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By SREEREMYA.S
The waste photographic films/X-ray contains
1.5 - 2 % (w/w) black metallic silver which is
recovered and
reused.
Around 18-20% of the world's silver needs
are supplied by recycling photographic waste.
Silver is a precious metal, further silver has
wide uses like in jewellery,dentistry,
photography, mirrors, optics, industries, etc.
 So the recovery of silver is beneficial in
industrial, chemical and economical aspects.
Increasing industrialization and urbanization
worldwide had caused serious pollution all around
the world, especially in the aquatic environment.
Wastewaters produced by humans are frequently
laden with toxic heavy metals such as copper, silver,
mercury,etc.
Silver is a precious metal widely used in the
photographic, electrical, electronics, chemical
andjewelry industries.
Even though it is not as expensive as gold or
platinum, silver is still only present in limited
amounts in nature, which contributes to the need for
efficient methods of recycling silver from waste
generated by the above industries
Inductively Coupled Plasma Optical Emission
Spectrometry (ICP-OES, Thermo-Fisher) was
used to determine the concentration of metal
ions. Synthesis of the Thiourea-Modified
Chitosan Resin
O-carboxymethyl-chitosan was prepared following the method
of Zhu et al. [23]. 2 g chitosan was immersed in 25 ml of 50 wt%
NaOH solution to swell and alkalize for 24 h. Five grams of
monochloroacetic acid was dissolvedin 25 ml of isopropanol, and
then added drop-wise to the flask containing the alkalized
chitosan after filtration for 20 min.
The reaction continued 8 h at room temperature and then the
mixture was filtered to remove the solvent.The filtrate obtained
was dissolved in 100 ml of water, and 2.5M HCl was added to it
to adjust its pH to 7. After this solution was centrifuged to
remove the precipitate, 400 ml of anhydrous ethanol was added
to it and the precipitate was O-carboxymethyl-chitosan. 3.0 g of
thiourea was dissolved in 60-ml distilled water. 17.1 ml of
(50%) glutaraldehyde solution was added to thiourea solution in a
round flask.
The mixture was heated on a water bath for 3 h
at 323 K. After completion of the
reaction, 1.36 g of carboxymethyl-chitosan was
dissolved in 30-ml distilled water, and the
solution was then added to the mixture of the
flask and heated for 8 h at 343 K.
 A large quantity of resin was formed, and
washed several times with dilute sodium
hydroxide, distilled water and acetone
respectively. The resin was dried at 333K for 3 h
and weighed about 2.96 g, and then sieved
where the particle size fraction 0.1–0.4mm was
used in this study
Characterization of the Resin
FT-IR-spectra were used to identify the
structure of the synthesized resin.
The sample was prepared mixing 1mg of the
material with 100mg of spectroscopy grade
KBr. The FT-IR-spectra were recorded using
Nicolet Magne-Avatar 360 equipment
Adsorption Kinetics
The effect of contact time on the uptake of
Ag (I) by the resin was done by placing 0.1 g
of dry resin in a series of flasks.
 To each flask, 100 ml of Ag (I) at pH 4.0 with
initial concentration of 1×10−2 M was added.
The flasks were shaken at 298 K. Samples of
5ml solution were withdrawn at scheduled
time intervals and analyzed for Ag (I)
concentration.
Adsorption Isotherms
0.1 g dry resin was swelled in a series of 250-ml
flasks
containing 50mL of distilled water for 1 h. In each
flask,50mL of metal ion solution at desired
concentration was added to the flask, and the pH
value was recorded.
 The flasks were shaken at 300rpm while keeping
the temperature at 298, 308, 318 and 328K for
12 h. Later on, the concentration of solution was
determined by ICPOES and the metal ion uptake
was calculated.
The adsorption band around 3300cm−1 in all spectrums, revealed the
stretching vibration of –NH2 and –OH groups in chitosan, and the bands
near 1641 and 1555cm−1 in the spectrum of the resin are assigned to
C=N of Schiff’s base moiety and C–N of thiourea moiety, respectively.
The spectrum of the resin also displays new bands near 1108 and
1053cm−1 corresponding to C–O, one of the characteristics of O-
carboxymethyl-chitosan. Besides, a lot of differences in the spectra
before and after silver sorption were observed.
The bands at 2917cm−1 strengthened. The intensity of the band around
1400cm−1 which is assigned to >N–C S group was substantially
decreased after Ag (I) binding, which confirms that sulphur groups were
involved in silver binding.
 In the spectrum of silver adsorbed onto the modified resin, the peak at
1641cm−1 disappeared and a new peak around 1703cm−1 came out.
Additionally, the changes in the spectra around 3300cm−1 and the
decreasing intensity at 1053cm−1 also indicated that the nitrogen
atoms as well as oxygen atoms in the –OH and –CO groups were
involved in silver adsorption.
The bands at 2917cm−1 strengthened. The intensity of
the band around 1400cm−1 which is assigned to >N–C
S group was substantially decreased after Ag (I) binding,
which confirms that sulphur groups were involved in
silver binding.
 In the spectrum of silver adsorbed onto the
modified resin, the peak at 1641cm−1 disappeared
and a new peak around 1703cm−1 came out.
Additionally, the changes in the spectra around
3300cm−1 and the decreasing intensity at
1053cm−1 also indicated that the nitrogen atoms
as well as oxygen atoms in the –OH and –CO
groups were involved in silver adsorption.
THANK YOU

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Extraction of silver from photographic waste

  • 2. The waste photographic films/X-ray contains 1.5 - 2 % (w/w) black metallic silver which is recovered and reused. Around 18-20% of the world's silver needs are supplied by recycling photographic waste. Silver is a precious metal, further silver has wide uses like in jewellery,dentistry, photography, mirrors, optics, industries, etc.  So the recovery of silver is beneficial in industrial, chemical and economical aspects.
  • 3. Increasing industrialization and urbanization worldwide had caused serious pollution all around the world, especially in the aquatic environment. Wastewaters produced by humans are frequently laden with toxic heavy metals such as copper, silver, mercury,etc. Silver is a precious metal widely used in the photographic, electrical, electronics, chemical andjewelry industries. Even though it is not as expensive as gold or platinum, silver is still only present in limited amounts in nature, which contributes to the need for efficient methods of recycling silver from waste generated by the above industries
  • 4. Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES, Thermo-Fisher) was used to determine the concentration of metal ions. Synthesis of the Thiourea-Modified Chitosan Resin
  • 5. O-carboxymethyl-chitosan was prepared following the method of Zhu et al. [23]. 2 g chitosan was immersed in 25 ml of 50 wt% NaOH solution to swell and alkalize for 24 h. Five grams of monochloroacetic acid was dissolvedin 25 ml of isopropanol, and then added drop-wise to the flask containing the alkalized chitosan after filtration for 20 min. The reaction continued 8 h at room temperature and then the mixture was filtered to remove the solvent.The filtrate obtained was dissolved in 100 ml of water, and 2.5M HCl was added to it to adjust its pH to 7. After this solution was centrifuged to remove the precipitate, 400 ml of anhydrous ethanol was added to it and the precipitate was O-carboxymethyl-chitosan. 3.0 g of thiourea was dissolved in 60-ml distilled water. 17.1 ml of (50%) glutaraldehyde solution was added to thiourea solution in a round flask.
  • 6. The mixture was heated on a water bath for 3 h at 323 K. After completion of the reaction, 1.36 g of carboxymethyl-chitosan was dissolved in 30-ml distilled water, and the solution was then added to the mixture of the flask and heated for 8 h at 343 K.  A large quantity of resin was formed, and washed several times with dilute sodium hydroxide, distilled water and acetone respectively. The resin was dried at 333K for 3 h and weighed about 2.96 g, and then sieved where the particle size fraction 0.1–0.4mm was used in this study
  • 7. Characterization of the Resin FT-IR-spectra were used to identify the structure of the synthesized resin. The sample was prepared mixing 1mg of the material with 100mg of spectroscopy grade KBr. The FT-IR-spectra were recorded using Nicolet Magne-Avatar 360 equipment
  • 8. Adsorption Kinetics The effect of contact time on the uptake of Ag (I) by the resin was done by placing 0.1 g of dry resin in a series of flasks.  To each flask, 100 ml of Ag (I) at pH 4.0 with initial concentration of 1×10−2 M was added. The flasks were shaken at 298 K. Samples of 5ml solution were withdrawn at scheduled time intervals and analyzed for Ag (I) concentration.
  • 9. Adsorption Isotherms 0.1 g dry resin was swelled in a series of 250-ml flasks containing 50mL of distilled water for 1 h. In each flask,50mL of metal ion solution at desired concentration was added to the flask, and the pH value was recorded.  The flasks were shaken at 300rpm while keeping the temperature at 298, 308, 318 and 328K for 12 h. Later on, the concentration of solution was determined by ICPOES and the metal ion uptake was calculated.
  • 10. The adsorption band around 3300cm−1 in all spectrums, revealed the stretching vibration of –NH2 and –OH groups in chitosan, and the bands near 1641 and 1555cm−1 in the spectrum of the resin are assigned to C=N of Schiff’s base moiety and C–N of thiourea moiety, respectively. The spectrum of the resin also displays new bands near 1108 and 1053cm−1 corresponding to C–O, one of the characteristics of O- carboxymethyl-chitosan. Besides, a lot of differences in the spectra before and after silver sorption were observed. The bands at 2917cm−1 strengthened. The intensity of the band around 1400cm−1 which is assigned to >N–C S group was substantially decreased after Ag (I) binding, which confirms that sulphur groups were involved in silver binding.  In the spectrum of silver adsorbed onto the modified resin, the peak at 1641cm−1 disappeared and a new peak around 1703cm−1 came out. Additionally, the changes in the spectra around 3300cm−1 and the decreasing intensity at 1053cm−1 also indicated that the nitrogen atoms as well as oxygen atoms in the –OH and –CO groups were involved in silver adsorption.
  • 11. The bands at 2917cm−1 strengthened. The intensity of the band around 1400cm−1 which is assigned to >N–C S group was substantially decreased after Ag (I) binding, which confirms that sulphur groups were involved in silver binding.  In the spectrum of silver adsorbed onto the modified resin, the peak at 1641cm−1 disappeared and a new peak around 1703cm−1 came out. Additionally, the changes in the spectra around 3300cm−1 and the decreasing intensity at 1053cm−1 also indicated that the nitrogen atoms as well as oxygen atoms in the –OH and –CO groups were involved in silver adsorption.