Acta Metallurgica Slovaca, 12, 2006, (235 - 241) 235

THE STUDY OF POSSIBILITIES OF SELECTIVE RECOVERY OF PALLADIUM (II)

FROM CHLORIDES SOLUTIONS BY ION EXCHANGE RESIN LEWATIT TP 214

Labošová L., Štofková M., Kračúnovská J.

Technical University of Košice, Faculty of Metallurgy, Department of Non-ferrous Metals and
Waste Treatment, Slovakia, e-mail: lenka.labosova@tuke.sk, magdalena.stofkova@tuke.sk

ŠTÚDIUM MOŽNOSTÍ SELEKTÍVNEHO ZÍSKAVANIA PALÁDIA (II)

Z CHLORIDOVÝCH ROZTOKOV POMOCOU IÓNOMENIČA LEWATIT TP 214

Labošová L., Štofková M., Kračúnovská J.

Technická univerzita v Košiciach, Hutnícka fakulta, Katedra neželezných kovov a spracovania
odpadov, e-mail: lenka.labosova@tuke.sk, magdalena.stofkova@tuke.sk

Abstrakt
V tejto práci sa študovala sorpcia paládia na makroporézny iónomenič chelátového
typu Lewatit TP 214 a vplyv zinku a medi na jeho sorpciu. Sorpcia bola uskutočnená zo
syntetických chloridových roztokov. Účinnosť sorpcie Pd (II) dosahovala 99%, Zn (II) 6 – 44 %
a Cu (II) 42 – 100% v závislosti od koncentrácie kovu v roztoku. Ako elučné činidlá pre elúciu
Zn (II) bola použitá kyselina sírová, okyslená tiomočovina a kyselina dusičná o rôznych
koncentráciách. Najvyššiu účinnosť elúcie zinku (63%) dosiahla 6M kyselina sírová.

Abstract
The sorption of Pd(II) on the macroporous chelating resin Lewatit TP 214 and
influence of Zn(II) and Cu(II) ions has been investigated. The results obtained in chloride media
showed adsorption for Pd (II) (99 %), for Zn (II) (6 – 44%) and for Cu (II) (42 - 100 %),
depending on metal concentration. Acidified thiourea, sulfuric acid and nitric acid at various
concentrations have been used for elution of Zn (II). The concentrated sulfuric acid (6M) being
the most effective one ( 63 %) for zinc elution.

Key words: ion exchange, Lewatit TP 214, Pd (II), Zn (II), Cu (II),

Introduction
Platinum group metals (PGM), include iridium, osmium, palladium, platinum,
rhodium and ruthenium, thanks to their rare properties have found many practical aplications in
different branch of industry. Early uses included crucibles, wires in incandescent lights, touch –
holes for flint – lock duns, sulfuric acid boilers, thermometers and contact points and wires for
telegraphs, in addition to decorative uses such as jewellery. Today, they are used for variety of
tools and vessels to produce glass products such as optical lenses and glas fibres, in fuel cell
technology, in stomatology and medicine, jewellery, etc. They found the largest aplication as
catalyst that reduce emmisions from automobiles (chiefly Pd, Pt and Rh). Today approximately
400 tones of PGMs are produced around the world each year [1].
The limited world sources, low contents of PMG in ores and high cost of their
recovery become serious problem and have led to the development of new processes for the
recovery of these metals from the spent materials. There is a need for new processes specially
Acta Metallurgica Slovaca, 12, 2006, (235 - 241) 236

focused on the recovery of these metals from waste treatment solution and diluted acid solutions
such as those resulting from mining and treatment activities or exhausted leaching liquors.
Classical lixiviation process with aqua regia produce solutions containing chlorocomplexes of
PGMs as well as base metals[2]
Several methods are aviable for the concentration nad separation of PGMs. The
traditional method for the preconcentration and recovery of platinum group metals from natural,
technological and waste solutions is liquid – liquid extraction. Despite its high selectivity, liquid
– liquid extraction has some major disadvantages (large amounts of solvents which are usually
toxic).
The sorption methods are widely used and they are the most effective at very low
metal concentration. Among the different types of sorbents, synthetic ion exchange resins have
substantial advantages, such as high selectivity, good kinetic properties and convenient form of
use: granules, powders, fibres, filters, etc. Majority of these resins are based on organic matrics
with chemically bound functional groups which can form coordination bonds or chelate
complexes with metal ions.
This article is considered with the possibilities of palladium, zinc and copper sorption
on resin Lewatit TP 214 and with elution of zinc, as one of the base metals occuring with PGMs
in waste solutions.
There have been several studies on the extraction of PGMs using ion exchange resins.
PGMs were preconcentrated and separated by commercional macroporous resin Duolite GT – 73
(Supelco) with a crosslinked polystyrene matrix bearing – SH groups [3], chelating resin
Amberilte IRC 718 [4], vinylparidine resins AN – 251M, ANKF – 5, VP – 14K [5], Duolite ED
– 465 [6], chitosan derivates [7] and functionalized copolymers [8].
The recovery of PGMs require their separation from other metals. Crucial point
becomes selective elution of metals from resins. There have been used different conditions and
solutions for elution of PGMs from sorbents.
Acidified thiourea, sodium thiocyanate and hydrochloric acid solution were used for
the elution of Pd (II) from Duolite GT – 73 [3]. Separate metal elution in column system can be
achieved by passing, firstly a sodium nitrate 2M solution with can elute palladium[9]. A second
elution with thiourea permits the total recovery of remaining base metals ions.
Since elution of ions from resins is the reverse of sorption, chemical and physical
factors that inhibit sorption will enhance elution and conversely those that enhance adsorption
will inhibit elution. Although elution can be enhanced by increasing the temperature or by using
stronger extractants, these measures may not be effective. For this reason the use of ultrasonics
has been investigated as a method for intensify elution process [10].
As mentioned in the introduction, PGMs are in solutions present together with
number of base metals, Zn, Cu, Ni, Fe, Al, etc. It’s necessary to treat waste water and launder
separation process water with content of palladium and base metals because of obtain of
expensive palladium (320 $/oz ) and remove of base metals because of environmental point of
view. The content of 0,01 – 1 mg/ml of Pd (II) and severalfold higher content of base metals is
characteristics for industrial effluents. Copper and zinc as one of the most often occuring base
metals in this type of solutions have been chosen for this work.
The aim of this work was to study the influence of Zn (II) and Cu (II) concentration
on Pd (II) sorption from chlorides solutions with high content of palladium and low content of
zinc and copper. The task was to find optimal operating condition for selective recovery of
palladium.
Acta Metallurgica Slovaca, 12, 2006, (235 - 241) 237

Exeperimental
Lewatit TP 214 monospherical, macroporous chelating resin has been used for study.
This resin was developed in Bayer company for removal of mercury from waste water
[Lewatit].

Fig.1 Lewatit TP 214

Table 1 Typical physical and chemical characteristics of Lewatit TP 214 resin [11]
Matrix crosslinked polystyrene
Functional group thiourea
Ionic form Na+
Moisture retention 43 – 48 %
Bead size 0,55 (+/- 0,05) mm
Total exchange capacity* 2 eq/l
Maximum operating temperature 80 °C
Operating pH range 0 - 10
*These data are specification values and are subject to continous monitoring

The batch method has been choosen as operating method. Experiments have been
realised with synthetics solutions with concentrations of metals correspond to the content in
actual solutions (Tab.2).
Table 2 Concentrations of metals in solutions
[Pd] mg/ml 0.01 0.05 0.1 0.25 0.5
[Zn] mg/ml 0.5 1 1.5 2.5 3
[Cu] mg/ml 0.5 1 1.5 2.5 3

All the sorption and elution experiments were conducted at an ambient temperature of
about 20 °C. Solutions were prepared with distilled water and all the used chemicals were of
analytical reagent grade. The Pd (II), Zn (II) and Cu (II) stock solutions were prepared by
dissolving of their chlorides salts in 2M HCl solution .
Sorption of Pd (II), Zn (II) and Cu (II) on the macroporous resin was studiet by the
batch method. Samples of 2 ml of swelled resin was contacted with 25 ml of solution containing
desired amounts of A. Zn (II) B. Pd (II) and Zn (II)and C. Pd (II), Zn (II) and Cu (II). After 3 h
with incessant shaking in stoppered 150 ml glass flask, the phases were separated by filtration
and metals concentration in filtrate was determined by atomic absorption spectrometry.
Elution of Zn (II) was studiet by the batch method. Samples of resin bearing Zn (II)
ions were contacted with eluant solution in ratio 1:25. After 1h shaking in stoppered 150 ml
glass flask samples were treated as written above. The shaking frequency was for sorption and
elution process 140 cycles per minute.

Results and discussion

Static sorption of Pd(II), Zn (II) AND Cu (II)
Influence of metals concentration on sorption efficiency
Acta Metallurgica Slovaca, 12, 2006, (235 - 241) 238

Synthetics monocomponent solutions have been used for experiments. The results
show Figures 2, 3 and 4.

99,8

99,6

Efficiency [%]
99,4

99,2

99,0

98,8

98,6
0,0 0,1 0,2 0,3 0,4 0,5 0,6

Pd [mg/ml]
Fig.2 Efficiency of Pd (II) sorption as a function of metal concentration

100 100

80 80
Efficiency [%]

Efficiency [%]

60 60

40 40

20 20

0 0
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5

Zn [mg/ml] Cu [mg/ml]
Fig.3 Efficiency of Zn (II) sorption as a function of Fig.4 Efficiency of Cu (II) sorption as a function
metal concentration of metal concentration

As can be seen, the resin sorbs metals with different efficiency. Results support
selectivity for palladium sorption.

Static sorption of Pd(II) - Zn (II), Pd (II) - Cu (II) AND Pd (II) – Zn (II) – Cu (II)
Synthetics multicomponent solutions have been used for experiments. The results of
sorption from two and three component solutions show Figure 5, 6 and 7.
It was established that copper and zinc do not influence palladium sorption. The
efficiency of palladium sorption is in all concentrations in a range 98,8 – 99,8 %. It has been
observed that Zn (II) can be separate from palladium with efficiency of about 60 -95 % and Cu
(II) with efficiency 0 – 80%, depending on metals concentration ratio. Efficiency of separation
increase with concentration of copper and zinc.
Similar tendency of metals sorption has been established in a case of three component
solution (Fig. 8). The base metals copper and zinc do not influence palladium sorption which is
almost 100 % effective. At the highest concentration of copper and zinc metals has been
separated with the same efficiency (30%).
Acta Metallurgica Slovaca, 12, 2006, (235 - 241) 239

100 100

80 80

Efficiency [%]
Efficiency [%]

Pd Pd
60 60
Zn Zn

40 40

20 20

0 0
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5

Zn [mg/ml] Zn [mg/ml]

Fig.5 Influence of Zn(II) concentration on Pd Fig.6 Influence of Zn(II) concentration on Pd

(II) sorption of, [Pd] = 0,01mg/ml - (II) sorption , [Pd] = 0,01mg/ml -
constantly constantly

100
100
Pd
80
80 Cu
Efficiency [%]
Efficiency [%]

Zn
60
60

40
40

20 20

0 0
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5

Cu [mg/ml] Zn, Cu [mg/ml]

Fig.7 Influence of Zn(II) concentration on Pd (II) Fig.8 Influence of Zn(II) and Cu (II) concentration
sorption, [Pd] = 0,01mg/ml-constantly on Pd(II) sorption , [Pd] = 0,01mg/ml –
constantly

Static elution of Zn (II)

Previous results confirm the possibility of selective recovery of palladium over zinc
and copper. To the effect of higher selective separation of base metals from palladium, second
step of ion exchange, static elution has been realized.
Different eluant solutions have been tested for elution of Zn (II) (Fig. 9, Tab. 3, 4).
The effect of concentration was also tested on order to determinate the best reagents and the best
conditions for the elution of zinc from the resin.
70

60

50
Elution [%]

40

30

20

10

0
1M 2M 3M 4M 6M

H2SO4
Fig.9 Efficiency of Zn (II) elution (resin: eluant solution = 1:25)
Acta Metallurgica Slovaca, 12, 2006, (235 - 241) 240

Table 3 Efficiency of elution

Zn (II) eluted
Eluant solution resin : eluant solution
[%]
Thiourea 20g/l + 1M HCl 6,4
Thiourea 40g/l + 0,55M HCl 34,6
Thiourea 40g/l + 1M HCl 50,8
Thiourea 40g/l + 2M HCl 1:25 25,8
Thiourea 40g/l + 3M HCl 23,7
Thiourea 40g/l + 4M HCl 30

Table 4 Efficiency of elution

Zn (II) eluted
Eluant solution resin : eluant solution
[%]
HNO3 0,55M 10
HNO3 1M 19,25
HNO3 2M 1:25 24,1
HNO3 3M 42,32
HNO3 4M 23,4

The concentrated 6M sulfuric acid has been the most effective eluant with efficiency
65%. Acidiefied thiourea gives efficiency of Zn (II) elution 6.4 – 50,8 % and nitric acid 10 –
42,32 %, depending on concentration. Application of eluant solution that has been used is
necessary verify for elution of Pd (II) and Cu (II).

Aknowledgment
This work is supported by Ministry of Education of the Slovac republic under Grand
VEGA1/0397/03 and also 1/3221/06.

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Acta Metallurgica Slovaca, 12, 2006, (235 - 241) 241

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