Separation and Purification Technology 53 (2007) 337341

Short communication

Selective extraction of palladium(II) from hydrochloric acid solutions

with pyridinecarboxamides and ACORGACLX50
Magdalena Regel-Rosocka a, , Maciej Wisniewski a , Aleksandra Borowiak-Resterna a ,
Anna Cieszynska a , Ana M. Sastre b
a

Institute of Chemical Engineering and Technology, Poznan University of Technology,

pl. M. Sklodowskiej-Curie 2, 60-965 Poznan, Poland
b Department of Chemical Engineering, Universitat Polit
ecnica de Catalunya,
E.T.S.E.I.B., Diagonal 647, 08028 Barcelona, Spain

Received 24 February 2006; received in revised form 11 August 2006; accepted 14 August 2006

Abstract
The selectivity of Pd(II) extraction over Pt(IV), Pb(II), Cu(II) and Fe(III) with N-dodecylpyridine-3-carboxamide (3-C12 ) and N-dodecylpyridine4-carboxamide (4-C12 ) is very high, compared with the commercial chelating extractant ACORGA CLX50; therefore, these pyridinecarboxamides
can be considered as effective extractants for Pd(II) separation from hydrochloric acid solutions. Over 90% of palladium(II) can be effectively
extracted with 3-C12 and 4-C12 in the presence of Pb(II), Cu(II) or Fe(III) over the studied HCl concentration range. While merely up to 5% of
the other metal is transported to the organic phase. Pd(II) can be separated from Pt(IV) efficiently at low HCl concentration. ACORGA CLX50
indicates a much lower extraction than do pyridinecarboxamides in the same time range. The effect of the presence of NaCl is negligible. Extraction
in a system with addition of NaCl is slightly lower than without the electrolyte.
2006 Elsevier B.V. All rights reserved.
Keywords: Pyridinecarboxamides; ACORGA CLX50; Palladium(II) extraction; Hydrochloric acid

1. Introduction
Nowadays, a huge demand for platinum group metals
(PGM), such as palladium(II), platinum(IV), iridium(IV), ruthenium(III), etc., as catalysts in organic processes and value added
components in metal alloys is noted [1]. A gap between demand
and natural sources potential must be replenished by recycling
spent materials containing these metals.
Solvent extraction is a very suitable method for metal recovery from low concentrated sources. Thus, a growing interest
in searching for effective and selective extractants of particular PGMs is observed. Several extractants have been proposed,
including hydroxyoximes [2,3], dialkyl sulphides [4,5], alkyl
derivatives of 8-hydroxyquinoline [6,7], hydrophobic amines
[8,9], esters of pyridine-carboxylic acids [10], trialkylphosphine
oxides and organophosphoric acids [11].

Corresponding author. Tel.: +48 61 665 37 71; fax: +48 61 665 36 49.
E-mail address: magdalena.regel@put.poznan.pl (M. Regel-Rosocka).

1383-5866/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.08.005

Palladium(II) extraction is a very slow process due to

both the nature of symmetrical palladium(II) chlorocomplex
(PdCl4 2 ) and high hydrophobicity of the extractants, dialkyl
sulphides [5] in particular. Looking for an extractant enabling
fast extraction of palladium(II), the authors have used various pyridinecarboxamides, that have been synthesized by them
and their use as copper(II) extractants was reported previously [12,13]. The pyridinecarboxamides have been examined as extractants of palladium(II) from hydrochloric acid
solutions, too [14]. It has been found that the extraction of
Pd(II) with monoalkylpyridinecarboxamides depends upon the
number, length and position of the alkylamide group. What
is the most important, extraction with N-dodecylpyridine-3carboxamide (3-C12 ) and N-dodecylpyridine-4-carboxamide (4C12 ) is efficient (Eex = 100%) and rapid; the equilibrium is
achieved in 3060 s. The phenomenon can be explained by
protonation of the reagent and phase transfer catalysis. Depending on HCl concentration, various palladium(II) species are
extracted. At 0.1 mol dm3 HCl PdCl2 L2 (where L denotes
pyridinecarboxamide) and at 3 mol dm3 HCl (HL+ )2 PdCl4 2
complexes have been determined spectrophotometrically. Thus,

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M. Regel-Rosocka et al. / Separation and Purication Technology 53 (2007) 337341

N-dodecylpyridine-3-carboxamide and N-dodecylpyridine-4carboxamide seem to be a prospective and efficient extractants

of palladium(II). From this point of view, it is very important to
examine the selectivity of palladium(II) extraction in the presence of other metals that accompany it in real solutions [1517].
Here, we report our selectivity studies on new palladium(II)
extractants over platinum(IV), copper(II), lead(II) and iron(III)
from hydrochloric acid solutions.

inductively coupled plasma spectroscopy (ICP, Spectro, Analytical Instruments, Germany) were used for determination of
metal concentrations at the wave length 340.5, 265.9, 217.0,
324.8 and 248.3 nm for Pd(II), Pt(IV), Pb(II), Cu(II) and Fe(III),
respectively.
Percentage of extraction (%E) was calculated from the contents of metal ions in the aqueous phases before (C0 ) and after
(C) extraction:

2. Experimental

%E =

Two pure individual monoalkylamides and the commercial reagent ACORGA CLX50 were used as extractants. Their
structures are presented in Table 1.
Synthesis, purity, structures and analytical data were described in previous papers [12,13]. The analytical and physicochemical data for the studied extractants were presented
[14]. ACORGA CLX50 (Zeneca Specialties, UK) contains
0.5 mol dm3 of active extractant.
Extraction has been carried out in a typical way with
5 mM solutions of N-alkylpyridinecarboxamides or ACORGA
CLX50 in toluene. Equal volumes (5 cm3 ) of phases were
mechanically shaken in glass tubes, then left to stand to effect
separation.
Since palladium recovery from automotive catalysts is an
important issue, the authors have decided to choose some metal
cations accompanying Pd(II), i.e. Pt(IV), Cu(II), Fe(III), Pb(II).
Equimolar aqueous feeds, containing 2.5 103 mol dm3 of
each of two metals: palladium(II) and platinum(IV), or lead(II)
or copper(II) or iron(III), added as chlorides in 0.13 mol dm3
HCl or 5 103 mol dm3 of individual metals in 0.1 mol dm3
HCl were mechanically shaken for a period of time between 30 s
and 50 min at a room temperature and left to stand for phase separation. The effect of the presence of NaCl on the extraction of
the studied metal species has been investigated. Atomic absorption spectroscopy (AAS, Varian Spectr AA-640, Australia) or

assuming that the volumes of phases did not change. This

assumption was valid.
The Medusa program [18] was used to simulate the distribution of metal chlorocomplexes in the aqueous feed at three
different ionic strength values (I). The values of I equal to 0.12;
0.62 and 3.02 refer to the feed containing 2.5 103 mol dm3
of each of two metals, 0.1 mol dm3 HCl; 0.1 mol dm3 HCl
and 0.5 mol dm3 NaCl and 3 mol dm3 HCl, respectively. The
program calculates the equilibrium composition of a required
system based on the Pitzer models and Specific Ion Interaction
Theory.

Table 1
Structures of extractants used

N-Dodecylpyridine-3-carboxamide (3-C12 )

C0 C
100
C0

(1)

3. Results and discussion

Extraction of the studied species depends on their form in
the aqueous phase. The distribution of metal chlorocomplexes
changes with the increase in hydrochloric acid concentration.
Distribution of Pd(II), Pb(II), Cu(II) and Fe(III) is presented
in Table 2. With increasing acid concentration a molar fraction of anionic chlorocomplexes increases. In case of palladium(II) the predominant species in 3 mol dm3 HCl is likely
to be PdCl4 2 . Pb(II), Cu(II) and Fe(III) are present mostly as
cationic and neutral species, even at high acid concentration.
Few stability constants were found for Pt(IV) chlorocomplexes
and they varied significantly from each other. Based on a stability constant of the sixth chlorocomplex (K6 ) given by some
authors as the only one [19], we assumed that Pt(IV) exists
mainly in the form of PtCl6 2 , even at low chloride concentration. The results presented below confirm correctness of this
approach.
For Pd(II), the extraction with pyridinecarboxamide (L) from
acidic media can be described as follows [14]:
at 0.1 mol dm3 HCl

PdCl2
4(w) + 2L(o) = PdCl2 L2(o) + 2Cl(w)

N-Dodecylpyridine-4-carboxamide (4-C12 )

at 3 mol dm3 HCl

2

+
PdCl2
4(w) + 2HCl(w) + 2L(o) = (HL )2 PdCl4(o) + 2Cl(w)

Diisodecyl pyridine-3,5-dicarboxylate
(ACORGA CLX50)

(2)

(3)

where the subscripts w, o stand for aqueous and organic phase,

respectively.
In the presence of other metals, the behavior of Pd(II) may
differ from that in the single metal system. However, extraction
percentages, presented in Table 3 indicate that Pd(II) extraction
is very effective in the presence of each additional metal. In

x, molar fraction.

PdCl6 4 (x = 0.46), PdCl4 2 (x = 0.34),

PdCl5 3 (x = 0.2)
3.0

3.02

CuCl+ (x = 0.62), Cu2+ (x = 0.23),

CuCl2 (x = 0.15)
CuCl+ (x = 0.4), Cu2+ (x = 0.29),
CuCl2 (x = 0.28), CuCl3 (x = 0.03)
PbCl+ (x = 0.49), PbCl2 (x = 0.21), Pb2+ (x = 0.12),
PbCl3 (x = 0.1), PbCl4 2 (x = 0.08)
PbCl4 2 (x = 0.82), PbCl3 (x = 0.11), PbCl2 (x = 0.07)
PdCl4 2 (x = 0.95), PdCl5 3 (x = 0.05)
0.62
0.1

339

general, extraction of Pt(IV), Pb(II), Cu(II) or Fe(III) is lower

than the observed for Pd(II), and in each case the differences
are one order of magnitude lower for both 3-C12 and 4-C12 .
ACORGA CLX50 indicates a much lower extraction than do
pyridinecarboxamides in the same time range (20 min). Lower
basicity of pyridine nitrogen caused by the presence of two
electron-attracting ester groups in ACORGA CLX50 structure,
is the reason for its lower extractive power, compared with
pyridinecarboxamides.
Results presented in Table 4 indicate that the behavior of
Pb(II), Cu(II) and Fe(III) in individual-metal-solutions is similar comparing to a mixture. The only exception is observed in
case of Pt(IV). The extraction from individual-Pt(IV)-solution
exceeds 90% for 3-C12 and equals almost 100% for 4-C12 . The
extraction of Pd(II) in comparison with the mixture of two metal
cations is higher and amounts to 100% for both extractants
(Table 4). In individual-metal-solutions no competition occurs
and both Pd(II) and Pt(IV) are extracted efficiently.
Selectivity (SPd/M ), defined as the ratio of distribution ratios
of Pd(II) and another metal, depends on the concentration of
hydrochloric acid, as shown in Fig. 1. The worst Pd(II) separation is obtained in the presence of Pt(IV). Selectivity is
below 1.5 over the whole studied range of HCl concentration,
and it decreases with increasing initial concentration of the
acid. Such a phenomenon is attributable to the formation of
PtCl6 2 anion (enhanced by HCl), competitive with PdCl4 2
in the extraction reaction. The tendency for the PGM chlorocomplexes to form ion pairs at low pH with anion exchangers
(e.g. protonated pyridinecarboxamides) changes in the following order: [MCl6 2 ] > [MCl4 2 ]  [MCl6 3 ] [20]. Our data for
Pd(II)Pt(IV) extraction are consistent with this theory. The
higher HCl concentration in the feed solution the stronger protonation of pyridinecarboxamide and better extraction of Pt(IV).
Thus, to selectively separate Pd(II) from Pt(IV), low acid concentration in the aqueous phase is recommended. A similar
trend is observed for other metal systems. However, selectivity of Pd(II) extraction over Pb(II) or Cu(II), or Fe(III) is much
higher than that for the system Pd(II)Pt(IV). Over 90% of palladium(II) can be effectively extracted in the presence of Pb(II),

Fe3+ (x = 0.61), FeCl2 + (x = 0.34),

FeCl2 + (x = 0.05)
FeCl2 + (x = 0.43), Fe3+ (x = 0.38),
FeCl2+ (x = 0.19)
FeCl2 + (x = 0.47), FeCl2+ (x = 0.32),
Fe3+ (x = 0.12), FeCl3 (x = 0.09)
Cu2+ (x = 0.88), CuCl+ (x = 0.12)
PbCl+ (x = 0.52), Pb2+ (x = 0.41), PbCl2 (x = 0.07)
PtCl4 2 (x = 1)
0.12
0.1

Lead(II)
Palladium(II)
I
HCl
(mol dm3 )

Table 2
Species of Pd(II), Pb(II), Cu(II) and Fe(III) found in chloride media according to theoretical calculations [18]

Copper(II)

Iron(III)

M. Regel-Rosocka et al. / Separation and Purication Technology 53 (2007) 337341

Fig. 1. Selectivity of palladium(II) extraction with 4-C12 from aqueous solutions at various concentrations of hydrochloric acid in the presence of: ()
Pd(II)Pt(IV); () Pd(II)Pb(II); () Pd(II)Cu(II); () Pd(II)Fe(III); M
denotes Pt(IV), or Pb(II), or Cu(II), or Fe(III).

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M. Regel-Rosocka et al. / Separation and Purication Technology 53 (2007) 337341

Table 3
Percentage of extraction of Pd(II), Pt(IV), Pb(II), Cu(II) and Fe(III) in a system comprising an extractant and an aqueous phase containing two metals
Extractant

NaCl (mol dm3 )

EPd (EPt )

EPd (EPb )

3-C12

0
0.5

90.0 (5.0)
82.2 (6.3)

97.0 (2.0)
88.9 (4.5)

97.5 (3.9)
90.8 (0.0)

94.5 (2.4)
93.3 (1.3)

4-C12

0
0.5

98.0 (10.1)
81.0 (11.7)

98.9 (0.2)
93.1 (0.25)

101 (8.9)
92.1 (3.3)

99.4 (1.0)
96.0 (1.3)

ACORGA CLX50

0
0.5

32.9 (6.7)
9.3 (7.3)

18.7 (3.1)
3.4 (3.2)

19.1 (1.6)
7.6 (0.14)

31.8 (1.2)
5.6 (1.3)

EPd (ECu )

EPd (EFe )

Aqueous feed: 2.5 103 mol dm3 Pd(II), 2.5 103 mol dm3 Pt(IV) or Pb(II), or Cu(II), or Fe(III), 0.1 M HCl, 0 or 0.5 mol dm3 NaCl; extractant:
5 103 mol dm3 3-C12 or 4-C12 , or ACORGA CLX50 in toluene; w/o = 1:1.

Table 4
Percentage of extraction of Pd(II), Pt(IV), Pb(II), Cu(II) and Fe(III) in a system
comprising an extractant and an aqueous phase containing one metal
Extractant

EPd

EPt

EPb

ECu

EFe

3-C12
4-C12

100
101

90.2
99.2

2.73
4.55

5.09
3.27

4.00
4.00

Aqueous feed: 5 103 mol dm3 Pd(II) or Pt(IV), or Pb(II), or Cu(II), or

Fe(III), 0.1 M HCl, extractant: 5 103 mol dm3 3-C12 or 4-C12 in toluene;
w/o = 1:1.

Cu(II) or Fe(III) over the studied HCl concentration range. While

merely up to 5% of the other metal is transported to the organic
phase due to predominance of cationic species in the feed solution.
The effect of the presence of NaCl is negligible. Extraction
of Pd(II) in a system with addition of NaCl is slightly lower
than this without the electrolyte. It is consistent with Eq. (3):
while chloride concentration increases, the equilibrium of the
extraction reaction is left shifted.
4. Conclusions
The results presented here provide evidence for high
Pd(II) selectivity over Pt(IV) and Pb(II), Cu(II), Fe(III) with
N-dodecylpyridine-3-carboxamide and N-dodecylpyridine-4carboxamide. The studied pyridinecarboxamides can be successfully applied to Pd(II) extraction from acidic media not only
due to fast kinetics of extraction but because of their selectivities with regard to palladium(II). Calculated distribution of metal
chlorocomplexes in the studied systems enhances the observed
results of extraction.
We are currently investigating selectivity in additional systems: Pd(II)Ru(III) and Pd(II)Rh(III). At the same time, Additional studies are also required to find out whether the metal ions
can be effectively stripped from the two pyridinecarboxamides.
Acknowledgements
This work was supported by the grant No. 32-139/06 DS.
M. Regel-Rosocka is a beneficiary of the Foundation for Polish
Science (FNP) domestic grant for young scientists in 2005 and
2006.

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