I), silver(I) 3.6. Polymeric resins in cyanide form
and copper(II) in ammonium buffer (100 g/L NH 3·H2 O, 5.00 g/L
(NH4 )2 SO 4 ). The concentrations of Au(I), Ag(I) and Cu(II) were So far, the gold sorption from ammoniacal solutions by polymeric
0.1090, 0.1130 and 0.3510 mmol/L, respectively. The selectivity coeffi- materials in the cyanide form has not yet been used or described in
cient (αsel) was calculated as the quotient of distribution coefficients the open literature.
calculated for gold and silver cations. The results are presented in The polymeric resins (1–6) were converted to cyanide form by
Table 5. It could be seen that featured resins were selective towards am- contacting the resin samples with 1% potassium cyanide solution in
mine complexes of gold(I) and silver(I) in relation to Cu(NH3)2+ 4 . The 0.3% hydrogen peroxide solution at room temperature for 24 h. Then,
cationic complexes of copper were not sorbed by the obtained resins these materials were used for gold recovery from single-component so-
from solution containing three-fold excess of copper in relation to the lution and ternary solution (Au + Ag + Cu) in ammonium buffer
gold or silver content in ammonium buffer. This fact could be explained (100 g/L NH3·H2O, 5.00 g/L (NH4)2SO4). Table 6 presents the results of
as a result of the presence of ligands with N- and S-donor centres, which gold sorption in resins 1–6 from single component solution. The poly-
had a high affinity for “soft” metals (Au, Ag, Pt), but minor affinity to- meric resins displayed high affinity towards gold(I) from ammoniacal
wards copper, which is known as a borderline metal and is “harder” solution, sorption degree of Au(I) in each case was 99.5% and the values
than Au. On the other hand it could be caused by the fact that ligands pre- of log Kd were above 4.00.
fer smaller complexes. Ammine complexes of gold and silver Au(NH3)+ 2 To check if the presence of cyanide anions, CN−, on the polymeric
and Ag(NH3)+ 2+
2 , display linear structure, whereas Cu(NH3)4 has tetrahe- surface could be useful in the separation of noble metal cations, selectiv-
dral structure. ity studies were realized in mixture of gold(I), silver(I) and copper(II) in
It could be concluded from these studies that a selective sorption of ammonium buffer (100 g/L NH3·H2O, 5.00 g/L (NH4)2SO4). Sorption
gold(I) and silver(I) on resins from solution containing copper(II), made was performed from solution containing three metal cations, each of
these polymeric materials potentially useful in the recovery of Au(I) and concentration 0.10 mmol/L. The selectivity coefficient (αsel) was calcu-
Ag(I) from various sources such as sulfidic and carbonaceous ores and lated as the quotient of distribution coefficients calculated for each cat-
jewellery scraps. ion. The results are presented in Table 7. The best sorption capacity
towards gold(I) showed 1,2-dimethylimidazole resin (5) and 1-(3-
aminopropyl)imidazole resin (6). The sorption degrees of gold were
99.5%. These resins were not removing ammine complexes of copper(II).
This could be useful in the separation of gold from mixtures containing
Table 6
other noble metals, e.g. as it occurs in precious metal scraps. Taking into
Sorption of gold(I) on the investigated resins in cyanide form.
account resins 1–4, sorption degree of gold was above 99.0% but sorption
Resin no Sorption of Aua from single- Sorption of Aua from single- log Kd degrees of silver and copper were 22.7–94.8 and 8.30–81.0, respectively.
component solution [mg/g] component solution [%]
These results showed that guanylthiourea resin (1), 1-methylimidazole
1 2.47 99.5 4.39 resin (2), 2-mercapto-1-methylimidazole resin (3) and dipropylamine
2 2.62 99.5 4.42 resin (4) were not selective in respect of gold.
3 3.60 99.5 4.56
The results of sorption from multicomponent solutions (Au +
4 2.89 99.5 4.46
5 5.56 99.5 4.75 Ag + Cu) on resins 1–6 in chloride form (Table 5) and in cyanide
6 2.44 99.5 4.39 form (Table 7), showed that resins in chloride form were more se-
CNH3H2O = 100 g/L, C(NH4)2SO4 = 5.00 g/L. lective in relation to gold(I) ions, because all these materials were
1. guanylthiourea resin. not removing cationic complexes of copper(II) and Cu(NH3)24 +. In
2. 1-methylimidazole resin. the case of resin in cyanide form, sorption degrees of gold were
3. 2-mercapto-1-methylimidazole resin. 5.50–27.0 greater than for resins in chloride form. Sorption capacities to-
4. dipropylamine resin.
5. 1,2-dimethylimidazole resin.
wards silver were also greater for resins in cyanide form, especially for
6. 1-(3-aminopropyl)imidazole resin. guanylthiourea resin (1), 1-methylimidazole resin (2) and 2-mercapto-
a
CAu = 19.90 mg/L (0.1006 mmol/L). 1-methylimidazole resin (3). Resins 1–4 in cyanide form also sorbed
 M. Pilśniak-Rabiega, A.W. Trochimczuk / Hydrometallurgy 146 (2014) 111–118 117

Table 7
Sorption of gold(I), silver(I) and copper(II) on the resins in cyanide form.

Resin no Sorption of Aua–Agb–Cuc Sorption of Aua–Agb–Cuc from log Kd αsel (Au/Ag) αsel (Au/Cu) αsel (Ag/Cu)
from three-solution [mg/g] three-component solution [%]

Au Ag Cu Au Ag Cu Au Ag Cu

1 2.55 1.04 0.71 99.7 70.8 81.0 4.63 2.49 2.75 138 75.9 0.550
2 3.81 1.43 0.11 99.5 64.8 8.28 4.58 2.55 1.25 107 2148 20.1
3 3.69 2.02 0.34 99.5 94.8 27.0 4.57 3.53 1.84 11.0 537 49.0
4 4.65 0.61 0.13 99.5 22.7 8.30 4.67 1.84 1.32 676 2238 3.31
5 6.27 0.44 0.00 99.5 12.0 0.00 4.80 1.64 – 1444 – –
6 2.62 0.30 0.00 99.5 20.0 0.00 4.42 1.52 – 797 – –

CNH3H2O = 100 g/L, C(NH4)2SO4 = 5.00 g/L.

1. guanylthiourea resin.
2. 1-methylimidazole resin.
3. 2-mercapto-1-methylimidazole resin.
4. dipropylamine resin.
5. 1,2-dimethylimidazole resin.
6. 1-(3-aminopropyl)imidazole resin.
a
CAu = 19.90 mg/L (0.1006 mmol/L).
b
CAg = 11.44 mg/L (0.1060 mmol/L).
c
CCu = 6.760 mg/L (0.1057 mmol/L).

copper(II) ions. Effective metal sorption on resins 1–6 in cyanide form
was caused by the formation of anionic complexes (cyanide complexes)
of gold(I), silver(I) and copper(I) and their preferential sorption on poly-
meric materials. Depending on the metals the following reactions could
take place:
• For 1,2-dimethylimidazole resin and 1-(3-aminopropyl)imidazole
resin in cyanide form, selective in relation to gold uptake over sil-
ver and copper was extremely high.

 þ  − Acknowledgements
1. AuðNH3 Þ2 þ 2CN− ¼ AuðCNÞ2 þ 2NH3
logβ2 ¼ 26:5 logβ2 ¼ 49:0 The work was financed by a statutory activity subsidy from the Pol-
ish Ministry of Science and Higher Education for the Faculty of Chemis-
 þ  − try of Wroclaw University of Technology.
2. AgðNH3 Þ2 þ 2CN− ¼ AgðCNÞ2 þ 2NH3
logβ2 ¼ 7:23 logβ2 ¼ 20:9

 2þ  3− References

3. CuðNH3 Þ4 þ 4CN− ¼ CuðCNÞ4 þ 4NH3
log β4 ¼ 12:9 log β4 ¼ 30:5:
The values of stability constants of complexes of gold, silver and cop-
per confirmed the formation of cyanide complexes of these metals,
which were more stable than ammine complexes.
Guanylthiourea resin (1), 1-methylimidazole resin (2), 2-
mercapto-1-methylimidazole resin (3) dipropylamine resin (4),
1,2-dimethylimidazole resin (5) and 1-(3-aminopropyl)imidazole
resin (6) were anion-exchangers and showed preferential sorption of
negatively charged complexes of Au(I), Ag(I) and Cu(II).
4. Conclusions
• The best results of the introduction of functional groups into the poly-
mer matrix were obtained using vinylbenzyl chloride/divinylbenzene
(VBC/DVB) copolymer, expanded gel type, containing 2% of crosslinking
agent.
• The kinetics of gold(I) sorption from ammonium buffer on 1-
methylimidazole resin was improved by immobilization of N,N-
dimethylethanolamine ligands, which increased the hydrophilicity
of the polymeric material.
• Resin with 1-methylimidazole ligands retained their capacity to-
wards gold in five consecutive sorption/desorption cycles.
• Resins in chloride form were useful for sorption of Au(NH3)+ 2 and
Ag(NH3 )+ 2 complexes from three-component mixture of Au(I),
Ag(I) and Cu(II) in ammonium buffer (100 g/L NH3·H2O, 5.00 g/L
(NH4)2 SO 4) and showed preferential sorption of gold and silver
in the presence of copper.
• Polymeric resins in cyanide form displayed high affinity towards
gold(I) from ammoniacal solution (100 g/L NH 3 ·H2 O, 5.00 g/L
(NH4)2SO4).
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