Resources, Conservation & Recycling 166 (2021) 105349

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Resources, Conservation & Recycling

journal homepage: www.elsevier.com/locate/resconrec

Microwave chloride leaching of valuable elements from spent automotive

catalysts: Understanding the role of hydrogen peroxide
Thomas Abo Atia a, 1, Wendy Wouters a, Giuseppe Monforte b, Jeroen Spooren a, *
a
Waste Recycling Technologies, Flemish Institute for Technological Research, VITO N.V., Boeretang 200, 2400 Mol, Belgium
b
CNR-ITAE, Istituto per le Tecnologie Avanzate “Nicola Giordano”, via S. Lucia sopra Contesse, 5, 98126 Messina, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: This study reports on the microwave-assisted leaching behavior of platinum group metals (PGMs) and light rare
End-of-life automotive catalysts earth elements (LREEs) from two representative end-of-life automotive ceramic catalyst materials in 6 M HCl at
Headspace gas study 150 ◦ C with and without the addition of 10 v/v% H2O2 solution. It was shown that the in situ generated
Microwave leaching
headspace gas in the pressure-tight reactor and the elemental speciation in the spent catalysts influence the
Platinum group metals (PGMs)
Rare-earth elements (REEs)
leachability of PGMs and LREEs. The formation of Cl2 in the headspace provided the 6 M HCl system with a
Recycling suitable oxidizing environment to leach PGMs as soluble chloro‑complexes. Indeed, spent catalyst containing
prevalently oxidized PGM species leached best in 6 M HCl (93.9 ± 0.7% Pd, 98±3% Pt, 70.7 ± 0.4% Rh).
Whereas, H2O2 addition moderately decreased the PGM leaching efficiency due to surface passivation by an
oxide layer. However, spent catalyst containing other oxidizable substrates (e.g. Ce3+, zerovalent PGMs) that
give rise to H2 evolution, compensated partially the oxidation potential of the HCl system. In such case, H2O2
addition slightly improved the PGM leachability (Rh 91.8 ± 0.1% Pd, 96±4% Pt, 89.9 ± 0.2% Rh).
Among the studied LREEs, Ce leaching was mainly affected by the passivation of Ce3+ through oxidation, thus
in the absence of H2O2 and at lower initial Ce3+ concentration Ce leached best (87–94%). The effect of hydrogen
peroxide was negligible for La and Nd, and moderate towards Y leaching. The leaching of these elements was
constrained by their association with Al and Zr oxides, respectively.

1. Introduction and recycling rely on hybrid pyro-/hydro-metallurgical processes (i.e.

The recovery of platinum group metals (PGMs) and light rare earth
elements (LREEs) from secondary raw materials is crucial for today’s
society due to supply risk and to their continuously growing demand
(Binnemans et al., 2015; Cowley, 2019; Ding et al., 2019a). PGMs and
LREEs are included in the list of the 30 critical raw materials (CRM) in
Europe (Blengini et al., 2020). Automotive catalysts contain both PGMs
and LREEs. With respect to primary ores that contain on average 0–20
ppm PGMs and 150–300 ppm LREEs, spent automotive catalysts exhibit
higher concentrations of these elements, ranging from hundreds to
thousands of ppm for PGMs and up to a few percent for LREEs, in
particular Ce (Dong et al., 2015; Dragulovic et al., 2008; Saguru et al.,
2018). Therefore, spent automotive catalysts are an important second­
ary raw material for PGMs, as today an estimate of ca. 43 metric t/y are
already recycled in Europe and North America, with a yearly growth of
2% (Raymond and Sebrell, 2019). Currently, the global PGM production
BASF, Johnson Matthey, Umicore, Nippon PGM) (Dong et al., 2015),
though hydrometallurgy is acquiring growing attention due to lower
processing temperatures, potential higher recovery rates, applicability
on smaller scale, safer handling of secondary streams (gaseous emissions
vs liquid effluents), etc. (Saguru et al., 2018).
Researchers extensively studied oxidative acid leaching for the
extraction of PGMs from waste automotive catalysts (Harjanto et al.,
2006; Nogueira et al., 2019; Safarzadeh et al., 2018), integrated with
hydro- and solvo-metallurgical separation steps (Saguru et al., 2018) as
alternative routes to pyrometallurgy. Combinations of oxidizing and
complexing lixiviants (e.g. ammonia, halides, cyanides (Mpinga et al.,
2015; Patel and Dawson, 2015; Sefako et al., 2017)) were exploited to
improve the dissolution of PGMs from catalysts.
Leaching with hydrochloric acid is particularly interesting for the
extraction of PGMs, as the presence of chloride ions stabilizes PGM
chloro-complexes in the leaching mixture and decreases the oxidation

* Corresponding author.
E-mail address: jeroen.spooren@vito.be (J. Spooren).
1
Current affiliation: KU Leuven, Department of Chemistry, Celestijnenlaan 200F, P.O. box 2404, B-3001 Leuven, Belgium.

https://doi.org/10.1016/j.resconrec.2020.105349
Received 8 September 2020; Received in revised form 10 December 2020; Accepted 11 December 2020
Available online 26 December 2020
0921-3449/© 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
T. Abo Atia et al. Resources, Conservation & Recycling 166 (2021) 105349

potential of metallic PGMs at 25 ◦ C, 1 atm (Eqs. (1)–(8)) (Vanysek, large scale encounters limitations (Saguru et al., 2018), mostly con­
2011). cerning the small penetration depth in aqueous systems of the 2.45 GHz
radiation (Al-Harahsheh and Kingman, 2004). However, such con­
Pt2+ +2e− ⇌Pt E0 =1.18V (1)
straints can be overcome by applying the 915 MHz frequency, and/or by
advanced engineering of the MW reactor, such as reactor geometry and
design, fluid dynamics enhancement, and multiple magnetrons inte­
Pd2+ +2e− ⇌Pd E0 =0.95V (2) gration (Singh et al., 2015). Nowadays, at the advent of the switch to
renewable energy, the application of microwave technologies in indus­
trial applications is growing.
Within this scenario, the purpose of this work was to compare the
Rh3+ +3e− ⇌Rh E0 =0.76V (3)
effectiveness of microwave-assisted leaching in 6 M HCl and 6 M HCl +
10 v/v% H2O2 of PGMs and LREEs for two representative spent auto­
motive catalyst materials. Because the effect of fast and efficient MW
[PtCl4 ]2− +2e− ⇌Pt+4Cl− E0 =0.76V (4) heating of the reaction mixture on the leachability of PGMs is already
well understood, this work focused on studying the influence of hy­
drothermal reaction conditions (i.e. the headspace gas composition), the
chemical speciation of elements within the starting materials and how
[PtCl6 ]2− +2e− ⇌[PtCl4 ]2− +2Cl− E0 =0.68V (5)
the leachability is influenced by the addition of an oxidation agent,
H2O2.

[PdCl4 ]2− +2e− ⇌Pd+4Cl− E0 =0.591 (6) 2. Experimental

2.1. Materials
2− 2−
[PdCl6 ] +2e− ⇌[PdCl4 ] +2Cl− E0 =1.29V (7)
Two representative samples were used in this work. Both samples
were pretreated and provided by MONOLITHOS Catalysts Ltd. (Greece)
from two sampling campaigns of spent automotive ceramic catalysts.
[RhCl6 ]3− +3e− ⇌Rh+6Cl− E0 =0.43V (8) The first sample (Batch 1) was obtained from the collection and sorting
of 100 exhausted automotive catalysts. The catalysts were dismounted,
For HCl leaching, nitric acid, hydrogen peroxide, hypochlorite, etc.
and the recovered monoliths were milled to below 2 mm and homoge­
have been investigated as additional oxidizing agents (Ilyas et al., 2020;
nized. A subsample was further milled to below 0.2 mm and used as
Jimenez De Aberasturi et al., 2011; Trinh et al., 2020). But, they showed
starting material in this work. For the second sample (Batch 2), first, 8
potential drawbacks in terms of process control and safety, due to
heavy duty diesel oxidation catalysts provided by Ford Otosan (Turkey)
thermal runaways, corrosion, and/or secondary emissions (e.g. H2, NOx,
were milled and homogenized according to the same procedure as
SOx, HOCl, NOCl, Cl2) (Jha et al., 2013). Alternatively, ferric or cupric
described above. Also, a mixture of 10 gasoline three-way catalysts, 3
chloride salts can be used as oxidizers, although PGM recoveries might
diesel lean NOx trap catalysts and 7 diesel oxidation catalysts, provided
be limited and the presence of interfering ions (e.g. Fe3 or 2+, Cu2 or 1+)
by CRF (Italy), was processed in the same way. Next a mixture of both
could make downstream separations more intricate (Ding et al., 2019b;
obtained samples in a 1:2 wt. ratio (Ford: CRF) was prepared to obtain
Nogueira et al., 2014). Whereas, on industrial scale, the Kell process
Batch 2.
makes use of a chlorination reaction with HCl/Cl2 mixtures, to extract
For MW leaching experiments HCl (Merck, fuming 37% p.a.), H2O2
PGMs directly from oxidized sulfidic ore leach residues, in order to avoid
(Merck, ultrapure 31% wt.) and DI water (Milli-Q) were used.
smelting operations (Liddell and Adams, 2012).
Automotive catalytic monoliths, on average, contain 3–5% of cerium
2.2. Methods
by weight, turning them into attractive resources of this element. Hy­
drochloric acid leaching is also a valid route to extract LREEs from their
2.2.1. Chemical characterization of the auto catalyst materials
oxides, which dissolve as chlorides (Mohammadi et al., 2015). In fact,
The mineralogy of the materials was defined by XRD analysis
hydrometallurgy was adopted for the extraction and recovery of REEs
(PANalytical EMPYREAN) at Co Kα radiation, using High-Score Plus for
from different types of valuable REE secondary resources (Binnemans
phase determination.
et al., 2013a, 2013b; Binnemans and Jones, 2014; Borra et al., 2019).
To allow for an accurate measurement of the PGM and base elements
This is also strictly related to the drawbacks of pyrometallurgy, wherein
content in solid materials, the samples (100 mg) underwent a 2-step
REEs are diluted and discarded in the slag (Steinlechner and Antreko­
microwave assisted digestion, first at 500 W and subsequently at 900
witsch, 2015). Proposed recovery routes for REEs from chloride leach­
W in a mixture of 3 ml H2O2, 4 ml HNO3, 5 ml HCl and 3 ml HBF4.
ates included cerium precipitation with a sulfate source, preferably
Subsequently, the resulting solutions were diluted to a known volume
Na2SO4 (Rumpold and Antrekowitsch, 2012; Steinlechner and Antre­
and analyzed by ICP-OES (Perkin Elmer, Optima 3000 DV, Avio 500). This
kowitsch, 2015), and selective solvent extraction (Ilyas et al., 2021a,
method was validated by measuring the PGMs concentrations of a
2021b; Trinh et al., 2020).
certified car catalyst material ERM®-EB504a. ICP-OES analysis pro­
Microwave heating can enhance hydrometallurgy (Al-Harahsheh
vided the same accuracy as ICP-MS (±5%).
and Kingman, 2004). And a recent work by Suoranta et al. pointed out
Energy dispersive XRF (X-LAB 2000, Spectro), using the Geo­
that microwave-assisted leaching in hydrochloric acid (37–38%) was as
ChemTraces method, validated for the measurement of low concentra­
effective as in concentrated aqua regia to extract ≥ 90% PGMs at T ≥
tions of REEs, was applied for determining the LREE content in the
150 ◦ C and a liquid-to-solid ratio ≥10 (Suoranta et al., 2015). Despite
starting materials.
honeycomb materials of spent catalysts scarcely heat under MW irra­
X-ray photoelectron spectroscopy (XPS) surveys have been acquired
diation, due to poor dielectric loss of their constituting minerals γ-Al2O3
on the starting materials using a Physical Electronics (PHI) 5800–01
and cordierite (He et al., 2019), aqueous lixiviants do heat fast and
spectrometer equipped with a monochromatic Al Kα X-ray source, at a
enabled a drastic lowering of processing time (Suoranta et al., 2015).
power of 350 W and a pressure in the analysis chamber of the spec­
Nevertheless, the implementation of MW leaching technology on
trometer of 1 × 10− 9 Torr.

2
T. Abo Atia et al.
2.2.2. Microwave assisted leaching
The leaching experiments were performed in a laboratory microwave
(MW) set-up (Milestone FlexiWave) equipped with a spinning carousel,
holding 15 pressure-sealed Teflon-lined reactors (Pmax=100 bar, Tmax=
250 ◦ C, 100 mL). The cavity is irradiated in multimode by a dual
magnetron system (950 W each) working at 2.45 GHz.
A solid load of 5 g catalyst in each 100 ml vessel was used for the
leaching experiments, applying a liquid-to-solid ratio (ml/g) of 10 in 6 M
HCl and of 11 in 6 M HCl + (10% v/v) H2O2. The concentration of 6 M
HCl was previously determined in optimization experiments to provide
suitable acidity and chloride concentration for satisfactory PGM
extraction and limited reagent consumption (Trinh et al., 2017). The
chosen reaction temperature profile (ramp time of 15 min to 150 ◦ C,
which was then held for 10 min) were based on the work by Suoranta
et al., who reached >90% PGM leachability in concentrated HCl
(37–38%) by MW leaching of automotive catalyst (Suoranta et al.,
2015). Additionally, internal magnetic stirring of approximately 990
rpm, was applied.
The PGM leaching efficiencies were calculated with two methods: (i)
and (ii), for comparison Eqs. (9) and ((10)). The first Method (i) is based
on direct ICP-OES (Perkin Elmer, AVIO 500) analyses of the leachates for
elemental concentration determination using the emission lines of Pd
(340.458 nm), Pt (299.797 nm), Rh (343.489 nm) corrected by Lu
(261.542 nm) as internal standard. The second Method (ii) was based on
the measurement of the residual amount of PGMs (and base metals) in
the leach residues by the above-mentioned optimized destruction
method.
mPGM in the leachate
(i) %Leachate = x 100
mPGM in the starting material
( )
mPGM − mPGM
(10)
in the starting material in the residue
(ii) %Residue =
mPGM
x 100
in the starting material
The LREE leaching efficiencies were determined in the same way by
(i), using ICP-OES concentrations of LREEs in the leachates, determined
at the less influenced emission lines of Ce (413.764 nm), La (408.672
nm), Nd (406.109 nm), and the LREE concentrations in the starting
material, measured by EDXRF.
XRD measurements have been performed on the dried leaching res­
idues. The dielectric properties of the autocatalyst materials and the 6 M
HCl solution were determined by a dielectric measurement kit (Püschner
GmbH & Co.) equipped with an open coaxial probe operating at a fre­
quency range of 1.8–2.6 GHz.
2.3. Headspace gas composition study
2.3.1. Headspace gas composition simulation
HSC chemistry 8.2.0 software, applying the Gibbs energy minimi­
zation method, GEM, was used to compute the headspace gas compo­
sitions in function of temperature inside a 100 mL closed reactor. The
modeling considered a 2-phase (gas-liquid) system. As liquid phase, H+,
Cl− and H2O species were considered in the presence and absence of
H2O2. While the gas phase included N2, HCl, HOCl, Cl2, H2O, H2 and O2
with and without H2O2. The chosen initial concentrations of species in
the liquid and gas phases of the model systems reflected the composition
of lixiviants and air in the headspace at atmospheric pressure, as applied
in the experimental systems (Tables S1, S2, SI).
A 21-step iteration calculation, defining N (amount), T (tempera­
ture), and V (volume), with T as independent variable (25–150 ◦ C);
applying the Mixing Entropy Conversion for aqueous species and
imposing target calculations for a set volume of 100 mL, was used.
2.3.2. Experimental headspace gas composition measurement
The MW reactors did not allow for sampling of the gas phase.
Therefore, an alternative reactor set-up was used to simulate the
leaching conditions in the MW system. A gas-tight glass reactor (200 ml)
Resources, Conservation & Recycling 166 (2021) 105349
equipped with a septum for gas sample, which could withstand 3 bar,
was used. The limited pressure range excluded the possibility to test the
HCl-H2O2 leaching system safely. Two experiments in duplicate were
performed with 10 g of each tested catalyst material (i.e. Batch 1 and 2)
in 100 ml of 6 M HCl. The mixture was heated to 125 ± 5 ◦ C for 10 min.
Once the temperature decreased below 100 ◦ C, the headspace gas was
sampled to avoid water condensation inside the syringe. The gas samples
were analyzed by gas chromatography (Trace GC Ultra, Thermo Scienti­
fic) calibrated for H2, O2, N2 and CO2 determination.
3. Results and discussions
3.1. Composition of the spent auto catalyst materials
The mineral composition of both samples consisted mainly of
cordierite Mg2Al4Si5O18, followed by other cubic oxide phases matching
substituted zirconia (Zr0.86Ca0.14O1.86, Zr0.72Y0.28O1.862, which can also
include Sr, Ti, etc.) and/or CeO2, in addition to Al0.5Si0.75O2.25 (Fig. S1).
Furthermore, Batch 2 contained BaCO3.
The total elemental concentrations of both samples are presented in
Table 1. The total PGM content in Batch 1 was about 0.3 wt%, while for
Batch 2 it was above 0.4 wt%. The determination of the LREE content by
ICP-OES analyses was inaccurate as these elements precipitated in the
presence of fluoride during MW digestion. Also, matrix elements, such as
Zr and Si, did not fully dissolve during digestion. Therefore, EDXRF was
used to determine the concentration of such elements in the solid
materials.
(9) 3.2. Microwave assisted leaching
Microwave leaching was carried out in pressure-sealed reactors,
whereby hydrothermal conditions (T > 100 ◦ C, P > 1 atm) were reached
through heating of the polar solvents by interaction with microwaves.
The dielectric properties of the spent ceramic automotive catalysts were
measured at 25 ◦ C and gave ε’ = 2.425 ± 0.004, ε’’ = 0.048 ± 1 and ε’ =
2.4 ± 0.1, ε’’ = 0.012 ± 0.004, for Batch1 and 2, respectively. These
values were comparable to available literature data (He et al., 2019).
The measured dielectric constants (ε’) and relative effective dielectric
loss factors (ε’’) were low and indicate that microwaves are scarcely
absorbed and transformed into heat by these materials. Therefore, MW
volumetric heating was assumed to purely occur through the coupling of
microwaves with the 6 M HCl lixiviant, that showed remarkable
dielectric properties (ε’ = 128.63 ± 0.03 and ε’’ = 42.11 ± 0.6).
3.2.1. Headspace gas study
The simulation of the headspace gas composition and of the pressure
build-up in HCl and HCl+H2O2 systems as a function of temperature
(Fig. 1) aimed at studying (i) the potential safety issues related to the
formation of harmful and explosive gases and (ii) the influence of the
formed gasses on the leaching mechanisms. The simulation indicated
that, upon increasing temperature and pressure in a closed reactor with
both 6 M HCl and 6 M HCl + 10% v/v H2O2 solutions, chlorine gas
evolves. The pressure build-up and the generation of an O2/Cl2-rich
atmosphere is low for the HCl system, in respect to HCl+H2O2, wherein
the pressure and O2 concentration increase stems from H2O2 decom­
position (Eq. (11)).
The 6 M HCl system exhibited a low O2 concentration upon
increasing temperature, as well as very low H2 and a moderate Cl2
concentrations, which allows to conclude that the risk for an explosive
reaction is low. According to the simulation, the oxidation of HCl vapors
to Cl2 by O2 may take place spontaneously (Eq. (12), Fig. S2). In
HCl+H2O2, Cl2 forms through a cascade of multiple reactions (e.g.
radical reactions) and the amount of produced Cl2 is determined by the
concentrations of HCl, H2O2 and native oxygen, as presented in the work
of Skudaev et al. (2008). Thus, in the presence of H2O2 the Cl2 gas
concentration was considerably higher, although H2O2 will also affect
3
T. Abo Atia et al. Resources, Conservation & Recycling 166 (2021) 105349

Table 1
Concentration of PGMs (Pd, Pt, Rh), LREEs (Ce, La, Nd, Y) and other elements in Batch 1 and Batch 2 materials.
Element Batch 1 (mg/kg) Batch 2 (mg/kg) Analytical method

PGMs Pd 1720 ± 50 2200 ± 70 ICP-OES

Pt 1020 ± 60 2100 ± 100 after MW destruction
Rh 324 ± 6 174 ± 4 (H2O2-HNO3-HCl-HBF4)
REEs Ce 27,600 34,000 EDXRF
La 3820 ± 40 3850 ± 40
Nd 909 655
Y 127 2259
Others Al 200,000 ± 30,000 280,000 ± 20,000 ICP-OES
234,000* 378,000* after MW destruction
Ba 5900 ± 200 9200 ± 100 (H2O2-HNO3-HCl-HBF4)
4512 ± 2* 8523 ± 3* *EDXRF
Ca 3400 ± 100 610 ± 40
3000* 400*
Fe 6900 ± 200 3250 ± 50
5520 ± 200* 2400 ± 2000*
Mg 52,800 ± 500 28,700 ± 1000
74,600* 35,000*
S 2300 ± 60 1080 ± 60
2318 ± 2* 1551 ± 2*
Si 106,000 ± 4000 133,000 ± 3000
98,000* 154,000*
Sr 2100 ± 120 2100 ± 100
1450 ± 3* 1391 ± 1*
Ti 3175 ± 5 2400 ± 200
Zr 26,000 ± 1000 29,000 ± 1500
32,095 ± 5* 38,410 ± 10*
Zn 2900 ± 100 205± 3
32,095 ± 5* 110 ± 1*
C 0.18 wt% 0.23 wt% TC
<LOD 0.15 wt% TOC

the equilibrium chlorine concentration through Eq. (13) (Skudaev et al.,
2008).
At the modelled internal pressures (P ≈ 5 or 32 bar) the amount of
dissolved Cl2 varied, because the solubility of Cl2 in water increases with
pressure according to the Raoult’s law, adapted to non-ideal mixtures:
yi ϕp,i P = xi γ i p∗i , where yi is the mol fraction in the gas phase, ϕp,i the
fugacity coefficient, P the total pressure, xi is the mol fraction in solution,
γi is the activity coefficient corrected for the molecular interaction in the
liquid phase, and pi* the partial pressure of the ith component.
Moreover, it is common knowledge that Cl2 hydrolyzes in water to
give hypochlorous acid (although the reaction is not spontaneous, Eq.
(14))(Sivey and Roberts, 2012). Nevertheless, when Cl2 is subtracted
from the headspace, the equilibrium in Eq. (12) proceeds to the right.
2H2 O2 ⇌2H2 O+O2 ΔG150∘ C =− 62.51kJ (11)

Fig. 1. Headspace gas composition and pressure build-up simulation for the HCl (up) and HCl+H2O2 (below) system from 25 to 150 ◦ C (50 mL HCl + 5 mL H2O2 in
100 mL reactor). HSC chemistry 8, GEM. Equilibrium calculations.

4
T. Abo Atia et al. Resources, Conservation & Recycling 166 (2021) 105349

2HCl(g) +0.5O2(g) ⇌Cl2(g) +H2 O(g) ΔG150∘ C =− 15.77kJ
H2 O2 +Cl2 ⇌O2 +2HCl
Cl2 +H2 O⇌HOCl+HCl
Cl2 +2e− ⇌2Cl−
While for Batch 1, CO2 mainly formed through the oxidation of soot.
The observed difference in H2 formation will be further explained in the
(12) following sections, as it was correlated to the difference in relative
abundance of metallic/oxidized PGMs and of Ce3+/Ce+4 species in the
two catalyst materials.
ΔG150∘ C =− 24.13kJ (13) All the MW experiments in this work were executed at a fill rate of
approximately 50 to 55% of the available reactor volume, with a load of
5 g of catalyst (specific gravity ≈ 2.6 g/cm3) plus 50–55 mL of lixiviant
in a 100 mL vessel. No temperature runaway or pressure release
ΔG150∘ C =16.77kJ (14) (overpressure) were experienced, both with and without hydrogen
peroxide present. It is noteworthy that the potential safety risk related
do hazardous headspace gas formation should be further investigated,
E0 =1.36V (15) particularly for HCl+H2O2 under MW radiation, whereby the headspace
gas needs to be analyzed for the presence of H2 and Cl-bearing gasses.

3.2.2. PGM leaching

2HOCl+2H+ +2e− ⇌Cl2 +2H2 O E0 =1.63V (16)
Dissolved Cl2 and HOCl play a key role as supplementary electron
acceptors Eqs. (15) and ((16)) from potential electron donor counter­
parties in the leaching mixtures (e.g. PGMs). Notwithstanding that HOCl
exhibits a more electrophilic nature, it is less reactive than Cl2 (Sivey and
Roberts, 2012). Therefore, the spontaneous Cl2 evolution under micro­
wave hydrothermal conditions provides additional oxidizing power to
the 6 mol L− 1 of H+ in the leaching system, which might be beneficial
towards PGM leachability (Asamoah-Bekoe, 1998), even in the absence
of H2O2 or other oxidants, as observed by Suoranta et al. (2015).
Experimentally, it was verified that the redox potentials measured
right after MW leaching both in HCl (775–930 mV vs. Ag/AgCl) and
HCl+H2O2 (940–945 mV vs. Ag/AgCl) were higher than in freshly
prepared lixiviants (600 and 890 mV vs. Ag/AgCl for HCl and
HCl+H2O2, respectively). Along with the dissolution of metal ions, the
presence of Cl2 and HOCl in solution contributes to the redox potential
increase. In fact, it was then observed that the potential of the recovered
leachates after reaction decreased over time until stabilizing at about
700 mV − accompanied with an orange color attenuation− for all
leaching experiments. This was associated to the slow release of Cl2 from
the leaching solutions over time.
Furthermore, the above models excluded the presence of metallic
species in the reaction mixture, which can lead to additional hydrogen
gas formation through reduction of HCl and water, or catalytic decom­
position of H2O2 (Barbier et al., 1992; Lin and Gurol, 1998; Lousada
et al., 2012; Michiels et al., 2015).
Therefore, an experiment was devised that allowed for the sampling
of headspace gas during reaction in 6 M HCl, which subsequently could
be analyzed by gas chromatography (GC) to determine the concentra­
tion of H2, O2, N2, CH4 and CO2.
For HCl leaching the measured hydrogen evolution remained below
its explosivity limit in air (4%) for Batch 1 and 2 material (Table 2).
However, the concentration of H2 and CO2 in the headspace gas differed
for Batch 1 and 2 leaching. These findings were correlated to the distinct
chemical composition of the autocatalyst materials.
The higher content of CO2 for Batch 2 was associated to the oxidation
of organic carbon (0.15 wt%) and the decomposition of BaCO3 (Eq. (17))
(Fig. S3).
Batch 1 and 2 materials were both leached in 6 M HCl in the absence
and presence of H2O2 and the PGM leaching efficiencies calculated by
methods (i) and (ii) are presented in Fig. 2. The two investigated catalyst
materials exhibited a distinct leaching behavior in terms of PGM
leaching efficiencies, as well as regarding the benefits derived from
hydrogen peroxide addition to improve leachabilities.
In the studied conditions, the leachabilities of Pd, Pt and Rh from
Batch 1 were 86 ± 3, 90 ± 1, 82 ± 3%, respectively, in 6 M HCl (775 mV
vs Ag/AgCl), and 91.8 ± 0.1, 96 ± 4, and 89.9 ± 0.2%, respectively, in
the presence of H2O2 (940 mV vs Ag/AgCl). The leaching trends deter­
mined by methods (i) and (ii) were the same, although the PGM
leachability determination might be underestimated by ICP analyses of
the leachates. Suppression of PGM signals (e.g. Pd) in ICP-OES analyze
might be caused by coextraction of interfering elements in Batch 1, such
as Fe, Al, Ce (Kim et al., 2018). Thus, a slightly higher Pd and Pt
extraction from Batch 1 took place in HCl+H2O2. Furthermore, a clearly
higher Rh leaching efficiency in the presence of H2O2 for Batch 1 was
observed. Contrarily to Batch 1, MW leaching of Batch 2 showed a
decrease in PGM recoveries upon H2O2 addition to the HCl leaching
solution (Fig. 2C and D). The Pd, Pt, and Rh leaching efficiencies for
Batch 2, calculated by method (i), were 93.9 ± 0.7, 98 ± 3, and 70.7 ±
0.4% in HCl (930 mV vs Ag/AgCl), and 88.1 ± 0.5, 91 ± 1, and 55.4 ±
0.8% in HCl+H2O2 (945 mV vs Ag/AgCl), respectively. It is noteworthy
that the by method (i) calculated Rh leachability was considerably
underestimated for Batch 2 material, showing a discrepancy of about
10–20% with the leachability derived by method (ii). This discrepancy
was ascribed to the spectral interference of the Rh signal with that of Al,
which was present at a higher concentration in the leachates from Batch
2, with respect to Batch 1 (Kim et al., 2018).
XPS analyses allowed to derive qualitative information on the
oxidation state of the Pd, Pt, and Rh particles’ surface (Fig. 2) in the
studied materials. Quantification was impossible as the signals of the
PGMs, present at low concentration, overlapped with those of more
abundant elements, i.e. Pd-Zr, Pt-Al, Rh-Mg.
In Batch 1, Pd and Rh mainly occurred in their metallic form Fig. 3C
and E) and their leaching was regulated by Eqs. (18)–((21). Whereas, in
the presence of H2O2, the metal oxidation was improved by native O2,
favoring the Pd and Rh dissolution (≈5–10%) through reactions 20, 21.

BaCO3 +2HCl⇌BaCl2 +CO2 + H2 O ΔG150∘ C = − 32.35 kJ (17) Pd + H+ +3Cl− +0.5Cl2 ⇌PdCl4 2− +0.5H2 ΔG150∘ C = − 55.05 kJ (18)

Rh + H+ +4Cl− +Cl2 ⇌RhCl6 3− +0.5H2 ΔG150∘ C = − 119.64 kJ (19)

Table 2
GC analyses of headspace gas generated during leaching of spent auto catalyst Pd + 4H+ +6Cl− + O2 ⇌PdCl6 2− +2H2 O ΔG150∘ C = − 119.13 kJ (20)
Batch 1 and 2 with 6 M HCl.
% vol. CO2 O2 N2 CH4 H2
2Rh + 6H+ +12Cl− +1.5O2 ⇌2RhCl6 3− +3H2 O ΔG150∘ C = − 402.32 kJ
(21)
Batch 1 1.286 21.33 78.0 < LOD 0.720
±0.002 ±0.07 ±0.1 ±0.001 Instead for Batch 2 material, Pd and Rh were partially oxidized,
Batch 2 8.16 19.62 72.57 < LOD 0.138 whereby Pd was present as Pd0, PdO, and PdO2 (Paredis et al., 2011),
± 0.01 ± 0.01 ± 0.06 ± 0.001

5
T. Abo Atia et al. Resources, Conservation & Recycling 166 (2021) 105349

Fig. 2. Leaching efficiency of PGM (Pd, Pt, and Rh) in 6 M HCl and 6 M HCl +10% vol. H2O2 for Batch 1(A) and Batch 2 (B), at T = 150 ◦ C, for 25 min (15 min ramp
+ 10 min holding time) determined by ICP-OES analyses of the leachates (Method (i)) and PGM leaching efficiencies determined by residue destruction followed by
ICP-OES analyses for Batch 1 (C), and Batch 2(D) (Method (ii)). N ≥ 2.

Fig. 3. XPS surveys for Pt Batch 1 (A) and 2 (B), Rh Batch 1 (C) and 2 (D), and Pd Batch 1 (E) and 2 (F). Qualitative interpretation by Origin 9.0 peak analyzer.

6
T. Abo Atia et al.
and Rh as Rh0, Rh2O3, and RhO2 (Cao et al., 2017), as shown in Fig. 3D
and F.
The higher relative abundance of metallic Pd and Rh in Batch 1 can
be a cofactor for the generation of more H2 gas during HCl leaching,
according to Eqs. (18) and (19). The reducing environment was higher
for Batch 1 in the 6 M HCl leaching system and can be associated to H2
gas evolution that competes with the oxidation/chlorination reactions of
PGMs to their soluble forms. This can also explain why the PGM leaching
increased in Batch 1 upon hydrogen peroxide addition and the leaching
redox potential resulted significantly lower when compared with that of
Batch 2 leaching in 6 M HCl.
The oxidized and zerovalent phases of Pd in Batch 2 may dissolve
spontaneously in HCl Eqs. (22) and ((23)), yet Pd and PdO might also
undergo further oxidation in acidic media at the measured redox po­
tentials during leaching Harrison and Whitfield, 1983; Juodkazis et al.,
2003; Vanysek, 2011), as in Eqs. (2), ((24), (25). Although previous
research showed that oxidized Pd phases may reduce the Pd leachability
(Juodkazis et al., 2003; Li et al., 2016; Trinh et al., 2017), the Pd
leaching efficiency for Batch 2 in 6 M HCl at 150 ◦ C was high (94%).
However, upon addition of hydrogen peroxide the Pd leaching efficiency
slightly decreased. This finding indicates that H2O2 addition led to
further oxidation of the solid catalyst substrate, e.g. PGMs, Ce (Fe, Ti, Zn
(Fig. S3)) and consequential passivation of PGM particles for further
leaching took place.
PdO + 2H+ + 4Cl− ⇌PdCl4 2− + H2 O ΔG150∘ C = − 80.34 kJ
PdO + 2H+ + 4Cl− + Cl2 ⇌PdCl6 2− + H2 O ΔG150∘ C = − 54.40 kJ
PdO2 +2H+ +2e− ⇌PdO + H2 O E0 = 1.02 V
Pd(OH)2 + 2e− ⇌Pd + 2 OH− E0 = 0.07 V
The Pt leachability was similarly high in all the leaching conditions
for both materials (≥ 90%). XPS suggested that PtO2, plausibly PtO, and
less likely Pt0 occurred on the Pt surface for both catalyst samples. The
influence of hydrogen peroxide and headspace gas composition showed
evident analogies with Pd leaching behaviors for Batch 1 and Batch 2, e.
g. the small increase in Pt leaching for Batch 1 in HCl+H2O2, while H2O2
addition reduced its leaching efficiency from Batch 2. The formation of
Pt oxides is also favored during MW chloride leaching according to Eqs.
(26) and (27) (Vanysek, 2011) and might affect Pt extraction through
surface passivation (Geiger et al., 2015; Hodnik et al., 2016; Trinh et al.,
2017; Wei et al., 2019)
+ −
PtO2 +2H +2e ⇌PtO + H2 O 0
E = 1.01 V
+ −
PtO2 +4H +4e ⇌Pt + 2H2 O E = 1.00 V 0
However, the MW leaching temperature of 150 ◦ C could enhance the
dissolution of both metallic and oxidized Pt as chloride complexes Eqs.
(28)-((31)), consistent with the experimental findings.
Pt + 2Cl− + 2Cl2 ⇌PtCl6 2− ΔG150∘ C = − 212.26 kJ
PtO + 2H+ + 4Cl− ⇌PtCl4 2− + H2 O ΔG150∘ C = − 30.75 kJ
−
PtO + 4Cl + Cl2 + 2H ⇌PtCl6 + 2−
+ H2 O ΔG150∘ C = − 150.89 kJ
+
PtO2 + 4H + 6Cl ⇌PtCl6 − 2−
+ 2H2 O ΔG150∘ C = − 99.06 kJ
The effect of the surface oxidation was more significant for Rh
leaching. Metallic Rh can be easily oxidized at the measured redox po­
tential Eqs. (32) and ((33)) Vanysek, 2011)) and its oxides (Rh2O3,
RhO2) are more averse to leach in hydrochloric acid (Saguru et al.,
2018). Even though, to a certain extent, Rh2O3 is able to leach in HCl, as
shown by Eq. ((34).
Rh+ +1e− ⇌Rh0 E0 = 0.60 V
Resources, Conservation & Recycling 166 (2021) 105349
Rh3+ +3e− ⇌Rh0 E0 = 0.76 V (33)
Rh2 O3 + 6H+ + 12Cl− ⇌2RhCl6 3− + 3H2 O ΔG150∘ C = − 170.94 kJ (34)
In Batch 2 material, Rh was partially present in its oxide forms which
inhibited its efficient leaching in 6 M HCl that was even further con­
strained by the addition of H2O2.
For Rh, and PGMs in general, leaching is a trade-off between
oxidation/passivation of its surface and the formation of soluble chloro-
complexes. The leaching efficiency of oxidized PGMs (i.e. Batch 2) can
be enhanced by reductive (pre-)treatments (Chen et al., 2014; Trinh
et al., 2017) or by increasing the leaching temperature that enhances the
conversion of oxidized Rh to soluble chlorides (Suoranta et al., 2015).
Alternatively, Rh recovery can be achieved through sulfation roasting
followed by leaching in less concentrated (1–2 M) HCl solution (Prase­
tyo and Anderson, 2020; Spooren and Abo Atia, 2020), at the expense of
Pt recovery.
3.2.3. LREEs and Y leaching
The leaching efficiencies for Ce, La, Nd, and Y are presented in
Fig. 4A for Batch 1 and in Fig. 4B for Batch 2. Both materials showed a
distinct leaching behavior. Nd was quantitatively leached from Batch 1
and only about 59–63% for Batch 2, La between 74 and 77% in Batch 1
and 60–62% in Batch 2, the Y leachability was below 30% for both
materials, and Ce leached more from Batch 2 than Batch 1.
(22) La, Nd, and Y oxides leach spontaneously in HCl Eqs. (35)-((37)) and
the effect of H2O2 addition on their leaching behavior was marginal. The
(23) leaching of these three elements is related to their intended function in
automotive catalysts. Namely, La2O3 and Nd2O3 are commonly used as
(24)
stabilizers for alumina (Ozawa et al., 2003), instead Y2O3 is applied as
additive to stabilize ZrO2 (Zr0.72Y0.28O1.862 was detected by XRD).
(25)
Therefore, the leachabilities of La and Nd were in several cases corre­
lated to that of Al (Fig. S4), with the exception of Nd leaching from Batch
1 material. The poor Y leachability was associated to the stability of ZrO2
(Fig. S4) at low pH through passivation (Vanwinkle, 1999). Moreover, Y
showed a leaching efficiency decrease for Batch 2 in the presence of
H2O2, which was observed also for Ti and Zn (Fig. S4). This indicates a
possible association of Y with Ti and Zn oxides (common passivating
agents) in the Batch 2 material, constraining the Y leaching in
HCl+H2O2.
La2 O3 +6H+ +8Cl− ⇌2LaCl4 − +3H2 O ΔG150∘ C = − 319.03 kJ (35)
Y2 O3 +6H+ +6Cl− ⇌2YCl3 +3H2 O ΔG150∘ C = − 238.01 kJ (36)
(26)
Nd2 O3 +6H+ +8Cl− ⇌2NdCl4 − +3H2 O ΔG150∘ C = − 268.65 kJ (37)
(27) XPS highlighted that the relative abundance of CeO2/Ce2O3 was
considerably higher in Batch 2 than Batch 1 (Fig. 4C and D). The
leaching of Ce2O3 follows Eq. (38). Whereas, thermodynamic constants
are missing for Ce4+chlorocomplexes due to their instability in aqueous
solutions (Kai et al., 2018) and the most accredited leaching mechanism
(28) includes the reduction of Ce4+to Ce3+to give soluble chloride complexes,
Eq. (39) (Borra et al., 2019).
(29)
Ce2 O3 +6HCl⇌2CeCl3 +3H2 O ΔG150∘ C = − 339.78 kJ (38)
(30)
2CeO2 +8HCl⇌2CeCl3 +4H2 O + Cl2 ΔG150∘ C = − 12.57 kJ (39)
(31) The leaching results showed that Batch 2 material containing more
Ce4+ achieved higher leaching efficiencies than Batch 1, presenting
more abundant Ce3+ species.
In addition, Ce showed a significant decrease in leaching efficiencies
upon addition of H2O2, passing from 87 ± 3 to 75 ± 1% for Batch 1 and
from 95 ± 3 to 82 ± 3% for Batch 2. Two explanations for this behavior
are given. Firstly, hydrogen peroxide acts as a reducing agent in the
presence of Cl2, converting Ce4+ to Ce3+ (Borra et al., 2018). Secondly,
(32) in an oxidizing environment enhanced leaching passivation of Ce3+
7
T. Abo Atia et al.
Fig. 4. Leaching efficiency of Ce, La, Nd, and Y in 6 M HCl and 6 M HCl +10% vol. H2O2 for Batch 1 (A) and Batch 2 (B), determined by ICP-OES analyses of the
leachates. XPS survey of Ce for Batch 1 (C) and Batch 2 (D). Qualitative interpretation by Origin 9.0 peak analyzer.
takes place, as different non-stoichiometric oxides of intermediate
oxidation state, such as Ce2O7, may generate in chloride media (John­
son et al., 2005). This second mechanism is consistent with the lower Ce
dissolution for Batch 1 as it contains more Ce3+ in respect to Batch 2
material. The oxidation/passivation mechanism of Ce3+ at Batch 1
catalyst surface can be responsible − in concomitance with the more
abundant oxidizable substrates, such as S, Fe, Pb (300 ppm vs. <LOD),
Cr (300 ppm vs. 100 ppm) (Bahaloo-Horeh and Mousavi, 2020)− for the
lower redox potential with respcect to Batch 2 in MW HCl leaching.
Furthermore, to a certain extent also the higher content of hydrogen
produced by Batch 1 material in HCl could be associated to the oxidation
of Ce3+ (supported by HSC calculations, Fig. S5), as in Eq. (40).
Ce2 O3 + xH2 O⇌2CeO2− x + xH2 (40)
where 0<x<1.
4. Conclusions
MW leaching of spent automotive catalysts in 6 M HCl, at 150 ◦ C and
a liquid-to-solid ratio of 10 to extract PGMs is as effective as in 6 M HCl
+ 10% vol. H2O2. It was shown that during HCl leaching under hydro­
thermal conditions the oxidation potential of the leachate changed to a
more oxidizing environment, which could be ascribed to the evolution of
Cl2 gas in the headspace. The in situ evolution of Cl2 might preclude the
use of costly oxidizing agents.
The effectiveness of oxidizing agent addition on PGM leaching from
spent automotive catalysts depended on the oxidation state of the PGM
8
Resources, Conservation & Recycling 166 (2021) 105349
surface in the material. Particularly, Rh oxides are less amenable to
leach than metallic Rh. Furthermore, the relative occurrence of
reduced/oxidized species of PGMs and Ce in the catalyst materials
influenced the headspace gas composition (e.g. the H2 formation) and
the leaching redox potential, affecting the PGM and Ce leaching,
accordingly.
The La, Nd, and Y leachabilities were mainly associated to the
leachabiliy of the phases in which these elements were doped as sta­
bilisers, i.e. Al2O3 (La and Nd) and ZrO2 (Y). The extraction of Ce was
negatively affected by the presence of H2O2 for both tested materials.
Moreover, the addition of H2O2 to the HCl leaching system poses
safety concerns as it increases the production of the flamable and cor­
risive gasses H2 and Cl2. In future work, the headspace gas composition
of the studied MW-assisted leaching systems should be analyzed to
provide further insights in the occurring leaching mechanisms and to
understand the safety risks for further upscaling of the process.
CRediT authorship contribution statement
Thomas Abo Atia: Conceptualization, Methodology, Formal anal­
ysis, Investigation, Writing - original draft, Visualization. Wendy
Wouters: Investigation, Data curation. Giuseppe Monforte: Investi­
gation. Jeroen Spooren: Conceptualization, Formal analysis, Writing -
original draft, Writing - review & editing, Supervision, Project admin­
istration, Funding acquisition.
T. Abo Atia et al.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
Dr. Deepak Pant is thanked for useful discussions and guidance on
the experimental headspace gas study. The presented work was executed
within the PLATIRUS project, which has received funding from the
European Union’s Horizon 2020 research and innovation program
under grant agreement No 730224. This work reflects only the author’s
view and the Agency is not responsible for any use that may be made of
the information it contains.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.resconrec.2020.105349.
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