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Solvent extraction of palladium from chloride

media by TBP
Article January 2015

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Nima Sadeghi

E. Keshavarz Alamdari

Sahand University of Technology

Amirkabir University of Technology

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Solvent extraction of Palladium from chloride media by TBP

Nima Sadeghi, Eskandar Keshavarz Alamdari
Department of Mining and Metallurgical engineering, Amirkabir university of Technology
(Tehran Polytecgnic), Tehran, Iran

Nima Sadeghi
Materials Engineering Faculty, Sahand university of Technology, Tabriz, Iran

Eskandar Keshavarz Alamdari

Research Center for Materials and Mining Industries Technology, Amirkabir University of
Technology, Tehran, Iran.
ABSTRACT
In recent years, precious metals production through hydrometallurgical process has been
attended; however the Low grade of metals is one of the main problems. Thus, solvent
extraction method was purposed for concentration and purification of aqueous solution. In this
study, Tri butyl phosphate (TBP) was used to PdCl 3 low concentrations of TBP could extract
Pd chloride ions. The Solution containing 180 mg /l Pd was extracted by 0.05-0.25 M TBP in
different HCl concentration. Increasing HCl concentration decreases Pd extraction percentage.
It seems that different chloride complexes formations cause the extraction percentage to
change in various HCl concentrations. The extracted macromolecule is determined PdCl 3.TBP.xH2O. HNO3 and NaCl has negative effect on Pd extraction.
Key words:, Solvent extraction, Palladium, TBP, Chloride media
1 INTRODUCTION
In recent years, consumption of palladium
has grown; in addition, this has extensive use
in jewellery, dentistry, electrical contacts,
Corrosion
resistant
apparatus,
and
biomedical devices. Thus there has been a
renewed interest in studying new approaches
for the recovery of this metal from raw and
secondary resources.
As we know, PGM (Platinum Group
Metals) resources are restricted. For metal
recovery, palladium source (primary or
secondary) was leached in aqueous solution.
But Pd concentration, basically, is low and
the impurities (such as Fe, Cu, Ni, PGM and
etc.) are dissolved. Concentration and
purification of pregnant solution have been
done in various methods. Solid/liquid
(Carbon active and ion exchange resin) and

liquid/liquid methods were proposed for Pd

ionic species transferring. Among them,
solvent extraction of Pd has been applied in
many cases to extract palladium from
aqueous hydrochloric acid solutions (Rane
and Gopal, 2006, Rovira et al., 1999,
Bendekar and dhadke, 1998).
Oximes (Shen and Xue, 2007) ,
phosphoric acids (Bendekar and Dhadke,
1998), phosphonic acid (Bendekar and
dhadke, 1998) and thiophosphinic acid
(Kakio and Goto, 1994) are the popular Pd
extractants from chloride media. Also, Lee
and et al. used Tri butyl phosphate (TBP) for
Pd extraction from chloride leach liquors of
spent automobile catalyst.
In the present work, extraction mechanism
of palladium from chloride solutions by TBP
is evaluated as well as the effect of pertinent
parameters, namely as HCl, NaCl and TBP

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Inter na tiona l Mining Congr ess a nd Exhibition Of Tur key(IMCET)

concentrations, on the extraction process that

are identified. Slope analysis method is
employed to clarify extraction mechanism of
palladium with TBP diluted in kerosene.
2 MATERIAL AND METHODS
Commercial tri-n-butyl phosphate (TBP
Fluka) as extractant and kerosene (Isfahan
Refinery Co) as diluents were utilized.
Hydrochloric acid (35%-37%vol) was
obtained from Dr. Mojallali chemical
laboratories in Iran. Also, Palladium ions
were prepared by the standard metal chloride
(PdCl, MERCK). Initially, kerosene was
purified being washed by 3M HC1 solution
then diluted with TBP. Palladium chloride
was diluted by HCl and distilled water in
different ratios. Batch experiments were
carried out in a flask containing equal
volumes (20 ml) of aqueous and organic
solutions. The mixture was agitated at
constant temperature (20 C) by a mechanical
shaker at 400 rpm. Agitation was carried out
for 30 min to assure equilibrium conditions
then agitated samples were poured in a
separating funnel for 15 min to allow
complete separation of the two phases. The
metal content of the aqueous phase was
determined
by
atomic
absorption
spectroscopy (varian, A240) and chemical
composition of the organic phase was
determined by mass balance calculations.
3 RESULTS AND DISCUSSION
3.1 Effect of HCl Concentration
Fig 1 illustrates the influence of
HC1concentration on palladium extraction
by TBP diluted in kerosene. As shown,
extractant concentration increased Pd
extraction percentage but an increase in
hydrochloric acid concentration leads to
lower extraction percentage.
Previous report [Alamdari et al., 2011],
shows that the mechanism of metallic
complexes extraction by TBP involves an ion

Fig 1: The influence of HCl and TBP

concentrations on palladium extraction
percentage

association process in which the protonation

of TBP molecules by H (H3O+), brings the
extraction ability for TBP to extract anionic
species. But in this case, increasing acid
concentration (or pH decreasing) leads to
negative effect on Pd extraction. It seems
that presence of acidic ions (H+ or Cl-) in
solution reduces Pd extraction.
3.2 Effect of Chloride Salts on Pd
Extraction
For a closer look at the anionic chloride
complexes formation, the chloride salt
(NaCl) was added to solution at constant acid
concentration.
Increasing
charged
components in aqueous media may change
chloride complex species and metal
extraction percentage.
Fig 2 shows the results obtained from
experiments carried out with organic
solutions of 0.25 M TBP in kerosene and
aqueous solutions which contained 0.1 M
HCl and various concentrations of NaCl. It
can be seen that the palladium efficiency
decreases with an increasing NaCl
concentration. By integrating the results of
Figs 1 and 2 can be concluded that chloride
ions have significant on palladium
complexes formation.

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Inter na tiona l Mining Congr ess a nd Exhibition Of Tur key(IMCET)

reported UV absorption peaks occurring on

210 and 240 nm. In a later report (Elding,
1972), they were defined as PdCl3- wave
length. Boily and coworkers have carried out
a comprehensive study on palladium chloride
formation at different condition. They
reported PdCl3-was formed in low HCl/Pd
(II) ratio, but palladium complexes changes
with HCl concentration increase, as UV
peaks were formed at 220 280 nm. These
wave lengths were known as PdCl42Characteristic peaks.
3.4 Effect of Extractant Concentration on
Pd Extraction

Fig 2: influence of NaCl concentration on

extraction percentage by 0.25 M TBP in
kerosene

3.3 Stability of Palladium

Complexes in Aqueous Media

Chloride

Reliable thermodynamic data on Pd-Cl

system make it possible to predict palladium
complexes stability. In aqueous solutions
containing theCl- ion, Pdchloride forms
complexes of the composition [PdCln]2n
(Polotnyanko and Khodakovskii, 2014).
This work, mechanism of palladium
chloride salt dissolution was assumed eq. 1
to eq.3:
Ksp 3 10-12(1)
PdCl 2 (S) PdCl 2 (aq )
PdCl 2 (s) Cl _ PdCl3_

(aq )

Ksp0.6

To make a better understanding of palladium

extraction, extraction efficiency in different
TBP concentration and constant HCl has
been shown in Fig 3. At lower HCl
concentration, TPB concentration increase
leads to increasing causes to higher
extraction percentage. But TBP does not
affect on extraction percentage at higher HCl
concentration.
PdCl3-, that forms low acid concentration,
was extracted by TBP, efficiently. But PdCl4couldnt be extracted by TBP, significantly.
Hence, different extraction mechanisms
should be assumed for palladium complexes.

(2)

PdCl3-+ Cl- PdCl42Ksp36.2

(3)
As can be seen, PdCl2 can't dissolve in
distilled water, significantly. But palladium
chloride solubility increased when low
amount of hydrochloride acid was added to
the system. In this case PdCl3- is the main
chloride complex. By adding further amount
of acid, palladium chloride complexes are
altered, again. Hence, PdCl3- and PdCl42- are
known as the main palladium chloride
complexes.
UV-visible spectrophotometry can be used
for palladium complexes detection. Biryukov
and Shlenskaya conducted spectrophotometric
studies of chloro palladate (II) at 25 and
I = 0.261.01 m in the UV regions. They

Fig 3: effect of TBP concentration on Pd

extraction percentage at constant HCl
concentration and [Pd]=180 mg/l

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3.5 Palladium Extraction Mechanism

The extraction reaction of Pd via TBP can be
represented by Eq.4.
[PdCl]nn-2 +H++H2O + nTBP = PdCln2-n.H.H2OnTBP (4)

and the corresponding equilibrium constant

is:
K=

HPdCl2 n .TBP.H o [HPdCl m

.nT BP.H 2 O]org
n
n

n
n
H + [H ] PdCl2 n [PdCl m
n ] TBP[T BP] a H2O

(5)

where
brackets
stand
represent
concentrations, and stands for activities
coefficient. Since TBP concentration is
varied in a specific range, TBP may be
considered
constant.
Beside,
our
observations indicate that pH variation in
given HCl concentration is negligible, and
2-n
H is also constant. Furthermore, PdCln is
in dilute (trace) concentration, the
concentrations of two palladium solutes in
aqueous and organic phases are very low in
which PdCl2n and HPdCl2n .nTBP can be
n
n
constant (Henry behaviour). So, product of
all the constant coefficients was represented
as Q.
Regarding the definition of distribution
coefficient (D= [Au]org / [Au]aq) as well
asEq. (5), can be written as:
K=Q.D.[TBP]n
(6)
Taking logarithm of Eq (6) leads to:
logK=logQ +logD + nlog[TBP]
(7)
At constant temperature, K and Q dont
change, so just logD and log TBP are
variable this equation. The plot of log D vs.
[TBP] yields a straight-line with slope n.
Such plots are depicted in Fig 4; the slopes
are estimated in the range 0.86 to 1. As be
shown in Fig 3, an increase in HCl
concentration decreases Pd extraction
percentage. Hence, PdCl42- is not extracted
by TBP. In the other hand, PdCl3-and TBP
significantly react with each other. So, the
extraction mechanism of was rewritten as eq.
7:
[PdCl]3- +H+ +H2O + TBP = PdCl3-.H.H2O.TBP (7)

Fig 4. Variation logD of palladium vs.

log[TBP] (Pd=180 mg/l)

3.6 Effect of Nitric Acid Concentration on

Pd Extraction
Since the use of nitric acid in the chloride
leaching of palladium bearing sources is a
conventional issue, the effect of NaCl on the
extraction efficiency of palladium was
evaluated. As observed in Fig 5, HNO3 have
a negative effect on the extraction percentage
of palladium. It seems that an increase of H+
and NO3- ions solution leads to the extraction
by TBP and he sit position on TBP
molecules has decreased. Hence, the
extraction percentage has been reduced.

Fig 5: effect of HNO3concentration on Pd

extraction percentage at 0.1 M HCl and
[Pd]=180 mg/l

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Inter na tiona l Mining Congr ess a nd Exhibition Of Tur key(IMCET)

4. Conclusion
1. Based on the obtained results, it was
shown that the commercially available
tributyl Phosphate (TBP) is an appropriate
extractant for the recovery of palladium
from low acidic solution.
2. Hydrochloride acid and chloride salts have
negative effect on palladium extraction.
3. Presence of nitric acid decreases the Pd
extraction percentage due to simultaneous
extraction.
4. In the aqueous media stable complexes of
palladium there are PdCl3- and PdCl42-,
that TBP could extract PdCl3-.
5. The organo-metallic complex of Au and
TBP is proposed as HPdC13L. H2O where
represents the extractant molecule.
References
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palladium (II) and platinum(IV)using LIX 84I,
Hydrometallurgy 84 (2006) 5459.

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