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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet
a r t i c l e
i n f o
a b s t r a c t
In this study, recovery of silver from X-ray lm processing efuents by precipitation was studied. Hydrogen
peroxide was used as the precipitating agent. A full factorial design (42) approach was adopted for the study. The
results have shown that precipitation process is highly exothermic in nature with the evolution of copious
amount of heat apparently owing to the concomitant oxidation of thiosulphate. The precipitation of silver by
hydrogen peroxide is a fast reaction, which is almost complete within minutes. It is also an acid consuming
reaction with the tendency of pH to increase towards neutral/alkaline conditions. The concentration of hydrogen
peroxide was proved to be statistically the most signicant factor affecting the precipitation process. High silver
recoveries (95%) from the waste solution (1.1 g/L Ag, 113 g/L S2O32 ) were obtained only at high levels of H2O2
(37.6 g/L). Over the reaction period, a substantial increase in the concentration of sulphate was noted
indicating the consumption of H2O2 mainly by the oxidation of thiosulphate. Increasing pH was found to have a
benecial effect on the recovery of silver noticeably at low H2O2 concentrations. The addition of ethylene glycol
(0.510 mL) enhanced the recovery of Ag (by 1.318.7%) presumably due to its stabilising effect on H2O2. SEM
EDS and XRD analyses of the precipitates have revealed that silver is present mainly as ne silver sulphide. These
ndings demonstrate that the waste photoprocessing solutions can be suitably treated by hydrogen peroxide to
recover silver and remove thiosulphate.
2012 Elsevier B.V. All rights reserved.
Article history:
Received 28 October 2011
Received in revised form 1 March 2012
Accepted 16 April 2012
Available online 23 April 2012
Keywords:
Silver
Waste X-ray solutions
Precipitation
Hydrogen peroxide
Ethylene glycol
1. Introduction
light
AgX Ag X
X : Halides e:g: Br ; I ; Cl
Corresponding author at: Karadeniz Teknik Univ. Maden Muh. Bol. 61080, Trabzon,
Turkey. Tel.: + 90 462 377 4113; fax: + 90 462 325 7405.
E-mail address: eyazici@ktu.edu.tr (E.Y.. Yazici).
0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2012.04.011
2S2 O3 H2 O2 2 H S4 O6
2H2 OG293 342:7 kJ=mol; pH 48
2
23
2. Experimental
2.1. Efuent sample and reagents
Table 1
Factors and their levels adopted for the experimental design.
Parameters
Levels
1
5.8
4.2a
22.4
5
37.6
6
51.6
7
24
Fig. 1. Kinetics of the precipitation of silver from waste X-ray solutions (34 g/L H2O2,
pH 4.2).
H2 O2 H2 O3SO3
4H
SO3 H2 O2 SO4 H2 O:
H2O2 (g/L)
pH
Ag recovery (%)
Final pH
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
5.8
5.8
5.8
5.8
22.4
22.4
22.4
22.4
37.6
37.6
37.6
37.6
51.6
51.6
51.6
51.6
4.2a
5
6
7
4.2a
5
6
7
4.2a
5
6
7
4.2a
5
6
7
22.7
35.2
53.4
79.1
63.4
71.5
75.4
84.5
94.5
95.9
96.1
96.5
100
99.9
99.0
99.6
5.56
7.77
8.30
8.28
7.08
7.73
7.92
8.20
7.00
7.64
7.87
8.04
5.22
6.15
6.52
8.27
25
Fig. 4. Effect of concentration of hydrogen peroxide (a) and pH (b) at four levels.
Table 3
Results of analysis of variance (ANOVA) for the effect of hydrogen peroxide
concentration and pH.
Source of
deviation
6971.8
907.1
1136.2
9015.1
2323.9
302.4
126.2
18.41
2.39
0.000
0.136
77.3
10.1
12.6
100
Fig. 5. Surface plot of silver recovery as a function of levels of H2O2 concentration and pH.
26
studies showed that the silver precipitate, which was nely grained,
was composed of silver and sulphur as the elemental phases present
(Fig. 7). Fig. 7 also illustrates a typical EDS prole where the chemical
composition of the precipitate was determined to be 86.5% Ag and
13.5% S, which is analogous to silver sulphide (Ag2S; 87.1% Ag). X-ray
diffraction pattern of the precipitate sample conrmed the presence
of silver sulphide, metallic silver and elemental sulphur with the
former being the most abundant silver phase (Fig. 8). These ndings
suggest that silver is precipitated from the waste solution mainly in
the form of silver sulphide (Ag2S). A chemical simulation and reaction
software (HSC Chemistry, 2011) with extensive thermochemical data
base was exploited to identify the thermodynamically feasible
reactions (Eqs. (10)(14)) for the precipitation of silver from such a
waste solution.
Fig. 6. Effect of the addition of ethylene glycol on the recovery of Ag from the asreceived waste solution (pH 4.2) at a H2O2 concentration of 22.4 g/L.
10
4AgS2 O3 2
4H2 O2 4 H 2Ag2 S S4 O6
7 S 6H2 O 4O2
6S2 O3
6H2 O2 S
SO4
3SO4
3SO4
6H2 O
11
12
13
Ag2 S 4S2 O3
14
20
Ag
15
10
5
Ag
S
0
2
Fig. 7. SEM image of the silver precipitate with EDS prole indicating the presence of silver sulphide.
27
Fig. 8. XRD pattern of the silver precipitate showing the presence of metallic silver,
silver sulphide and elemental sulphur.
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