SILVER AND PALLADIUM RECYCLING FROM THE SECONDARY

RESOURCES
Vadász P., Rabatin Ľ., Tomášek K.,
Institute of Metallurgy and Materials, Faculty of Metallurgy,
Technical University of Košice, Slovakia
Abstract
Elektrochemical and chemical technology for the treatment of the separated electrotechnic scrap with silver and
palladium content in laboratory scale were tested and verified. Separated electrotechnic Ag-Pd scrap is mainly
represented by various types of contacts from the electric and electronic devices and apparatuses. As a basic
material of the body of these contacts is most frequently used copper alloys for example different types of
bronzes or brasses. Contact layer is presented by galvanically coated silver surface or silver-palladium alloy
surface. Silver and palladium content in such separated contacts is 5 - 23 % Ag and 2,5 - 8,5 % Pd according to
the grade of separation.
There steps electrochemical and chemical method of the treatment of separated electric contacts is suggested,
described and verified in this paper. The first step is based on copper electrolysis, the second step is based on
silver electrolysis and the third step is presented by selective chemical Pd precipitation.
There were verified, that is possible to obtain in the first step by Cu electrolysis metallic copper with the 96,06
% purity and 76 % efficiency. In the second step is possible by Ag electrolysis to obtain metallic silver with the
purity 99,95 % Ag and 82 % efficiency. In third step is possible by chemical precipitation to obtain palladium-
sponge with the purity 99,75 % Pd and 95 % efficiency. In the case of low Pd content solutions recycling is
possible to raise the efficiency of palladium extraction.
Key words: palladium, silver, electrolysis.

1. Introduction
It is estimated that about 90% of all contacts, used in electrical engineering is made of silver
and its alloys [1]. This stems from a very good electrical and thermal conductivity of silver
and its alloys, as well as its resistance to oxidation. Silver oxide (Ag2O) is at higher
temperatures (above 190 ° C) unstable and decays back to metallic silver and oxygen [8].
Virtually the contact area of contact itself clean. Another advantage of silver is its low contact
resistance and relatively low abrasion resistance. Contacts made from pure silver having
fineness 999/1000, such silver is very well molded and nicely rolled and cold drawn into
sheets, wires and other profiles. In the event that the required higher mechanical properties of
contacts (eg, hardness, strength, abrasion resistance) or increased chemical resistance,
producing the electrical contacts with silver alloy metals, respectively and non-metals. The
most commonly used systems are Ag - Cu, Ag - Cd, Ag - Au, Ag - Pd, Ag - Pt, Ag - Ni, Ag -
Mo, Ag - W and to a lesser extent Ag - CdO and Ag - C (graphite) [1 ].
Increasing the hardness of the contacts is done by adding a small amount of silver in a
suitable metal or its alloys [1]. For example, addition 1 to 2% Si alloy will significantly
increase the hardness of silver and called it "hard silver". Similar effects have also alloy with
1% Ni, respectively. 0.15 to 0.5% Mg. To increase the hardness of silver contact method is
used with a small amount of alloying metal on the high affinity to oxygen, and which is
soluble in silver (eg, Al, Mg, Be. Mn, Ti). The content of these alloying additions is 2 to 3 at.
%. The literature is well-known effect of absorption of oxygen into silver in increasing the
temperature [8]. Silver alloys are annealed at 800 ° C, whereas silver oxide at these
temperatures cannot be there to create oxides of alloying metals. The result is a substantial
increase in hardness with no major change in electrical resistance of silver alloys [1]. Leaner
production for silver contacts material contact plates on the carrier. As carriers are used brass
contacts (eg, Ms. 63), Tin bronze (eg Bz 6), Beryllium aluminium or bronze, respectively.
Steel and other materials [1, 2].
These data show the complexity of the processing electronics scrap containing precious
metals to the metal. In the present work is given technological scheme for processing of
silver, silver - copper and silver - palladium contacts, has been tested on about 2000 g sample
of separated electrical scrap.

2. EXPERIMENTAL PART
2. 1 Characteristics of starting materials
Simulation technology has been tested on a sample, which was formed about 6 types of
contacts from telephone exchanges, which were manually separated. Separate contact was
formed by the carrier and contacts, and mass ratio (carrier to contact) was about 4: 1
Therefore, we propose additional contacts, thereby cutting the share of interest metals (Ag
and Pd) in the separated electrical scrap. Chemical analysis of starting materials is described
in Table 1
Table 1 Chemical composition of Ag-Pd contacts [wt.%]
Where:
A 1-1 separated contacts after smelting
A 1-2 contacts with metallic bodies before smelting
A 1-3 contacts with metallic bodies after smelting
1-4 A metallic bodies of contacts after smelting
For those of chemical analysis it is clear that the sample was made up of electrical scrap
various types of contacts, which corresponds to the composition of the alloy Ag - Pd 30 [1],
while the carrier was likely to nickel-brass [2].
2.2 Description of the processing technology of waste electrical
The chemical composition of the sample melted and 1-1 shows that it consists of copper,
silver, zinc, nickel and palladium. Therefore, we separated technology of the contacts divided
into three stages. In the first phase of contacts obtained metallic copper and removes the bulk
of zinc and nickel. In the second stage to obtain silver and sludge containing palladium. The
third step is to obtain technologies Pd; i.e. dissolution of Pd-selective precipitation of sludge
and palladium complexes, their stabilization, washing, drying, annealing and reduction of Pd-
up.
Technological scheme of the first two stages of processing contacts on copper and silver is
shown in Fig.1.
2.2.1 Stage of obtaining copper
For the first stage of the procedure used as in conventional electrolytic copper. Contacts are
rendered and odliali in Cu-anode, whose chemical composition corresponds to sample A 1-1.
The electrolysis of copper sulphate in the electrolyte (aqueous solution of CuSO4 + H2SO4)
gave the cathode copper, while zinc and nickel concentrate in the electrolyte and sludge
remained silver and palladium (Table 2). Parameters of model copper electrolysis were as
follows:
Electrolysers dimensions: 300 x 300 x 150 [mm].
Electrolyte quantity: about 1 10-2 m3
The initial composition of the electrolyte: 30 gl-1 Cu and 220 gl-1 free H2SO4
Current density: 200 A.m-2
Distance between anode and cathode: 120 to 130 [mm]
Anode: 150 x 130 x 10 [mm], 2 pcs cathode (Cu-plate): 150 x 130 x 0.5 [mm]
Electrolyte temperature: 20 to 23 ° C
Fig.1 Technological flow sheet of copper and silver extraction from separated electronic
contacts
Electrolyte together with the sludge is continuously pumped and filtering out the sludge is
returned to the electrolyser. The sludge was washed with hot water and dried. Thus, treated
sludge is melted and cast into Ag-anode, which is refined electrolytically in the second stage
of the proposed technology. Chemical composition of the products from electrolysis of
copper is shown in Table 2
Table 2 Chemical composition of Cu electrolysis products [wt.%]
Where:
B 1-1 Cu cathodes [wt.%]
C 1-1 Ag anodes from anode slime [wt.%]
D 1-1 spent copper electrolyte [g.l-1]
From the above results it is clear that in this stage of electrical scrap removed about 95%
copper and 99% zinc and nickel. She won the copper purity about 96%, as sales and product
solution containing about 45 gl-1 Cu, 22.7 g.l-1 Zn and 22.2 gl-1 Ni in sulphate form.
Processing or deponácia this solution depends on the amount of processed contacts. One
option is electrolysis processing solution with the insoluble anode and the cathode copper is
excreted, followed by a concentrated solution of nickel sulphate and acquisition and zinc
sulphate.
2.2.2 Phase extraction of silver
In the second stage of technology (Fig. 1) is factored sludge from copper electrolysis, i.e. Ag-
anode electrolytic refined Nitrate in an electrolyte (an aqueous solution of AgNO3 + HNO3)
to give the silver cathode, which is melted and poured (ingots or granules). The fineness of
the silver smelting was 999.5 / 1000 Palladium is concentrated in the sludge and partially in
nitrate electrolyte. Model parameters are given silver electrolysis work Rabatin et al. [9].
Chemical composition of products from electrolytic refining of silver is given in Table 3
Table 3 Chemical composition of Ag electrolysis products [wt. % G. l-1]
Where:
E 1-1 Ag cathodes [wt. %]
F 1-1 Ag anode slime from electrolysis [wt. %]
G 1-1 Ag spent electrolyte [g. l-1]
H 1-1 Pd - Sponge [wt. %]
I 1-1 rafinated Pd - Sponge [wt. %]
The product of this phase of treatment contact is silver purity 99.95% as sales product in the
form of ingots or granules. Palladium in the anode sludge nakoncentrovalo and part remains
in the electrolyte. Palladium content in the electrolyte is continuously monitored and worn
electrolyte is processed cyclically. Selectively from it acquires AgCl paladičito ammonium
chloride and progressing to the third stage of technology.
2.2.3 Phase extraction of palladium
Technological scheme of processing of the anode sludge containing palladium from
electrolytic refining of silver is in Figure 2.
Fig.2 Technological flow sheet after extraction of Pd Ag electrolysis
Palladium dissolves sludge in hot Aqua Regia acid to form tetrachloropaladnatej (H2PdCl4)
according to the following reactions:
+ HNO3 = 3HCl NOCl + Cl2 + 2H2O (1)
Pd + 2 NOCl + Cl2 + 2H2O = H2PdCl4 + NO + NO2 + H2O (2)
The acid solution tetrachloropaladnatej selectively obtained palladium ammonium chloride
(NH4Cl) in the form of palladium chloride ammonium (NH4) 2PdCl4, which is soluble in
solution, according to the reaction:
H2PdCl4 + 2 NH4Cl + H2O = (NH4) 2PdCl4 + 2HCl + H2O (3)
Oxides of nitrogen present in the solution react with water to form nitric acid, which is a
medium strong acid. The solution is unstable and easily decomposes to nitric acid and nitrous
oxide by reactions 4 and 5 [10]:
NO + NO2 + H2O = 2 HNO2 (4)
3 HNO2 = HNO3 + 2 NO + H2O (5)
Palladium chloride ammonium is oxidized with sodium chloride in the presence of nitric acid
to the compound (NH4) 2PdCl6, which creates a deep red precipitate in this environment,
stable [3, 4, 6], according to the reaction:
(NH4) + 2PdCl4 4HNO3 2NaCl + + H2O = (NH4) 2PdCl6 2NaNO3 + + 3H2O + 2NO2 (6)
The resulting red precipitate was filtered and washed with a concentrated solution of
ammonium chloride; the composition of the filtrate is continuously monitored and processed.
The content of palladium in the filtrate is 0.3 to 0.5 g.l-first after filtration and drying, the
precipitate (NH4) 2PdCl6, annealed in air atmosphere at 650 ° C, which occurs by the
decomposition reaction:
(NH4) 2PdCl6 + O2 = PdO2 NH4Cl + 2 + 2 Cl2 (7)
Retrieved paladičitý oxide was subsequently reduced at 1000 ° C in a stream of hydrogen; the
product is Pd-sponge and water vapor, according to the reaction:
PdO2 + 2 H2 = Pd + 2 H2O (8)
Table 3 is the chemical composition of the obtained Pd-mushrooms, respectively. After one-
stage refining. Purity Pd-fungi increased from about 95% to 99.75% purity. Palladium sponge
having purity above 99% is selling product. If the requirements of higher purity can be
repeated chemical refining. Pd-up can be rewarded in a vacuum induction furnace or in a
protective atmosphere and cast into ingots.

3. CONCLUSION
The present paper includes a proposal technology for processing electrical scrap containing
silver and palladium. The technology was tested at approximately 2000 g sample of separated
contacts, and won the silver metal of purity 99.95% Ag with 82% efficiency and palladium
sponge having a purity 99.75% Pd with 95% efficiency. As a by-product to obtain cathode
copper of purity 96.06% Cu, with effect 76%. This efficiency is calculated on the amount of
metal acquired marketable products, it should be noted that the efficiency of obtaining silver
and palladium, copper and possibly increasing the processing solutions and electrolytes from
the process. Silver from these solutions can be obtained by selective precipitation of AgCl,
which is filtered, dried and reducing melt with the addition of Na2CO3. Yielding metallic
silver purity min. 98%, this returns to the process of electrolytic refining of silver. In this
case, the silver collection efficiency increases to about 99%. Similarly, it is possible to
increase the efficiency of obtaining palladium when the technology to include additional
processing solutions with low content of palladium. Processing of these solutions is
economically and environmentally challenging, because it works with an alcohol solution
diacetyldioximu, respectively. with an alcohol solution dimethylglyoximu [4,6]. The
extraction of noble metals from solutions of the poor must pay more attention, given the
existence of large amounts of electronics scrap with low noble metal.
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