Beruflich Dokumente
Kultur Dokumente
Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet
Review
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
24
24
25
25
26
26
27
28
28
29
30
30
30
30
24
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
25
Table 1
Composition and other properties of spent catalyst.
Catalyst
composition
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
Zanjani and
Baghalha (2009)
26
NO3 4H 3e NO 2H2 O
2NOClg2NOg Cl2 g
Pt 4NO3 8H Pt
Table 2
Leaching in acidic solutions after pre-treatment.
Material
Reference
Spent reforming
catalyst
Aqua regia
solution
Baghalha
et al.
(2009)
Pt gauze dust
Aqua regia
solution
Perte et al.,
1988
6H 4NO 8H2 O
4NO 8H2 O
4NO2 4H2 O:
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
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)
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
LEACHING
FILTRATION
Residue
Alternative method
Pt solution
NH4Cl
TOA
SOLVENT EXTRACTION
Pt PRECIPITATION
NH4OH
PRECIPITATION
STRIPPING
(NH4)2PtCl6
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
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
NaOH
BASIC LEACHING
Leach liquor
Sodium aluminate
ACID LEACHING
Leach liquor
(Cobalt nitrate)
Aqua-regia
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.
H2 O2 2H 2e 2H2 O
2H 4H2 O:
10
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:
Spent catalyst
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
Pt-Pd-Rh recovery
30
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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