Separation and Purification Technology 18 (2000) 89–92

www.elsevier.com/locate/seppur

Recovery of silver from industrial wastes,

cassava solution effects
V.I.E. Ajiwe *, I.E. Anyadiegwu
Department of Science Technology, Nnamdi Azikiwe University, Awka, Nigeria

Received 29 September 1998; received in revised form 12 May 1999; accepted for publication 30 August 1999

Abstract

In this work, silver was recovered from X-ray films by dissolving the silver compounds with concentrated nitric
acid. Internal electrolysis and external electrolysis methods were carried out using a steel electrode as cathode and a
copper electrode as anode. Similarly, internal electrolysis and external electrolysis were carried out by adding cassava-
derived cyanide solution. The results of recovery by internal and external electrolysis were compared. Addition of
cassava-derived cyanide solution proved to give a better recovery in both methods. The results showed that external
electrolysis also gave a better recovery. However, on the basis of energy consumption, silver recovery by internal
electrolysis with cassava-derived cyanide solution is recommended for both solid and effluent wastes from industries.
© 2000 Elsevier Science B.V. All rights reserved.

Keywords: Cassava solution (cyanide); Silver recovery from wastes

1. Introduction another metal such as zinc by electrolysis or by

Silver is recovered from used photographic film
by burning the film and dissolving the silver in the
ashes with nitric acid. The silver is precipitated
with sodium chloride and the resulting precipitate
is filtered. Frequently, industrial waste waters may
be acidic or basic and may require neutralization
prior to any other treatment or prior to release to
a municipal sanitary sewage system. Acid waste
waters may be neutralized with slake lime
(Ca(OH ) ), caustic soda (NaOH ) or soda ash
2
(Na CO ). Alkaline waste waters may be neutral-
2 3
ized with a strong mineral acid, such as H SO or
2 4
HCl or with CO [1].
2
Silver is also recovered from photographic pro-
cessing solution by replacing the silver with
* Corresponding author.
chemical precipitation with chemicals such as
sodium hydroxide or sodium sulphide [2]. Silver
is often recovered from silver residue. This involves
purification of the waste and fusion with anhy-
drous sodium and potassium trioxocarbonate( V )
[3]. Silver is equally recovered from photographic
films. When silver halide in the residue is
coagulated by boiling with concentrated
trioxonitrate( V ) acid, the resulting crude product
is washed with water and dissolved in the minimum
concentrated amount of ammonia. The silver is
then extracted using Zolon red which is dissolved
in benzyl alcohol and the solution is then adjusted
to pH 3.7. The extracting reagent is regenerated
by adding the aqueous phase as a bright red dye
for more extractions [4].
Recovery of metals from aqueous solution of
their salts by electrolysis can be realized by two

1383-5866/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S1 3 8 3- 5 8 66 ( 9 9 ) 0 00 4 8 -9
90 V.I.E. Ajiwe, I.E. Anyadiegwu / Separation and Purification Technology 18 (2000) 89–92

methods. The first method consists of the electroly-
sis of solutions obtained after leaching of the
corresponding metal from ores or concentrated
with the use of insoluble anodes [5]. The second
method consists of the electrolytic refining of the
metal. Here the crude metal to be refined serves
as the anode and the pure metal is deposited at
the cathode. This is a better method for noble
metal recovery [6 ]. Most world silver is recovered
from scraps such as photographic films, X-ray
films and jewellery [7]. Internal electrolysis is a
form of electrode deposition [8,9] without an
applied external voltage. It has been used little in
recent years. Internal electrolysis has been used in
this project in order to minimize the energy cost
in the recovery of silver [10].
2. Experimental
2.1. Sampling and recovery of silver from industrial
waste
X-ray films were collected from hospitals and
photo-processing industries in Awka, Anambra
State, Nigeria.
X-ray film was weighed and was cut into pieces.
The pieces were collected into a 1 l beaker. Then
10 ml of concentrated nitric acid was poured into
the beaker that contained the X-ray film. The
pieces of film were shaken to dissolve the silver
compounds. The solution so formed was diluted
to 800 mark with distilled water and the washed
film pieces were removed. The quantity of nitric
acid that was added was the quantity sufficient to
dissolve the silver compounds in the film plate.
After the dissolution, the whole mixture was
diluted with distilled water and was stirred to
ensure proper mixing of the solution. After this, a
steel electrode (21.98 cm2 size) connected to a
copper electrode (2.5 mm diameter by 12 cm
length) was inserted into the mixture, i.e. the
the silver deposition and copper was the anode
which was sacrificed at a very slow rate.
To desilver the cathode, it was removed care-
fully from the mounting beaker. The cathode was
placed on a clean surface (a polythene sheet or tin
foil ) and was carefully brushed to remove silver
plating. The cathode was then re-cleaned with a
wire brush several times before replacement into
the plating solution.
In a second procedure, 10 ml of conc. nitric
acid was used to dissolve silver salt from X-ray
films and after dilution with water, 30 ml of cya-
nide solution derived from a saturated solution of
mashed cassava was poured into the plating solu-
tion (the solution pH rose to 2.60), the experiment
was repeated as described above until all the silver
from the X-ray film had deposited on the steel
cathode. The results of experiment one was com-
pared with those of experiment two in terms of
recovery mass and time (see Tables 1 and 2). It
should be noted that the cyanide concentration of
the cassava was determined as 194.5 mg l−1 by the
method reported by Ikediobi et al. [11]. Equally,
Table 1
Result of internal electrolysis recovery without cyanide
Parameter Value
Steel cathode size (cm2) 21.98
Copper anode size 2.5 mm diameter
×12 cm
Size of X-ray film (cm2) 1131.0
Temperature of electrolyte solution (°C ) 28.0±1.5
Total time for recovery (h) 112.06
Mass of silver (g) 0.21
Mass (g h−1) 1.9×10-3
Conductivity of electrolyte solution 0.083 S cm−3
pH of electrolyte solution 2.50
Table 2
Result of internal electrolysis recovery with cyanide
Parameter Value

electrolyte was made up of silver nitrate–nitric Size of X-ray film (cm2) 1131.0
acid water solution (temperature 28±1.5°C, Total time (h) 110.65
pH 2.5 and conductivity 0.083 S cm−3). After Mass of silver (g) 0.78
about 20 h, the electrodes were removed from the Mass (g h−1) 7×10-3
Cassava cyanide concentration (mg l−1) 194.5
electrolyte. The steel electrode was dried and pH of electrolyte solution 2.60
weighed. The steel electrode was the cathode for
 V.I.E. Ajiwe, I.E. Anyadiegwu / Separation and Purification Technology 18 (2000) 89–92 91

it should be noted that the cassava solution cyanide Table 3

exists in two forms as aliphatic cyanogenic gluco- Result of external electrolysis without cassava cyanide solution
side, linamarin and lotaustralin or bound cyanide Parameter Value
and as free nonglycosidic cyanide.
Current (mA) 0.5
2.2. External electrolysis without cassava solution Size of film (cm2) 1131.0
Time (h) 12.24
Mass of silver (g) 0.25
A weighed X-ray film was cut into pieces and
Mass (g h−1) 20.4×10-3
collected into a beaker. 10 ml of nitric acid was
added into it to wash off the silver in the film. The
beaker was swilled very well before diluting with Table 4
water. After the dilution the washed films were Result of external electrolysis with cassava cyanide solution
removed from the electrolyte. The whole mixture
was stirred very well to ensure proper mixing of Parameter Value
the solution. A direct current was connected to Current (mA) 0.5
two electrodes (steel cathode and copper anode) Size of film (cm2) 1131.0
inserted into the electrolyte and the time was Time (h) 8.16
taken. It is noteworthy that the current for depos- Mass of silver (g) 0.58
ition was set to 0.5 mA using a rheostat. After a Mass (g h−1) 71.07×10-3
few hours, the cathode was removed, dried and
weighed before desilvering as described above.
electrolysis without cyanide while Table 2 depicts
2.3. External electrolysis with cassava solution the result of internal electrolysis with cassava-
derived cyanide. Table 3 is the result of external
10 ml of conc. nitric acid was added to the electrolysis without cyanide while Table 4 is the
weighed X-ray film inside a 1 l beaker and after result with cyanide addition.
the removal of the washed X-ray film, 30 ml of
cyanide derived from cassava solution was added. 3.2. Discussion
The whole mixture was stirred very well to ensure
proper mixing of the solution. External electrolysis From the results in Tables 1–4, the amount of
was then carried out as before. After 8.16 h, it was silver recovered by internal electrolysis without
removed, dried, weighed and desilvered as before. cyanide derived from cassava solution is three
times smaller than when cyanide from cassava
2.4. Preparation of AgNO solution was added. Similarly, the external electrol-
3
ysis without cassava cyanide solution is three times
0.5 g of recovered silver was heated with 10 ml smaller than that with cassava cyanide solution. It
conc. HNO to a temperature of 70–80°C with is obvious that the recovery of silver by external
3
stirring. The AgNO solution was later crystallized
3 electrolysis with cassava-derived cyanide solution
from a cold solution [12]. The silver nitrate pro-
is the greatest. However, considering the fact that
duced was further used to test the presence of
internal electrolysis does not need external power,
chloride in water. This confirmed the purity of the
internal electrolysis is recommended for a con-
AgNO and silver deposited.
3 tinuous extraction of silver from such solid wastes.
It is noteworthy that the silver extracted was
3. Results and discussion confirmed to be silver by using it to prepare
AgNO , which was used to confirm the presence
3
3.1. Results of chloride in water. Similarly, it is recommended
for recovery of silver from any other industrial
The results of the analysis are as shown in effluent. Since the use of cyanide addition derived
Tables 1–4. Table 1 shows the result of internal from cassava to the electrolytic solution yields a
92 V.I.E. Ajiwe, I.E. Anyadiegwu / Separation and Purification Technology 18 (2000) 89–92
result three times greater than that without cya-
nide, the addition of cyanide to the electrolytic
solution will give better extraction efficiency for
both solid wastes and effluents from industries.
This result is in conformity with the reports of
Loto [12].
It is recommended that silver should be reco-
vered by percolation of the effluents in ditches
with immersed steel and copper electrodes (by
internal electrolysis). When the recovery is needed
in a short time, external electrolysis with cassava-
derived cyanide added to these ditches is obviously
the best option.
4. Conclusion
The experiment has proved that silver can be
recovered or recycled from industrial solid wastes
and effluents and can be used to prepare such
compounds as silver nitrate so as to save our
surroundings from silver and silver salt pollution.
It is recommended to the Federal Environmental
Protection Agency ( FEPA) and other World pollu-
tion bodies to advise the photographic processing
industries to adopt internal electrolysis as a means
of cleaner production and waste minimization.
References
[1] P.B. Norton, The New Encyclopaedia Britanica Vol. 10,
Encyclopaedia Britanica, Chicago, IL, 1994, pp. 447–449.
[2] M.W. Dempsey, Metals (1968) 12, 46, 59.
[3] J. Lambert, T.A. Murr, Practical Chemistry, 2nd Edition,
Heinemann, London, 1966, pp. 67, 336–364.
[4] Recovery of silver as silver trioxonitrate ( V ) from labora-
tory waste, J. Sci. Eng. Technol. (1999) in press.
[5] E.A. Cotton, G.W. Ikinson, Advanced Inorganic Chemis-
try, 3rd Edition, Wiley, New York, 1972, pp. 721–725.
[6 ] E. Horwood, Industrial Chemistry Vol. 1, E. Stoochi, New
York, 1990, pp. 76–79.
[7] Encyclopedia of Science and Technology Vol. 5, Van
Nostrand, New York, 1976, pp. 595–596.
[8] Encyclopaedia of Science and Technology Vol. 4,
McGraw-Hill, New York, 1977, pp. 536–538.
[9] Encyclopaedia of Science and Technology Vol. 4,
McGraw-Hill, New York, 1977, pp. 601–604.
[10] V. Alexeyev, Quantitative Analysis, Mir, Moscow, 1979,
pp. 480–492.
[11] C.O. Ikediobi, G.O.C. Onyia, C.E. Eluwa, A rapid and
inexpensive enzymatic assay for total cyanide in cassava
(Manihot esculenta crantz) and cassava products, Agric.
Biol. Chem. 44 (2) (1980) 2803–2809.
[12] C.A. Loto, Effect of sugarcane and cassava juices as addi-
tion agents in the electrodeposition of zinc, Discovery and
Innovation 5 (3) (1993) 247–253.