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Article history:
Received 6 December 2013
Received in revised form 21 April 2014
Accepted 23 April 2014
Available online 4 May 2014
Keywords:
Precious metals
Automotive catalysts
Hydrometallurgy
Acid leaching
a b s t r a c t
To recover platinum group metals (PGMs) from spent automotive catalytic converters with a smaller environmental load, a Zn-vapor treatment prior to acid leaching was previously proposed. Because PGMs and Zn form
alloys which dissolve easily, the pretreatment is believed to reduce the use of both chemical agents and processing time. In this study, effects of this treatment on PGM leaching were examined using simulated catalysts.
Leaching tests in aqua regia demonstrated that Zn-vapor treatment enhanced the dissolution of PGMs, and
was especially effective on Rh. Pretreatments were also found to enhance PGM extractions in hydrochloric acid
depending on the conditions. Reactions on Zn-treated catalysts in the solution are discussed based on these
results.
2014 Elsevier B.V. All rights reserved.
Automotive catalysts account for large portions of the world consumption of platinum (Pt), palladium (Pd) and rhodium (Rh) (Butler,
2012). Because of their limited production and high prices, the recovery
of these platinum group metals (PGMs) is an important issue. A representative structure of an automotive catalytic converter is shown
in Fig. 1 (Gandhi et al., 2003; Heck and Farrauto, 2001; Jimenez de
Aberasturi et al., 2011; Matsumoto and Shinjoh, 2008). A monolithic
ceramic substrate with a honeycomb structure is coated with porous
oxides such as alumina (Al2O3), ceria (CeO2) and zirconia (ZrO2), to
which PGM particles several nanometer thick adhere. The PGMs work
as active sites for catalytic reactions such as the oxidation of carbon
monoxide and hydrocarbon. Porous oxides have a role in dispersing
the PGMs and maintaining their large surface area. CeO2 also acts as a
promoter of the catalytic reactions by storing and releasing oxygen
(Reaction (1)) depending on the situation (Gandhi et al., 2003; Heck
and Farrauto, 2001; Matsumoto and Shinjoh, 2008).
PGMs (Habashi, 1997; Suzuki et al., 2007; Yoo, 1998). In pyrometallurgical processes, spent catalysts are melted with metals such as copper
(Cu) to separate PGMs and ceramics into the metal phase and slag
phase, respectively. Smelting at high temperatures, however, requires
extensive equipment as well as a high amount of energy. In hydrometallurgical processes, PGMs are dissolved into an aqueous solution
and then recovered by various methods such as solvent extractions
(Marinho et al., 2010; Reddya et al., 2010) and ion-exchange methods
(Kononova et al., 2011; Sun et al., 2012), which continue to be under intensive investigation. Although the hydrometallurgical processes might
be effective in separating PGMs from ceramics because of the selectivity
of chemical agents on the metals, it requires strong acid and oxidizing
agents to dissolve PGMs. Dissolutions of Pt, Pd and Rh in an aqueous solution containing chloride ions are represented by Reactions (2)(4)
(Jimenez de Aberasturi et al., 2011). The standard potentials for the reactions, E, are high, and thus oxidizing agents such as nitric acid, Cl2 or
H2O2 are required (Habashi, 1997; Jimenez de Aberasturi et al., 2011;
Yoo, 1998).
Pt 6Cl PtCl6
1. Introduction
Solid solutions of CeO2 and ZrO2 are widely used to improve the oxygen storage property (Gandhi et al., 2003; Matsumoto and Shinjoh,
2008).
Pyrometallurgical and hydrometallurgical processes combined with
physical separation have conventionally been used for the recovery of
Corresponding author. Tel.: +81 3 5452 6298; fax: +81 3 5452 6299.
E-mail address: hideakis@iis.u-tokyo.ac.jp (H. Sasaki).
http://dx.doi.org/10.1016/j.hydromet.2014.04.019
0304-386X/ 2014 Elsevier B.V. All rights reserved.
4e
E B 0:62V
E B 0:44V
Pd 4Cl PdCl4
2e
3e
Rh 6Cl RhCl6
E B 0:74V
60
Fig. 1. Representative structure of automotive catalytic converter and presumed recovery process in this study.
these are also believed to oxidize PGMs (Angelidis and Skouraki, 1996;
Baghalha et al., 2009; Habashi, 1997).
Pt 2NO3
8H 8Cl PtCl6
4H2 O 2NOCl
5
6
the process of the alloy dissolution (Habashi, 1997; Sasaki and Maeda,
2013).
The purpose of this study was to examine the effect of Zn-vapor
treatment on PGM extraction from catalysts. The use of actually spent
catalysts, however, presents the following difculties. Firstly, there are
many kinds of catalytic converters used industrially, and detailed information on their composition and structure is not available to the public.
Secondly, PGMs are distributed inhomogeneously in converters to optimize catalytic reactions (Lucena and Laserna, 2001). In addition, characteristics of spent catalysts depend on their usage environment, so that
PGM particle sizes and the degree of their contamination vary. To conduct a systematic investigation, therefore, this study used simulated catalysts specically prepared for the leaching tests.
Fig. 2. Experimental ow chart and appearance of the simulated catalyst prepared for this
study.
2. Experimental
61
PtO2 Ti Pt TiO2
10
62
Table 1
Experimental conditions.
#
Test I
Test II
Test III
Test IV
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Pretreatment
None (unused)
Heating in air (spent)
Deoxidizing
Zn-vapor
Unused
Spent
Deoxidizing
Zn-vapor
Zn-vapor
Zn-vapor
Zn-vapor
Spent
Zn-vapor
Spent
Spent
Zn-vapor
Zn-vapor
Spent
Deoxidizing
Zn-vapor
Unused
Spent
Deoxidizing
Zn-vapor
Zn-vapor
Zn-vapor
Leaching
T1/C
T2/C
Time/h
Extractant
T/C
Time/min
600
600
600
700
800
(Same as #10)
(Same as #10)
(Same as #10)
600
600
700
800
600
620
620
715
815
1
4
4
4
Aqua regia
60
30
Aqua regia
17
30
17
620
620
715
815
1
4
4
Hydrochloric acid
17
30
30
15
60
15
60
30
Hydrochloric acid
60
30
3. Results
3.1. Observation of a spent catalyst
A backscattered electron image of coating on an actual spent catalyst is shown in Fig. 3, in which white dots about of 100 nm can be
observed. These are believed to be PGM particles, and an EDX spectrum conrmed the existence of Pd and Rh. The observation conrmed a coarsening of PGM catalysts during use at high temperatures
(Matsumoto and Shinjoh, 2008).
Fig. 4 shows an image of the spent catalyst which was treated with
Zn vapor. Particles on the coating layer are larger than in Fig. 3, and
EDX analysis showed that Zn coexisted with Pd and Rh. The observation
demonstrated the reaction between the PGM catalysts and Zn vapor,
which was supplied through the gas phase.
3.2. Leaching tests on simulated catalysts
3.2.1. Leaching in aqua regia at 60 C (Test I)
Fig. 5(a) shows the extractions of PGMs after leaching in aqua regia
at 60 C for 30 min. Firstly, dissolutions of PGMs from an unused catalyst
(#1) were more difcult than from a simulated spent catalyst (#2).
Although further study is required to clarify the reason, the results indicated that PGMs might have been strongly bound or covered with oxide
or solvent in the coating layer before being used, and thus some heat
treatment would help the leaching of unused catalysts. Meanwhile,
Fig. 5(b) shows the extractions of oxides, which were lower after
heating than from the unused catalyst. The dissolution of the heattreated oxide is believed to be difcult due to its sintering at high temperatures (Graham et al., 1999).
Extractions of PGMs from spent catalysts were enhanced by
deoxidizing (#3), and that of Pt and Pd reached about 100%. (Here,
the excess of Pt extraction over 100% must have been caused by an
error involved in the experimental method, e.g. the PGM content in
each test piece estimated using a represented composition.) One possible reason for the enhanced extraction was a reduction of oxide layers
formed on PGM particles (Jimenez de Aberasturi et al, 2011). Because
surfaces of PGMs form oxides such as PtO2 and PdO in air (Barin,
1989; Glin and Primet, 2002) and the oxide layer makes PGMs passive
in a solution, their reduction to a metallic surface is assumed to enhance
the dissolution.
In addition, the deoxidization enhanced dissolutions of oxides as
shown by #3 in Fig. 5(b). Thus the shrinkage or dissolution of the oxides
also might have helped the extraction of PGMs by improving their exposure to the leaching solution. The effect of the deoxidizing on the dissolution of CeO2 will be discussed in Section 4.1.
Compared to deoxidizing (#3), Zn-vapor treatment (#4) was similarly effective for Pt and Pd, which attained the extraction of about
100%. The advantage of the treatment was obvious on Rh, of which
extraction was 60%. The alloying pretreatment is considered to be
more effective for Rh than Pt and Pd because its dissolution is intrinsically slow and passivation is likely to occur (Jimenez de Aberasturi
et al, 2011; Llopis et al., 1965).
3.2.2. Leaching in aqua regia at 17 C (Test II)
PGMs were extracted in aqua regia at 17 C in Test II, where Znvapor treatments were conducted at various temperatures (Table 1).
Fig. 6 shows the result; the extractions after leaching for 30 min were
generally lower at 17 C than at 60 C. For example, PGM extractions
from a spent catalyst (#6) were much lower compared to #2 in Test I
(Fig. 5). In regard to the effect of pretreatments, a similar tendency
was observed at 17 C and 60 C, i.e., deoxidizing (#7) and Zn-vapor
treatments (#8#11) enhanced the dissolution of PGMs. Extractions
of Pt and Pd from the Zn-treated catalysts were over 90%, and that of
Rh was about 60% except for #8. These achievements were comparable
to leaching at 60 C. In addition, extractions of PGMs were higher in #9
than #8, indicating that the prolonged Zn-vapor treatment was effective. The extraction of Rh was further improved in #10 and #11,
where Zn-vapor treatment was conducted at higher temperatures.
3.2.3. Time dependency of extraction in diluted aqua regia (Test III)
The extraction of PGMs was examined in diluted aqua regia, which
was prepared by mixing aqua regia with an equal volume of water. As
shown in Fig. 7, the Zn-vapor treatment promoted PGM extractions in
the diluted aqua regia (#12, #13) as was the case of undiluted aqua
regia (#6, #10). Furthermore, while the dilution slightly decreased
63
Fig. 3. Scanning electron micrograph of spent catalyst and EDX spectrum obtained from a region assumed to be a PGM particle.
2CeO2 8HCl2Ce
11
64
Fig. 4. Scanning electron micrograph of spent catalyst treated with Zn vapor and its EDX spectrum.
This presumption is consistent with the result that more CeO2 dissolved in hydrochloric acid than in aqua regia, which has an oxidizing
ability. In addition, PGMs on CeO2 probably promoted the dissolution
because they can provide active sites for the evolution of chlorine
(Yokoyama and Enyo, 1982). Thus the dissolution of CeO2 presumably
progresses through a mechanism of galvanic corrosion. For an example
of a similar experiment, Virot et al. (2012) reported that reductive dissolution of CeO2 was promoted by the oxidation of formic acid or
hydrazinium nitrate on PGMs.
Fig. 9(b) shows that deoxidizing promoted the dissolution of CeO2
(#23); a part of CeO2 was probably reduced (Reaction (9)), which improved its solubility. The dissolution of Ce was further promoted by
the Zn-vapor treatment indicating the reduction of CeO2 by Zn (Reaction (8)), and the extraction reached 70% in #26. The dissolution of
ZrO2 was also enhanced by the pretreatments in Fig. 9, presumably because ZrO2 existed as solid solutions with CeO2 (Matsumoto and
Shinjoh, 2008). Al2O3 was not much affected by these pretreatments.
4.2. Dissolution of PGMs in hydrochloric acid
Fig. 9(a) showed the dissolution of PGMs from simulated catalysts in
hydrochloric acid without adding an oxidizing agent. One presumable
CeO2 e 4H Ce
2H2 O
E B 1:66V
12
65
Fig. 5. Extraction of (a) PGMs and (b) oxides after immersion in aqua regia at 60 C for
30 min (Test I).
Fig. 6. Extraction of (a) PGMs and (b) oxides after immersion in aqua regia at 17 C for
30 min (Test II).
of Pt, Pd and Rh in aqua regia were promoted by deoxidizing. The Znvapor treatment was effective as well for Pt and Pd, and further
enhancement was observed on Rh. Time variation of the extractions
showed that the pretreatment not only accelerated the dissolution
of PGMs, but also increased their extraction ratios after prolonged
leaching. PGMs considerably dissolved also in hydrochloric acid, especially at an elevated temperature. The experimental results indicated
5. Conclusions
Extractions of PGMs from spent catalysts and the effects of various
pretreatments were examined using simulated catalysts. Extractions
66
Acknowledgments
The authors appreciate Toyota Motor Corporation for providing simulated catalysts, which were prepared specically for this study. A part
of this work was conducted in the Center for Nano Lithography & Analysis of The University of Tokyo, supported by the Ministry of Education,
Culture, Sports, Science and Technology (MEXT), Japan. This study was
nancially supported by the Ministry of the Environment in Japan
through a Grant-in-Aid for Scientic Research about Establishing a
Sound Material-Cycle Society (Grant K2120, K22089, K2346).
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Fig. 9. Extraction of (a) PGMs and (b) oxides after immersion in hydrochloric acid for
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