Hydrometallurgy 169 (2017) 16–25

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Hydrometallurgy

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

An analysis of the efficiency and sustainability of the

thiosulfate-copper-ammonia-monoethanolamine system for the
recovery of silver as an alternative to cyanidation
D.M. Puente-Siller, J.C. Fuentes-Aceituno ⁎, F. Nava-Alonso
Centro de Investigación y de Estudios Avanzados del IPN Unidad Saltillo, Av. Industria Metalúrgica No 1062, Ramos Arizpe, Coahuila CP 25900, Mexico.

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

Article history: In this research, silver leaching experiments from pure phases of Ag and Ag2S were done using the S2O2− 3 -Cu
2+
-
Received 8 July 2016 MEA-NH4 alternative system and varying the S2O2− 3 and MEA concentrations. The results revealed that MEA can
Received in revised form 23 November 2016 stabilize the cupric ions forming several Cu-MEA complexes. It was also found that MEA can form Ag-MEA com-
Accepted 8 December 2016
plexes, and thus it can work as a co-leaching agent for silver, mainly when metallic silver is used.
Available online 11 December 2016
Furthermore the leaching experiments with metallic silver showed a continuous oscillation process (silver
Keywords:
dissolution-precipitation phenomenon), which was related to the formation of the redox couples Ag-MEA/Ag
Thiosulfate and Cu-NH3/Cu-MEA, as well as with the oxidative decomposition of thiosulfate which could lead to the forma-
Silver tion of copper sulfide species. The leaching experiments with silver sulfide revealed that the presence of MEA in
Silver sulfide the leaching system is advantageous in two ways: a) it decreases the precipitation of copper oxides and b) it as-
MEA sists the stabilization of silver in solution avoiding its precipitation.
Recycling Furthermore, the pregnant leaching solutions were treated by cementation using a metallic copper wire and the
chemical and microstructural characterizations revealed that silver was deposited on the copper wire surface.
When the leaching solution is re-utilized after the cementation step in a second leaching with Ag2S, it is possible
to dissolve 85% of silver. This paper presents an alternative-sustainable thiosulfate leaching system which per-
mits the recovery of silver from metallic silver or silver sulfide at short processing times.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction can be considered an alternative less toxic system to the conventional

Since the 1980's the search of alternative-green processes to
cyanidation has been intensified due to two issues: a) the environment
i.e., nowadays the environmental regulations are becoming more severe
with respect to the use of cyanide and b) the process kinetics, i.e., the
enhancement of the gold and silver dissolution rates (Abbruzzese
et al., 1995).
The recovery of precious metals using thiosulfate, was proposed for
the first time in 1900, in a process known as “Von Patera” (Aylmore and
Muir, 2001). Thiosulfate is an intermediate product of the oxidation of
iron sulfides; due to this fact, many of the leaching solutions, used in
the processing of sulfur minerals, contain thiosalts (S2O23 −, S4026 −,
S3O2− 6 ), such compounds are produced from the degradation of the sul-
fur minerals (Senanayake, 2005a). The last fact, represents an interest-
ing advantage, i.e., many of the worldwide reserves of iron and copper
are found in the terrestrial cortex as sulfur minerals, which can be an
important source to produce thiosulfate. Therefore, thiosulfate leaching
⁎ Corresponding author.
E-mail address: juan.fuentes@cinvestav.mx (J.C. Fuentes-Aceituno).
cyanidation (Abbruzzese et al., 1995).
Several investigations have been done for the leaching of gold and
silver using thiosulfate solutions (Aylmore, 2001; Aylmore and Muir,
2001; Balaz et al., 2000; Breuer and Jeffrey, 2003; Fuentes-Aceituno
et al., 2005; Lam and Dreisinger, 2003; Muir and Aylmore, 2005;
Senanayake, 2005b; Zipperian et al., 1988); these researches showed
that leaching solutions containing thiosulfate-copper-ammonia are effi-
cient to dissolve the precious metals from sulfide ores in 48 h, approxi-
mately. Furthermore, Senanayake (2007) reported that thiosulfate is
considered the most promising non-cyanide complexing agent for the
recovery of precious metals from refractory ores. Thiosulfate needs to
be in contact with co-leaching agents such as ammonia or thiourea, as
well as in the presence of oxidizing agents such as copper (II) or iron
(III) (Senanayake, 2007).
During the thiosulfate leaching of precious metals, several chemical
and electrochemical reactions take place, such as: oxidation, dissolution
and complexes formation. Only few oxidizing agents are adequate to
work in ammoniacal solutions, such as cupric ions (Abbruzzese et al.,
1995). Its catalytic power promotes the dissolution of gold in thiosulfate
solutions, accelerating the dissolution rate from 18 to 20 times. Howev-
er, the chemistry of this system is very complex and the presence of

http://dx.doi.org/10.1016/j.hydromet.2016.12.003
0304-386X/© 2016 Elsevier B.V. All rights reserved.
 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25
cupric ions in solution can promote the loss of thiosulfate up to 50% pro-
ducing tetrathionate and other sulfur compounds (Aylmore and Muir,
2001).
Due to the persistent instability of the cupric ions in ammoniacal so-
lutions, it is necessary to introduce additives to stabilize the copper in
solution at high concentrations of ammonia, copper and thiosulfate
(Feng and Van Deventer, 2010). EDTA is one of the most studied reac-
tants to stabilize the cupric ions in the leaching solution (Feng and
Van Deventer, 2010; Puente-Siller et al., 2013); however, Puente-Siller
et al. (2013) reported the precipitation of copper sulfides and copper
oxides in the system containing EDTA. Alternative complexing agents
for cupric ions have been also studied, such as sodium citrate (Puente-
Siller et al., 2014). These researchers found that the presence of sodium
citrate favors the silver sulfide dissolution rate; however the precipita-
tion of copper sulfides and copper oxides from the leaching solution
persisted.
Due to the necessity to find a stabilizer agent for cupric ions in
thiosulfate leaching solutions, this work proposes the use of
monoethanolamine (MEA) in thiosulfate solutions. It is known that
MEA can form Cu-MEA complexes. Shih et al. (2002) carried out a
study on the dissolution of copper in MEA solutions at alkaline pH;
they found that MEA can form complexes with copper ions. Further-
more, Kwang and Gyu (2010) studied the ability of MEA to solubilize
copper oxides and stabilize copper ions as Cu-MEA complexes at differ-
ent pH values. It has been also reported the ability of MEA as a
complexing agent-inhibitor of corrosion, which avoids the formation
of copper oxides on copper surfaces (Kwang and Gyu, 2010). Cho et al.
(2014) used MEA as a copper complexing agent in the processing of
thin films.
Copper oxides present an acceptable dissolution rate in MEA con-
taining alkaline solutions at (pH ≥ 9), it is important to mention that
the solubility of copper oxides, in the presence of MEA, is decreased
when the solution becomes more acid (Kwang and Gyu, 2010). The abil-
ity of MEA to complex cupric ions at pH values higher than 9 can be an
advantage in this research. It is worth mentioning that thiosulfate
leaching is carried out, in the most of cases, in alkaline solutions, due
to the fact that thiosulfate can form more stable complexes with the
precious metals when the leaching system is operated at pH values
from 8.5 to 10.5 approximately.
This work presents a kinetic and thermodynamic study of the S2O3-
Cu-NH4-MEA alternative system for the leaching of the pure species of
silver and silver sulfide. This process would be able to dissolve silver
in short processing times, to recover the silver in its metallic form, and
to re-utilize the leaching solution.
2. Materials and methods
The experimental work was divided in three sections: Section 2.1,
silver leachings from pure metallic silver with the thiosulfate-copper-
ammonia-MEA system; Section 2.2, elaboration of the thermodynamic
diagrams for the Ag-MEA-H2O and Cu-MEA-NH3-H2O systems, and;
Section 2.3, silver leachings from pure silver sulfide followed by the ce-
mentation of metallic silver and re-utilization of the leaching solution
with the thiosulfate-copper-ammonia-MEA system.
All leaching experiments were performed in an agitated batch reac-
tor (250 mL glass beaker), magnetically stirred at 400 min−1. The reac-
tor was provided with a pH electrode (SENSOREX) and a redox potential
electrode with calomel reference (Cole-Parmer); the pH and the redox
potential were measured before the metallic silver or silver sulfide addi-
tion and during the leaching experiments. Samples of the leach solu-
tions were withdrawn at different times during the leach period for
analysis of silver by atomic absorption spectrophotometry (VARIAN
Spectra AA 240). All samples were analyzed at the end of the experi-
ments, and until the analysis they were kept in dark vessels to prevent
the precipitation of silver by light. The quantification of the thiosulfate
17
decomposition was done in some leaching experiments, using the
iodometric titration method reported by Paredes-Soto (2014).
It is worth mentioning that all experiments were performed at room
temperature and all solutions were prepared with reagent grade
chemicals and deionized water. The leaching experiments for silver
and silver sulfide are described in the next sections.
2.1. Leaching tests using metallic silver with different thiosulfate and MEA
concentrations
The leachings were carried out adding 0.125 g of metallic silver (1-
3 μm, Alfa Aesar, 99.999%) in 200 mL of the leaching solution which
contained 0.05 M Cu2 +, 0.1, 0.2 or 0.3 M thiosulfate and 0,
1.25 × 10− 4, 0.025 or 0.05 M MEA at room temperature and pH =
10.20 adjusted with ammonium hydroxide. The leachings were stirred
at 400 min−1 during 6 h.
2.2. Elaboration of the thermodynamic diagrams
Thermodynamic diagrams for the Ag-MEA-H2O and Cu-MEA-NH3-
H2O systems were constructed using the Medusa© Software. The dia-
grams were constructed considering the equilibrium data contained in
the Hydra database of the Medusa© suite software (Puigdomenech,
2004), complemented with thermodynamic data for some silver and
copper species reported by Aylmore and Muir (2001), and Smith and
Martell (1975). The software is based in an algorithm developed by
Eriksson (1979), which minimizes the Gibbs free energy of reactions
in equilibrium that can occur in the aqueous leaching systems, and de-
termines the predominating species under specific solution conditions.
Table 1 presents the thermodynamic data used in this work.
2.3. Leaching of silver sulfide, cementation of metallic silver and re-
utilization of the leaching solution (LCRL process)
The LCRL process i.e., the leaching of silver sulfide followed by the ce-
mentation of metallic silver and re-utilization of the solution in a second
leaching of fresh silver sulfide, was studied employing two leaching so-
lutions containing: 0.2 or 0.3 M thiosulfate, 0.05 M Cu2+ and 0.025 or
0.05 M MEA. Both leaching steps i.e., before and after the cementation
process, used 0.1435 g of pure silver sulfide (− 400 + 500 mesh, Alfa
Aesar 99.99%) and 200 mL of the leaching solution at pH = 10.20 adjust-
ed with ammonium hydroxide.
The total experimental time of the LCRL process corresponds to 6.5 h.
The LCRL process was divided in three steps: a) silver sulfide leaching
using both leaching solutions mentioned above during 3 h, b) after
this time, the pregnant leaching solution was filtered and the silver ce-
mentation step was triggered immersing 10.95 g of copper wires
(0.5 mm diameter) in the pregnant leaching solution during 30 min,
c) after this time, the copper wires coated with metallic silver were
withdrawn from the reactor, and the leaching solution was used to
carry out a second leaching employing fresh silver sulfide (0.1435 g),
in order to evaluate the performance of the system when the leaching
solution is recycled. The copper wire coated with metallic silver was
chemically and morphologically characterized by SEM (Phillips
XL30ESEM). The local chemical composition on the wire surface was de-
termined by EDXS (EDAX Genesis).
3. Results and discussion
The results of this research are presented and discussed in this sec-
tion. The first section corresponds to the effect of thiosulfate and MEA
concentrations on the metallic silver leaching; the second section
shows a thermodynamic analysis focused to explain the phenomena ob-
served in the first section, and the last section presents the silver sulfide
leaching using this alternative thiosulfate system followed by a
18 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25

Table 1 shows an oscillatory behavior. This suggests, that in a certain way,

Gibbs free energy of formation and Log K for silver, copper, ammonia and MEA species there exists a competence of some reactants contained in the system
used in the construction of thermodynamic diagrams.
to complex silver through different reactions that are occurring in this
Chemical species ΔG0298 (KJ/mol) Reference leaching system, and probably, some silver complexes can be unstable
Ag2+ 268.200 Aylmore and Muir (2001) which lead to the partial precipitation of silver.
Ag2O3 87.000 In addition to the above, other simultaneous reactions may occur
Cu(NH3)2+
2 −32.259 such as the oxidative decomposition of thiosulfate involving the forma-
Cu(NH3)2+ −73.212
3
tion of additional sulfur compounds such as tetrathionate, as well as the
Chemical reactions Log K precipitation of copper sulfides species such as CuS or Cu2S (Eqs. (1) and
Ag+ + 2H2O = 2H+ + Ag(OH)− 2 −24.000 Software Medusa© (2)) (Abbruzzese et al., 1995).
Ag+ + H2O = H+ + AgOH −12.000
+ −
2H + 2e = H2 −3.150
2H+ + 2e− = H2(g) 0.000 Cu2þ þ S2 O3 2− þ H2 O→CuS þ SO4 2− þ 2Hþ ð1Þ
2H2O = 2H+ + 2e− + H2O2 −59.601
2H2O = 4H+ + 4e− + O2 −86.080
2Cuþ þ S2 O3 2− þ H2 O→Cu2 S þ SO4 2− þ 2Hþ ð2Þ
2H2O = 4H+ + 4e− + O2(g) −83.120
3H2O = 6H+ + 6e− + O3 −156.050
3H2O = 6H+ + 6e− + O3(g) −153.250 Once the copper sulfide species are formed, the silver contained in
H2O = H+ + OH− −14.000 the thiosulfate complex (Ag(S2O3)5−3 ) could precipitate as silver sulfide
2H2O = 3H+ + 2e− + HO− 2 −71.251
according to Eq. (3) (Zipperian et al., 1988):
Ag+ + e− = Ag(c) 13.510
2Ag+ + H2O = 2H+ + Ag2O(c) −12.580
Ag+ + H2O = 2H+ + e− + AgO(c) −29.950 Cu2 S þ 2AgðS2 O3 Þ3 5− →Ag2 S þ 2CuðS2 O3 Þ3 5− ð3Þ
Cu2+ + 4NH3 = Cu(NH3)2+
4 12.464
Cu2+ + 2e− = Cu(c) 11.395
Cu 2+ −
+ e = Cu +
2.833 This reaction would also explain the decrease on silver concentra-
Cu2+ + 2NH3 + e− = Cu(NH3)+ 2 13.333 tion in the leaching curves of the Figs. 1 and 2. Once the silver sulfide
2+
Cu + H2O = 2H+ + CuO (cr) −7.675 is formed, it is possible to redissolve it by a substitution of copper by sil-
2Cu2+ 7.216
ver in the sulfide matrix, with the consequent formation of a silver thio-
+ 2e− + H2O = 2H+ + Cu2O(c)
Ag+ + MEA = Ag(MEA)+ 3.130 Smith and Martell (1975)
sulfate complex in solution (Aylmore and Muir, 2001):
Ag+ + 2MEA = Ag(MEA)+ 2 6.680
Cu2+ + MEA = Cu(MEA)2+ 5.700 2Cuþ þ Ag2 S→2Agþ þ Cu2 S þ 6S2 O3 2− →2AgðS2 O3 Þ3 5− ð4Þ
2+
Cu + 2MEA = Cu(MEA)2+2 9.800
Cu2+ + 3MEA = Cu(MEA)2+ 3 13.000
Cu 2+
+ 4MEA = Cu(MEA)2+4 15.200 Furthermore, the precipitation of silver is more pronounced in the
leaching system without the presence of MEA (see Fig. 2) than in the
leaching systems containing MEA. This could be related to a higher thio-
cementation process, in order to recover the metallic silver and re- sulfate decomposition in the case of the leaching system without MEA
utilize the leaching solution for the dissolution of fresh silver sulfide. than in the cases with MEA. Actually, Fig. 3 illustrates the evolution of
the thiosulfate decomposition % for the leaching systems containing
3.1. Effect of thiosulfate and MEA concentrations on the metallic silver 0.2 M thiosulfate, 0.05 M Cu2+, pH = 10.20 adjusted with ammonium
leaching hydroxide, with (0.025 M) and without MEA. It is possible to observe,
that the presence of MEA in the leaching system decreases the thiosul-
Fig. 1 displays the silver extraction (%) vs time curves for the fate decomposition, i.e., the thiosulfate decomposition percentage cor-
leaching of metallic silver with a solution containing 0.1 M thiosulfate, responds to 20% and 50% for the leaching systems with and without
0.05 M Cu2+, pH 10.20 adjusted with ammonium hydroxide at three MEA, respectively. These results reveal the beneficial effect of this
different MEA concentrations. It is possible to observe that all leaching complexing agent (MEA) on the silver extraction and stabilization of
solutions present high silver dissolution rates during the first 10 min, the leaching solution.
producing silver-thiosulfate complexes such as: Ag(S2O3)5− 3 , however, Table 2 shows the results corresponding to the silver extraction (%)
when the processing time is increased, the amount of dissolved silver at selected times for the leaching experiments carried out with 0.3 M
varies with time and the leaching curves present oscillations. In a partic- thiosulfate, 0.05 M Cu2 +, pH = 10.20 adjusted with ammonium hy-
ular way, if the leaching curve for 1.25 × 10−4 M MEA is observed, it is droxide at three different MEA concentrations. It is observed, that
possible to say that at the beginning, this solution showed a higher silver when the MEA concentration is increased, the silver dissolution kinetics
extraction (87%) than that found with 0.025 and 0.05 M MEA (82 and and recovery are favored, e.g., a silver recovery of 32.37, 79.25 and
84%, respectively); however, the efficiency is considerably decreased 84.99% is obtained at 0.1667 h with the leaching system containing
at 2 h, where the silver extraction only corresponds to 70%. In spite of 1.25 × 10− 4, 0.025 and 0.05 M MEA, respectively. Furthermore, it is
this, the leaching solution containing 1.25 × 10− 4 M MEA had the also possible to observe at 2 h that the most efficient system for silver
highest silver extraction (89%) at 6 h; on the other hand, the leaching leaching corresponds to the solution containing 0.05 M MEA.
solutions containing 0.025 and 0.05 M MEA reached a silver extraction On the other hand, when Figs.s 1, 2 and Table 2 are compared for the
of 85 and 69%, respectively. leaching system containing 0.05 M MEA, it is possible to observe at 6 h,
Fig. 2 illustrates a comparison of the silver extraction (%) vs time that the silver recovery is affected by the concentration of thiosulfate
curves for the leaching of silver using a solution containing 0.2 M thio- available in the system, i.e., a 70, 80 and 95.51% of silver is leached
sulfate, 0.05 M Cu2+, pH = 10.20 adjusted with ammonium hydroxide with the leaching system containing 0.1, 0.2 and 0.3 M thiosulfate, re-
at three different MEA concentrations and without MEA. It is possible to spectively. This behavior can probably be related to the formation of dif-
observe an unstable behavior or pronounced oscillations in all leaching ferent concentrations of the silver-MEA complexes along with the
curves; however, a silver recovery higher than 80% can be obtained at silver-thiosulfate complexes. In this sense, it is expected that an increase
6 h in all leaching experiments. The leaching system containing in the thiosulfate concentration, for example 0.3 M thiosulfate; de-
0.025 M MEA reached a silver recovery of 100% during the first creases the formation of silver-MEA complexes due to the predominant
30 min; however, when the leaching experiment continues, the effi- formation of silver-thiosulfate complexes, which are more stable than
ciency of this system decreased at 1 h, after this time silver leaching the silver-MEA complexes.
 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25
Fig. 1. Silver extraction with the leaching systems containing different MEA
concentrations, 0.125 g metallic silver, 0.1 M thiosulfate, 0.05 M Cu2+, pH = 10.20
adjusted with ammonium hydroxide at room temperature.
3.2. Thermodynamic study of the Ag-MEA-H2O and Cu-MEA-NH3-H2O
systems
As mentioned before, the oscillations found in the leaching curves
can be related to the thiosulfate decomposition as shown
inEqs. (1)–(4). However, besides thiosulfate, another reagent of the
leaching system compete to complex the silver; MEA may possibly
have two effects on this alternative leaching system, i.e., it can complex
cupric ions promoting the silver oxidation, and it can also act as a co-
leaching agent for silver. MEA can form complexes with silver (Smith
and Martell, 1975), according to Eqs. (5) and (6).
Agþ þ MEA ¼ AgðMEAÞþ
Agþ þ 2MEA ¼ AgðMEAÞ2 þ
On the basis of the last statement, the oscillations (precipitation and
re-dissolution of silver) found in the leaching curves can also be, possi-
bly, explained as follows: e.g., the redox potential measured in the
leaching experiment carried out with 0.025 M MEA and 0.2 M S2O2− 3 plex (6.68). Furthermore, these Log K values reveal that the Ag(MEA)+
varies between 0.43 and 0.45 V vs SHE; therefore, according to the
Pourbaix diagram of the Ag-MEA-H2O system shown in Fig. 4, the
leaching experiment was operated in the predominance area of the
Fig. 2. Silver extraction with the leaching systems containing different MEA
concentrations, 0.125 g metallic silver, 0.2 M thiosulfate, 0.05 M Cu2+, pH = 10.20
adjusted with ammonium hydroxide at room temperature.
19
Fig. 3. Thiosulfate decomposition with the leaching systems containing 0 and 0.025 M
MEA, 0.125 g metallic silver, 0.2 M thiosulfate, 0.05 M Cu2+, pH = 10.20 adjusted with
ammonium hydroxide at room temperature.
Ag(MEA)+ 2 complex. Furthermore, this Ag-MEA complex can form a gal-
vanic couple with metallic silver which equilibrium potential corre-
sponds to 0.300 V vs SHE; this indicates that the silver precipitation
phenomenon found in the leaching curves must be also related to the
reduction of the Ag(MEA)+ 2 complex to Ag, and when the process con-
tinues, the precipitated silver can be re-oxidized producing silver com-
plexes with thiosulfate and MEA. The formation of the Ag-thiosulfate
and Ag-MEA complexes is justified, due to the fact, that the redox couple
Ag(S2O3)53 −/Ag has an equilibrium potential of − 0.044, − 0.089 and
−0.119 V vs SHE for the leaching solutions with 0.1, 0.2 and 0.3 M thio-
sulfate, respectively (Puente-Siller et al., 2013). Furthermore, the gal-
vanic couple Ag(MEA)+ 2 /Ag has an equilibrium potential of 0.3 V vs
ð5Þ SHE. All these equilibrium potentials lie below the measured redox po-
tential, it is important to remember that for the leaching system con-
ð6Þ taining 0.025 M MEA and 0.2 M S2O2− 3 the measured redox potential
varies between 0.43 and 0.45 V vs SHE, and the formation of Ag-
thiosulfate and Ag-MEA complexes is thus possible. However, it is
worth mentioning that complexation of silver by thiosulfate is favored
due to its Log K (13.823) which is bigger than that for the Ag-MEA com-
2
complex is less stable than the Ag(S2O3)5− 3 complex, which indicates
that the precipitation of silver from the Ag(MEA)+ 2 complex is more
feasible.
The presence of a reducing agent or a chemical species which is sus-
ceptible to the oxidation is necessary in order to promote the reduction
of Ag(MEA)+ 2 to Ag. Fig. 5 illustrates the Pourbaix diagrams constructed
for the Cu-MEA-NH3-H2O system. Fig. 5a only shows the predominant
aqueous species in the system, and Fig. 5b shows the predominant
aqueous and solid species in the system. It is possible to observe (Fig.
5b) the formation of cupric oxide species at the measured pH and
redox potential of 10.2 and 0.46 V vs SHE, respectively. This is congruent
with typical thiosulfate-copper leaching systems, where the formation
Table 2
Silver extraction with the leaching systems containing different MEA concentrations,
0.125 g metallic silver, 0.3 M thiosulfate, 0.05 M Cu2+, pH = 10.20 adjusted with ammo-
nium hydroxide at room temperature.
Silver extraction (%)
Time (h) MEA concentration (M)
1.25 × 10−4 0.025 0.05
0.1667 32.37 79.25 85.01
2 66.82 89.17 91.95
6 95.31 94.01 95.51
20 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25

cathodic reaction is related to the formation of the galvanic couple

Ag(MEA)+ 2 /Ag.
It is worth mentioning that the reduction of the complexed silver in
solution only comes from the silver complexed by MEA, as shown be-
fore, and not from the silver complexed by thiosulfate. This is evident
if it is considered that the equilibrium potential of the galvanic couple
Ag(S2O3)5− 2+
3 /Ag is lower than that of Cu(MEA)4 /Cu(NH3)2 .
+

The stabilization of cupric ions was one of the main reasons to study
the effect of MEA in this leaching system. Actually MEA is an efficient
complexing agent to stabilize cupric ions in solution. In the diagram
shown in Fig. 6, it is observed that Cu-MEA species are quantitatively
higher than the Cu-NH3 species at pH higher than 9.5; however, the
concentration of cupric tetraamine is only surpassed by the
Cu(MEA)2+ 4 species, due to the fact, that cupric tetraamine has a lower
Log K than Cu(MEA)2+ 4 , according to Table 1. The complexation reac-
tions for Cu-MEA species (Smith and Martell, 1975), involved in this
leaching system, can be represented as follows (Eqs. (7)–(10)):
Fig. 4. Pourbaix diagram for the Ag-MEA-H2O system. The conditions for the diagram
construction were: 0.025 M MEA and 1 × 10−5 M Ag at 25 °C.
Cuþ þ MEA ¼ CuðMEAÞ2þ ð7Þ

of copper oxides species is unavoidable at alkaline conditions. However, Cu2þ þ 2MEA ¼ CuðMEAÞ2 2þ ð8Þ
the negative effect of copper oxides species can be discarded, if it is con-
sidered that MEA is a good chelating agent for cupric ions which retards
Cu2þ þ 3MEA ¼ CuðMEAÞ3 2þ ð9Þ
the formation of copper oxides. In Fig. 5a, it is possible to observe the
predominant formation of the complex Cu(MEA)2+ 4 for the system con-
taining 0.025 M MEA and 0.05 M Cu2+ at pH 10.2 and measured redox Cu2þ þ 4MEA ¼ CuðMEAÞ4 2þ ð10Þ
potential of 0.46 V vs SHE. Furthermore, the complex Cu(MEA)2+ 4 forms
a galvanic couple with the Cu(NH3)+ 2 species revealing an equilibrium It is possible that the complexation of cupric ions by MEA, (Eqs.
potential of 0.147 V vs SHE (see Fig. 5a). This thermodynamic data indi- (7)–(10)) retards the oxidative decomposition of thiosulfate, as demon-
cate that, during the leaching, it is possible to reduce the Ag(MEA)+ 2 strated in Fig. 3.
complex to Ag and oxidize the Cu(NH3)+ 2 species to Cu(MEA)4
2+
in the
presence of MEA. This is evident since the equilibrium potential of the 3.3. Leaching of silver sulfide, cementation of metallic silver from the preg-
galvanic couple Ag(MEA)+ 2 /Ag (Fig. 4) is higher than that of the galvanic nant solution and re-utilization of the leaching solution (LCRL process)
couple Cu(MEA)2+ +
4 /Cu(NH3)2 (Fig. 5a). In order to clarify this aspect,
Fig. 6 illustrates the distribution of copper species for the system con- Since silver is mainly found in nature in the form of silver sulfide, in
taining 0.05 M Cu2+ and 0.025 M MEA at 0.44 V vs SHE (experimental this section, it is presented the evaluation of the leaching system (Cu-
ORP measured in the leaching system with 0.2 M S2O2− 3 ). It is possible MEA-S2O3-NH3) for the recovery of silver from pure silver sulfide. Fur-
to observe the presence of the cupric and cuprous complexes thermore, thinking in terms of the process sustainability and the
(Cu(MEA)24 + and Cu(NH3)+ 2 , respectively), which form the galvanic recycling of the solution, a copper wire was used in order to promote
couple Cu(MEA)24 +/Cu(NH3)+ 2 , this result shows that despite of the the cementation of the leached silver, and then to know the efficiency
ORP of the leaching system is above the equilibrium potential of the gal- of the un-pregnant solution in a second leaching employing fresh silver
vanic couple Cu(MEA)2+ +
4 /Cu(NH3)2 , it is possible to find both copper sulfide (as described in the experimental section).
species, which reveals that the re-oxidation of Cu(NH3)+ 2 to Two leaching systems were evaluated using the LCRL process; Fig. 7
Cu(MEA)24 + species is possible, as mentioned before the half cell illustrates the results of silver extraction (%) vs time for the systems

Fig. 5. Pourbaix diagrams for the Cu-MEA-NH3-H2O system. The conditions for the diagrams construction were: 0.025 M MEA, 0.05 M Cu2+ and 0.09 M NH3 at 25 °C, a) soluble species and
b) soluble and insoluble species.
 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25 21

Fig. 6. Distribution of copper species at different pH values for the Cu-MEA-NH3-H2O system. The conditions for the diagram construction were: 0.025 M MEA, 0.05 M Cu2+, 0.09 M NH3
and EH = 0.44 V at 25 °C.

containing: a) 0.2 M thiosulfate, 0.05 M Cu2 +, 0.025 M MEA and leaching using fresh silver sulfide. It can be observed in Fig. 7 (second
b) 0.3 M thiosulfate, 0.05 M Cu2+, 0.05 M MEA, at room temperature. leaching), that at 3 h both systems can leach similar amounts of silver
The pH of both systems was adjusted at 10.20 with ammonium hydrox- to those obtained in the first leaching, e.g., a 85% and 82% of silver can
ide. When the performance of both leaching systems is compared, it is be leached with the recycled leaching solution containing 0.2 M thiosul-
observed in the first leaching, that the silver dissolution kinetics is con- fate with 0.025 M MEA and 0.3 M thiosulfate with 0.05 M MEA,
siderably higher, during the first 1.5 h, with the system b) than with the respectively.
system a). However, at the end of the first leaching i.e., 3 h, the silver ex- The previous results reveal that the recovery of silver employing
traction is practically the same in both leaching systems. After this time, thiosulfate-ammonia-MEA-copper leaching solutions corresponds to
the silver cementation step commenced, it is possible to observe that an alternative-sustainable process (especially the system containing
silver deposition on copper is more efficient in the system b) than in 0.3 thiosulfate and 0.05 M MEA), due to the fact, that under these con-
the system a). With respect to the system b), the silver contained in ditions, it is possible to dissolve the highest amount of silver at relative
the leaching solution (%) decreased from 83% at the beginning of the ce- short processing times, and it is also viable to obtain metallic silver using
mentation process, to 5% at the end, during 0.5 h. On the other hand, the a simple-conventional cementation process. According to Figs. 9 and 10,
dissolved silver (%) decreased from 79 to 22% during the same cementa- the predominant copper species that can be obtained from the oxida-
tion time using the system a). tion of metallic copper corresponds to Cu(MEA)24 + and Cu(NH3)+ 2 .
Fig. 8 presents the thiosulfate decomposition percentage recorded Therefore the cementation reactions, that are taking place in this system
during the experiments shown in Fig. 7. The results of Fig. 8 reveal the are shown in Eqs. (11) and (12):
beneficial effect of MEA on the diminution of the thiosulfate decompo-
sition in these leaching systems, e.g., the average thiosulfate decompo-
1=2Cu0 þ AgðS2 O3 Þ3 5− þ 2MEA ¼ 1=2CuðMEAÞ4 2þ þ Ag0
sition corresponds to 25% and 15% for the leaching systems containing
þ 3S2 O3 2− ð11Þ
0.025 and 0.05 M MEA. On the basis of the results shown in Figs. 3 and
8, it is possible to say that MEA is useful to complex the cupric ions in
these leaching systems, as well as it can decrease the thiosulfate decom- Cu0 þ AgðS2 O3 Þ3 5− þ 2NH3 ¼ CuðNH3 Þ2 þ þ Ag0 þ 3S2 O3 2− ð12Þ
position during the leaching of Ag and Ag2S
The behavior of both systems during the cementation step, can be
explained from a thermodynamic view point. Figs. 9 and 10 show the
distribution of copper species in the form of Log Concentration vs E
(SHE), for the systems containing a) 0.025 M MEA and b) 0.05 M MEA,
respectively. When both figures are compared, it is possible to observe
that an increase in the MEA concentration from 0.025 to 0.05 M pro-
motes an increase in the concentration of Cu-MEA soluble species. For
example, this is evident at the equilibrium potential of − 0.132 V vs
SHE, approximately, for the predominant redox couple Cu/
Cu(MEA)2+ 2+
4 , i.e., the Log concentration of the Cu(MEA)4 complex, cor-
responds to − 7.5 and − 6 M, for the system containing 0.025 M and
0.05 M MEA, respectively. Therefore, it is possible to say that when the
copper wire is employed in the cementation step, the complexation/dis-
solution of this copper is favored when the MEA concentration is in-
creased, i.e., the dissolution (anodic reaction) of the metallic copper to
Cu(MEA)2+ 4 is increased; which indicates that the half cell cathodic re-
action (silver deposition) can be also favored. In this way, the cementa-
tion of silver would be more favored in a leaching system containing
0.05 M MEA than in a system with 0.025 M MEA, as shown in Fig. 7.
Up to now, it has been demonstrated that silver can be leached from
silver sulfide and recovered in its metallic form. However, the most im-
portant issue, corresponds to the recycling of the leaching solution ob- Fig. 7. Comparison of the silver sulfide leaching followed by cementation with copper wire
tained from the cementation step in order to carry out a second and re-utilization of the leaching solutions with the S2O3-MEA-NH3-Cu system.
22 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25
Fig. 8. Comparison of the thiosulfate decomposition during the silver sulfide leaching
followed by cementation with copper wire and re-utilization of the leaching solutions
with the S2O3-MEA-NH3-Cu system.
The recycled leaching solutions have the ability to dissolve high per-
centages of silver from silver sulfide. Fig. 11 illustrates a comparison of
the silver leaching shown in Fig. 7 using the recycled leaching solutions.
However, it is worth noting that the silver extraction (%) only corre-
sponds to the silver that was dissolved from the fresh silver sulfide,
i.e., the complexed silver that was not deposited during the cementation
step is not being considered in the silver extraction calculations. In this
figure it is possible to observe that the silver dissolution kinetics is faster
in the leaching system containing 0.3 M thiosulfate and 0.05 M MEA
than in the leaching system with 0.2 M thiosulfate and 0.025 M MEA.
Furthermore the silver recovery reaches a 80% approximately in 3 h
with the system containing 0.3 M thiosulfate and 0.05 M MEA. Actually
this silver recovery is very similar to that obtained during the first
leaching (see Fig. 7).
3.3.1. Analysis of the silver sulfide leaching steps in the LCRL process
The behavior of this alternative leaching system for the dissolution
of silver from silver sulfide can be explained from a mechanistic view
point, according to the next: silver sulfide leaching takes place accord-
ing to the typical substitution reaction, as shown in the next reactions
Fig. 9. Distribution of copper species at different potentials for the Cu-MEA-NH3-H2O system. The conditions for the diagram construction were: 0.025 M MEA, 0.05 M Cu2+, 0.09 M NH3,
pH = 10.2 at 25 °C.
(Aylmore and Muir, 2001):
2Cuþ þ Ag2 S→2Agþ þ Cu2 S ðChalcociteÞ
þ 4S2 O3 2− →2AgðS2 O3 Þ2 3− ð13Þ
Cu2þ þ Ag2 S→2Agþ þ CuSðCovelliteÞ þ 4S2 O3 2− →2AgðS2 O3 Þ2 3− ð14Þ
According to the thermodynamic data shown in Table 1, the Log K
for the cupric tetraamine species (Cu(NH3)2+ 4 ) corresponds to 12.464,
while the Cu-MEA species present a Log K value that varies from 5.7
to 15.2 (Cu(MEA)2 + = 5.7; Cu(MEA)22 + = 9.8; Cu(MEA)23 + = 13.0
and Cu(MEA)2+ 4 = 15.2). Therefore, based on the stability of the differ-
ent cupric ion complexes, it is evident that the cupric mono-MEA and
cupric di-MEA species (Cu(MEA)2 + and Cu(MEA)22 +, respectively)
present a Log K value smaller than those of the Cu(NH3)24 +,
Cu(MEA)23 + and Cu(MEA)24 + species. This indicates, that the
Cu(NH3)2+ 4 , Cu(MEA)3
2+
and Cu(MEA)2+ 4 species are more stable than
the Cu(MEA)2+ and Cu(MEA)2+ 2 species. Therefore, it is probable, that
the Cu(MEA)2+ and Cu(MEA)2+ 2 species are more susceptible to carry
out the chemical substitution of cupric ions by silver contained the sul-
fide lattice (Eq. (14)). It does not mean that the other cupric ion com-
plexes i.e., Cu(NH3)24 +, Cu(MEA)23 + and Cu(MEA)24 + cannot
participate in the chemical substitution shown in Eq. (14). Actually,
these species can also participate in the silver sulfide leaching; however,
due to their higher stability, it is probable that the chemical substitution
(Eq. (14)) occurs at a lower kinetics than with the Cu(MEA)2 + and
Cu(MEA)2+ 2 species.
The solid residues obtained from the silver sulfide leaching were
characterized by SEM. It was found the predominant presence of copper
sulfide with small amounts of copper oxides. It is worth mentioning that
the copper sulfides correspond to the product obtained from the chem-
ical substitution of cupric ions by silver contained in the sulfide matrix
(Eq. (14)), while the copper oxides are obtained from the precipitation
of cupric ions at the alkaline pH. In this sense, Fig. 12 presents the micro-
structural characterization of the solid residue obtained from the silver
sulfide leaching with 0.3 M thiosulfate and 0.05 M MEA. Fig. 12a
shows the morphology of the solid residue, where it is possible to ob-
serve the presence of small particles. These particles are mainly com-
posed of copper sulfide, as shown in the EDXS analysis of Fig. 12b. It is
also evident the almost negligible presence of oxygen in the solid resi-
due (Fig. 12b), which can be related to the formation of small amounts
of copper oxides. As mentioned before, MEA is considered a chelating
agent-inhibitor of corrosion which avoids or decreases the formation
of copper oxides.
 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25 23

Fig. 10. Distribution of copper species at different potentials for the Cu-MEA-NH3-H2O system. The conditions for the diagram construction were: 0.05 M MEA, 0.05 M Cu2+, 0.09 M NH3,
pH = 10.2 at 25 °C.

Fig. 11. Comparison of the silver leaching from fresh silver sulfide re-utilizing the leaching
solutions obtained from the cementation process.
Fig. 13 illustrates a general scheme of the three steps that take place
during the silver sulfide leaching with the S2O3-MEA-NH3-Cu alterna-
tive system. The first step corresponds to the silver sulfide leaching,
which leads to the formation of CuS at step II; during this step, the for-
mation of copper oxides also takes place due to the precipitation of cu-
pric ions; finally step III exhibits that the copper oxide can be
considerably leached when it is in contact with MEA, producing a
layer composed of copper sulfides which act as a physical barrier for
the direct contact between the fluid reactants and the unreacted core
of silver sulfide. Actually, these copper sulfide layers can be responsible
to avoid the complete dissolution of silver sulfide, which promotes a
constant silver extraction of 80% approximately (Figs.s 7 and 11).
On the other hand, it was evident in Figs.s 7 and 11 that the leaching
curves of silver sulfide, did not present the oscillations (dissolution-pre-
cipitation) which are characteristic of the silver leaching from metallic
silver (Figs. 1 and 2). An analysis of the last results, revealed that the
only difference in both systems is the silver phase, i.e., Ag or Ag2S,
which consequently reflects a difference in the reaction mechanism,
i.e., the silver dissolution from Ag and Ag2S takes place through an elec-
trochemical event and a chemical substitution reaction, respectively.
From a mechanistic view-point the oxidation of Ag requires the

Fig. 12. Microstructural characterization of the solid residues obtained from the silver sulfide leaching with the system containing 0.3 M S2O2−
3 , 0.05 M Cu
2+
, 0.09 M NH3 and 0.05 M MEA
at pH = 10.2. a) Morphology; b) chemical characterization carried out with EDXS.
24 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25

Fig. 13. Scheme of the silver sulfide leaching with the S2O3-MEA-NH3-Cu system.

reduction of cupric ions to cuprous ions. The cupric and cuprous ions
can precipitate in the leaching system producing CuS and Cu2S, respec-
tively, as shown in Eqs. (1) and (2), respectively. According to Zipperian
et al. (1988), the silver-thiosulfate complex (Ag(S2O3)5−3 ) could precip-
itate, in the presence of chalcocite (Cu2S), as silver sulfide according to
Eq. (3).
On the other hand, the silver dissolution from Ag2S takes place
through a chemical substitution reaction, as shown in Eq. (14). The cu-
pric complexes predominate in the present leaching system with Ag2S.
Therefore, these cupric aqueous species promote the silver dissolution
producing covellite (CuS), according to Eq. (14). This difference in the
formation of Cu2S and CuS, suggests that the precipitation of the
silver-complexes is more favored in the presence of Cu2S than in the
presence of CuS as in the case of the leaching system with Ag and
Ag2S, respectively.
3.3.2. Characterization of the deposited silver in the LCRL process
Fig. 14 exhibits the microstructural characterization (SEM and
EDXS) of the metallic silver deposited on the copper wire with the sys-
tem containing: 0.05 M MEA, 0.3 M thiosulfate, 0.05 M Cu2+ at pH 10.20
adjusted with NH4OH. Fig. 14a and b show the morphology of the silver
coating at 100× and 2500×; it is possible to observe on the surface of

Fig. 14. Morphology and chemical composition of the copper wire surface obtained from the silver cementation with the leaching system containing 0.05 M MEA, 0.3 M S2O2−
3 , 0.05 M
Cu2+ and pH 10.20 adjusted with NH4OH at room temperature. a) Surface observed at 100×; b) Surface observed at 2500×; c) EDXS of thin layer and d) EDXS of the layer with larger
thickness.
 D.M. Puente-Siller et al. / Hydrometallurgy 169 (2017) 16–25
Fig. 15. Scheme of the LCRL process “leaching-cementation-reutilization” for the recovery of silver from silver sulfide with the S2O3-Cu-MEA-NH3 system.
the copper wire, the presence of layers composed of particles of irregu-
lar sizes. The EDXS analysis shows that the thin layer (Fig. 14c) and the
layer composed of bigger particles (Fig. 14d) are mainly composed of
metallic silver. With respect to the layers mentioned above, it is possible
to think that a thin layer of metallic silver is formed on the copper wire
at the beginning of the cementation step, once this layer is formed; the
continuous deposition of metallic silver promotes an increase in the
thickness of the silver coating.
According to the last results, this process can be considered sustain-
able due to the next issues: a) leaching of metallic silver or silver sulfide
can be carried out relatively fast at room temperature, b) metallic silver
can easily be recovered from the pregnant solution using a simple ce-
mentation process with metallic copper at room temperature and
c) the leaching solution can be re-utilized (without adding more re-
agents) to perform a second leaching of fresh silver sulfide. A scheme di-
agram of the process is shown in Fig. 15.
4. Conclusions
On the basis of the results obtained, the following facts can be stated:
1. The S2O3-Cu-NH3-MEA system is efficient for the silver extraction
from pure silver, however, the extraction curves are very unstable
(precipitation and re-dissolution of silver) due to the competition
between thiosulfate species and MEA to form complexes with silver.
The silver precipitation could be possibly related to the thiosulfate
decomposition and the reduction of the Ag(MEA)+ 2 complex to Ag.
2. The presence of MEA in the leaching system decreases the thiosulfate
decomposition.
3. It is possible to leach N80% of silver from silver sulfide using the S2O3-
Cu-NH3-MEA system at 1.5 and 3 h with 0.05 and 0.025 M MEA, re-
spectively. Furthermore, the silver leaching from pure silver sulfide
in the presence of 0.05 M MEA, 0.3 M thiosulfate and 0.05 M Cu2+
at pH 10.2 did not present the precipitation of silver during the
leaching process.
4. It is possible to recover most of the metallic silver through the ce-
mentation process with copper at short processing times (b 30 min).
5. The silver leaching process using this system (S2O3-Cu-NH3-MEA)
can be considered a sustainable system due to the fact that it is pos-
sible to re-utilize the leaching solution obtaining a high silver extrac-
tion (80%) from fresh silver sulfide.
Acknowledgements
The authors are grateful to CONACyT (México) for the postgraduate
scholarship awarded to Damaris M. Puente Siller.
25
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