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Applied Catalysis A: General 301 (2006) 182186

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Recovery and separation of palladium from spent catalyst


M.A. Barakat *, M.H.H. Mahmoud, Y.S. Mahrous
Central Metallurgical R & D Institute, P.O. Box 87, Helwan 11421, Cairo, Egypt
Received 20 July 2005; received in revised form 28 October 2005; accepted 30 November 2005
Available online 23 January 2006

Abstract
An efficient and complete separation of precious metals from the containing secondary materials has a vital economic impact. Palladium loaded
on alumina support is usually used as a catalyst in fertilizers industry where the recovery of the metals from the spent catalyst is practically
important. Palladium was partially dissolved from the spent catalyst in hot concentrated hydrochloric acid where a large amount of aluminum is
also dissolved. The main objective of this work is to find out the optimum conditions for efficient and clean dissolution of palladium with minimum
attack to the alumina carrier. Palladium can form different soluble chloro-complexes which can enhance the dissolution process if an oxidizing
agent is added. A small amount of hydrogen peroxide could greatly improve the dissolution of palladium in dilute hydrochloric acid while the
alumina support was left nearly unaffected. Complete dissolution of palladium was achieved by leaching with a solution contains 7% HCl and 5%
H2O2 at 60 8C for 2 h with a liquid/solid ratio of 10/1. The leach liquor contained 0.04% palladium and 0.5% aluminum and the filtered solids was a
pure aluminum rich residue. Palladium could be separated from the leach liquor by reduction with formic acid solution. Heating the solution
increased the efficiency of palladium reduction and also produced larger palladium particles those can be easily separated by filtration. Palladium
powder of 98% purity was produced with recovery efficiency >99%.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Palladium; Spent catalyst; Recovery; Separation

1. Introduction remained as sludge. However, this process requires a large


amount of reagents. In the second process; the noble metals are
Palladium has a vital importance in human life due to the extracted from the support by an acidic solution of an oxidant,
frequent increase in its demands in the different ordinary and leaving the bulk of the support. However, in most of these
advanced fields of industry such as: jewellery and ornaments, processes, g-alumina is partially dissolved and interfere with
electronics, telephone circuits, heat and corrosion resistance the precious metals. Processes based on heat treatment of the
apparatus, catalysts and dental alloys [14]. Due to its low spent catalyst to promote the transformation of the acid soluble
natural abundance, it is a trend in the world to recover and refine g-alumina to the acid insoluble a-alumina usually suffers from
Pd from different containing spent materials [57]. A critical low recovery of the precious metals. Most of the other processes
stage in the whole recovery procedure is the efficient and used for the dissolution of precious metals are based on
complete separation of Pd. Spent precious metal catalysts are aggressive reagents and sometimes high pressure leaching
usually consisted of a coat of the metal supported on g-alumina which are environmentally unsafe, highly corrosive and costly.
(which is frequently used as a support. Hydrometallurgical Unlike platinum group metals, Pd can be brought somewhat
techniques are common for recovery and separation of precious easily into solution. Different leaching mixtures [4,1117] such
metals from the spent catalysts. The processes are classified as HCl, H2SO4, or chloride salt, e.g., NaCl in the presence of
into support dissolution and noble metal dissolution [810]. In oxidizing agent, e.g., HNO3, Br2 or Cl2 have been used as
the first process; the support is dissolved with a non-oxidizing leachants for Pd. However, most of theses leachants cause an
acid or base where the noble metals are not dissolved and environmental pollution. As an instance, although palladium is
known to be easily soluble in concentrated nitric acid, this
method is not favorable due to the high cost of the acid and the
* Corresponding author. Tel.: +20 25010642; fax: +20 25010639. evolution of hazardous nitric oxides. In addition, after leaching,
E-mail address: mabarakat@gmail.com (M.A. Barakat). nitric acid should be repelled out of the solution completely
0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.11.028
M.A. Barakat et al. / Applied Catalysis A: General 301 (2006) 182186 183

prior to Pd separation. The highly oxidizing nature of the


remained nitric acid will prevent Pd reduction. Thus, an
alternative leaching process is necessary for Pd recovery.
Separation process of Pd from solution was carried out by
different techniques such as: reduction in phosphoric acid
solutions by formalin at 150 8C; reduction by aluminum
powder; or bioreduction [1823].
The aim of this work is to recover and separate pure Pd
from spent Pd/Al2O3 catalyst utilizing a clean and simple
technique. A mixture of dilute hydrochloric acid and
hydrogen peroxide was investigated for achieving the
optimum recovery of Pd. Formic acid was used to separate
Pd from the leaching liquor.

2. Experimental
Fig. 1. The flowsheet of the recovery and separation of palladium from the
2.1. Materials spent Pd/Al2O3 catalyst.

A sample of spent Pd/Al2O3 catalyst weighed 2 kg was solution was heated. Then, the solution was filtered off, and
provided by Kima Co. for fertilizers, Aswan, Egypt. The the produced Pd powder was dried and weighed to calculate
original catalyst was used for de-oxygenation during produc- the reduction efficiency. Also, the remained Pd in solution
tion of hydrogen. The spent catalyst was in the form of was analyzed for balance. Fig. 1 shows the flowsheet of
cylindrical pellets of alumina coated with a thin layer of selective recovery and separation of Pd from the spent Pd/
palladium. The pellets have a diameter of 2 mm and a length of Al2O3 catalyst.
3 mm.
2.4. Assay methods
2.2. Chemicals
One gram of the ground spent catalyst was subjected to X-
Hydrochloric acid (37%) and hydrogen peroxide (50%) ray analysis with Philips X-ray diffractometer model PW/1710
were used for the preparation of leaching solutions. Formic acid with Ni-filter, Cu-radiation (=1.542 A ) at 40 kV, 30 mA and
(97%) was used as a reducing agent for palladium. A 0.1 M scanning speed 0.02 8/s. The diffraction charts and relative
sodium carbonate was used for pH adjustment. All used intensities were obtained and compared with JCPDS files. The
chemicals were of high grade for the laboratory usage. Doubly XRD pattern of the Pd spent catalyst sample (Fig. 2) showed
distilled water was used for dilutions. that Boehmite (a-AlOOH) and synthetic aluminum oxide (g-
Al2O3) were the major components while Gibbsite, Al(OH)3,
2.3. Recovery and separation of palladium was the minor one and palladium was the trace constituent.
Palladium concentration in the solution was assayed by using
Preliminary experiments showed that grinding of the spent atomic absorption spectroscopy, model Perkin-Elmer A
catalyst is not a controlling parameter in Pd recovery Analyst 200 at wavelength 244.8 nm with airacetylene flame.
procedure. However, the grinding is important for homo- The Pd content in the spent catalyst sample was assayed to be
genization of the sample. Therefore, a sample of 500 g of the 0.40% while the remainder was aluminum compounds. No
spent catalyst was crushed, ground, passed through a sieve of other metals were found in the spent catalyst sample.
particle size 250 mm and used for leaching experiments.
Solutions of different reagent combinations were prepared in
a 250 ml conical flask fitted with a reflux condenser. Two
grams of the spent catalyst was then put into the flask and the
mixture stirred with a magnetic stirrer. The flask was
immersed in a thermostatic water bath, model, Julabo
SW22. At the end of each experiment interval, the solution
was filtered off and was analyzed for Pd concentration from
which the recovery of Pd was calculated. A stock solution
containing Pd was prepared from the spent catalyst at the
optimum leaching conditions and used for Pd separation
experiments. In this case, samples of 10 ml of the leach
solution was mixed with different volumes of concentrated
formic acid in a 100 ml conical flask. The pH was adjusted, if Fig. 2. The XRD pattern of the spent catalyst sample. B = boehmite (syn.-
necessary, with few drops of 0.1 M sodium carbonate and the AlOOH), A = g-Al2O3, G = gibbsite Al(OH)3, P = palladium.
184 M.A. Barakat et al. / Applied Catalysis A: General 301 (2006) 182186

Fig. 3. The calculated distribution graph of Pd species as a function of free


chloride concentration. Fig. 4. The effect of hydrochloric acid concentration on the efficiency of Pd
recovery at different concentration of H2O2, at 80 8C, 2 h, L/S = 20:1.

3. Results and discussion absence and in the presence of 2.5 and 5% hydrogen peroxide,
at liquid:solid ratio (L/S) of 20:1 was studied and results are
Palladium can be oxidized in the presence of a suitable shown in Fig. 4. The leaching conditions were maintained at
oxidizing agent with a standard electrode potential value of 80 8C for 2 h. In the absence of H2O2, palladium extraction was
0.915 V [2426]. Distribution graphs of the various chloro- gradually increased with increasing hydrochloric acid con-
complexes of Pd as a function of chloride ion concentration was centration reaching a constant maximum value of 72% at 10%
calculated using Stabcal for windows software. As is shown in HCl. In the presence of hydrogen peroxide, Pd extraction
Fig. 3 palladium can form stable chloro-complexes such as significantly increased at low acid concentrations (from 0.25 to
PdCl+, PdCl2, PdCl3 and PdCl42in acidic chloride solutions. 2%) and then gradually increased at higher concentrations
At about 0.1 M Cl and higher, the predominant species in reaching about 95.5 and 99.9% at 7% HCl, with 2.5 and 5%
solution is PdCl42. The formation of this complex in solution H2O2, respectively. Further increase in HCl concentration only
will enhance the dissolution of Pd from the containing materials. slightly increased the Pd recovery with 2.5% H2O2.
Palladium can be oxidized with a standard electrode potential When Pd catalyst is stored in the atmosphere, its surface is
0.62 V in the presence of chloride ions according to the reaction: covered with adsorbed oxygen. The unusual dissolution of Pd in
hydrochloric acid in the absence of H2O2 is attributed to the
Pd 4Cl PdCl4 2 2e E0 0:62 V (1) oxidizing effect of the adsorbed oxygen that is formed on the Pd
Hydrogen peroxide as oxidant can be reduced in the acid surface as follows [27]:
media to water with a standard electrode potential, 1.763 V, Pd Oads 4Cl 2H PdCl4 2 H2 O (5)
according to the reaction:
Further, Pd present as a thin metallic layer on the support
H2 O2 2H 2e 2H2 O E0 1:763 V (2) pellets with a large surface area which assists its attack by
hydrochloric acid.
According to these standard electrode potentials, hydrogen
Palladium recovery from the spent catalyst was studied as a
peroxide can be considered as a suitable oxidizing agent for
function of time at a wide range of temperature (from 20 to
palladium. Thus, it can be predicted that, palladium can be
80 8C) at 7% HCl, 5% H2O2, and L/S ratio of 20:1 and results
dissolved with the help of hydrogen peroxide as oxidizing agent
are shown in Fig. 5. Generally, Pd extraction continuously
in the presence of an acid medium such as hydrochloric acid
increased with the increase in time and temperature. At low
with a total standard potential, 2.383 V, according to the overall
temperature range 2040 8C, Pd recovery gradually increased
reaction:
with time but did not exceed 45 and 70% after 2 h, respectively.
Pd H2 O2 4HCl H2 PdCl4 2H2 O E0 2:383 V (3) However, at higher temperature range (6080 8C), the Pd
recovery fast increased at early time (during the first 10 min)
On the other hand, H2O2 is decompesd with oxygen and then gradually increased till a maximum recovery values of
evolution according to the following equation: 99.8% after 2 h. Palladium recovery profiles at leaching
H2 O2aq 2H O2 2e E0 0:68 V (4) temperatures of 60 and 80 8C are superimposed and the next
experiments were held at 60 8C.
Accordingly, palladium leaching with hydrogen peroxide in The L/S ratio in leaching processes is an important factor from
hydrochloric acid was studied to optimize the different the economical point of view because it determines the reagent
parameters that control the dissolution process. consumption. The effect of the L/S ratio on the leaching of Pd
The effect of hydrochloric acid concentration (from 0 to from the spent catalyst at 60 8C for 2 h was studied using leaching
20%) on palladium dissolution from the spent catalyst in the solutions of 1, 2, and 7 HCl containing 5% H2O2 (see Fig. 6).
M.A. Barakat et al. / Applied Catalysis A: General 301 (2006) 182186 185

Fig. 5. The recovery of Pd as a function of time and temperature, at 7% HCl, Fig. 7. Effect of time on Pd separation at different temperatures, formic acid
5% H2O2, L/S = 20:1. vol. ratio = 2: 1, pH 7.

It can be noticed that Pd recovery increased with increasing the over other precipitating reagents. Formic acid reduces
L/S ratio with all studied HCl concentrations but it remained palladium directly to metallic form which does not require
nearly constant at L/S ratios higher than 10. At L/S ratio as high as any further treatment other than simple drying. Formic acid
20, the Pd recovery values were only 70% and 80% with 1% and decomposes to carbon dioxide which neither contaminates the
2% HCl, respectively. This indicates that, increasing the L/S ratio solution nor creates a pollution problem. Unlike other
to the high value of 20 cannot achieve the quantitative metal precipitation techniques, reduction by formic acid is known
recovery when the HCl concentrations are lower than 7%. On the to separate palladium efficiently with high recovery. Therefore,
other hand, almost all Pd could be dissolved at L/S ratio of 10 formic acid was used for the reduction of Pd from the leach
when 7% HCl is used. It is obvious from the results of the studied liquor of the spent catalyst where the different parameters those
parameters that the optimum conditions for Pd recovery is: affecting the process were studied in the following experiments.
leaching solutions contain 7% HCl and 5% H2O2, 2 h retention The effect of time on Pd separation was studied using formic
time, heating at 60 8C and L/S ratio of 10/1. acid: Pd solution volumetric ratio of 2, at 60 and 100 8C and at
A stock leach solution was prepared at the optimum leaching pH 7, as shown in Fig. 7. At 60 8C, the amount of separated Pd
conditions, and was found to contain 0.04% Pd and 0.5% Al. gradually increased with time in the first 30 min and then very
This stock solution was used for palladium separation slowly increased, reaching the value of 67% after 1 h. At
experiments. Palladium can be separated from the leach 100 8C, Pd was separated very quickly and attained about 100%
solution by reduction with formic acid [25], according to the after only 1 min. It is worthy mentioning that, heating the
general reaction: solution mixture at 100 8C for time less than 30 min separated
the Pd into a very fine and colloidal form which was hardly
heat
H2 PdCl4 HCOOH! Pds 4HCl CO2 (6) separated by filtration. However, heating the solution mixture
for longer time created larger black particles of Pd metal that is
In such reaction, Pd2+ is reduced to Pd0. Separation of easily filtered. Thus, although at 100 8C Pd can be reduced
palladium by reduction with formic acid has several advantages completely at as short time as 1 min, continued heating for at
least 30 min is favorable for the purpose of better filtration of
the precipitated palladium powder.
Fig. 8 shows the effect of the amount of formic acid added
to the Pd solution (represented as volumetric ratio) at
different temperatures, pH 7, for 30 min. In general, Pd
separation increases with increase in both temperature and
formic acid volumetric ratio. At low temperature as 40 8C,
the Pd separation started at only high formic acid volumetric
ratio (1.5). At higher temperatures as 60 and 80 8C, Pd
separation increased gradually with the formic acid ratio. At
100 8C a sharp increase in Pd separation was obtained at
considerably lower formic acid volumetric ratio where a
nearly complete Pd separation was obtained at a volumetric
ratio of only 0.5.
Fig. 9 shows the efficiency of palladium separation as a
Fig. 6. Effect of solid/liquid ratio on Pd recovery at 5% H2O2, 60 8C, 2 h. function of pH in a range extends from acidic pH up to the
186 M.A. Barakat et al. / Applied Catalysis A: General 301 (2006) 182186

4. Conclusion

A simple and environmentally friendly process was


proposed for the recovery of palladium from a spent catalyst
based on alumina carrier. Complete dissolution of palladium
was achieved by leaching with a solution contains 7% HCl and
5% H2O2 at 60 8C for 2 h with a liquid/solid ratio of 10/1.
Palladium was reduced efficiently with formic acid at 100 8C
for 30 min with 0.5 formic acid volumetric ratio. Palladium
recovery efficiency of >99%, with 98% purity was achieved.

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