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Recovery of silver from X-ray film processing


effluents by hydrogen peroxide treatment
Article in Hydrometallurgy May 2012
DOI: 10.1016/j.hydromet.2012.04.011

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

Recovery of silver from X-ray lm processing efuents by hydrogen


peroxide treatment
A.D. Bas, E.Y. Yazici , H. Deveci
Div. of Mineral & Coal Processing, Dept. of Mining Engineering, Karadeniz Technical University, 61080, Trabzon, Turkey

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

AgX 2S2 O3 AgS2 O3 2 X :


Owing to its prominent photosensitivity of silver halides, approximately 8.3% of silver is used in photography (GMSF, 2011). When
exposed to light, silver-halides such as AgBr on photographic lms
are reduced to metallic silver (Eq. (1)). During the development and
xing of lm, silver-halide crystals that are not exposed to light are
removed/leached by thiosulphate (Eq. (2)) from the lm into the
processing solution (Bober et al., 2006). Since photoprocessing
solutions are used over and over, the efuents may contain high
levels of silver. To illustrate, the efuents of X-ray lm processing
facilities can reach a silver content of 112 g/L (Kodak, 1999a). Silver
is one of the most toxic metals regulated by the regulatory bodies
(Ba, 2009) and the lm processing efuents are classied as
hazardous waste since they may cause soil and water pollution, if
not properly disposed of or treated (Kodak, 1996; USEPA, 1991).

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

World silver production was reported to be insufcient to meet the


demand, which steadily increases by ~22.5% per annum (Butterman
and Hilliard, 2005; GMSF, 2011). In this regard, recycling of silver
assumes prime importance for the market. Photographic wastes
including scrap lms/papers and efuents with their high silver content
offer a signicant resource potential for secondary silver (Butterman
and Hilliard, 2005; Nakibolu et al., 2003). There are over 1350 public
and private hospitals and healthcare centres in Turkey and, in 2009, a
total number of about 96 millions of medical X-ray lms were recorded
to be processed in all 683 public hospitals of the Turkish Ministry of
Health (Yazici et al., 2011). It can be estimated from these data that
scrap lms and X-ray lm processing efuents discarded only in these
public hospitals carry approximately 69 tonnes of silver. Therefore,
treatment of these efuents for reclamation of silver provides
signicant economic as well as environmental benets.
A variety of recovery methods for silver from photoprocessing
efuents appear to be available. Electrolysis, metallic replacement
and chemical precipitation have received the most attention to date
(KODAK, 1999a; USEPA, 1991). Electrolysis is capable of producing
silver with high purity by suitable control of operating conditions.
However, it is used suitably only for silver-rich efuents and unable
to reduce the silver levels below 100 mg/L with the requirement for

A.D.. Bas et al. / Hydrometallurgy 121124 (2012) 2227

further treatment by ion exchange or metallic replacement to


generate environmentally acceptable efuents (i.e. b5 mg/L Ag)
(KODAK, 1999a; Yazici et al., 2011). Metallic replacement based on
the use of more active metals such as Fe, Al, Zn and Cu than silver is an
effective method for the recovery of silver (Aktas, 2008; Bober et al.,
2006; Krmzkan et al., 2006). However, it introduces metal
impurities (e.g. Fe 2 +, Al 3 +, Zn 2 +, Cu 2 +) to the efuent and silver
sludge produced is not pure and needs costly renement processes
(KODAK, 1999a). Several chemicals including sodium sulphide
(Na2S), sodium dithionate (Na2S2O4), potassium borohydride
(KBH4) and 2,4,6-trimercapto-s-triazine (TMT; C3N3S33 ) have been
used as precipitating agents to recover silver from waste photoprocessing solutions (Blais et al., 2008; KODAK, 1999b; Rivera et al.,
2007; Yazici et al., 2011; Zhouxiang et al., 2008). Silver can be readily
recovered from the waste solutions by sulphide precipitation leading
to the efuent silver levels as low as 0.11 mg/L. However, careful
control of precipitation process and sulphide dosing are essential to
prevent the release of noxious hydrogen sulphide gas (H2S) (KODAK,
1999a). Despite its relatively high cost and neness of precipitates
with potential ltering problems, TMT appears to be a promising
agent for the recovery of silver since it is effective with a low labour
cost, easy control of operation and relatively low toxicity (Bober et al.,
2006; Yazici et al., 2011).
Hydrogen peroxide with oxidising and reducing properties under
suitable conditions is often regarded as a green chemical with no
hazardous by products since it decomposes only into oxygen and water
(Eq. (3)) (FMC, 2002; Yazc and Deveci, 2010). Reduction of silver ion
to metal by hydrogen peroxide appears to be thermodynamically
feasible (Eq. (4)). Furthermore, inorganic compounds e.g. thiosulphate
and sulphite, and organic compounds e.g. formaldehyde and hydroquinone, which are abundantly present in the photoprocessing efuents
(Yazici et al., 2011), can be readily destroyed by hydrogen peroxide (e.g.
Eqs. (5), (6)) (Jones, 1999; US Peroxide, 2011). These environmental
and technical attributes make hydrogen peroxide a potential alternative
for the treatment of photoprocessing efuents.
H2 O2 H2 O 1=2O2g

2Ag H2 O2 2Ag 2 H O2g


2

G293 20:3 kJ=mol

2S2 O3 H2 O2 2 H S4 O6
2H2 OG293 342:7 kJ=mol; pH 48
2

S2 O3 4H2 O2 2OH SO4


5H2 O G293 1307 kJ=mol; > pH 8:

In this study, the treatment of X-ray lm processing efuents by


hydrogen peroxide to recover silver was investigated. Effect of
concentration of hydrogen peroxide (5.851.6 g/L H2O2) and pH
(4.27.0) on the rate and extent of the recovery of silver were studied
within a full factorial design (42). Furthermore, the inuence of the
addition of ethylene glycol on silver recovery was also examined. Silver
precipitates were characterised by chemical analysis, SEMEDS and
XRD to identify the nature of precipitates and provide an insight into the
precipitation process.

23

to prepare test solutions using deionised-distilled water. Ethylene


glycol (C2H6O2, 99%) was also tested to stabilise hydrogen peroxide.
2.2. Precipitation tests and analytical methods
In the current study, the experiments were designed by using a
full factorial design (4 2) (Montgomery, 2001) to investigate the
effects of concentration of hydrogen peroxide (5.851.6 g/L H2O2)
and pH (4.27) on the recovery of silver. The range of concentration
of hydrogen peroxide was determined by the preliminary tests and
theoretical calculations based on silver and thiosulphate content of
the efuent sample. Factors and their levels are shown in Table 1.
Furthermore, the addition of ethylene glycol (0.510 mL) on the
recovery of silver was also investigated at pH 4.2 and 22.4 g/L H2O2.
Precipitation tests were carried out in 50-mL Erlenmeyer asks. pH
of the waste solution was, if required, adjusted using 4 M NaOH before
the addition of hydrogen peroxide (35% w/w). The asks were then
placed on a reciprocal shaker operating at 140 min 1. Due to the
exothermic nature of the reactions, hydrogen peroxide was added at a
predetermined rate of 0.5 mL per 1.5 min unless otherwise stated. Over
the reaction period, 5-mL aliquots were removed at preset intervals and
ltered through 0.45 m cellulose nitrate lters. These samples were
then used for the analysis of residual silver (Ag) and sulphate (SO42 ).
Silver was analysed using an atomic absorption spectrophotometer
(AAS; PerkinElmer AAnalyst 400). Thiosulphate content (S2O32 ) of the
efuent was determined by iodometric titration (Jeffery et al., 1989)
while sulphate (SO42 ) in samples was monitored colorimetrically using
a lter photometer (Palintest 5000) at a wavelength of 520 nm. Due to
the interference by the intermediate sulphur compounds and the residual H2O2 the concentration of thiosulphate was not monitored over the
reaction period. The statistical analysis of the experimental data based on
ANOVA was performed using Minitab statistical software (2004).
2.3. Characterisation of silver precipitates
A waste solution with a high silver content (4.5 g/L) was used to
obtain sufcient amount of precipitate for chemical and mineralogical
analysis. Precipitates were collected via ltration (0.45 m, cellulose
nitrate lter) and washed twice with deionised-distilled water prior to
drying at 105 C for 6 h. Dried precipitates were xed on conductive
carbon tabs and examined under a Scanning Electron Microscope (SEM)
(Zeiss EVO LS10) coupled with an Energy Dispersive Spectrometry
(EDS) unit. X-ray diffraction (XRD) analyses of the precipitates were
carried out using a Rikagu D/max-IIIC X-ray diffractometer, operating
with CuK1 radiation source ( = 1.54059 ) at 40 kV and 30 mA. The
sample was scanned over a 2 range of 580 with a 0.005 step size.
Chemical analysis of the precipitate sample was also undertaken by hot
aqua-regia digestion followed by the spectrophotometric nish.
3. Results and discussion
3.1. Kinetics of silver precipitation
Kinetics of precipitation of silver by hydrogen peroxide (34 g/L)
was initially determined from the as-received photoprocessing waste
solution (pH 4.2). Fig. 1 illustrates that it is a fast reaction as the

2. Experimental
2.1. Efuent sample and reagents

Table 1
Factors and their levels adopted for the experimental design.
Parameters

A sample of X-ray lm processing efuent obtained from Farabi


Hospital (Karadeniz Technical University, Trabzon, Turkey) was used in
this study. The efuent sample was characterised to contain 1.1 g/L Ag,
17 g/L SO42 and 113 g/L S2O32 at pH 4.2. Reagent grade sodium
hydroxide (NaOH) and hydrogen peroxide (H2O2, 35% w/w) were used

(A) H2O2 (g/L)


(B) pH
a

Levels
1

5.8
4.2a

22.4
5

37.6
6

51.6
7

Original pH of the solution (no addition of NaOH).

24

A.D.. Bas et al. / Hydrometallurgy 121124 (2012) 2227

precipitation of 77% Ag already occurred within 5 min under these


conditions. Silver recovery remained at these levels over an extended
period of 60 min. with the indication of the completion of the
reaction. Formation of sulphate through the oxidation of thiosulphate
was also monitored (Fig. 1). A substantial increase in the sulphate
concentration from 17.4 g/L to 71.1 g/L was recorded over the
reaction period of 60 min. This suggests that hydrogen peroxide is
mainly consumed via the oxidation of thiosulphate present in the
waste solution. During the treatment, pH tended to increase with a
nal pH of 5.22, which is consistent with Eq. (5) (Jones, 1999).
Preliminary tests indicated that the reactions involved in the
hydrogen peroxide treatment of the waste solution are highly
exothermic in nature (e.g. H293 = 74.1 kcal/mol for Eq. (5)) with
the generation of copious amount of heat. Decomposition rate of
hydrogen peroxide was reported to increase rapidly with increasing
temperature (Yazc and Deveci, 2010) resulting in excessively high
consumption of hydrogen peroxide. Therefore, the tests were performed to monitor the evolution of temperature at different rates of
addition of hydrogen peroxide (Fig. 2). It can be deduced from Fig. 2 that
dosing of hydrogen peroxide is required to control the temperature.
Accordingly, an addition rate of 0.5 mL H2O2 per 1.5 min was selected
for the precipitation tests.
3.2. Effect of concentration of hydrogen peroxide and pH
A full factorial design approach was adopted to evaluate the effect of
initial concentration of hydrogen peroxide (5.851.6 g/L H2O2) and pH
(4.27) on the precipitation of silver. The results are presented in
Table 2. Recovery of silver was found to depend strongly on the
concentration of H2O2. High silver recoveries (95%) were achieved at
H2O2 concentrations of 37.6 g/L, which is considerably higher than the
stoichiometric requirement for the recovery of silver (Eq. (4)) apparently due to the concurrent oxidation of thiosulphate. An increase in pH
was observed to improve the precipitation of silver, which was evident
particularly at low concentrations of H2O2 (Table 2). To illustrate, the
recovery of silver was enhanced by 34% with increasing the initial pH
from 4.2 to 7 at a H2O2 of 5.8 g/L while the corresponding increase in the
silver recovery was 21% and only b2% at 22.4 and 37.6 g/L H2O2,
respectively. pH was noted to deviate from the initially set values
towards neutral/alkaline region (Table 2).
The formation of sulphate due to the oxidation of thiosulphate
was also monitored during the precipitation tests (Fig. 3). The
concentration of sulphate in solution was determined to depend
essentially on the concentration of H2O2 with no marked effect of pH.
The oxidation of thiosulphate into sulphate (Eqs. (5), (7)(9)) was
reported to proceed through the formation of intermediates such as
tetrathionate (S4O62 ) (Eq. (5)), trithionate (S3O62 ) (Eq. (7)) and
sulphite (SO32 ) (Eq. (8)) (Solvay Interax, 2001). Although

Fig. 1. Kinetics of the precipitation of silver from waste X-ray solutions (34 g/L H2O2,
pH 4.2).

Fig. 2. Temperature proles at different rates of H2O2 addition (volume of waste


solution: 50 mL).

tetrathionate is the primary reaction product at low concentrations


of H2O2, the formation of the intermediates and sulphate increases
with increasing the concentration of H2O2 (Fig. 3). The presence of
metals catalyses the conversion of thiosulphate by hydrogen peroxide
into sulphate (Jones, 1999; US peroxide, 2011).
2

S4 O6 3H2 O2 S3 O6 SO4 2H2 O 2 H


S3 O6

H2 O2 H2 O3SO3

4H

SO3 H2 O2 SO4 H2 O:

Statistical assessment of the results was carried out by the analysis


of variance (ANOVA) (Table 3). P values were determined for the
parameters tested. The P value shows the probability that the test
statistic will take on a value that is at least as extreme as the observed
value of the statistic when the null hypothesis (H0) holds true
(Montgomery, 2001). In this respect, the calculated P values (Table 3)
conrmed that the effect of concentration of H2O2 in the range tested
was statistically highly signicant even at 99.9% ( = 0.001) condence level while pH was not a signicant factor under these
conditions. Statistical analysis of the data also indicated that the
contributions of H2O2 concentration and pH to the response i.e. silver
Table 2
Recovery of silver from the waste solution under different conditions of pH and
hydrogen peroxide concentration (addition rate: 0.5 mL H2O2 per 1.5 min; precipitation time: 45 min).
Exp. no.

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

Original pH of the solution. No addition of NaOH.

A.D.. Bas et al. / Hydrometallurgy 121124 (2012) 2227

25

Fig. 3. Initial and nal concentrations of sulphate in solution at different concentrations


of hydrogen peroxide (as the mean of data obtained at different pHs tested with error
bars showing standard deviation).

recovery were 77.3% and 10.1%, respectively (Table 3). Contribution


values also reect the relative importance of each parameter tested.
Fig. 4 illustrates the main effects plots based on the mean values
for the concentration of H2O2 and pH showing the silver recovery at
each level of these factors as if they are independent. This plot
conrms the positive effect of increasing the concentration of H2O2
and pH in the range tested. The surface plot of silver recovery (%)
versus the levels of H2O2 concentration and pH was also presented in
Fig. 5 to depict the interaction effects of these parameters on the
response. Accordingly, the effect of pH on the precipitation of silver
was discernible only at low levels (1 and 2) of H2O2 (i.e. 5.822.4 g/L)
while the most signicant enhancement in the recovery of silver was
achieved by increasing H2O2 concentration from 5.8 g/L to 37.6 g/L at
all levels of pH tested.
Despite its great potential with technical and environmental
benets, the utilisation of hydrogen peroxide in the treatment of
waste photographic solutions has appeared to receive limited interest
with no detailed data being available. Rabah et al. (1989) investigated
the acid and alkaline treatment of spent colour-photography solutions
to obtain a silver sludge followed by its thermal treatment (at 980 C) to
produce silver metal. They also tested the addition of H2O2 (74 mL of
30% H2O2 by volume per litre of waste solution) in a single experiment
and did not provide data for silver recovery (though it was assumed to
be 89% in their cost analysis). Based on the yield of silver sludge, these
investigators also provided a cost analysis and claimed that the acid
treatment by a mixture of sulphuric and nitric acids was more effective
than H2O2 and alkaline treatments. However, it appeared that they did
not consider the factors such as neutralisation of the acidic efuents and
the formation of hazardous NOx gases in the acid treatment. In an earlier
patent, Daignault et al. (1982) proposed the treatment of waste
photographic solutions with a mixture of peroxide and ozone to
destroy the complexing agents (EDTA, NTA and thiosulphate) thereby
recovering/removing the heavy metals present. They also demonstrated that 91% of silver could be recovered with the addition of 1020%
H2O2 (using 70% H2O2 solution) by volume of the waste solution at pH

Fig. 4. Effect of concentration of hydrogen peroxide (a) and pH (b) at four levels.

4.5 followed by increasing pH to 9.5 by the addition of NaOH. They also


showed that further treatment of the efuents with ozone and then
Na2S were required to achieve high levels (98%) of recovery/removal
of Ag, Cd, Fe and Pb.
3.3. Effect of addition of ethylene glycol
Hydrogen peroxide is relatively an expensive reagent and has
inherently low stability in that its catalytic decomposition occurs in the

Table 3
Results of analysis of variance (ANOVA) for the effect of hydrogen peroxide
concentration and pH.
Source of
deviation

Degree of Sum of Mean


F value P value Contribution
freedom
squares squares
(%)

(A) H2O2 (g/L)


3
(B) pH
3
Residual error
9
Total
15

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

A.D.. Bas et al. / Hydrometallurgy 121124 (2012) 2227

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.

2AgS2 O3 2 H2 O2 2 H 2Ag 2S4 O6


2H2 O G293 96:2 kcal=mol

10

6AgS2 O3 2 13H2 O2 6 H 3Ag2 S 5S4 O6


16H2 O 6O2 G293 492:8 kcal=mol
presence of metal ions and solids, and at high temperatures and pHs
(Yazc and Deveci, 2010). The severe detraction to hydrogen peroxide
treatment is therefore its high consumption. Rabah et al. (1989) found
that H2O2 treatment had the highest reagent cost compared with acid
and alkaline treatments. In this study, the effect of the addition of
ethylene glycol was examined to reduce the consumption of hydrogen
peroxide per silver recovery. Fig. 6 illustrates a 1.3 to 18.7%
improvement in the recovery of silver with increasing the addition of
ethylene glycol from 0.5 to 10 mL. This improvement in the silver
recovery can be attributed to the stabilising effect of ethylene glycol on
hydrogen peroxide apparently mitigating its decomposition during the
precipitation process. Mahajan et al. (2007) also reported the stabilising
effect of ethylene glycol for hydrogen peroxide during the leaching of
chalcopyrite at elevated temperatures. They demonstrated that the
addition of ethylene glycol signicantly slowed down the decomposition of hydrogen peroxide i.e. the complete loss of H2O2 even after 2 h
compared with only 25% loss (after 4 h) in the presence of 8 mL/L
ethylene glycol.
3.4. Characterisation of silver precipitates
Chemical and mineralogical characterisations of silver precipitates
were performed to provide an insight into the precipitation process.
Silver content of the precipitate was determined to be 65.1%. SEM

4AgS2 O3 2

4H2 O2 4 H 2Ag2 S S4 O6

7 S 6H2 O 4O2
6S2 O3

6H2 O2 S

SO4

3SO4

G293 48:4 kcal=mol


2S4 O6

3SO4

6H2 O

11

12
13

G293 415:0 kcal=mol


2AgS2 O3 2

Ag2 S 4S2 O3

14

G293 43:8 kcal=mol:


Rabah et al. (1989) proposed that the oxidising reagents e.g. HNO3
under acidic conditions attack thiosulphate leading to the formation
of sulphate, elemental sulphur or polysulphates. Furthermore, these
investigators mooted that, in addition to these sulphur species,
hydrogen sulphide may also form during the acid and peroxide
treatment, and reacts with the liberated silver to yield insoluble silver
sulphide. This was consistent with their XRD analysis of the silver
sludge in which silver sulphide (Ag2S) and halide (AgBr) are the main
phases identied. It may be relevant to note that, in the current study,
the treatment of the silver precipitate by hot concentrated nitric acid
resulted in a ne residue, which was also examined under SEMEDS
and determined to be AgCl (not shown). Silver halides (e.g. AgCl and

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.

A.D.. Bas et al. / Hydrometallurgy 121124 (2012) 2227

27

treatment of X-ray photoprocessing efuents allowing the recovery of


silver as well as the removal of thiosulphate and possibly other
constituents present.
Acknowledgement
The authors would like to express their sincere thanks and
appreciations to the Research Foundation of Karadeniz Technical
University for the nancial support (Project no: 2006.112.008.1) and
to Mr. Fatih Erdemir (Dept. of Metallurgical & Materials Eng., KTU) for
SEMEDS analysis.
References

Fig. 8. XRD pattern of the silver precipitate showing the presence of metallic silver,
silver sulphide and elemental sulphur.

AgBr) would form provided that thiosulphate was extensively


decomposed at sufciently high concentrations of hydrogen peroxide.
The reagent cost based on the data (i.e. 37.6 g/L H2O2, 95% Ag
recovery) obtained in the current study was estimated to be ~$63/m 3 of
the efuent corresponding to ~$61/kg of silver recovered at an efuent
concentration of 1.1 g/L Ag and a H2O2 (50% w/w) price of $911/m3. It is
pertinent to note that the efuent sample used in the current study is
relatively lean in silver content and the reagent cost will be considerably
reduced with an increase in the silver content of the efuent. In the
current study, ethylene glycol was used as a stabiliser to mitigate the
catalytic decomposition of H2O2 and an improvement in the recovery of
silver at the same level of H2O2 was achieved. However, this
improvement will not compromise its use due to its addition at high
concentrations (i.e. 20% v/v), which prohibitively increases (e.g. by up
to 8-fold) the reagent costs for the treatment process. Further treatment
of the silver precipitate obtained in the peroxide process is also required
to produce metallic silver. In this regard, Rabah et al. (1989) proposed
the thermal treatment of the silver sludge containing silver as sulphide
and halide at 980 C to yield metallic silver with a purity of 99.8%.
4. Conclusions
This study has demonstrated the treatment of the waste X-ray lm
processing solutions by hydrogen peroxide for the recovery of silver.
Kinetics tests have shown that the precipitation of silver from the
waste solution is a rapid process, but, highly exothermic in character
with the generation of large amount of heat presumably due to the
side reactions i.e. the concomitant oxidation of thiosulphate. Dosed
addition of hydrogen peroxide was found to be required to control
the temperature. A full factorial design (4 2) for the factors, H2O2
concentration and pH was developed for the experiments. The
concentration of hydrogen peroxide (5.851.6 g/L H2O2) was identied to be the most signicant parameter affecting the extent of silver
recovery as veried by the statistical analysis of data. Increasing pH
(4.27) appeared to improve the recovery of silver discernibly at low
levels of H2O2. The addition of ethylene glycol (0.510 mL) was
shown to enhance the silver recovery apparently due to its stabilising
effect on hydrogen peroxide. Characterisation studies have revealed
that silver is precipitated as ne grains predominantly in the form of
silver sulphide. It can be inferred from this study that hydrogen
peroxide as a green chemical is potentially a suitable reagent for the

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