Hydrometallurgy 133 (2013) 2332

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Review

Hydrometallurgical recovery/recycling of platinum by the leaching of spent catalysts:

A review
Manis Kumar Jha a, Jae-chun Lee b,, Min-seuk Kim b, Jinki Jeong b, Byung-Su Kim b, Vinay Kumar a
a
b

Metal Extraction and Forming Division, National Metallurgical Laboratory, Jamshedpur-831007, India
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources, Daejeon 305-350, Republic of Korea

a r t i c l e

i n f o

Article history:
Received 17 April 2012
Received in revised form 3 November 2012
Accepted 22 November 2012
Available online 28 November 2012
Keywords:
Spent catalyst
Platinum
Leaching
Recycling
Hydrometallurgy

a b s t r a c t
Platinum is one of the precious metals with many applications, including in catalysis, electronic devices and
jewelry. However, its limited resources are becoming depleted. To meet the future demand and conserve
resources, it is necessary to process spent platinum-containing materials, such as catalysts, electronic scraps
and used equipment. These materials are usually processed by pyro/hydrometallurgical processes consisting of
thermal treatment followed by leaching, precipitation or solvent extraction. This paper reviews platinum
leaching from such resources using acidic and alkaline solutions in the presence of oxidizing agents, such as nitric
acid and hydrogen peroxide, sodium cyanide and iodide solutions. The results of the study are described with
respect to the recovery of platinum and other metals under the optimized conditions of leaching with lixiviants.
Previous studies have achieved platinum recovery using aqua regia and acidic solution in the presence of chlorine
to produce platinum from spent catalysts on a commercial scale; however, the process generates toxic nitrogen
oxide and chlorine gases. This paper reports the salient ndings of efforts to replace the aqua regia with hydrogen
peroxide in acidic solution, chloride salts, sodium cyanide and iodide solution to improve the economics of the
existing processes and reduce the environmental pollution.
2012 Elsevier B.V. All rights reserved.

Contents
1.
2.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . .
Processing of spent materials . . . . . . . . . . . . . . . . . . .
2.1.
Thermal pre-treatment of materials . . . . . . . . . . . .
2.2.
Hydrometallurgical processing . . . . . . . . . . . . . . .
3.
Leaching of materials . . . . . . . . . . . . . . . . . . . . . .
3.1.
Leaching in aqua regia solutions . . . . . . . . . . . . . .
3.1.1.
Leaching in aqua regia and after pretreatment . . .
3.1.2.
Leaching with aqua regia after acid/alkali treatment
3.2.
Leaching in the presence of chloride ions . . . . . . . . . .
3.3.
Leaching in the presence of hydrogen peroxide . . . . . . .
3.4.
Leaching in cyanide solution . . . . . . . . . . . . . . . .
3.5.
Leaching with iodide/iodine solution . . . . . . . . . . . .
4.
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
Platinum (Pt) is a costly precious metal with applications in the
manufacturing of catalysts, electronic devices, space materials, biomedical
Corresponding author. Fax: +82 42 868 3415.
E-mail address: jclee@kigam.re.kr (J. Lee).
0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2012.11.012

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23
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devices and jewelry, among others, due to its chemical resistivity,

high-temperature stability and stable electrical properties. The natural
resources of platinum and platinum group metals (PGMs; platinum,
palladium, rhodium, ruthenium, iridium and osmium) are limited and
mainly found in Russia, North America, Canada and South Africa. South
Africa is the world's largest producer of platinum, which is mined in an
area called the Bushveld Igneous Complex. The PGM concentration is

24

M.K. Jha et al. / Hydrometallurgy 133 (2013) 2332

low, in the range of 210 ppm (g/t), and generally associated with base
metal sulde minerals. PGMs are recovered as a byproduct or coproduct depending on their concentration in the ore. The Pt demand is
increasing worldwide due to its versatile applications in various industries. The global Pt demand increased by 16.0% and 19.0% in 2010 and
2011, respectively, in comparison to 2009 (Matthey, 2011).
To recover Pt, the PGMs present in the ore as their suldes, arsenides
or tellurides are concentrated by physical beneciation followed by
pyro/hydrometallurgical processes (Seymour and O'Farrelly, 2006). The
concentrate is then leached in aqua regia to produce a leach solution
containing Pt and other precious metals, such as Au, Ag, Pd and Rh. The
metals from the leach solution are separated by precipitation or solvent
extraction (SX). The Pt is precipitated as ammonium hexachloroplatinate
(IV) [(NH4)2PtCl6] with NH4Cl from the puried solution. The precipitate
is then calcined to produce Pt sponge, which is further treated to produce
pure Pt metal. Other metals present in PGMs are recovered by further
processing the solutions. Cramer (2001) reviewed the processes for the
production of Pt from South Africa's PGM ore concentrate following
pressure leaching in HCl solution and the separation of PGM, including
Pt, by SX. The classical chemical approach for Pt recovery from ore has
been documented by Gouldsmith and Wilson (1963).
The depletion rate of high-grade PGMs resources has been increasing
due to increasing demand, and the cost of production has been increasing
due to the decreasing PGMs concentration in the remaining naturally
occurring ore. Therefore, it is necessary to process secondary materials,
such as spent catalysts, electronic scraps, used equipment, fabricated
ware and membrane electrode assemblies, for Pt recovery and recycling.
This process will conserve the resources to meet the future demand for
Pt and other PGMs and also reduce environmental pollution. Pt is
employed as a catalyst in various chemical reactions; thus, spent catalysts
are an important secondary source for recovering Pt and other associated
metals.
Platinum group metals are employed as the active species for catalysts. A number of platinum-based catalysts are available and applicable
for various purposes, as follows:
PtPdRh auto catalyst: Reduction of toxic gases of automobile
(Aberasturi et al., 2011)
Spent PtRh or PtPdRh alloys: Catalytic oxidation of ammonia to
nitrogen oxide by air (Mahmoud, 2003)
Pt gauze catalyst: Oxidation of ammonia to produce nitric acid
(Barakat and Mahmoud, 2004)
Pt/Rh bimetallic catalyst: Catalytic reforming to upgrade the low
octane naphtha to higher octane aromatic hydrocarbons (Kluksdhal,
1971; McCoy and Munk, 1971)
PtZnHy catalyst: Hydro-isomerisation of n-heptane (Saberi et al.,
2001)
Pt-alumina catalyst promoted by Fe-oxide: Oxidation of CO in H2 (Liu
et al., 2002)
Pt and Ni catalyst: Acetophenone hydrogenation (Malyala et al., 2000),
steam reforming of n-butane to produce hydrogen (Avci et al., 2004)
and aromatic nitro compounds reduction (Ghosh et al., 2004)
Bimetallic PtCu catalyst: Nitrate reduction (Epron et al., 2002)
PtC catalyst: Hydroxylamine sulfate manufacturing (Grzelczuk et al.,
1985)
Pt-base metals catalyst: Reforming and isomerization catalyst
(Jeliyaskova et al., 1982)
Ptcobalt based catalyst: FischerTropsch (FT) process to produce
hydrocarbons from synthesis gas (Matjie et al., 2005)
PtAl2O3 catalyst: Catalytic reforming (Pinheiro et al., 2004)
PtSnIn/Al2O3Li catalyst: n-Parafn dehydrogenation to produce
alpha-olens (Pinheiro et al., 2004).
Catalyst deactivation: Catalysts are deactivated during use due to fouling, poisoning and/or thermal degradation/sintering (Bartholomew et al.,
1982; Dowden, 1983; Gates et al., 1979; Trimm, 1997, 1980; Twig, 1989).
The deposition of coke is the most common form of catalyst fouling, and

poisoning occurs because of strong chemical bonds between a feed

component, such as sulfur, or catalytic reaction products with active
sites on the catalyst surface. Thermal degradation is induced by thermal
shocks due to heating and cooling during operation. The deactivated
catalysts are discarded or sometimes regenerated in situ or replaced by
fresh catalyst. The composition of some spent catalysts is shown in
Table 1.
2. Processing of spent materials
Spent catalysts containing Pt and other ingredients are processed to recover and recycle metals, which are considered environmentally hazardous waste due to the presence of various ionic
constituents. To recover the metals from different spent materials,
pyro/hydrometallurgical processes are usually employed for the effective extraction and separation of metals, depending on the
presence of other constituents, by different corporations and industries (e.g., Umicore, Belgium; Hereaus, Germany; BASF/Engelhard,
USA; Johnson Matthey, UK; Nippon/Mitsubishi, Japan). The spent
materials are segregated, crushed, ground and then processed by pyro/
hydrometallurgical processes to recover the PGMs. BASF, USA and
Johnson Matthey, UK employed smelting, chemical leaching and rening
to recover Pt, Pd, Rh and other associated metals (http://www.
converter-recycling.basf.com/p02/USWeb-Internet/converter-recycling/
en_GB/; http://www.jmrening.com/page-view.php?pagename=Theprocess). At the Umicore precious metals rening plant, Belgium,
spent catalysts and e-wastes are smelted in a furnace to produce
a concentrate containing Cu, Pt and other metals, which is further
processed by hydrometallurgical route to recover the metals
(Hageluken, 2006). The selection of processing steps depends on
the metallic constituents and other associated materials. The details of the processes are not available in the literature. The results
of studies available in literature are mentioned below.
2.1. Thermal pre-treatment of materials
Thermal pre-treatment is employed during the processing of different spent materials, such as organometallic catalysts from chemical
and petrochemical industries, to improve the leaching efciency for
metal recovery. The materials are thermally pretreated in a suitable
environmentally friendly atmosphere, such as hydrogen, oxygen, nitrogen or air, depending on the undesired organic constituents to be
removed to produce ash containing PGMs (Aberasturi et al., 2011).
Spent automotive catalysts containing PGMs (Pt, Pd, Rh) were heated
under a hydrogen atmosphere at 250 C, which improved metal recovery during leaching due to the elimination of the hydrocarbons and
charcoal present on the catalyst surface and reduction of oxidized
PGMs (Bolinski and Distin, 1992; Williams et al., 1998). The catalyst
samples (Pt/Al2O3 and PtSn/Al2O3) were heated under oxidizing conditions in a furnace under air (400 C, 1 atm, 5 h) to eliminate coke and
water, producing a mass loss of 68 wt.% (Pinheiro et al., 2004). The
carbon and iron were quantitatively removed as CO2 and Fe2O3 dust,
respectively, and no losses of other elements were observed. Matjie et
al. (2005) reported the removal of wax from spent catalysts by calcination at 800 C before metal recovery by leaching. Some authors (Jafarifar
et al., 2005) have treated Pt/Rh bimetallic catalysts using microwave
heating before leaching in aqua regia. Spent Pt-based commercial
catalysts (Pt and PtSnIn/Al2O3) were fused with KHSO4 at 450 C for
3 h to recover Pt and other metals (Junior and Afonso, 2010). The
fused mass was dissolved in water. Pt was recovered as a waterinsoluble residue and tin and indium as suldes at pH 1.
Chlorine and carbon monoxide are also employed at high temperature
to produce Pt carbonyl chloride [Pt(CO)Cl2] vapor for metal recovery (Kim
and Woo, 2000). The precious metals on automotive catalysts or spent
materials are chlorinated with chlorides at an elevated temperature to
vaporize these metals (Shoji, 1987, 1990).

M.K. Jha et al. / Hydrometallurgy 133 (2013) 2332

25

Table 1
Composition and other properties of spent catalyst.
Catalyst
composition

Composition and other details

Reference

Spent
PtNiO/
-Al2O3
Spent Pt
gauze catalyst
Spent Auto
catalyst

Nitrogen production unit of petrochemical plant. The spent catalyst is in the form of cylindrical pellets (6.56.5 mm) which is ground to 200
mesh powder by porcelain ball mill. The powder was dried (by heating 120 C for 24 h) before dissolution experiments. Chemical analysis of
powder is (in % w/w wet basis): 0.125 Pt, 2.5 Ni, 0.28 Zn, 0.05 Zn, 0.02 Cu, 2.8 carbonaceous material, 5 humidity.
Spent catalyst dust collected from a fertilizer plant: (wt.%) as 13.7 Pt, 1.3 Rh, 16.9 Fe, 2.46 Ni, 0.15 Cu, 0.17 Zn, 0.17 Pb, 1.15 Ca, 1.35 Mg, 0.84 Re,
8.25 Si X-ray diffraction analysis indicated the presence of Pt, quartz and hematite as the major phases.
The most common car catalytic converters are the honeycomb type cordierite skeleton (2MgO2Al2O35SiO2), (Cuif et al., 1997; Lucena et al.,
1999) and ~90% -Al2O3 and a mixture of base metals additives, mainly oxides of Ce, Zr, La, Ni, Fe and alkaline-earths (Palacios et al., 2000). The
PGMs Pt, Pd, Rh are present on wash coat, in all the cases the total content of PGMs is always lower than 0.1%.
Catalytic oxidation of ammonia to nitrogen oxide by air contains 16.76% Pt, 1.87% Rh, 0.14% Pd, 0.01% Ag and 0.0012 Au and major amount of
iron oxides and silica.

Angelidis and
Skouraki (1996)

Spent catalysts
PtRh or
PtPdRh
alloys
Spent Fischer
Tropsch
catalyst
Pt/Al2O3
PtSnIn/
Al2O3Li
Pt catalyst

Barakat and
Mahmoud (2004)
Aberasturi et al.
(2011)
Mahmoud
(2003)

Used to produce hydrocarbons from synthesis gas. The process is catalyzed using Fe or other transition metals, including cobalt and promoted Matjie et al.
(2005)
with minute quantities of group VIII noble metals such as Pt, Pd and Rh.
Wax (6070%), cobalt oxide (810%), aluminum oxide (2027%) and minute amount of platinum
Pt/Al2O3 (wt.%: 0.37 Pt, 0.05 Fe, 3.5 C, 50.60 Al) and Pt-Sn/Al2O3 (wt.%: 0.37 Pt, 0.41 Sn, 0.26 In, 0.44 Li, 0.15 Fe, 5.0 C, 48.30 Al) catalysts
Pinheiro et al.
(2004)
Spent reforming catalysts composition in wt.% 91.9 Al2O3, 0.19SiO2, 0.13TiO2, 0.30S, 0.28C, 0.24 Pt, 0.24 Re, 5.98 LOI, and minor constituents

The smelting process is also employed to produce concentrate

containing Pt and other metals for subsequent hydrometallurgical
processing (Benson et al., 2000; Chiang et al., 2011; Day, 1984;
Keyworth, 1992; Mishra and Reddy, 1986). Low-grade scrap from the
electronics industry and catalysts, among other sources, is incinerated
to remove non-metallic components, such as insulation and plastics,
and then heated in a furnace together with ore and scraps to produce
concentrated Pt for subsequent recovery. The catalyst supports, such
as alumina, mullite or cordierite (2MgO2Al2O35SiO2), are melted, in
some cases with CaO at elevated temperatures, to obtain a lowviscosity slag. Precious metals in the melt are separated by allowing
them to adsorb on Fe or Cu with high specic gravity. Kayanuma et al.
(2004) reported the recovery of PGMs from scrap by smelting with
copper to obtain metals for further processing to dissolve metals in a
suitable lixiviant. This process has serious environmental effects, and
the lengthy overall ow sheet results in unavoidable PGM losses. The
process is energy intensive and generates atmospheric pollution due
to the evolution of toxic gases. However, metal recovery (or recycling)
through hydrometallurgical route is important because of its low cost
and eco-friendliness in comparison to other recycling processes.
2.2. Hydrometallurgical processing
In hydrometallurgical processing, metals are leached directly or
after pretreatment using suitable acidic and alkaline solutions in the
presence of oxygen, iodine, bromine, chlorine, hydrogen peroxide,
etc. (Angelidis, 2001; Bolinski and Distin, 1992; Duyvesteyn et al.,
1994; Han and Meng, 1996; Meng and Han, 1995; Mishra, 1993,
1988; Yoo, 1998). Many authors have studied Pt recovery from
waste catalysts and secondary materials, as evident from the various
papers appearing in journals, proceedings and patents (Eugenia et
al., 1983; Ezawa, 1989; Harjanto et al., 2006). Nippon PGM Co.
reported commercial-scale PGM production from different resources
(Suzuki et al., 2007). Heraeus, Germany recovered precious metals,
including Pt, from spent materials using hydrometallurgical processes consisting of leaching in hydrochloric acid under oxidizing
conditions followed by selective precipitation and ion exchange
(http://www.corporate.heraeus.com/media/webmedia_local/media/
presse/termine/earthday2010/PreciousMetalsRecycling_technology_
report_02_E.pdf). BASF Catalysts LLC, USA reported a new process
for precious metal recovery from membrane electrode assemblies
(MEAs) eliminating the emission of hydrogen uoride, a highly
polluting gas generated by the current combustion-based recycling

Zanjani and
Baghalha (2009)

process (Shore, 2009). The new process consists of grinding the

material followed by leaching with HCl/HNO3 to dissolve the Pt in
the solution. The Pt in the solution is concentrated by evaporation
to recover Pt while recycling HCl for leaching. Hoffmann (1988)
reviewed processes for the recovery of Pt, Pd and Rh from spent
automotive catalysts and described the problems faced due to the
presence of other metallic constituents. Narita (1998) investigated
a method of recovering Pt from sludge and dust. In this process, the
leached chloroplatinic acid solution is puried with respect to base metals
by precipitation. Pt is then recovered as ammonium chloroplatinate with
the addition of ammonium chloride, which was subsequently heated
to yield platinum sponge.
Colombo and Bowman (1996) reported a process for recovering Pt
from a naphtha reformate spent catalyst using carbon tetrachloride
vapor in air or N2 and obtained over 95% Pt recovery. McVicker et
al. (1985) used oxalic acid to leach out precious metals from bimetallic reforming catalysts, PtReAl2O3, PtIrAl2O3, FePtReAl2O3
and FePtIrAl2O3, and PtAl2O3. Platinum Lake Technology Inc.,
Canada (Ryder and Dymock, 1990) developed a hydrometallurgical
process for the recovery of precious metals from spent automotive
catalysts following acid leaching in chloride medium. The smallscale process with 95% Pt and 98% Pd recovery was used for commercial applications. Mishra and Ramadorai (1988) studied the continuous leaching of automotive catalyst in HCl and its regeneration process
scheme on the bench scale with PGMs recoveries of 95% Pt and 91%
Pd. The effects of different process parameters, e.g., time, temperature,
concentration and pressure, were studied for Pt leaching from different
spent materials (Kikuchi and Eto, 1994; Ryder and Dymock, 1990). The
results of Pt leaching from different secondary materials are classied
and presented below.
3. Leaching of materials
The leaching of Pt and other metals is usually carried out using different lixiviants, such as sulfuric acid, hydrochloric acid, nitric acid, sodium
cyanide, chloride or iodide solutions. The oxidizing agents are also added
to enhance the leaching efciency of the metals. These are classied as
given below.
3.1. Leaching in aqua regia solutions
3.1.1. Leaching in aqua regia and after pretreatment
3.1.2. Pt leaching with aqua regia after acid/alkali treatment
3.2. Leaching in the presence of other chloride ions

26

M.K. Jha et al. / Hydrometallurgy 133 (2013) 2332

3.3. Leaching in the presence of hydrogen peroxide

3.4. Leaching in cyanide
3.5. Leaching with iodide/iodine solution
3.1. Leaching in aqua regia solutions
The leaching of a metal is mainly governed by the formation of a complex under the potential and pH of the solution in the presence of ionic
species. As Pt forms stable chloro-complexes in chloride solution at high
acid concentration, Pt could be leached at a higher potential using an
oxidizing agent (Lide, 1995). The other associated metals (Pd, Rh, etc.)
also form chloro-complexes at lower potential and will also be leached,
but the Rh leaching rate is relatively low. The oxidizing agent, HNO3, is
suitable for Pt leaching because of its high oxidation potential of 0.96 V
according to reaction (1). In the case of metal dissolution with aqua
regia, the formed nascent chlorine (Cl2) and nitrosyl chloride (NOCl)
provide high oxidation potential and the high chloride-ion concentration
acts as the complexing agent (Burkin, 2001). HNO3 and HCl undergo
through reactions (2) and (3) (Massucci et al., 1999).

NO3 4H 3e NO 2H2 O

2NOClg2NOg Cl2 g

NOCl H2 OHNO2 HCl

3Pt 4NO3 16H 3Pt

Pt 4NO3 8H Pt

Table 2
Leaching in acidic solutions after pre-treatment.
Material

Leaching agent Results

Reference

Spent reforming
catalyst

Aqua regia
solution

Baghalha
et al.
(2009)

Pt gauze dust

Aqua regia
solution

The Pt leaching reaction was

controlled by surface chemical
reaction and activation energy
was found to be 72.1 kJ/mol.
Spent catalyst containing 13.7%
Pt and 1.3% Rh was reuxed with
aqua regia at an L/S ratio of 7.5 for
1.5 h to solubilize Pt. Pt was
separated using trioctylamine
and recovered by precipitation.
97.5% Pt recovery was achieved.
Pt and Pd leached at 95 C

Ammonium hydroxide used to

get salts of
hexachlorocomplexes which
are then reduced with
hydrazine hydrate to produce
PtRh powder.
The material was dissolved in
aqua regia and precipitated
with NH4Cl. Calcination of
precipitate gives high
purity Pt (>99.99%)
Recovery of 90% Pt and 70% Pd
in 5 h leaching time.

Perte et al.,
1988

HNO3 3HClNOCl Cl2 2H2 O

3Pt 18HCl 4HNO3 3PtCl6 

(1988) patented a process for the recovery of Pt along with Rh from

spent catalyst using aqua regia leaching. The solution is then puried
by ion exchange to obtain pure solution, which is then treated with ammonium hydroxide to obtain salts of hexachlorocomplexes. The salts are
then reduced with hydrazine hydrate to produce PtRh powder, which
is washed to produce the high-purity product (98%).
Tyson and Bautista (1987) leached Pt and Pd of the spent catalysts
within a given particle range ( 60 + 70 mesh to 120 + 140
mesh) with 3791 ppm Pt and 1306 ppm Pd in a packed bed reactor
using different HCl:HNO3 concentration ratios. Based on these studies, a kinetic expression was determined empirically for the experimental data. The reaction rate was initially high but dropped
quickly with time for both metals. The leaching extent was 90% and

6H 4NO 8H2 O

4NO 8H2 O

4NO2 4H2 O:

Spent auto catalyst HCl and HNO3

Pt-alumino-silicate Sulfuric acid,

catalyst
HClCl2
Ash of calcined PtC Aqua regia
spent catalyst.

3.1.1. Leaching in aqua regia and after pretreatment

Different authors have used aqua regia to dissolve Pt and other associated metals in catalysts (Muraki and Mitsui, 1986). The salient details are
summarized in Table 2. Tanaka Noble Metal Ind. (Tadashi, 1982) has
taken out a patent for the recovery of metals from spent catalysts
containing 1000 ppm Pt, 200 ppm Pd and 300 ppm Rh on Al2O3 substrate
in aqua regia. The recoveries of Pt, Pd and Rh were 99.0, 100, and 86.7%,
respectively. Bonucci and Parker (1984) dissolved Pt along with Pd from
the crushed spent automotive catalyst in an agitated reactor in HCl solution using nitric acid as oxidant at 95 C. The alumina co-dissolution
was reduced by the thermal pre-treatment of the catalyst without affecting Pt solubility. The rhodium present in the catalyst could be selectively
dissolved with sulfuric acid, leaving Pt and Pd in the residue.
Aqua regia was used to dissolve Pt at 80 C in 1 h from the ash
obtained after the calcinations of spent PtC catalyst from a hydroxylamine sulfate manufacturing plant (Grzelczuk et al., 1985). Almost all
of the Pt were recovered and recycled to produce PtC. Muraki and
Mitsui (1986) patented a process for recovering Pt and Pd loaded on
granular or honeycomb Al2O3, SiO2 or carbon support by leaching with
aqua regia. The resulting leach solution was ltered at pH 1.0, and metals
from the solution were precipitated with addition of Fe powder. The
residual Fe powder was separated magnetically and recycled. The Pt
and Pd recoveries were 95.0% and 92.7%, respectively. Perte et al.

Spent Pt gauze

Aqua regia

Pt/Rh bimetallic
reforming
catalyst

Aqua regia
solution

Reforming and
isomerization
catalyst
FischerTropsch
catalysts

Sulfuric acid
followed
by aqua regia
Acidic and
alkaline
solutions and
aqua regia

PtReAl2O3
catalyst

Hot sulfuric
acid

Pt and Pd
honeycomb
Al2O3, SiO2
or carbon
Spent catalyst

Aqua regia

Scrap from glass

industry

Aqua regia

Spent catalysts

HCl:HNO3
concentration

Aqua regia

Barakat
and
Mahmoud
(2004)

Bonucci
and Parker
(1984)
Al leached with sulfuric acid
Eugenia et
followed by Pt with HClCl2
al. (1983)
Pt dissolve at 80 C in 1 h from Grzelczuk
et al.
the ash obtained after
(1985)
calcinations of PtC spent
catalyst
Pt precipitated as (NH4)2PtCl6 Horner
with ammonium chloride and and
decomposed at 800900 C to McGrath,
1994
obtain Pt black.
The sample was reuxed with Jafarifar et
al. (2005)
aqua regia at liquid to solid
ratio 5 and 2.5 h, >95% Pt and
Rh recovered.
Jeliyaskova
Leaching of alumina with
et al.
sulfuric acid followed by Pt
(1982)
leaching with aqua regia
Pt dissolved in aqua regia, not Matjie et
in other lixiviants. Almost of Al, al. (2005)
Pt and Co species dissolves
during NaOHHNO3aqua
regia leaching.
McVicker
Re and most of Al2O3 are
et al.
dissolved from catalyst by
H2SO4 followed by Pt recovery (1985)
from residue
Recoveries of Pt and Pd were
Muraki
95.0% and 92.7%, respectively. and Mitsui
(1986)

Schreier
and
Edtmaier
(2003)
Tyson and
Bautista
(1987)

M.K. Jha et al. / Hydrometallurgy 133 (2013) 2332

70% for Pt and Pd, respectively, in 5 h. Horner and McGrath (1994) also
reported the use of aqua regia to dissolve Pt from spent Pt gauze
followed by precipitation as (NH4)2PtCl6 with ammonium chloride and
thermal decomposition at 800900 C to obtain Pt black (Yoo, 1998).
Spent Pt gauze catalyst dust (wt.%: 13.7 Pt, 1.3 Rh, 16.9 Fe, 2.46 Ni,
0.15 Cu, 0.17 Zn, 0.17 Pb, 1.15 Ca, 1.35 Mg, 0.84 Re, 8.25 Si) generated
during nitric acid manufacturing by ammonia oxidation was studied, revealing that the b 106 m fraction is suitable for leaching Pt with aqua
regia at a liquid/solid (L/S) ratio of 7.5 in 1.5 h at 109 C with 98% recovery (Barakat and Mahmoud, 2004). The claried solution was obtained
by ltering the slurry for subsequent Pt recovery, as shown in Fig. 1, by
direct precipitation as diammonium hexachloroplatinate and SX using
trioctylamine in kerosene. The precipitate was decomposed by ignition
to produce Pt powder with a purity of 97.9% and 99.9% for the direct
and SX routes, respectively. A Pt recovery of 97.5% was achieved by
both routes. Jafarifar et al. (2005) investigated two alternative methods
for leaching the Pt/Rh bimetallic catalyst, widely used in the reforming
process for the production of high-octane fuels containing 0.2% Pt,
0.43% Re and other impurities. In the rst method, the sample was
reuxed with aqua regia at a liquid/solid ratio of 5 for 2.5 h. In the
second case, 150 W microwave radiation was used with aqua regia at
a liquid/solid ratio of 2 for 5 min. After leaching, Pt was recovered as
diammonium hexachloroplatinate after separating Rh. The recoveries
of Pt were 96.5% and 98.3% using rst and second method, respectively.
Rh was recovered as potassium perrhenate with 94.2% and 98.9% recovery using the rst and second methods, respectively. Commercial spent
reforming catalysts were studied in aqua regia solution under atmospheric pressure at 100 C for the dissolution of Pt by Baghalha et al.
(2009), which showed that particle sizes b100 m and agitation speeds
>700 rpm eliminated the internal and external mass-transfer resistances, respectively. The Pt extraction rate was increased signicantly
by increasing the L/S mass ratio and the reaction temperature. The
leaching kinetics followed the power-law rate with an activation energy
for the platinum surface dissolution reaction of 72.1 kJ/mol. This large
value indicates that Pt extraction in aqua regia solution is controlled by
surface chemical reactions. The reaction order was 1.5 for Pt concentration in solid and 1.3 for the hydrogen ion molarity in solution.
HCl/ HNO3

27

3.1.2. Leaching with aqua regia after acid/alkali treatment

Different authors studied the dissolution of metals after treatment
with acid to remove certain components of the spent material followed
by aqua regia to dissolve Pt. McVicker et al. (1985) employed hot sulfuric
acid to dissolve Re and most of Al2O3 from the calcined PtReAl2O3
catalyst. Subsequently, the residue of the rst-stage leaching was treated
to recover Pt. The Re from the leach solution was then recovered by an
anion exchange resin. Jeliyaskova et al. (1982) reported the recovery
of Pt from the spent reforming and isomerization catalysts by selective
dissolution of the base metals with 50% sulfuric acid followed by the
leaching of Pt from the residue with aqua regia. The spent Ptaluminosilicate catalyst was treated in sulfuric acid to dissolve Al as
aluminum sulfate, leaving Pt in the residue. The residue is then leached
with concentrated HCl and chlorine gas at 95 C to dissolve Pt (Eugenia
et al., 1983). The leachate was an aqua regia-type solution in which part
of the HCl content was replaced by aluminum chloride to lower the acid
consumption. The scrap produced in glass industries during sheets cutting contains Pt along with other elements (8636 mg/kg Ir, 5455 mg/kg
Rh and 168 mg/kg Pd) was studied for the recovery of metals using aqua
regia (Schreier and Edtmaier, 2003). Pt from the leach liquor was precipitated with ammonium chloride after dilution with water or HCl, leaving
other PGMs in the solution. High-purity Pt (99.99%) was produced by
the calcination of the precipitate.
The spent cobalt-based catalyst of the FischerTropsch (FT) process
(wt.%: 810 cobalt oxide, 2027 aluminum oxide, small amount Pt,
6070% wax) was processed to recover Pt by alkali and then acid treatment, as shown in Fig. 2 (Matjie et al., 2005). The sample was initially
calcined at 800 C to remove the wax, which can react with sodium
hydroxide and inorganic acids, resulting poor leaching efciency. The
calcined catalyst (wt.%: 6065 Al2O3, 18.719.6 Co and 0.040.05 Pt)
was studied for the selective recovery of alumina, high-value cobalt
and platinum using different lixiviants, such as sodium hydroxide, nitric
acid/hydrochloric acid/sulfuric acid and aqua regia. Approximately 89%
of the aluminum species present in the calcined spent catalyst was
selectively dissolved in sodium hydroxide (6.25 M) at pressure ~9 bar
and 170 C during two consecutive leaching steps. Subsequently, Pt
and Co were leached from the residue obtained after the alkali pressure
Platinum dust

LEACHING

FILTRATION

Residue

Alternative method
Pt solution

NH4Cl

TOA
SOLVENT EXTRACTION
Pt PRECIPITATION
NH4OH
PRECIPITATION
STRIPPING

(NH4)2PtCl6

FILTRATION AND WASHING

Filtrate for Rh
recovery

(NH4)2PtCl6

IGNITION

IGNITION

Pure Pt

Pt powder

Fig. 1. Flow sheet for the recovery of platinum by hydrometallurgical process from platinum dust.

28

M.K. Jha et al. / Hydrometallurgy 133 (2013) 2332

leaching of Al by acid-aqua regia leaching or alkali pressure leachingaqua regia. Almost all of the platinum species present in the nitric acid
insoluble residue was dissolved in aqua regia at 80 C and atmospheric
pressure for 4 h to form a chloroplatinic acid solution. The solution
could then be used to produce Pt sponge or Pt salt.
3.2. Leaching in the presence of chloride ions
Many authors have investigated the leaching of Pt from spent catalysts in the presence of aluminum chloride to reduce the hydrochloric
acid consumption and the generation of gases during dissolution with
aqua regia (Letowski and Distin, 1985, 1987, 1989). During leaching
with aqua regia above 70 C, high amounts of gaseous nitrogen oxides
and HCl vapors are generated. The replacement of a part of HCl with
another complexing agent sources, such as non-volatile chloride salts,
will be benecial (Distin and Letowski, 1984). Aluminum chloride is
preferred because it provides three chloride ions per AlCl3 molecule,
unlike other common chloride salts (NaCl, KCl, CaCl2 or MgCl2), and
the presence of aluminum ions will reduce the substrate dissolution
rate. The spent automobile converter catalyst containing approximately
400 mg/t Pt and 150 mg/t Pd in alumina beads (Letowski and Distin,
1985) was leached in a column using an aluminum chloride and
hydrochloric acid solution with nitric acid as the oxidant at 90 C.
Their studies showed that up to 64% of the chloride ions from HCl can
be substituted with AlCl3 without sacricing the extraction of Pt and
Pd. Angelidis and Skouraki (1996) studied Pt recovery from spent Pt
NiO/Al2O3 industrial catalysts in the presence of aluminum chloride
solutions, with low concentrations of nitric acid as an oxidant, instead
of aqua regia. The effect of the aluminum chloride and nitric acid concentrations on the platinum dissolution yield was studied. The substitution of

hydrochloric acid by aluminum chloride, with low nitric acid concentration, does not affect the platinum dissolution yield while, minimizing
the consumption of excess reagents. Angelidis (2001) reported the reduction leaching of automotive catalyst in the presence of hydrazine sulfate
in sulfuric acid followed by oxidative leaching with HCl/AlCl3 to dissolve
Pt and Rh. The reduction leaching destabilizes the refractory catalyst
wash-coat, which improves the PGM recovery, even from larger particles,
avoiding the signicant loss of PGMs during grinding. The application of
AlCl3 also reduces the required HCl content as a lixiviant without affecting
the recovery. The spent catalysts (PtRh or PtPdRh alloys) from nitric
acid manufacturing plants were processed to recover PGMs using a mixture of sulfuric acid and sodium chloride to replace aqua regia or autoclave leaching (Mahmoud, 2003). The sample containing 16.76% Pt,
1.87% Rh, 0.14% Pd, 0.01% Ag and 0.0012% Au and a large content of iron
oxides and silica was ground and then leached with 60% sulfuric acid
and 0.1 M NaCl at 125 C. A recovery of 99% Pt was obtained under optimum conditions of 60% H2SO4 and 0.1 M NaCl at 125 C in 10 h. These
processes should be subjected to large-scale validation to assess their
commercial viability.
3.3. Leaching in the presence of hydrogen peroxide
The leaching of Pt in aqua regia is not environmentally friendly method because of its toxic gas emissions according to the reactions (1)(7)
even in the absence of any dissolution process. On mixing HCl and
HNO3, toxic gases nitrosyl chloride (NOCl) and chlorine gas are formed.
Nitrosyl chloride further decomposes into nitric oxide and chlorine.
During this dissolution, NO2, another element of air pollution, may form
NO depending on the solution condition. Therefore, in addition to
nitrosyl chloride and chlorine, the fumes over aqua regia contain

Calcined spent catalyst

NaOH

BASIC LEACHING

FLOCCULATION AND FILTRATION

Leach liquor
Sodium aluminate

Sodium leached residue

Nitric acid

ACID LEACHING

FLOCCULATION AND FILTRATION

Leach liquor
(Cobalt nitrate)

Nitric acid leached residue

CALCINATION

Aqua-regia

AQUA- REGIA LEACHING

FLOCCULATION AND FILTRATION

Leach liquor
(Platinic acid)

Aqua-regia residue
Fig. 2. A ow-diagram for dissolving metal species from the calcined spent catalyst with basic and acidic lixiviants.

M.K. Jha et al. / Hydrometallurgy 133 (2013) 2332

nitric oxide. It is toxic and causes ozone layer depletion (Dessler,

2000). In the atmosphere, it may further convert to nitric acid, an
important contributor of acid rains (Kennedy, 1992). Therefore, NO
gas generated in automobiles exhaust is also removed by using automobile catalyst.
Hydrogen peroxide is a strong oxidizing agent with a standard electrode potential of 1.77 V and has been employed to improve Pt leaching
from spent catalysts and other materials. Pinheiro et al. (2004) studied
the recovery of Pt from Pt/Al2O3 (wt.%: 0.37 Pt, 0.05 Fe, 3.5 C, 50.60 Al)
and PtSn/Al2O3 (wt.%: 0.37 Pt, 0.41 Sn, 0.26 In, 0.44 Li, 0.15 Fe, 5.0 C,
48.30 Al) catalysts after oxidation in a furnace under air. The leaching of
the calcined mass in the presence of HCl and uoride ions was not effective. However, the dissolution of Pt was effective in the presence of strong
inorganic acids, and the support material dissolved in 24 h at 60 C.
Further studies carried out in the presence of hydrogen peroxide
improved the leaching kinetics to less than 1 h in the absence of strong
mineral acid. The study showed the possibility of replacing the HNO3 of
aqua regia with hydrogen peroxide. Pt dissolution may be represented
by the equation:

H2 O2 2H 2e 2H2 O

Pt 2H2 O2 4HClPtCl4 4H2 O

Pt 6HCl 2H2 O2 PtCl6 

2H 4H2 O:

10

Kizilaslan et al. (2009) studied the possibility of replacing aqua regia

with HCl and H2O2 lixiviant for the dissolution of Pt from spent catalytic
converters, achieving a recovery of 95% Pt under the optimized lixiviant
concentration with the oxidizing agent in a 10 HCl:1 H2O2 solution. The
process could be easily adaptable for industrial application under the
moderate experimental conditions. Aberasturi et al. (2011) recently
proposed a process ow sheet (Fig. 3) for the dissolution of PGMs,
including Pt, from different types of car catalytic converter catalysts
with honeycomb monolith supports with wash-coats onto which the
PGMs are adsorbed. The ground sample was thermally pretreated at
250 C for 22 h before leaching in HCl and H2SO4 in the presence of
oxidizing agents, hydrogen peroxide and nitric acid. The uoride ion
was also employed by adding NH4F, which improved the dissolution
efciency by attacking the interface between the PGMs and the catalyst
substrates. A recovery of 95% was obtained by leaching at 90 C for 6 h
after thermal pre-treatment with both oxidizing agents. Other associated
metals, Pd and Rh are also leached in the presence of H2O2. The presence
of H2SO4 as a proton source also improves the leaching of Rh. Recently,

29

Sun and Lee (2011) also reported the leaching of the spent catalyst
(wt.%: 0.08 Pt, 10.15Al, 0.85 Si, 0.28 Fe, 0.005 Ni) with mixture of 10%
HCl and 1% H2O2 at 70 C for 2 h at 50 g/L pulp density after pretreatment
at 800 C. The leach solution was used to separate the metals by solvent
extraction and ion exchange. The process is relatively environmentally
friendly because Pt dissolution in this solution yields less hazardous gases.
3.4. Leaching in cyanide solution
Sodium cyanide has also been employed for the leaching of Pt and
other associated metals of the spent materials because it forms stable
complexes with PGMs (Atkinson et al., 1992; Chen and Huang, 2006;
Chen et al., 2005; Hancock et al., 1977; Kuczynski et al., 1995a, 1995b).
The reaction of Pt with sodium cyanide under pressure has been reported
(Chen and Huang, 2006).
2Pt 8NaCN O2 2H2 O 2Na2 PtCN4  4NaOH:

Atkinson et al. (1989) compared the dissolution of Pt from virgin

and used monolith automotive catalysts using sodium cyanide solutions
and reported recoveries of 75% and 95% of the PGM, respectively,
with 5% NaCN and 1% promoter at pH 11.8 and 80 C in 1 h. A high
recovery was obtained by leaching with NaCN at elevated temperatures in an autoclave (Desmond et al., 1991). Under the optimum
conditions of leaching with 5% NaCN at 160 C in 1 h, recoveries of
97% and 85% of PGM were obtained from the virgin and used catalyst, respectively. However, almost all of the PGM was leached in
an autoclave above 250 C in 1 h. The results were further validated
on a 2 kg/day scale (Kuczynski et al., 1992, 1993) in two-stage autoclave leaching at 160 C for 1 h with 0.10 N NaOH and 1% NaCN
leach solutions. A lower dissolution of 8590% was found for the
used monolith catalyst under the same experimental conditions in
three leaching stages due to contamination with combustion
byproducts and sintering of the used catalyst substrate, which decreased the solutionsolid contact area. The process validated on a
pilot scale (45 kg scale) (Kuczynski et al., 1995a, 1995b) obtained
9597% Pt recovery from used pellet catalysts. The Pd and Rh recoveries were 9495% and 6481%, respectively. The PGM from the
leach solution was recovered by thermal hydrolysis of the cyanide
complexes, and over 99.8% PGM contained was removed. The residue was also suitable for disposal, satisfying environmental regulations. The dissolution chemistry and complex formation of PGMs in
the solution were reported by Sibrell and Atkinson (1994). The
rapid decomposition of cyanide at elevated temperatures was
found to be due to hydrolysis of cyanide to formate and ammonia.
Shams et al. (2004) reported the leaching in cyanide solution and
recovered 85% of Pt under the optimum conditions of a NaCN:catalyst

Spent catalyst

CRUSHING AND MILLING

THERMAL PRE-TREATMENT

Sample-A
HCl, H2SO4, NH4F
Oxidizing agent:
HNO3
Solid

OXIDATION LEACHING

FILTRATION

Pt-Pd-Rh recovery

11

Hydrogen pre-treatment

Sample-B
OXIDATION LEACHING

FILTRATION

HCl, H2SO4, NH4F

Oxidizing agent:
H2O2,
Solid

Pt-Pd-Rh recovery

Fig. 3. A simplied ow diagram for recovery of Pt and other associated metals.

30

M.K. Jha et al. / Hydrometallurgy 133 (2013) 2332

weight ratio of 2:1, 140180 C in pH 89 in 1 h from the spent dehydrogenation catalyst. The dissolved Pt was recovered using an anion
exchange resin. The resin on which the platinum complex is adsorbed
is dried and burned in an oxidizing atmosphere at 800850 C. The
recovered metallic powder is mainly platinum. The results show that
the presence of coke does not have an adverse effect on platinum recovery in cyanide leaching, and in practice, there is no need for the decoking
of spent catalysts in this method. The cyanidation process has also been
studied by Chen and Huang (2006) to recover PGMs from spent automotive catalysts containing 818.3 g/t Pt, 516.7 g/t Pd and 213.8 g/t Rh. As the
leaching was slow at room temperature and pressure, the studies were
carried out at elevated temperatures and pressures, showing a cyanide
leaching order of Pt>Pd>Rh due to the metal bonding strength of their
complexes, which are ranked as Rh(CN)63 >Pd(CN)42 >Pt(CN)42.
Huang et al. (2006) reported the recovery of Pt along with Pd and Rh
from spent automotive catalysts by pressure alkaline treatment followed
by cyanide leaching. These studies showed that the PGM metals are liberated from their carrier under high-temperature and pressure treatment
with NaOH. The pretreated material is then ground for subsequent
leaching in cyanide solution. Under the optimized conditions, the metal
recoveries were 96% Pt, 98% Pd and 92% Rh. In the cyanide dissolution
of PGMs, the reaction rate has been proposed to be controlled by a surface
chemical reaction, similar to the gold cyanide reaction mechanism
(Wadsworth et al., 2000). However, the reaction occurs at higher temperatures than gold because the metallic bonding strength of PGMs is higher
than that of gold and a surface oxide passivating layer is present.
3.5. Leaching with iodide/iodine solution
As the standard redox potentials of platinum in its iodide ion, PtI62,
(0.40 V) is lower than that of other ionic species at 25 C such as Pt4+
(1.15 V), PtCl62 (0.744 V) and PtBr62 (0.657 V), the dissolution of Pt
using iodine/iodide solutions is more promising than the other halogen
systems (Bard et al., 1985). This difference is due to the formation of stable Ptiodide complexes more easily at lower potentials, in which, the
aqueous ions I, I2, I3, HIO, and IO readily form. HIO and IO species
then slowly disproportionate to IO3 and other highly oxidized iodine
oxygen species (Bard et al., 1985). The major platinum-iodide ion
is PtI62 under acidic conditions. The oxidation and reductions in this
system are presented by the equations given below.

Pts 6I PtI6 4e

I3 2e 3I :

12

13

Although the iodide system is promising, very little work has been
reported so far on platinum/iodine leaching. Mahmoud (2007) used iodide solution for extracting precious metals under pressure in an autoclave. Meng and Han (1996) reported the leaching behavior of Pt
powder in iodide solutions with oxygen. Zanjani and Baghalha (2009)
reported the Pt recovery from the spent reforming catalysts (wt.%:
91.9 Al2O3, 0.19 SiO2, TiO2, 0.30 S, 0.28C, 0.24 Pt, 0.24 Re, 5.98 LOI, and
minor constituents) using iodide solutions from 25 to 95 C. The metallic platinum was nely dispersed on the walls of the nano pores of the
gamma alumina support. The studies carried out under different conditions showed that the use of catalyst particles b106 m and an impeller
agitation speed above 700 rpm eliminated the mass-transfer effects
during the leaching. The leaching of Pt was controlled by the surface reaction. The leaching rate increases with increasing initial iodineiodide
concentration and liquid:solid ratio because they increase the concentration of the active iodine species (HIO, I2(aq), I3). The leaching rate
was also higher for higher HCl concentration and temperature.
The active iodine species concentration decreased mostly due
to conversion to inactive iodineoxygen species and evaporation
from the solution. The aluminum of the catalyst support was also

partially leached with the acid present in the lixiviant. This process
has potential use after validating the results for Pt dissolution on a larger
scale.
4. Conclusions
Based on this review of the leaching of platinum from different waste
materials, particularly spent catalysts, using acidic and alkaline solutions,
the following conclusions can be made.
The studies carried out in different lixiviants, such as aqua regia,
hydrochloric acid in the presence of oxidizing agent, sodium cyanide
and iodide solution, showed the possibilities of leaching of Pt and
other associated metals. Some of the spent materials may require thermal treatment before leaching under suitable conditions.
Aqua regia has been studied by several authors to leach Pt and other
PGMs. The process is employed on the commercial scale to recover Pt,
Pd and Rh from different spent catalysts and electronic scrap. However,
the process suffers from an environmental viewpoint as it generates
NOx and chlorine and acid fumes during leaching due to the presence
of HNO3 in the leaching agent. A high concentration of HCl in the
leaching solution also generates fumes and Cl2 gas. Although the Pt
leaching rate is high in aqua regia, the economy of the process needs
further improvement due to the dissolution of the alumina matrix and
their separation.
To reduce the emission of HCl fumes during the leaching, sulfuric acid
and salts of chloride ions such as AlCl3 or NaCl have been employed to
form stable chloro-complex without affecting the efciency of Pt
leaching.
An alternative approach to dissolving the substrate using sulfuric acid or
alkali has been proposed, leaving Pt in the residue, which could be subsequently leached in aqua regia to recover Pt. The process consumes a
large amount of acid to leach out the base metals and the alkali used
to dissolve alumina and requires high temperature and pressure.
To replace the HNO3 oxidizing agent, H2O2 also has potential to be used
for the leaching of Pt. Similarly, other leaching agents, such as sodium
cyanide and iodide solutions, are also effective as leaching agents for
the dissolution of Pt. Sodium cyanide has also been used for the
leaching of Pt from spent catalyst. Pt extraction by cyanidation exhibits
poor kinetics at room temperature and atmospheric pressure. The consumption of cyanide is also high, as it is affected by the composition of
catalyst substrate. The desired leaching of the PGMs requires high temperature and pressure. The leaching of the Pt is also effective in iodide
solutions, but it requires high pressure to dissolve the metals.
The above-mentioned processes must be evaluated on a large scale before commercial exploitation. The environmental impact of these processes must be observed for the selection of a suitable process based
on the presence of impurities and other associated constituents present
in the spent materials and efuent generation.
Acknowledgments
The paper is based on the Basic Research Project of the Korea Institute of Geoscience and Mineral Resources (KIGAM) funded by the
Ministry of Science and Technology of Korea.
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