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Minerals Engineering 18 (2005) 1269–1276

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Silver recovery from synthetic photographic and medical


X-ray process effluents using activated carbon
K.G. Adani, R.W. Barley *, R.D. Pascoe
Camborne School of Mines, School of Geography, Archaeology and Earth Resources, University of Exeter, Tremough Campus,
Treliever Road, Penryn, Cornwall TR10 9EZ, United Kingdom

Received 29 April 2005; accepted 24 May 2005


Available online 28 July 2005

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.

Keywords: Hydrometallurgy; Waste processing; Activated carbon; Silver

1. Introduction thermodynamically stable at slightly alkaline pH. The


simplified mechanisms for dissolution of AgCl in thio-
Reade discovered dissolution of silver halides in pho- sulfate solutions are proposed in Eqs. (1) and (2).
tographic fixing process using ammonium thiosulfate
AgClðsÞ þ 2ðNH4 Þ2 S2 O3ðaqÞ
(ATS) and sodium thiosulfate solutions (STS) as fixing
baths in 1837 (Eaton, 1965). Conventional fixing of  ðNH4 Þ3 ½AgðS2 O3 Þ2 ðaqÞ þ NH4 ClðaqÞ ð1Þ
AgX in photographic and medical X-ray films has been
extensively used in the photo-industry for more than AgClðsÞ þ 2Na2 S2 O3ðaqÞ
two centuries. The dissolution of silver halides by thio-  Na3 ½AgðS2 O3 Þ2 ðaqÞ þ NaClðaqÞ ð2Þ
sulfates and thiocyanates are usually rapid and do not
need any catalytic influence; hence they are highly solu- ATS and STS are commonly used in fixing baths that
ble in these lixiviants and are considered to be contain a number of other chemicals like acids, preser-
vatives, hardeners and buffers, which perform various
*
functions in the photographic fixing process. This results
Corresponding author. Tel.: +44 1326 371825; fax: +44 1326 in spent fix solutions having a complex silver composi-
371859.
E-mail addresses: k.adani@ex.ac.uk (K.G. Adani), r.w.barley@ex-
tion and thus this preliminary test work was performed
eter.ac.uk, rwbarley@csm.ex.ac.uk (R.W. Barley), R.D.pascoe@exe- on synthetic solutions. AgCl and AgBr were dissolved in
ter.ac.uk (R.D. Pascoe). ATS and STS to produce synthetic spent fix solutions

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

(SFS) as effluents with similar silver concentrations. Table 1


These synthetic solutions were used in the initial exper- AAS results of initial metal ion concentrations in the as received
medical X-ray and photographic effluents
iments. The use of carbon to selectively adsorb silver is
based on the gold–silver cyanide complex adsorption Metal ion Concentration (mg/dm3)
principles as in carbon in pulp and leach circuits in min- Medical X-ray SFS Photographic SFS
ing operations. Ag +
4196 4050
Carbon adsorptions for Au/Ag complexes were Na+ 3809 3050
observed in the order of high to low affinity as; Au K+ 6471 3500
 þ 3 Cu2+ 0.15 0.01
halide > AuðCNÞ2 > Au½CSðNH2 Þ2 > Au2 ðS2 O3 Þ2 as Ca2+ 29.0 18.9
reported by Gallagher et al. (1990) and Nicol et al. Fe2+ 1.00 0.350
(1987). Ag, Hg, Fe, Cu, Zn, Ni and other metal com- Al3+ 762.10 220.54
Cr2+ 0.46 0.031
plexes of these ligands also adsorb on carbon in that
Au is considered to adsorb on carbon at twice the rate
of Ag from Au/Ag cyanide complexes (Davidson,
1974). Gold thiosulfates and cyanides adsorption studies Cornwall College Photography laboratories, respec-
from various authors can be used as an analogy for tively. The analysis of these samples was determined
silver adsorption in the following order of preference by atomic adsorption spectrophotometer (AAS) as
 þ
on carbon as; AgðCNÞ2 > AgSCN > Ag½CSðNH2 Þ2 shown in Table 1.
þ
> CH3 COOAgþ > AgðNH3 Þ2 > AgNO3 > Ag2 SO4 >
3
AgðS2 O3 Þ2 as reported by Gittins (1990) and Adani 2.2. Adsorption studies
(2003). Although there are other competing metal ions
in SFS, silver is considered to have a greater affinity Batch adsorption experiments were done by adding
for carbon surfaces. Most alkali and alkaline metal ions 10 g of carbon to 1.5 dm3 aqueous silver thiosulfate of
are present at low concentrations in SFS effluents except the varying concentrations. The experiments were car-
for K+ and Na+ ions having average concentrations ried out in a temperature-controlled water bath at
above 3500 mg/dm3. Synthetic solutions of various sil- 25 °C where test bottles were agitated with overhead
ver concentrations were investigated in batch adsorption stirrers at 100 rpm in 24 h. The pH 3.5 was maintained
tests to establish a clear picture on the effects of silver by addition of nitric acid. 10 cm3 aliquots were sampled
adsorption in photographic and medical X-ray process at marked time intervals, filtered and analysed to obtain
effluents. kinetic data. Table 2 shows the experimental programme
for silver adsorption using the pre-treated carbon. Car-
bon samples of 10 g were used for each adsorption test.
2. Experimental The selected reagents used are shown in Table 2. The
10 g of carbon samples were immersed in 50 cm3 of pre-
2.1. Materials pared reagents for 2 h. The surface treated carbons were
then introduced into synthetic solutions in their wet
Commercially available carbons (GoldCarb 207C forms in 24 h and maintained at pH 3.5.
and 208C), obtained from the Sutcliffe Speakman Car- Other solutions used were 0.2 mol/dm3 of CuSO4,
bons UK Ltd. were employed for batch silver adsorp- K2Cr2O7, FeSO4 and 0.5 mol/dm3 of aqueous ammonia
tion experiments. The carbons were initially alkaline in (NH3). NH3 was used to raise the pH in order to inves-
nature and showed a pH of between 9 and 11 when tigate the effect of silver adsorption at alkaline condi-
10 g were contacted with 1.0 dm3 of deionised water. tions. Pre-treated carbons were added to solutions in
This was done by allowing a known mass of carbon to their wet forms to avoid any alteration to the already
come into contact with required volume of deionised formed surface functional groups that may promote sil-
water. The photographic and medical X-ray SFS were ver thiosulfate adsorption on carbon. The untreated car-
obtained from the Camborne-Redruth Hospital and bon was used in these tests for comparison purposes.

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

introduced predominantly the acidic surface groups like


quinone-type carbonyl (–C@O), carboxylics (–COOH), 0
lactones (–C–O), phenolic hydroxyl (–OH), sulfonates 0 3 6 9 12 15 18 21 24
(–SO3H), and nitrogen group (–NO3H). This had made contact time (hr)

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

100 tained at 3.5 for untreated carbon, hence the pH had


risen to 8.5 resulted in a very low silver recovery. The
silver recoveries on the H2SO4 and HNO3 pre-treated
silver recovery (%)

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.

100 face to promote effective silver adsorption via ion pair


Ag-NaSCN
Ag-KSCN mechanism. Fig. 5(a) shows the possible speciation of
NH 4SCN silver thiocyanate that may be anticipated to adsorb
80 2
on carbon at pH 8.5 in the form of AgðSCNÞ3 and
3
AgðSCNÞ4 including Ag(s) when the Eh 6 0.0. How-
silver recovery (%)

60 ever, Ag2O3(s) could also be reduced as precipitates if


the Eh P 1.5 at pH 8.5, which is seen in Fig. 5(a). The
concentration of thiocyanate must be always higher to
40 compensate for the protonation of the free thiocyanate
into HSCN, which occurs at pH 6 1.5 as shown in
Fig. 5(b) and at the same time prevents any AgSCN(s)
20 precipitation as shown in Fig. 5(b). At pH P 1.0 and
a Eh of 60.5 V, silver seemed to exist as thermodynam-
3 2
ically stable in the form of AgðSCNÞ4 and AgðSCNÞ3
0
0 3 6 9 12 15 18 21 24 27 ions in solution as shown in Fig. 5(a). The pH of solu-
contact time (hr) tion increased from initial 5.9 to 8.5 was due to the
alkalinity of the as received carbons and the Eh was ob-
Fig. 4. Silver recovery using the as received carbons in aqueous silver
thiocyanate at pH 8.5.
served to be above 0.5 V.
The overall proposed existence of silver thiocyanate
complex species at these Eh–pH conditions can be seen
3.4. Thermodynamics consideration in Fig. 5(a). The silver thiocyanate and thiosulfate sys-
tems are usually very complex and basically unstable at
This adsorption phenomenon can be best explained low pH and Eh values including the changes in concentra-
using Fig. 5(a), which shows the Eh–pH diagram of tions. The thermodynamic consideration must be taken
Ag–SCN–H2O systems as predicted for silver speciation into account for such systems in order to indicate the type
at the concentration of 500 mg/dm3 whilst Fig. 5(b) of silver complex species in solution that are likely to ad-
shows the stability diagram for oxidation of thiocya- sorb on carbon under known Eh–pH conditions. The sil-
nates to sulfates, carbonates, and ammonia including ver species from thiosulfates systems that were adsorbed
the related species along the pH range that corresponds on carbon are presently unknown and can be suggested
to the similar work using low silver concentrations that to report on carbon in one of the following possible forms
3
was reported by Barbosa and Monhemius (1989). The as; AgðS2 O3 Þ2 , (NH4)3[Ag(S2O3)2], AgSO4, Na3[Ag
consideration of thiocyanate oxidation using Eh–pH (S2O3)2], Cx–H3[Ag(S2O3)2], AgCl or Ag2S. The Eh–pH
diagram is vital in proposing the possible type of silver diagrams are useful to thermodynamically determine
thiocyanate species that may have adsorbed on carbons. the stability and the type of silver species recovered on
Fig. 5(a) predicts the possible silver thiocyanate species carbon under experimental conditions.
that are more likely to report on carbon as ions at equi-
librium pH of 8.5. 3.5. Stripping
The oxidation of thiocyanate in Fig. 5(b) shows the
formation of carbonic acids and sulfates at Eh P 0.1 The stripping of silver from carbon was done to
and pH P 1, which may have influenced the carbon sur- recover silver in eluate that was initially recovered on
1274 K.G. Adani et al. / Minerals Engineering 18 (2005) 1269–1276

3.0 Ag = 4.6 M 2.0


SCN = 1.0 M

Ag2O3(s) NH4+
+ NH+4
2.0 H2CO3 + NH4+

NH3 (aq) + HCO3- + SO42-


1.0 + 1
Ag(SCN)3 2- + H2CO3
HSO4- + H2CO3 NH3+
SO42- + +

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)).

carbon. Fig. 6 shows the concentrations of silver in elu- 100


ate in the form of silver nitrate (AgNO3) electrolyte for silver from STS solution
each bed volume (BV) after stripping using 2 M HNO3. Silver recovery in eluate (%) 80 silver from ATS solution
The initial silver concentrations in synthetic ATS before
adsorption were 514 and 675 mg/dm3, respectively. Sil-
ver concentrations after stripping and recovery results 60
are shown in Figs. 6 and 7. This indicated the potential
of achieving the improved purification and concentra- 40
tion of silver via selective adsorption followed by strip-
ping. The initially pre-treated H2SO4 carbon in ATS
20
solution shows a low recovery of 27%. The differences
in silver recovery from ATS and STS systems were
observed. 0
The silver recovery via elution showed the silver 1 2 3 4 5 6 7 8 9 10
Bed volume
recoveries in eluate with 60.4% and 27% that initially ad-
sorbed from STS and ATS, respectively. The 60.4% Fig. 7. Silver recovery after elution using 2.0 mol/dm3 HNO3 at 85 °C.
recovery from STS solution suggests an ion exchange ef-

fect during stripping. This corresponds to similar effects


4000 observed in aqueous Au/Ag systems as reported by
Adsorbed from ATS solution Davidson (1974), where he noticed that the presence of
K+ and Na+ seemed to enhance elution of Au/Ag cya-
Ag+ concentration in eluate (mg/dm3)

Adsorbed from STS solution


nide complex from carbons. This is also related to
3000
McDougall et al. (1980) showing that the presence of
K+ and Na+ ions in such solutions catalysed the Au/
Ag complex desorptions. This indicates the possibility
2000
to improve silver recovery via stripping by the presence
of Na+ or K+ ions in eluants composition. The presence
of Na+ ion initially present on carbon during adsorption
1000 has been observed to induce a catalytic effect on strip-
ping results. The eluate was in the form of aqueous
AgNO3 as pregnant liquor with traces of Na+ and
0 NHþ 4 ions initially obtained from STS and ATS,
1 2 3 4 5 6 7 8 9 10 respectively.
Bed volume The resultant AgNO3 electrolyte is considered to be
Fig. 6. Silver concentration in eluate after elution using 2.0 mol/dm3 ideal for further silver recovery via electrolysis or precip-
HNO3 at 85 °C. itation processes is due to its high recovery perfor-
K.G. Adani et al. / Minerals Engineering 18 (2005) 1269–1276 1275

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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