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Abstract
Adsorption of silver from synthetic photographic and spent fix solutions on granulated activated carbon in a batch process has
been investigated. The synthetic solutions prepared had similar properties to medical X-ray and photographic process effluents.
Sodium and ammonium thiosulfates are the major lixiviants used in the dissolution of silver halides present in photographic and
medical X-ray films. The resultant solutions contain substantial amounts of recoverable silver complexes in the form of thiosulfates.
The as received carbons were alkaline in nature when contacted with deionised water. These carbons showed very low silver recov-
eries. However, when these carbons were pre-treated with 0.5 mol/dm3 sulphuric and nitric acids at 25 °C, it had resulted in signif-
icant silver recoveries of 98.5% and 95% from sodium and ammonium thiosulfate solutions, respectively. These results were achieved
in a narrow range of pH between 3 and 4. Batch atmospheric stripping of adsorbed silver by 2.0 mol/dm3 HNO3 at 85 °C was also
investigated.
Ó 2005 Elsevier Ltd. All rights reserved.
0892-6875/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.05.021
1270 K.G. Adani et al. / Minerals Engineering 18 (2005) 1269–1276
Table 2
Carbon treatment of 1.6 +0.5 mm size fraction at 25 °C for 2 h
Parameter HNO3 H2SO4 CH3COOH K2Cr2O7 CuSO4 FeSO4 NH3
pH treatment of carbon 1.0 1.0 1.0 1.5 1.5 1.5 12.5
Molarity (mol/dm3) 0.5 0.5 0.5 0.2 0.2 0.2 0.5
Resultant solution (pH) 3.5 3.5 3.8 3.8 3.9 3.9 12.5
Volume used (dm3) 0.05 0.05 0.05 0.05 0.05 0.05 0.05
Carbon dosage (g/dm3) 6.67 6.67 6.67 6.67 6.67 6.67 6.67
K.G. Adani et al. / Minerals Engineering 18 (2005) 1269–1276 1271
2.3. Elution studies the silver thiosulfate anions and protonated carbon sur-
face. This allowed the carbon surface to act as a strong
Elution of silver from the 50 g of carbon by a batch anion exchanger. The HNO3 and H2SO4 pre-treatments
process was done using 2.0 mol/dm3 HNO3 heated to of carbon have indicated high silver recoveries. This may
85 °C. The total volume of HNO3 as eluant was probably be due to the promotion of H+ bond between
3
750 cm3, which is equivalent to 10 bed volume (BV). the AgðS2 O3 Þ2 anions thus forming a H3[Ag(S2O3)2]
10 cm3 aliquots were taken from the eluate from each complex, which may have existed as either a neutral or
BV for AAS analysis. The stripping was done at a flow charged ion and subsequently bound on carbon.
rate of 0.70 cm3 s1 at 0.056 BV per minute. The total This seemed to agree with earlier work by Gupta
stripping time was 30 min. (1982) where he noticed that most untreated carbon
have their zeta potential of zero point charge (zpc) at
pH between 4.5 and 7.5. This implies that the surface
3. Results and discussion charges on most carbons are basically positive at
pH 6 4.5 and are negative at pH P 7.5. The silver
3.1. Silver adsorption using the as received effluents adsorption experiments were done under maintained
pH range between 3 and 4, which significantly improved
Initial adsorption tests were carried out in adsorbing the silver recoveries as shown in Figs. 1 and 2 using
silver from the as received solutions of photographic H2SO4 and HNO3. The direction and rate of silver thio-
and medical X-ray process effluents. The particle size sulfate anions adsorption depends on the nature of
range and dose rate of carbon were altered to investigate charges on the carbon surface.
the effects on silver recovery. The pH was increased from Such an electro-kinetic phenomenon is known as
its initial value of 6.5 to 8–10. There were no indications electrophoresis, which in essence involves the interrela-
of significant silver recoveries under alkaline conditions. tion between the mechanical and electrical effects of a
Meanwhile there were improved silver recoveries ob- moving interface, which are expressed in terms of zeta
served when the pH was lowered from the as received potential. This behaviour is contrary to that observed
pH 6.5 to 3–4. This indicated that improved silver recov- in the case of carbon treatment using K2Cr2O7, FeSO4,
eries could be achieved under acidic conditions. The re- and CuSO4 at similar pH where silver recoveries were
sults showed that adsorptions under alkaline conditions observed to be very low as shown in Fig. 1.
have shown very low silver recoveries; hence synthetic The pre-treatment of carbon using synthetic solutions
tests were done for similar silver concentrations under in aqueous H2SO4 and HNO3 clearly indicated to have
acidic conditions. The as received SFS and synthetic promoted the H+ bond between AgðS2 O3 Þ3 2 , which sub-
solutions were observed to have a relatively neutral sequently adsorbed on carbon via the oxidised func-
pH, respectively. tional groups in the form of H3[Ag(S2O3)2]. The
3
possible interactions between H+ and (S2 O3 Þ2 ions in
3.2. Mechanisms of adsorption ATS are expressed in Eqs. (3) and (4) just before being
adsorbed on carbon. Eq. (5) shows the interaction of sil-
The experiments were done to see if pre-treated car- ver ammonium thiosulfate ion with aqueous ammonia
bons could enhance silver recovery from synthetic thio- in solution. It is apparent that the pH of solution in-
sulfate solutions. The 0.5 M HNO3 and H2SO4 creases with the excess ammonium ions that seemed to
pre-treated carbons have shown to yield the significant
silver recoveries of 95.3% and 98.5% in ATS and STS,
respectively. Pre-treating carbon using 0.2 M potassium 100
dichromate (K2Cr2O7), copper sulfate (CuSO4) and iron
sulfate (FeSO4) solutions was found to be ineffective as 0.5M nitric acid
75
shown in Fig. 1. The use of pre-0.5 M NH3 to pre-treat 0.2M K-dichromate
silver recovery (%)
carbon resulted in the rise in pH and hence produced the 0.5M sulfuric acid
very low silver recoveries of 15.5% and 12.5% in two 50 0.2M copper sulfate
tests, respectively. 0.2M Fe(II) solution
Lago et al. (2003) and Leon and Radovic (1994) have 0.5M ammonia
shown that HNO3 and H2SO4 treatments of carbon 25
the carbon surface to be more receptive to the complex Fig. 1. Silver recovery (%) on the pre-treated carbons from STS
anions in solutions via electrostatic attraction between solution in 22 h.
1272 K.G. Adani et al. / Minerals Engineering 18 (2005) 1269–1276
75
0.5M sulfuric acid
carbons were 98.5% and 77.5%, respectively, as shown
0.5M nitric acid
0.5M ammonia
in Fig. 2. This may imply that nitrate ions in solution
50
0.5M acetic acid alter further adsorption, which corresponds to previous
untreated carbon work by Bailey (1987) showing that the presence of
25 NO 3 ions in solution discouraged effective adsorption
for ligands such as cyanides, thiocyanates and thiosul-
fates of gold and silver. The carbon surface was chemi-
0
0 3 6 9 12 15 18 21 24 cally treated to introduce oxygen (O), sulfur (S) and
contact (hr)
nitrogen (N) containing groups. The effective silver
Fig. 2. Silver recovery on pre-treated carbon from ATS solutions in 24 h. recovery on HNO3 and H2SO4 pre-treated carbon may
have occurred under a two-way mechanism where silver
was probably adsorbed as a H3[Ag(S2O3)2] complex ion.
discourage effective silver recoveries as observed in the
The M3[Ag(S2O3)2] complex ion may probably then
initial test work.
being reduced by substituting the M+ for H+ to form
ðNH4 Þ3 ½AgðS2 O3 Þ2 ðaqÞ þ 3HNO3ðaqÞ the H3[Ag(S2O3)2] complex just before being adsorbed
H3 ½AgðS2 O3 Þ2 ðaqÞ þ 3NH4 NO3ðaqÞ ð3Þ on carbon. The M represents simple cations of Na+
or NHþ 4 in STS and ATS, respectively. This suggests
that 3H+ may have substituted M3+ in synthetic solu-
2ðNH4 Þ3 ½AgðS2 O3 Þ2 ðaqÞ þ H2 SO4ðaqÞ
tions to produce H3[Ag(S2O3)2] when in contact with
2H½AgðS2 O3 Þ2 ðaqÞ þ 3ðNH4 Þ2 SO4ðaqÞ ð4Þ excess H2SO4 and HNO3. The NO
3 and SO4 ions are
believed to remain in solution and could also be at-
2ðNH4 Þ3 ½AgðS2 O3 Þ2 ðaqÞ þ NH3ðaqÞ þ H2 OðlÞ tracted towards the protonated carbon surface.
ðNH4 Þ3 ½AgðS2 O3 Þ2 ðaqÞ þ NH4 OHðaqÞ ð5Þ The H3[Ag(S2O3)2] then gradually moved towards the
protonated carbon surface and attached on the func-
2+ 2+ 2+
The adsorption of Cu , Cr and Fe from syn- tional groups within the carbon matrixes via coulombic
thetic solutions could have possibly occupied the sites attraction. This may have possibly formed a complex sil-
on the carbon surface hence reducing site availability ver species, which is attributed in the form of Cx–
for further silver adsorption, which has not been inves- H3[Ag(S2O3)2] where (Cx) represents one of the oxidised
tigated in this work. The addition of aqueous NH3 has surface functional groups. The H3[Ag(S2O3)2] is ad-
increased the pH by making carbon more alkaline with sorbed either as a charged or neutral ion depending on
an increase in ammonium ions thus produced a basic the distribution of charges on the carbon surface. Silver
functional groups on carbon such as chromenes, ethers, may have also being absorbed via electrostatic attrac-
and carbonyls as reported by Krizstina et al. (2001). The tion that existed between the protonated carbon surface
increased in pH of solution provided a more negatively and silver thiosulfate anions as illustrated in Fig. 3.
charged surface on carbon. This must have induced a
more electrostatic repulsive surface to the silver thiosul- 3.3. Silver thiocyanate
fate complex anions that resulted in very low silver
recoveries. Genik et al. (1985) noticed that thiosulfate Thiocyanates are also used as alternative lixiviants
ions are thermodynamically unstable under acidic con- for silver halides dissolution in photographic and medi-
ditions and form thionates, which subsequently reduce cal X-ray film processing. It also produces substantial
to sulfites and elemental sulfur. This was noticed to have amount of recoverable silver as in thiosulfate fixation
an adverse effect on silver recovery at pH < 2.9, where process, hence it is therefore investigated for its effects
fine precipitates were observed forming. Rabah et al. on silver recovery on carbon. The silver recovery in
(1989) reported that 98% of silver was deposited as sul- aqueous sodium thiocyanate was 56% as shown in
fide sludge at pH 1.5. There were no indications of silver Fig. 4. The pH was not maintained at 3.5 as in previous
adsorption on carbon under these conditions. experiments and it gradually rose to attain equilibrium at
The three types of acids employed for further tests pH 8.5. Silver thiocyanate complexes were observed to
were acetic acid (CH3COOH), HNO3 and H2SO4 Æ NH3 report on carbon in the order of high to low adsorption
was also employed in this treatment for comparison pur- affinity as; Ag–NaSCN > Ag–NH4SCN > Ag–KSCN.
poses. The CH3COOH pre-treated carbon showed very Silver thiocyanate is considered to be thermodynami-
low silver recovery of 17% at pH 3.5 and the as received cally unstable under acidic and low potentials (Eh)
(untreated) carbon showed the lowest silver adsorption conditions as reported by Barbosa and Monhemius
of 9.7% at pH 8.5. The pH of solution was not main- (1989) as best illustrated in Fig. 5(a).
K.G. Adani et al. / Minerals Engineering 18 (2005) 1269–1276 1273
Fig. 3. Simplified mechanism involving the silver thiosulfate complex anion adsorption on carbon under the alkaline and acidic conditions.
Ag2O3(s) NH4+
+ NH+4
2.0 H2CO3 + NH4+
AgSCN(s)
Eh SO42- CO32-
(V) 1.0 Eh +
1 (V) 0.0 SO42-
Ag(SCN)43-
2
10-1 1
0.0 -1.0
Ag (s) 10-2
HSCN SCN-
2 -3
10
-1.0 -2.0
-2 0 2 4 6 8 10 12 14 -2 0 2 4 6 8 10 12 14
a pH b pH
Fig. 5. (a) Eh–pH diagram for Ag–SCN–H2O systems at 25 °C and silver concentration of 4.64 mol/dm3. (b) The SCN–H2O systems at 25 °C (redox
potential versus SHE). (Adapted from Barbosa and Monhemius (1989)).
mances than that of the silver thiosulfate electrolytes. a relatively low recovery of 27% as shown in Fig. 7. This
AgNO3 would seem to overcome the existing problems indicated that excess ammonium ions did not play any
encountered during direct electrolysis and precipitation significant role in the both the adsorption and desorp-
of silver from thiosulfate electrolytes where pH and sul- tion of silver.
fite controls have usually affected the precipitation and
electrolytic efficiency and recovery.
4. Conclusions
3.6. Mechanisms of elution
The use of synthetic spent fixing solutions have high-
The presence of the NO 3 anions in HNO3 during lighted the potential of recovering silver from the medi-
stripping process was observed to promote silver desorp- cal X-ray and photographic process effluents using
tion from the carbon. This corresponds to similar inves- activated carbon under acidic conditions. High silver
tigations done by Bailey (1987) and Gittins (1990), adsorptions and recoveries in thiosulfate solutions were
which showed that the presence of nitrates indicated observed when carbon was pre-treated using the 2 mol/
poor adsorption, but improved desorption. Bailey dm3 HNO3 and H2SO4 at 25 °C, respectively. The high
(1987) also observed that the increase of anions in solu- silver recoveries were observed when the pH of solutions
tion seemed to discourage aqueous Au/Ag complex was maintained between 3 and 4.
adsorption from the cyanide solutions but did promote HNO3 and H2SO4 pre-treatment of carbon probably
the Au/Ag desorption in the order; NO 3 > Cl > resulted in the formation of nitrogen and sulfur groups
2
OH > S > CN . The silver recovery of 60% in eluate that resulted in the improved silver recoveries of 98.5%
by stripping at pH 1.0 as shown in Fig. 7 was promoted and 91% in STS and ATS, respectively. The silver
by the effect of NO 3 ions in solution. The other 40% sil- adsorptions under the alkaline conditions indicated very
ver remained on carbon was probably held by a strong low silver recoveries of usually less than 15%. This
bond that existed between the protonated surface of car- shows that silver adsorptions in thiosulfate solutions
bon and H3[Ag(S2O3)2]. This could be due to the electro- are pH dependent. The NHþ 4 ions were seen to have
static attraction. The reactions on carbon by HNO3 no influence on both the adsorption and elution of sil-
stripping may have involved the simultaneous accumu- ver. The presence of excess NO +
3 and Na ions were ob-
lation of both the H+ and NO 3 ions. The net surface served to improve silver desorption.
charge on carbon by H+ and NO 3 ions via HNO3 strip- The silver concentration in eluate was increased by
ping determines the amount of silver being eluted. The threefold from 500 to 3250 mg/dm3. This indicates the
increased H+ on carbon seemed to reduce the effective- objective of this work with its potential to purify and
ness of elution by maintaining a strong electrostatic concentrate silver from large volumes of medical X-ray
bond between the silver thiosulfate anions and proton- and photographic process effluents into small workable
ated carbon surface. However, the increase in NO 3 ions volumes as pregnant liquors bearing very high silver
tend to induce an opposite effect by promoting silver concentrations. The AgNO3 electrolyte is considered
desorption. for its ease in handling during subsequent recoveries
The excess NO 3 ions in eluant seemed to substitute via precipitation or electrolysis and is also thermody-
thiosulfate ligands with nitrate ions, which then subse- namically stable at low pH and Eh than the silver thio-
quently desorbed from carbon matrixes as eluate. The sulfate electrolytes.
Na+ and NHþ 4 ions in the form of nitrates under alkaline
conditions were not investigated in this report. The effect
of NO 3 ions was observed to promote repulsive interac- Acknowledgements
tions between like charges and hence forced silver ions
off the carbon thus resulted in elution of silver in the I would like to greatly thank the Institute of Materi-
form of AgNO3 as pregnant silver electrolyte. als, Minerals and Mining (IOM3) for their invaluable
The result shows that presence of Na+ initially pres- and continuous financial support for this project
ent on carbon during adsorption from STS may have through the Stanley Elmore Fellowship grant. My
substituted the H+ on carbon and believed to be eluted appreciation goes to Mr. Dave from Camborne-Redruth
in the form of NaNO3. The catalytic effect of simple cat- Hospital for providing medical X-ray SFS samples. I
ions during elution may be presented in a proposed would also like to extend my gratitude to Dr. R.W. Bar-
order of desorption enhancement as; K+ > Na+ > Li+ > ley and Dr. R.D. Pascoe of the Camborne School of
H+ > NHþ 4 > Mg
2+
> Ca2+ as suggested by Davidson Mines, University of Exeter for their invaluable com-
+
(1974). The Na may have been introduced to the eluant ments and contributions to produce the final manu-
in the form of NO 3 or OH via simple hydrolysis. script. I would also like to acknowledge the Suttcliffe
þ
The presence of NH4 ions initially adsorbed on car- Speakmans Carbon UK Ltd. for supplying carbon sam-
bon via silver adsorption from ATS solutions showed ples free of charge to carry out this project.
1276 K.G. Adani et al. / Minerals Engineering 18 (2005) 1269–1276
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