Materials Transactions

© 2022 The Japan Institute of Metals and Materials REVIEW

Trends of Technological Development of Platinum Group Metal Recycling:

Solubilization and Physical Concentration Processes+
Yu-ki Taninouchi1,2 and Toru H. Okabe1
1
Institute of Industrial Science, The University of Tokyo, Tokyo 153-8505, Japan
2
Department of Materials Science & Engineering, Kyushu University, Fukuoka 819-0395, Japan

Spent automobile catalysts are the most important secondary resource for platinum group metals (PGMs), and their recycling is essential
not only to ensure a steady supply of PGMs but also to preserve the natural environment. However, several factors limit the efficiency of PGM
recovery in current recycling processes. Specifically, PGMs represent a small proportion of the entire catalyst and are difficult to dissolve in
aqueous solutions for subsequent separation. In recent decades, multiple technologies have been developed to make the recycling of PGMs more
efficient and environmentally-friendly. Herein, we introduce the typical industrial processes for recovering PGMs from spent catalysts, along
with established and emerging trends in the technological development of PGM recycling. Furthermore, we review novel recycling techniques
for converting PGMs in spent catalysts into more soluble states and/or physically concentrating PGMs from spent catalysts.
[doi:10.2320/matertrans.MT-M2022150]

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(Received September 15, 2022; Accepted October 28, 2022; Published December 16, 2022)
Keywords: platinum group metals, recycling, recovery, automobile catalyst, solubilization, physical separation

1. Introduction

va Because of the high price of PGMs, they are already being

recycled from spent catalysts in industries. However, current

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Platinum group metals (PGMs) consist of 6 elements: Pt, recycling processes are highly time- and energy-intensive,
Pd, Rh, Ir, Ru, and Os. In view of their high resistance to heat consume large amounts of chemicals, and generate huge
and corrosion and unique catalytic properties, PGMs find amount of hazardous waste, which highlights the need for
numerous industrial applications. In particular, catalysts for more advanced and efficient recovery technologies.
purifying automobile exhaust gas (automobile catalysts)
account for a large fraction of the global demand for Pt,
Pd, and Rh (Fig. 1).1)
Over the past 30 years, the demand for PGMs as eV Japan has a competitive nonferrous smelting industry.
Domestic nonferrous smelters not only produce a wide
variety of nonferrous metals from imported natural resources,
but also collect precious metal (Au, Ag, and PGMs)-

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automobile catalyst components has significantly increased containing scraps (end-of-life products and wastes) from
in response to the tightening of environmental regulations around the world and process them for recycling. There are
and the increasing automobilization of developing countries also many companies in Japan that specialize in the recycling
(Fig. 2).2) Although the shift to electric vehicles will progress and refining of precious metals. With this background, the
mainly in developed countries, the global demand for PGMs domestic industry and academia have actively engaged in
as automobile catalyst components is expected to further the research and development (R&D) of the separation
increase over the next decade or more. Given that the and recovery of precious metals. This review outlines the
currently recycled catalysts were installed in automobiles current commercial processes used to recover PGMs from
manufactured ³15 years ago, the amount of PGMs recovered spent catalysts and describes trends in technological develop-
from spent automobile catalysts will significantly increase in ment with an aim to upgrade these processes. Furthermore,
the coming decades. solubilization techniques and physical concentration process-
Currently, the reserve-to-production ratios do not raise es for PGMs are reviewed as examples of novel technologies
any concern regarding the immediate depletion of PGM developed mainly by domestic researchers.
natural resources. However, PGM ore deposits are highly
localized in South Africa and Russia.3­5) Furthermore, the 2. Typical Methods of PGM Recovery from Spent
content of PGMs in the ores is only ³5 ppm, even in high- Automobile Catalysts
grade ores. Thus, millions of tons of ore must be mined
and processed to produce just a ton of a given PGM. The The appropriate recycling method should be selected
production of PGMs from natural resources is highly energy- according to the content and form of the recovered elements,
consuming and results in the discharge of large amounts of coexisting substances, and amount of treatment. The
gangue and tailings, thereby placing a significant burden on industrial recycling of precious metals, including PGMs, is
the natural environment around mines and smelters in currently accomplished using various methods, because the
resource-supplying countries. Therefore, the recovery of scale of recycling plants is relatively small, and the economic
PGMs from spent automobile catalysts is important from value of recovered elements is sufficiently high. This section
the perspectives of both resource security and global describes the typical methods of recovering PGMs from spent
environment preservation. automobile catalysts. Further information on the smelting and
recycling of precious metals can be obtained elsewhere.4­14)
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This Paper was Originally Published in Japanese in J. Japan Inst. Met. Automobile catalysts mostly consist of honeycomb-
Mater. 85 (2021) 294­304. structured ceramic substrates with a porous catalyst layer
2 Y. Taninouchi and T.H. Okabe

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Fig. 2 Growth in demand of Pt, Pd, and Rh for use in automobile
catalysts.2)

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eV
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Fig. 1 Global demand for (a) Pt, (b) Pd, and (c) Rh in 2019.1)

(Fig. 3). These substrates are typically composed of

cordierite (Mg2Al4Si5O18), which exhibits excellent thermal
shock resistance. The catalyst layers are mainly composed
of £-alumina, which has a high specific surface area, and
PGMs and their compounds are dispersed and supported as
Fig. 3 (a) Photograph of automobile catalysts. SEM images of (b) the cross
nanoparticles. Additionally, ceria or ceria/zirconia solid
section and (c) the surface of catalyst.
solutions are often present in catalyst layers as promoters
(or cocatalysts). The composition and amount of PGMs in
automobile catalysts vary depending on the type of engine The concentration of PGMs in automobile catalysts is 100­
and the production age of the catalyst. A rough estimate of 1000 times higher than in natural ores. However, automobile
the total content of PGMs in the catalysts is 500­5000 ppm.6) catalysts contain a small amount of PGMs compared to the
 Trends of Technological Development of Platinum Group Metal Recycling: Solubilization and Physical Concentration Processes 3

Fig. 5 Extraction of PGMs from spent automobile catalysts via the ROSE
process.17­19)

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alloying with collector metals facilitates the subsequent

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dissolution of PGMs in aqueous media.
Smelting processes using Fe as a collector have been
conducted in the United States and other countries,15,16) and

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Fig. 4 Typical commercial procedures for recovering PGMs from spent these processes are based on the heating of pulverized
automobile catalysts. catalysts in a plasma arc furnace together with Fe, fluxes
(e.g., CaO), and reductants (e.g., coke). High operating
temperatures (1500­1600 °C) are required to maintain Fe and
various PGM-containing recycled raw materials. Further-
more, because of the high chemical stability of PGMs, their
separation and recovery from spent catalysts is difficult.
A well-developed network for collecting spent catalysts eV slag in molten states. In Japan, Nippon PGM Co., Ltd. uses
a so-called ROSE process, in which the pulverized spent
catalysts are smelted in an electric furnace together with
Cu or its oxide, fluxes (e.g., CaO and SiO2), and reductants

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from end-of-life automobiles allows for the continuous (e.g., coke) (Fig. 5).17­19) The operating temperature (1300­
processing of substantial amounts of scrap. Existing smelting 1400 °C) is relatively lower than that employed in the case
techniques developed for natural resource processing (i.e., of Fe. After the removal of slag from the metal phase, the
smelting process of PGMs, Cu, Pb, etc.) can be used to PGM-containing Cu alloy is melted in an oxidizing furnace.
recover PGMs from spent catalysts in high yield. However, Air or oxygen is injected into the melt to gradually oxidize
locations of the smelter are limited, and the lead time for Cu, and the Cu alloy enriched with PGMs is separated and
PGM recovery is long. Because PGMs have a high risk of recovered.
price fluctuation, it is important to recover PGMs in the In hydrometallurgical (i.e., post-smelting) processing, the
shortest possible lead time. Therefore, the recovery of PGMs PGM-containing alloy is typically dissolved in a strongly
from spent catalysts is often performed using specialized oxidizing acidic solution, such as HCl/Cl2 (mixture of
processes and equipment. hydrochloric acid solution and Cl2 gas) and aqua regia, to
Figure 4 presents an overview of PGM recovery from efficiently extract PGMs into the solution. After the PGMs
spent automobile catalysts. Collected catalysts are mechan- are extracted into the acidic solution as chloro-complexes,
ically pulverized prior to the extraction of PGMs. An accurate multi-stage treatment including precipitation, ion exchange,
assessment of precious metal content in raw materials is and solvent extraction is conducted to remove non-PGM
important for the recycling business. The homogenization elements, as well as to separate individual PGMs and recover
of collected catalysts through pulverization and mixing is an them as pure metals or compounds. The details of these
indispensable pretreatment for determining the economic separation and purification processes are company secrets;
value of the processed scraps. however, solvent extraction is often used as the main
PGM recovery from pulverized spent catalysts is typically technology because it enables refining in a shorter time and
achieved through a combination of pyro- and hydro- with a simpler process. The hydrometallurgical processing
metallurgical processes. The former processes are used to of PGMs and/or their chemical properties in aqueous
concentrate PGMs, while the latter ones are then used for solutions have been extensively reviewed.20­25)
their final separation and purification. During pyrometallur- PGMs can be directly leached from pulverized spent
gical processing, the spent catalysts are smelted with catalysts without preconcentration by smelting. However, this
collector metals such as Cu, Fe, and Pb, which results in approach suffers from low recovery of PGMs (especially Rh),
the extraction of PGMs into the molten metal phase and the the discharge of large quantities of toxic wastewater, and the
removal of cordierite and alumina as slag. Although smelting generation of harmful exhaust gases. Therefore, in countries
requires large and specialized equipment, it allows PGMs to with strict environmental regulations, such as Japan, direct
4 Y. Taninouchi and T.H. Okabe

leaching is currently not implemented on a large industrial authors believe that the direct concentration of PGMs using
scale. physical separation techniques is particularly beneficial and
important. Physical separation techniques are originally
3. Trends of Technological Development developed to crudely separate solid particles in mineral
processing, and include particle size classification, gravity
In view of the low content of PGMs in spent catalysts separation, flotation, and magnetic separation. Compared to
(within several thousand ppm), the difficulty of dissolving metallurgical processes, physical separation can be performed
PGMs in aqueous media, and the arduousness of separating at a lower cost using simpler equipment. Generally, all of the
individual PGMs from their mixtures, the current recycling pulverized spent catalysts are metallurgically processed for
methods are still time-consuming, labor-intensive, and extracting PGMs. If physical separation can be incorporated
environmentally hazardous. Consequently, a variety of as a pretreatment to concentrate PGMs through the rough
research has been conducted to achieve more efficient, removal of non-recoverable ceramics, subsequent extraction
environmentally friendly, and energy-saving PGM recy- can be conducted more efficiently. Thus, physical concen-
cling.26­29) tration will be a key pretreatment technology for reducing
The development of effective dissolution (or leaching) the energy consumption and environmental impact of PGM
methods for PGMs is one of the most important challenges. recycling.

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To dissolve PGMs in spent catalysts by acid dissolution Development of effective physical concentration technol-
efficiently, enrichment and alloying by smelting are ogy may result in new material flows and business models for
performed in industries. However, such high-temperature recycling spent catalysts because PGMs can be crudely
treatment requires the use of large and costly equipment and separated at spent catalyst collection sites and automobile

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consumes large amounts of energy, solvents, and reducing dismantling yards. PGMs are both expensive and fluctuate
agents. Additionally, even after smelting, strong acids with greatly in price. Thus, shortening of the lead time from spent
high oxidizing power must be used to dissolve PGMs, and catalyst collection to refined PGM production is an important

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the process is inherently environmentally hazardous in terms issue. Currently, the collection of spent catalysts from used
of generation of toxic waste liquids and exhaust gases. For automobiles is conducted worldwide including urban areas,
this reason, R&D aimed at establishing a dissolution method whereas smelters and recycling plants for extracting PGMs
that directly leaches PGMs from spent catalysts and/or has from scrap are limited in location because of the need for
a low environmental impact has been actively conducted to
date. Many studies have focused on the optimization of
extraction medium parameters such as solution composition
(oxidizing agent, complexing agent, acid concentration, etc.) eV
special equipment. Therefore, the collected spent catalysts are
often transported by way of sea or land for further treatment
in smelters or recycling plants. The concentration of PGMs
at spent catalyst collection sites will improve the economic

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and temperature. Furthermore, in recent years, pretreatments value of the collected scraps and will reduce the volume of
for changing the chemical state of PGMs (solubilization) are scrap to be transported. With a higher economic value, the
also being actively researched. In Japan, Okabe and Maeda’s processed scrap could then be transported by air, which will
group (Institute of Industrial Science, The University of significantly reduce the lead time for recovering PGMs from
Tokyo) has been conducting pioneering research on this old automobiles.
solubilization technology since the early 2000s.30­34) The Owada’s group (Waseda University) has studied the
details of solubilization processes studied by them and other physical separation of PGMs from spent automobile catalysts
groups are described in Section 4.1. since the 1990s.39­44) In recent years, Okabe’s group (Institute
R&D on the separation and purification (mutual separa- of Industrial Science, The University of Tokyo) has proposed
tion) of PGMs using solvent extraction is also very active. a new group of physical concentration technologies
The solvent extraction method was introduced to separate and combining chemical pretreatments,45) some of which have
purify PGMs in the 1970s and has developed as an efficient been demonstrated to be effective. Further details of research
alternative to conventional methods such as precipitation. on physical concentration techniques are described in
Currently, solvent extraction is industrially used in the Section 4.2.
separation of Pt and Pd; however, the employed extractants
present the drawbacks of insufficient extraction speed and 4. New Recycling Technologies in R&D Stage
low stability in acidic solutions. Furthermore, effective
solvent extraction techniques for Rh, Ru, and Ir are not well 4.1 Solubilization of PGMs in spent catalysts
established. Therefore, much effort is currently being directed Okabe and Maeda’s group proposed a solubilization
at the optimization of extraction conditions and the develop- process for precious metals existing as trace components in
ment of more efficient extractants. R&D on this aspect is complex structures (e.g., PGMs in spent catalysts); the
also active in Japan. For example, Narita’s group (National proposed process involves an alloying treatment using metal
Institute of Advanced Industrial Science and Technology) vapor, as shown in Fig. 6, and its development has been
reported that amide-containing tertiary amine compounds underway since the early 2000s.10,14,30­34,46­53) Some active
show excellent performance for Rh extraction from hy- metals used, such as Mg, Ca, and Zn, are highly volatile.
drochloric acid solutions.35) Further details on recent research Their vapors can be easily supplied to the surface of the
trends in solvent extraction can be found elsewhere.24,36­38) porous catalyst layer and are suitable as reactants for alloying
Other separation and recovery technologies are also being PGMs. In typical commercial recycling processes, PGMs
improved and developed from various perspectives. The are extracted and separated from spent catalysts as alloys
 Trends of Technological Development of Platinum Group Metal Recycling: Solubilization and Physical Concentration Processes 5

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Fig. 6 Schematic illustration of the novel process for treating PGMs in

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scraps (e.g., spent automobile catalysts) to produce more soluble
species.46­53) The solubilization process is based on alloying treatment
with the vapor of active metals.

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Fig. 7 Results of dissolution experiments using aqua regia for initial
samples of (a) Pt powder and (b) Rh powder, which were performed
with collectors, such as Fe and Cu, through pyrometallurgical after alloying the PGMs with reactive metals through a gas-phase
smelting. However, temperatures required for such conven- reaction.10,46­48,50)
tional techniques are very high (>1200 °C), and a large

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amount of collector metals must be fed for the process. The
alternative treatment with active metal vapor can be
performed at significantly lower temperatures (<1000 °C)
than smelting, and also minimizes the amount of alloying
metal required and consumed.
Figure 7 shows the representative results demonstrating
the effectiveness of the alloying treatment using active metal
vapors.10,46­48,50) Among PGMs, Pt and Rh are particularly
difficult to dissolve in acid. Powder samples of Pt and Rh
were exposed to the vapors of Mg, Ca, Zn, and Li under
a reducing atmosphere at 700­800 °C and subsequently
leached with aqua regia. Even under the leaching condition
where less than 10% of the untreated sample was dissolved,
PGMs were effectively leached after the treatment with
metal vapors. The increased dissolution ratio was explained
by the preferential dissolution of active metals from PGM-
containing alloys, inducing the remaining PGMs to become Fig. 8 Extraction of Pt from pure Pt metal, Ca­Pt alloy, and oxidized
porous and particulate. Porous and fine particulation Ca­Pt alloy using aqua regia or concentrated HCl solution at room
increases the reaction area in contact with aqueous solutions. temperature.47) The Ca­Pt compound, which was obtained via alloying
Additionally, through investigation of the anodic dissolution treatment with Ca vapor and subsequent heat treatment at 900 °C in air,
was dissolved in HCl solution.
behavior of Zn­PGM alloys in HCl(aq.),54­57) it has been
shown that the change in the chemical state of PGMs owing
to atomization (i.e., thermodynamic destabilization due to
increased surface energy contribution) also contributes to tests on Ca­Pt alloy obtained by Ca vapor treatment and on a
their dissolution. sample of the same alloy oxidized in air at 900 °C for 24 h.47)
It was also reported in the early 2000s that oxidation For the sample after atmospheric oxidation, Pt could even be
treatment after alloying with active metals enables the extracted using oxidant-free concentrated HCl(aq.), likely
dissolution of PGMs in HCl solution without the addition because the Ca­Pt alloy was converted into a complex oxide.
of oxidizing agents. Figure 8 shows the results of leaching However, the chemical state (e.g., valence) of Pt after
6 Y. Taninouchi and T.H. Okabe

reaction behavior of the ceramic components of spent

catalysts, are required.
In recent years, R&D on the solubilization pretreatment for
PGMs has been actively pursued. In addition to the new
technology, which is based on alloying treatment using active
metal vapors (Fig. 6), various other processes have been
proposed, and the usefulness of some of these processes has
been demonstrated.
For example, Nomura’s group (National Institute of
Advanced Industrial Science and Technology) reported a
process that utilizes oxidative volatilization of PGMs and the
absorption of PGM oxides in LaScO3-based perovskite-type
oxides.58,59) Although the proposed process requires a high
temperature of over 1500 °C, it allows PGMs to be physically
separated from scrap via the gas phase and collected as
complex oxides that can more easily dissolve in acid.

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Additionally, Nagai et al. (Chiba Institute of Technology)
proposed an advanced version of this method in which Pt,
Pd, and Rh are absorbed by different oxides, and they are
searching for suitable oxides.60,61)

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Fig. 9 Extraction of Pt from pure Pt metal, chlorinated Pt, and chlorinated The oxidation treatment proposed by Kasuya’s group
Mg­Pt alloy using concentrated HCl solution at 80 °C. The Mg­Pt (National Institute of Advanced Industrial Science and
compound, which was obtained via alloying treatment with Mg vapor and Technology) is a solubilization process that has seen

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subsequent chlorination treatment using CuCl2 at 500 °C, was dissolved in significant R&D.62­70) In this method, alkali metal carbonates
HCl solution. This figure is reconstructed from Ref. 51) with permission
from Springer Nature.
such as Li2CO3 and Na2CO3 are mixed with pulverized spent
catalysts and calcined in air at 600­800 °C. As a result,
PGMs are converted into alkali metal­PGM complex oxides
solubilization treatment and the details of the dissolution
reaction in HCl(aq.) have not been elucidated.
The environmental impact of the dissolution step in
recycling can be significantly reduced if leaching of PGMs eV (e.g., Pt + Li2CO3 + O2 ¼ Li2PtO3 + CO2), which can be
dissolved in concentrated HCl(aq.) without the addition of
strong oxidants. Experiments with PGM powders revealed
the relationship between the process conditions and reaction

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can be performed with oxidant-free HCl(aq.) rather than with products as well as the dissolution behavior of the produced
strongly oxidizing acids such as HCl/Cl2 and aqua regia. oxides.62­67,69) PGM-loaded alumina powder and pulverized
Recently, Okabe’s group further investigated chemical spent catalysts were also processed, and effective extraction
treatment after alloying with active metals and reported the of PGMs with HCl(aq.) was demonstrated.68) An important
usefulness of chlorination.51) When a Mg­Pt alloy was mixed advantage of this new technology is that the solubilization of
with CuCl2 and reacted at 500°C for 3 h, the obtained sample PGMs in spent catalysts can be achieved by relatively simple
completely dissolved in concentrated HCl(aq.) at 80 °C after and mild pretreatment. Among the investigated alkali metal
0.25 h (Fig. 9).51,52) When Pt was subjected to chlorination carbonates, Li2CO3 exhibited the best performance. The
and leaching under the same conditions without prior alumina in the catalyst also reacts with the alkali metal salt,
alloying treatment, its dissolution efficiency was as low as and in some cases, becomes soluble in HCl(aq.). Therefore,
21%. The chemical state of the Mg­Pt sample after reduction of the required amount of lithium salt and
chlorination remains unclear, for example, it is not known suppression of the solubilization of alumina contained in
whether the product was a complex chloride or a mixture of spent catalysts will be important issues for the practical
MgCl2 and PtClx. Nevertheless, alloying with an active metal development. In addition, because the complex oxides are
followed by chlorination has high potential as an effective believed to form only when the PGMs and alkali metal salts
solubilization technique for PGMs or poorly soluble metals. are in physical contact, the particle size of alkali metal
In the experiment shown in Fig. 9, the chlorinating agent carbonates and their mixing with the spent catalyst will be
(CuCl2) was physically mixed with the Mg­Pt alloy, but in important factors affecting the process efficiency in practical
principle, chlorination by gas phase reaction is also possible. applications.
For example, Cl2 generated by the thermal decomposition of The conversion of PGMs to complex chlorides by
CuCl2 (CuCl2 ¼ CuCl + 0.5 Cl2) can act as a chlorinating chlorination in molten salts has also been investigated.71­73)
agent. Under appropriate conditions (temperature, chlorinat- For example, Yoshimura et al. (Chiba University) reported
ing agent, and reaction vessel shape), the PGM alloy in that Pt can be converted to K2PtCl6 by keeping in FeCl3­KCl
catalyst scraps can be directly and efficiently chlorinated molten salt at 350 °C.72)
through a gas-phase reaction. At present, this technology is
still in its infancy and has only been successfully 4.2 Physical concentration of PGMs in spent catalysts
demonstrated by Pt powder processing. For practical use of In spent catalysts, the concentration of PGMs to be
this technology, further studies on the relationship between extracted and recovered is less than 1 mass%. Considering
process conditions and PGM leachability, as well as the the overall recycling efficiency, it is beneficial to use physical
 Trends of Technological Development of Platinum Group Metal Recycling: Solubilization and Physical Concentration Processes 7

separation prior to metallurgical processing to coarsely

remove non-recoverable ceramics and concentrate PGMs.
Owada’s group conducted pioneering research on the
physical concentration of PGMs in spent catalysts. In the
early 1990s, this group processed pulverized spent catalysts
with a wet high-intensity magnetic separator, and it was
reported that PGMs could be separated when the catalysts
contained Ni as a promoter.39,40) However, as only old-type
automobile catalysts contain a sufficient amount of Ni, the
development of this method has not progressed since then.
Owada’s group also studied the enrichment of PGMs by
flotation, which is a solid/solid separation technique
exploiting differences in surface hydrophilicity.40,41) Solid
particles are suspended in an aqueous solution into which
bubbles are blown, and particles with a hydrophobic surface
attach to the bubbles to float and separate. The usefulness Fig. 10 Novel physical concentration techniques in which chemical

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of flotation using dodecylamine hydrochloride or sodium pretreatments are used to improve the efficiency of PGM separation from
dodecyl sulfate as the collecting agent has been preliminarily scraps (e.g., spent automobile catalysts).45)
investigated, but the method has been limited by the low
separation efficiency of PGMs.

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Since the 2000s, there have been several reports on
physical concentration based on particle size sorting. As the
catalyst layer is more fragile than the cordierite substrate,

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PGMs are preferentially distributed in the finer particles than
in the coarse particles after pulverization. Kim et al. (Korea
Institute of Geoscience and Mineral Resources) conducted
attrition scrabbing under wet conditions and reported that
the recovery of Al2O3 and total PGMs in particles with size
<300 µm increased with increasing residence time.74) Under
appropriate conditions, the recovery efficiency of PGMs
reached ³80%, and the concentration factor reached ³2.5. eV
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A similar study was conducted by Owada’s group wherein
it was confirmed that a combination of jaw crusher, roll
crusher, and surface grinding using an attritor promotes the
distribution of PGMs to fine particles.43) Furthermore, based
on mathematical calculation and modeling, Owada’s group
reported that heating-quenching of spent catalysts will be
a useful pretreatment step for the physical concentration of
PGMs.42,44) When spent catalysts are heated to 600­800 °C
and subsequently quenched in water, the interface between
the catalyst layer and substrate cracks due to differences in
their thermal expansion rates. After thermal shock and
appropriate pulverization, PGMs are expected to be more
efficiently concentrated by particle size sorting.
Although several physical concentration processes have
been studied, an effective method that can be widely used in
industry has not yet been established. Recently, Okabe’s
group has proposed a new technology combining chemical
treatment with physical separation (Fig. 10)45) and is
working to demonstrate the feasibility and usefulness of Fig. 11 Schematic illustration of the novel technique for physically
this approach. separating PGMs from spent catalysts.75­77) In this technique, PGMs are
For example, the usefulness of a technique combining concentrated magnetically by depositing a ferromagnetic metal such as Fe
or Ni on the catalyst layer using electroless plating.
electroless plating and magnetic separation (Fig. 11) has
been demonstrated in a series of studies by the present
authors.75­77) In this technique, a ferromagnetic metal (Ni or Subsequently, the spent catalysts are pulverized, and PGMs
Fe) is deposited on the surface of PGM particles and/or are magnetically separated and concentrated.
the porous catalyst layer using electroless plating. To improve Electroless plating on ceramics usually involves compli-
the adhesion between the deposited ferromagnetic metal and cated surface pretreatments, such as sensitization and
the catalyst layer and to promote alloying of PGMs with the activation. However, when the appropriate plating conditions
deposited metals, heat treatment is performed as necessary. (such as bath composition and temperature) are selected,
8 Y. Taninouchi and T.H. Okabe

Fig. 12 Photograph of a honeycomb-type catalyst sample after electroless

Fe plating.77) The attraction of the catalyst sample to the magnet indicates
that ferromagnetic Fe was successfully deposited on the surface of the
catalyst layer.

Fig. 13 (a) Vacuum-sealed quartz ampoule used for the reaction between
PGM particles act as catalyzer and promote electroless Pt and FeCl2 vapor. Pure Pt samples were placed in the L-shaped unit and

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plating of Fe and Ni on the catalyst surface without any did not come into direct contact with the Fe and FeCl2 powder mixture.
special pretreatment (Fig. 12). Pt, Pd, and Rh were efficiently (b) Pt powder after alloying treatment with FeCl2 vapor at 927 °C for 1 h.
The Pt was converted into ferromagnetic alloy. This figure is reproduced
concentrated when the simulated catalysts processed by from Ref. 79) with permission from the Mining and Materials Processing
electroless plating were subjected to pulverization and Institute of Japan (MMIJ).

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magnetic separation. However, enhancement of process
efficiency is essential for the practical use of this technology,
as PGM concentration factor and recovery rate from actual

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automobile catalysts were only ³2 and 70%, respectively.
In our earlier studies, pulverization and magnetic separation
were performed in a primitive manner (i.e., pulverization by
hand using a mortar and separation using a handheld
magnet).75,76) The optimization of these physical operations
is expected to further improve the efficiency of PGM
enrichment and separation.
The physical concentration process, which combines eV
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magnetic separation with a gas-phase chemical reaction for
alloying with Fe, is another effective technique for extracting
PGMs.77­80) Fe­PGM alloys are ferromagnetic at room
temperature when the content of Fe is sufficiently high.
Therefore, alloying with Fe is a suitable pretreatment for
magnetic separation. However, unlike Mg and Zn, Fe is a
low-volatility metal, making it impractical to use Fe metal
vapor for the alloying treatment. Consequently, the authors
conducted thermodynamic analyses and experiments on
alloying treatment using FeClx (x = 2, 3) vapor, showing
that PGMs can be efficiently converted to ferromagnetic
alloys upon contact with FeCl2 vapor in a reaction system
containing metallic Fe.
For example, when Pt powder and a mixture of Fe/FeCl2
powders were vacuum-sealed in a quartz ampoule
(Fig. 13(a)) and heated at 927 °C for 1 h to fill the ampoule
interior with FeCl2 vapor, Pt was converted to a
ferromagnetic Fe­Pt alloy (mainly £ 2-FePt with an L10
structure) without physical contact with metallic Fe
(Fig. 13(b)).79) Although the disproportionation (3 FeCl2 ¼
Fe + 2 FeCl3) and decomposition (FeCl2 ¼ Fe + Cl2) of
FeCl2 vapor can be considered as alloying mechanisms, the Fig. 14 Schematic illustration of (a) FeCl2 vapor-based alloying treat-
former reaction was predicted to be the dominant one through ment77) and (b) the reaction mechanism underlying the alloying of PGMs
thermodynamic analysis. Other precious metals including Au with Fe through disproportionation of FeCl2 vapor ((b) is reused from
can also be alloyed with Fe using FeCl2 vapor treatment; in Ref. 80) with permission from Springer Nature).
particular, Pd and Rh were converted into ferromagnetic
alloys.77,78,80) On the other hand, cordierite and alumina Figure 14 shows a schematic of the reaction chamber (that
(the major catalyst components) remained unreacted under could be industrially viable) and the underlying mechanism
the same vapor-treatment conditions.80) for alloying treatment. The spent catalysts are heated and held
 Trends of Technological Development of Platinum Group Metal Recycling: Solubilization and Physical Concentration Processes 9

in a steel chamber filled with FeCl2 vapor. The disproportio-

nation of FeCl2 proceeds on the surface of PGM particles in
the spent catalysts, and the PGMs are alloyed with Fe. FeCl3
vapor, a byproduct of the disproportionation reaction,
diffuses in the gas phase and reacts with metallic Fe (e.g.,
inner wall of steel chamber) to regenerate FeCl2. Overall,
FeCl2 vapor serves as a medium for transporting Fe into
PGMs and is not consumed in principle. As spent catalysts
have a complex and porous surface structure, FeClx species
may attach to their surfaces in large quantity after the
alloying treatment. However, these species can be easily
separated and recovered from catalyst scraps via volatiliza-
tion (e.g., vacuum distillation). Therefore, the consumption
of FeCl2 and the generation of toxic waste can be minimized.
In fundamental experiments with simplified catalyst
samples, PGMs were successfully concentrated by magnetic

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separation after alloying treatment with FeCl2 vapor and
pulverization.80) However, future studies are required to
demonstrate the usefulness of this technology using actual
spent catalysts as well as to optimize the process conditions.

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Chemical treatment with electroless plating and FeCl2
vapor is not only useful as pretreatment for physical
separation but also enhances the dissolution of PGMs in

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acids. For example, when Rh-loaded alumina powder was
kept in aqua regia at 40 °C for 1 h, almost no Rh was leached.
Meanwhile, after electroless iron plating and heat treatment,
almost all of the Rh could be extracted in only 0.5 h due to
the alloying effect.81) It is also of interest to note that, after
alloying treatment with FeCl2 vapor, Pt powder easily
dissolved even in diluted aqua regia.77) Acid dissolution of
PGMs in the alloyed state requires an oxidizing agent. eV Fig. 15 Novel pretreatment processes involving solubilization and/or
physical concentration treatment for precious metals in scraps with
complex structures (e.g., PGMs in spent automobile catalysts). The
pretreatment processes allow precious metals to be leached rapidly and

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However, if chlorination (or oxidation) treatment described selectively, thereby reducing the environmental burden.
in the previous section is applied after the physical
concentration, PGMs may be efficiently extracted using
oxidant-free HCl(aq.). Acknowledgments

5. Conclusion Research on physical concentration processes conducted

by the authors (described in Section 4.2) was financially
Japanese industry and academia have significantly supported by the Japan Society for the Promotion of Science
contributed to the R&D of technologies for recovering PGMs (JSPS) through a Grant-in-Aid for Scientific Research (S)
from end-of-life products and waste, as exemplified by the (KAKENHI Grant No. 26220910) and by the Mazda
solubilization and physical concentration processes intro- Foundation.
duced in this review. The new technologies presented herein
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