Journal of Sustainable Metallurgy (2020) 6:259–268

https://doi.org/10.1007/s40831-020-00272-9

RESEARCH ARTICLE

Single‑Step Hydrometallurgical Method for the Platinum Group

Metals Leaching from Commercial Spent Automotive Catalysts
Iakovos Yakoumis1 · Anastasia Moschovi1 · Marianna Panou1 · Dimitris Panias2

Published online: 22 April 2020

© The Minerals, Metals & Materials Society 2020

Abstract
Platinum group metals (PGMs) are considered critical raw materials, thus their recycling and re-use is of outmost importance.
Among the PGMs, platinum (Pt), palladium (Pd) and rhodium (Rh) are the basic metals used in catalytic converters. Con-
cerning the stringent EU standards for emission control imposed to car manufacturers (Euro 6d nowadays), the worldwide
demand for PGMs is being increased. As for PGM recovery methods, research is focusing on greener, plain recovery tech-
niques, which utilize milder reagents and offer energy efficiency. In this work, a state-of-the-art hydrometallurgical process
is proposed resulting in recovery rates for Pt, Pd and Rh, namely 100%, 92% and around 60%, respectively. A batch of more
than 20 commercial spent catalyst samples has been mechanically pre-processed (i.e. sorted, decanned, milled, grinded,
homogenized and characterized), in order for a 20 kg sample of homogenized fine pent catalytic powder to be derived. The
proposed hydrometallurgical method does not involve any kind of thermal pre-treatment or chemical reduction, thus energy
consumption is minimized, while the use of chemicals has been restricted to simple and cheap inorganic solvents (namely
HCl, NaCl and H ­ 2O2). The aforementioned recovery rates have been validated through X-ray fluorescence spectroscopy
analysis (XRF). The equipment used has been successfully calibrated to measure low PGM concentrations (less than 50 ppm
for each metal). The kinetics of the hydrometallurgical process have also been studied, in short intervals, and spent catalyst
material has been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy analysis
(EDS) and X-ray powder diffraction (XRD).
Graphical Abstract

Keywords Platinum group metals · Hydrometallurgy · One-step leaching · Spent automotive catalysts · XRF calibration

Introduction
The contributing editor for this article was T. Hirato.
Platinum group metals (PGMs) are widely used in vari-
* Iakovos Yakoumis ous industrial areas, being part of exhaust catalytic system,
yakoumis@monolithos‑catalysts.gr
electronics, photovoltaics, dental materials, pharmaceuticals,
Extended author information available on the last page of the article

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260 Journal of Sustainable Metallurgy (2020) 6:259–268

jewelry, nuclear reactors, glass, ceramics and pigments. by-products can be eliminated in case of diluting the acid
More than 57% of PGM supply is used in catalytic con- reagents using lower acid concentrations, or by minimizing
verters. Processing 2 mg of spent automobile catalysts to total solution volume.
recover PGMs can prevent the mining of 150 kg of their ores The most common, traditional leaching solutions contain
[1]. Platinum group metals are rare, due to their low natu- aqua regia and cyanide systems. Concerning aqua regia [4],
ral resistance, complicated extraction and refining process. leaching at temperatures above 70 °C is considered haz-
Classified as critical raw materials (CRMs), PGMs have high ardous in plant scale, due to the aggressive nature of the
economic importance and supply risk. To conserve the PGM solution and the decomposition of gaseous products ­(NOx,
resources and meet the future market demand, it is necessary ­Cl2, acid fumes). As for cyanide leaching, huge amount of
to develop economical and eco-friendly processes, in order waste is produced, and specialized equipment is required. It
to recover noble metals from secondary resources, particu- is inferred that the leaching process should be in line with
larly from spent automotive catalytic converters. green chemistry principles. State-of-the-art leaching sys-
Assuming that secondary PGM resource equals the pri- tems, such as HCl, ­H2SO4, NaCN, ­HNO3, combined with
mary supply, multiple industrial approaches have been devel- oxidizing agents and chloride salts, enhance the leaching
oped, such as pyrometallurgy, hydrometallurgy and biomet- efficiency, following greener approaches. Aberasturi et al.
allurgy. Pyrometallurgy has been widely used in plants for [5] claimed that 95% of PGMs have been recovered from
many decades and has been further improved. Through the spent catalysts, via dissolution in HCl (12 M), ­H2SO 4
pyrometallurgical process, high recovery rates of PGMs can (18 M), ­H2O2 leaching system at 90 °C for 6 h, after thermal
be achieved (88% Pt, 66% Pd, 57% Rh), especially through pre-treatment at 250 °C for 22 h. Mahmoud used acid agent
PGM-Cu collection technology [2]. Τhe demand for eco- 60% ­H2SO4 and reduction agent NaCl (0.1 M) achieving
friendlier, cost-efficient and high purity approaches led to 95% Pt, 85%Rh, 85% Pd recoveries [6]. In this case, the
the development of hydrometallurgical processes. Follow- noble metal extraction follows the order Pd > Pt > Rh at low
ing hydrometallurgical procedures, the PGMs recovery acid concentration (< 50% ­H2SO4), but at higher acid con-
reaches almost 95%, by using various leaching solvents and centrations the order was somewhat reversed Pt > Rh > Pd.
extractants. As for bio-metallurgical method, bacteria with Serife Sariog et al. [7] used milder reagents and less hazard-
metal-sequestering properties, like Chromobacterium viola- ous leaching conditions, where 98% Pd has been extracted
ceum, Pseudomonas fluorescens, and Bacillus megaterium, from spent catalyst, using mixture of HCl (10%) and ­H2O2
can sequester the dissolved precious metals ions of dilute (5%) at 90 °C for 3 h, and precipitation with ­NaBH4. Paiva
complex solutions (i.e. cyanide complexes). An optimized et al. [8], recovered 84% of Pd, using a leaching solution of
bioleaching procedure is capable of leaching Pt, Pd, Rh at a HCl (2 M), ­H2O2 (1 M) at 25 °C for 1 h, where the oxidiz-
rate of 63.1%, 38.4% and 99.3%, respectively [3]. ing agent ­H2O2 accelerated the dissolution after 10 min of
Regarding the hydrometallurgical methods, consider- reaction. The same leaching system is examined [9], giv-
able advantages are offered, such as suitability for various ing significant recovery rates, namely Pt 88%, Pd 99%, Rh
scales, use of mild temperatures, waste control and high 77%, which seem to be improved with the partial substitu-
metal purification. The hydrometallurgical process consists tion of HCl (5Μ) with NaClO (3%vol), obtaining lower acid-
of two main stages, the leaching stage, where metals are ity conditions without changing the dissolution efficiency.
leached from their ores in an aqueous media, and the separa- In one-step leaching reported by Harjanto et al., reduction
tion stage, where the leached metal complexes are extracted pretreatment (350 °C, 3 h) was conducted, affecting the dis-
from the pregnant solution. After separation, further refining solution rate of Rh. An even more appropriate alteration
steps lead to noble metals of high purity. of the leaching system HCl-H2O2 is conducted [10], where
The PGMs dissolution tends to be challenging, as noble dissolution of Pt is maximized, after roasting pretreatment
metals are highly resistant to acid solutions. More specifi- (700–900 °C, 10 °C/min), using HCl (10%), oxidizing agent
cally, Rh forms an oxide protective layer that inhibits Rh ­H2O2 (1%), at 70 °C for 2 h. Further chloride leaching media
complex dissolution. In this aspect, pretreatment stages, examined conclude ­Cu2+/HCl [11], HCl/HNO3 [12], HCl/
such as hydrogen reduction, roasting and calcination, facili- HClO4 [12], HCl/FeCl3/NaCl [13]. Additional sources of
tate the dissolution stage. Although pretreatment stages chlorines, namely NaClO, NaCl, ­AlCl3, ­CuCl2, improve the
improve recovery rates, such processes tend to be costly PGMs dissolution, tending to partially substitute high acidity
and energy intensive. Remarkably, prereduction in hydro- reagents (HCl, aqua regia).
metallurgy processing is quite similar to reduction melting In this work, PGMs have been leached directly (no ther-
stage in pyrometallurgy, where the noble salts are reduced mal or chemical pre-treatment is involved) under mild exper-
to their metallic form at temperatures above 250 °C. From imental conditions, by using low acidity reagents, namely
an environmental viewpoint, strong acid solvents produce the widely tested leaching system, HCl–H2O2–NaCl at
remarkable amounts of waste. It has been proved, that liquid 70 °C for 2 h. As it can be deduced from the aforementioned

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systems, the addition of oxidizing agent ­H2O2 together with automotive catalytic converter analytical samples (almost
the additional source of chlorine leads to promising leaching 1000 Euros per 100 g of sample). Furthermore, the use of
yields for PGMs, prohibiting high acidity. The novelty of the a single homogenized batch is necessary, so that all disso-
leaching system of this work attributes to high solid to liq- lution/separation/recovery experiments followed are refer-
uid (S/L) ratio leached (70%) without any pre-concentration ring to a common sample of homogeneous monolith ceramic
or further pretreatments (reduction, roasting). Moreover, a powder. The steps of spent catalyst mechanical pretreatment
large homogenized batch of spent automotive catalysts has are represented in Fig. 1. The samples have been analyzed
been gathered, characterized and leached, ensuring repro- before and after leaching, determining their PGM concentra-
ducibility. The spent catalyst has been characterized by scan- tions. An external calibration has been obtained by MONO-
ning electron microscopy (SEM)/energy dispersive X-ray LITHOS Ltd to precisely determine the PGM concentration
spectroscopy analysis (EDS) and X-ray powder diffraction ranges, namely low concentrations (after leaching process)
(XRD). The efficiency of leaching is ensured through X-ray and higher concentrations (before leaching process).
fluorescence analysis (XRF), where the leaching rates of
PGMs are determined. As for the XRF analysis, an exter- Leaching Procedure for the PGMs Recovery
nal calibration has been performed, regarding X-ray fluo-
rescence analysis (XRF) and Inductively coupled plasma- A predetermined quantity of catalyst powder is received
optical emission spectrometry (ICP-OES). Finally, a brief after milling processing, without further thermal or chemi-
kinetic evaluation of the leached catalyst sample has been cal pre-treatment (one-step hydrometallurgical leaching pro-
conducted. cess). The leaching reagents used refer to HCl (37%), 1% v/v
­H2O2 (30%), NaCl (99.5%), deionized H ­ 2O under magnetic
stirring conditions (magnetic stirrer MSH-A analog up to
Experimental Procedure 380 °C 1500 rpm, Witeg, Germany). The leaching takes
place at 70 °C for 2 h (or 3 h for kinetic experiments). It
Preparation of Homogenized Catalytic Converter should be noticed that adding reagents in a different order
Batch than HCl, ­H2O2, NaCl, ­H2O, results in a high exothermal
reaction. The S/L ratio is finally adjusted by the addition of
In this work, a plethora of spent catalyst samples from a deionized water. Selected concentrations of HCl, NaCl, as
homogenized batch are processed and characterized. The well as S/L ratio have been examined. Once leaching process
prepared homogenized batch derived from 25 commercial has been completed, the solution is filtrated under vacuum,
spent catalytic converters (Table 1), producing a 20 kg batch following the Buchner method, and several washes are fol-
of spent automotive catalyst powder. The method has been lowed. Finally, the solid phase is dried overnight at 120 °C,
described in detail by Yakoumis et al. [14]. The final sample pulverized and subjected to X-ray fluorescence spectroscopy
produced, about 20 kg of fine homogeneous powder from (XRF), in order to determine the after leaching PGMs’ con-
spent automotive catalytic converters enables authors to con- centrations. All the experiments have been repeated twice,
duct multiple leaching experiments optimizing all param- with the view to confirming the confirm reproducibility of
eters involved (reagents concentration, different sources of process and experiment conditions. X-ray fluorescence spec-
­Cl−, reaction kinetics and important industrial parameters troscopy (XRF) measurements were recorded twice as well,
like S/L ratio). The quantity of the sample is crucial for PGM in order to prevent significant variations.
research, since most of the published works involve limited
experimental tests, due to the extremely high cost of spent Characterization Methods

Table 1  Models of 25 spent catalytic converters that were used for Morphological Characterization of the Batch Catalyst
the batch formation Powder
Audi A3 Citroen Saxo Toyota Carina
The representative sample from the 20 kg batch has been
Fiat Tipo Fiat Stilo Volvo
collected and subjected to basic characterization techniques,
Ford Fiesta Ford Focus Suzuki Swift
in order for its morphology and elemental analysis to be
Ford Focus_2 Ford Mondeo Toyota Corolla
defined. These characterizations refer to before leaching cat-
Daihatsu Feroza VW Golf Rover 416
alyst sample. Scanning electron microscopy analysis (SEM)
Opel Astra Honda Civic Suzuki Vitara_2
combined with energy-dispersive X-ray spectroscopy analy-
Kia Sorento Mazda 323 Seat Cordoba
sis (EDS) provides additional understanding of the surface
Nissan Almera Nissan Xtrail Renault Megane
material composition. The quantitative element determina-
Peugeot 106
tion, as well as semi-quantitative analysis are conducted in

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Fig. 1  Spent catalysts pre-process, leaching and analysis (Color figure online)

different sample areas under × 200 magnification conditions. then grounded, in order to obtain specific granulometry
X-ray powder diffraction analysis (XRD) is used for the min- (< 350 μm) or pulverized, using an agate mortar. Under
eralogical characterization of sample. The crystallography of standard deviation lower than 5%, the concentration of the
the PGMs, namely crystal lattice, crystallite size and shape, noble metals is defined from the mean concentration value of
could be examined in case of significant PGM loading. 10 scans (90 sec/scan), taking into consideration the proper
calibration mode. The recovery rate percentage of PGMs is
X‑ray Fluorescence Analysis (XRF) calculated as: leaching rate (%) = [(Ci−Cf)/Ci] × 100, where
Ci refers to the initial PGMs concentrations (before leach-
The PGM content was determined with X-ray fluorescence ing), while Cf refers to the final PGMs concentrations (after
spectroscopy. The XRF spectrometer (VANTA Olympus leaching). In this work, the differentiation of the mass of the
2017, Waltham, MA, USA) was calibrated by the manufac- solid residue before and after the leaching has not been taken
turer to measure precisely Pt, Pd and Rh in spent catalysts into account for two reasons: (a) for comparison purposes,
of average PGM concentrations of 1000 ppm, 1700 ppm since all the literature data report leaching efficiency calcu-
and 300 ppm (PGM reference sample by BAM Berlin), lated as the difference between the obtained concentration
respectively. Further to manufacturer’s calibration, a series versus the calculated one and (b) in the laboratory scale we
of measurements took place, by using commercial samples examined solid losses in the filter affecting the total mass of
of different PGM concentrations. By following this pro- the solid residue.
cess, the accuracy of metal determination was validated by
the specific method and calibration curves. Moreover, sev- Kinetics of the PGM Complex Formation
eral research groups, such as Spooren and Abo Atia [15]
have already used spent automotive catalysts samples that The kinetic response of the leached sample has been evalu-
have been characterized with the specific method. In order ated for different leaching time. The PGM concentrations
to define the recovery yields of PGMs, two X-ray fluores- (ppm) are defined as a function of leaching time (0.5 h,
cence measurements have been conducted, corresponding 1 h, 2 h, 3 h), in order for the most efficient leaching dura-
to the before leaching sample and the after leaching one. tion to be verified. According to the anodic reactions of
Before any XRF measurement, the dried catalyst sample is PGMs in HCl–H2O2–NaCl systems (E° = − 0.744 V for
milled into an analytical mill downsizing its’ particle size, Pt, E° = − 0.620 V for Pd, E° = − 0.450 V for Rh), it is

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suggested that, compared to Rh complex, Pd and Pt chloro- Leaching Temperature

complexes are more easily dissolved into the chloride media.
It is expected that Rh should exhibit lower kinetics, due to In order to preserve a low energy consumption, all leaching
its passivation layer and stereotactical structure. tests took place at 70 °C according to the findings of Har-
janto et al. [9]. Low leaching temperature minimizes energy
consumption, leading to a cost-effective and environmentally
Results friendly process.

Leaching Parameters
Leaching Solution Acidity (HCl Molarity)
In this one-step leaching method, noble metal oxidation
and dissolution take place and PGM chloro-complexes are As illustrated in Table 2, two different HCl-concentrated
formed. In HCl media, the most stable species formed are leaching systems have been examined (70 °C, 2 h). As it
­PtCl62− ­PdCl42−, ­RhCl63−. The PGM-chloro-complexes get is clearly observed, leaching acidity plays a crucial role
diluted in the acid chloride solution, by using H ­ 2O2 oxidiz- in leaching efficiency, especially in case of Rh recovery.
ing agent. Hydrogen peroxide (­ H2O2) is a strong oxidizing The experiment that took place under 6 M HCl conditions,
agent with standard electrode potential of + 1.77 V. The enhanced Rh recovery, which reached almost 60%. However,
addition of ­H2O2 in leaching media proved to act synergisti- minimizing HCl concentrations in order to follow greener
cally in recovery rate, as well as assists in the use of milder leaching processes, is of high need.
acid concentrations. Concerning the findings of Harjanto
et al. [9], the addition of ­H2O2 by > 0.5 vol% increases the
PGM dissolution, while the > 1 vol% addition does not result Balance of ­CNaCl/CHCl
in a significant melioration. The optimized ­H2O2 addition
is 1 vol%, though even in this low percentage, the corro- As demonstrated in Table 3, various balances of NaCl and
sive nature of H ­ 2O2 should be considered in case of fur- HCl molarities have been examined. In leaching solutions,
ther extraction. Partial replacement of HCl with NaCl salt HCl provides the appropriate acidity for the leaching to take
resulted in effective PGMs’ dissolution, without substrate place, where additional chlorine anions introduced by dif-
dissolution. The use of NaCl proved to facilitate the forma- ferent sources, chlorides salts mainly, provide the required
tion of stable chloro-complexes, acting as additional source ­Cl− concentration for the chloro-complexes to be formed.
of chlorides. Furthermore, NaCl salt assists in less acid By utilizing the additional source of NaCl, balanced with the
vapors, formed by partial HCl evaporation, as less acidity HCl concentration, milder leaching conditions are required,
is obtained. Numerous leaching experiments conducted at compared to leachates without any additional chloride
70 °C for 2 h optimizing all crucial parameters of the pro- source.
cess. As for the parametrization, chloride source, HCl acid- According to presented data of Table 3, acidity of the
ity, NaCl-HCl balance, S/L ratio, and H ­ 2O2 concentration solution plays a crucial role in the leaching process, thus
have been studied. Experimental conditions and recovery the solution with 6 M HCl and 3 M NaCl added exhibits the
yields are presented in the parametrization tables. highest recovery percentages for Rhodium.

Table 2  PGM leaching S/L HCl H2O2 NaCl Pt% Pd% Rh%
efficiencies obtained when using
different HCl concentrations 10 6M 1% v/v 3M 100 94.8 59.8
10 4.5 M 1% v/v 3M 100 94 53.8

Table 3  PGM leaching S/L HCl H2O2 NaCl Pt% Pd% Rh%
efficiencies obtained when
using different NaCl–HCl 10 6M 1% v/v 3M 100 94.8 59.8
concentrations
10 4.5 M 1% v/v 3M 100 94 53.8
10 4.5 M 1% v/v 4.5 M 100 94 46
10 3M 1% v/v 6M 100 93 50

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H2O2 Concentration S/L Ratio

The oxidizing agent ­H2O2 is proved to ameliorate the leach- The S/L ratio is a crucial factor for the industrial design of
ing effectiveness, at a percentage of > 0.5 vol% [9]. Two leaching processes, since the higher the S/L ratio the less
experiments have been conducted to validate the oxidizing solvents are used, offering both economic and environmental
agent effect. Molarity of HCl and NaCl remained constant at advantages, in case of proper waste management. Evalua-
6 M and 3 M, respectively, where solid to liquid ratio (S/L) tions on S/L ratio took place, in order to reduce the gener-
was 10%. Evaluation on higher concentration of v/v% ­H2O2 ated waste from the leaching process. By processing higher
has also been conducted (Table 4), ensuring that more than amount of catalyst powder under milder conditions, namely
1% v/v ­H2O2 affects reversibly the recovery. high S/L ratio, hydrometallurgy gains a foothold in PGMs
recovery. The optimum S/L ratio achieved is 70% (namely
Effect of Other ­Cl− Sources 70 g of solid catalyst leached at 100 ml of total solution),
providing promising recovery yields for industrial scale. As
The effect of the anions of chloride salts other than NaCl, it is clearly observed, when S/L > 70% the solid cannot react
namely ­AlCl3 and C ­ uCl2, has been studied and demonstrated properly with the leaching solvent. (Table 6).
in Table 5. In case of A­ lCl3, three times more chloride ions
were provided to the leachate compared to NaCl, with Process Optimization
respect to the same molarity in the leaching solution. How-
ever, the addition of A
­ lCl3 into leaching media caused highly According to the Table 6, the highest S/L ratio achieved is
aggressive exothermal reaction, where the temperature was 70%, resulting in promising leaching yields for Pt (100%),
hardly controlled, even with the use of water bath. Pd (93%) and Rh (50%). As is can be seen in Table 7, leach-
In case of ­CuCl2 salt, which introduces into the solu- ing optimization for Rh can be monitored by altering NaCl
tion twice the number of Cl ions but less compared to and HCl concentrations. By increasing the molarity of NaCl,
­AlCl3, lower recovery values for Rh have been observed, higher Rh leaching yield is revealed, namely from 50 to 56%.
with respect to A­ lCl3 salt. Moreover, the leachate of C
­ uCl2 Another optimization has been achieved by decreasing the
(4.5 M), HCl (4.5 M), 1% v/v ­H2O2 solution resulted in molarity of HCl, leading in milder leaching acidity and
unstable dispersion, forming crust on the solutions’ surface higher Rh dissolution.
and aggregation. The cause for this destabilization might According to the experimental parametrization, it is
refer to ­CuCl2 quantity, which could not fully react with the observed that, leaching solution of HCl (3 M), S/L: 70%,
liquid solution (S/L ratio factor). The additional source of NaCl (4.5 M), oxidizing agent 1% v/v ­H2O2 at 70 °C for 2 h
NaCl is preferable, giving promising recovery results, thus gives promising recovery yields, following green chemistry
has been further investigated. rules. Reagents should be added in a specific order, namely

Table 4  PGM leaching S/L HCl H2O2 NaCl Pt% Pd% Rh%
efficiencies obtained when using
different ­H2O2 concentrations 10 6M 1% v/v 3M 100 93.7 60.9
10 6M 2% v/v 3M 87 93 47

Table 5  PGM leaching S/L HCl H2O2 NaCl CuCl2 AlCl3 Pt Pd Rh

efficiencies obtained when
using different chloride source 10 6M 1% v/v – – 3M 100% 94% 63%
leaching
10 6Μ 1% v/v – 3Μ – 100% 94% 53%
10 6M 1% v/v 3M – – 100% 94% 60%

Table 6  PGM leaching S/L HCl H2O2 NaCl Pt% Pd% Rh%
efficiencies obtained when
using different S/L ratio 10 4.5 M 1% v/v 3M 100 94 53.8
50 4.5 M 1% v/v 3M 100 94 57
70 4.5 M 1% v/v 3M 100 93 50
80 4.5 M 1% v/v 3M 56 93 26.4

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Table 7  Leaching system S/L HCl H2O2 NaCl Pt% Pd% Rh%
optimization
70% 4.5 M 1% v/v 3M 100 93 50
70% 4.5 M 1% v/v 4.5 M 100 93 56
70% 3M 1% v/v 4.5 M 100 92 61

Fig. 2  Energy dispersive X-ray

spectroscopy analysis (EDS)
of spent catalyst sample (Color
figure online)

catalyst powder, HCl, 1% v/v H ­ 2O2, NaCl and deionized

water. As for the sample preparation before the leaching pro-
cess, fine grinding affects the total recovery rate by increas-
ing the leaching efficiency.
Compared to previous studies, the low concentration
of HCl achieved minimizes the production of C ­ l2 gas and
fumes, confirming a safer leaching procedure. The liquid
wastes depend strongly on the S/L ratio and washing stage,
as well. Although S/L of 70% contains an elevated cata-
lyst content and lower amount of reagents, more washing
is required to remove chlorine anions from the leaching
residue. Thus, chloride sources need to be minimized in an
adequate for the leaching percentage.

Morphological Characterization of the Catalyst

Sample

As it can be seen from the energy dispersive X-ray spec- Fig. 3  Histogram of particle size distribution (Color figure online)
troscopy analysis (EDS), the spent catalyst sample contains
amounts of Al (38–46%), Si (9–33%), Ce (11–27%), Zr
(6–27%), Mg, (5–9%) Ca (~ 1%), Na (~ 1%) (Fig. 2). This histogram drawn by OriginLab (Fig. 3), a slightly heter-
result is expected, as the sample derived from spent auto- ogenous particle size distribution might be observed. Via
motive catalyst, where cordierite monolith contains Mg, micrograph evaluation, the catalyst sample reveals mean
Al, Si, O, with the formula of (Mg,Fe)2Al3(Si5AlO18) to particle size 20 μm, maximum size 27 μm and the mini-
(Fe,Mg)2Al3(Si5AlO18). Furthermore, the cordierite has mum 7 μm. The formation of a fine, homogeneous powder
been impregnated with alumina, or silica or ceria washcoat. is expected, as sieving and milling have been conducted
SEM image (SE, magnification of × 5000, × 10,000) (< 250 μm). It is suggested that both homogeneity and
illustrates the surface topography of the spent catalyst fine powder formation promote the leaching efficiency, due
sample, that derives from mixed monoliths of distinct to the increased surface area. Furthermore, small PGMs
PGMs concentrations. The structure analysis has been prills might be distinguished, which have nano-dimensions
performed using Image J program. According to the (× 10,000 magnification). (Fig. 4).

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intensities. Since the detection limit of the method is > 5%,

crystal phases that might be formed from PGM chlorides,
can not be detected.

Kinetic Approach

A brief kinetic investigation about the optimized leaching

system, namely 3 M HCl—4.5 M NaCl—1% v/v H ­ 2O2 at
70 °C, is represented (Fig. 6). According to Fig. 6, 2 h
leaching duration is appropriate for the PGMs dissolution,
as concentrations do not further increase (3-h leaching
period). Concerning the findings, PGMs chlorides forma-
tion accelerates from 0 to 0.5 h, while after 0.5 h there is
a stabilization period. Leaching time 0.5 h is inadequate
Fig. 4  Small PGMs prills on ceramic grain (× 10,000) for the PGMs dissolution, especially in case of Rh. In case
of Pd, after 0.5 h a plateau is observed, where Pd total
dissolution occurs. In case of Pt, fast kinetics can be seen
According to the XRD pattern (Fig. 5), the mail peaks between 0.5 and 1 h, while Pt plateau appears between 1
correspond to indialite (syn-Mg 2Al 4Si 5O 18), cordierite and 2 h. Both Pt and Pd reach equilibrium values up to
­( Mg 2Al 4Si 5O 18) and cerianite (Ce, syn-CeO 2). Moreo- 2 h, while Rh dissolution decreases after around 2 h of
ver, crystal phase of potassium magnesium aluminum leaching. A further investigation should be held, about the
silicate ­( KMg 2AlSi 4O 12) has been detected. The XRD Rh relation to the catalyst matrix system, in order to fully
results for the spent catalyst are in line with EDS analy- understand Rh kinetic chloro-formation. Comparing leach-
sis. In both characterization techniques PGMs content is ing among PGMs, the dissolution follows the order Pd, Pt,
not observed, because of their low loading on the catalyst Rh starting from the highest one. It is proved that Rh has
monolith. Regarding the phase characterization, more than the slowest kinetics, due to its’ stereo tactical structure and
two crystal phases have been identified in the structure of passivation layer formed in acid conditions.
the powder, according to the reflections and their relative

Fig. 5  X-ray powder diffraction pattern for spent catalyst batch samples (Color figure online)

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Journal of Sustainable Metallurgy (2020) 6:259–268 267

batch, as the same sample is examined both before and after

leaching process.
The accuracy of XRF measurements is further improved by
external calibration mode, by MONOLITHOS Ltd. The deter-
mination of the PGMs recovery yields requires calibration of
higher accuracy, detecting both high (before leaching) and
low (after leaching) concentration ranges, because even small
variations may affect the leaching procedure. In this respect,
external calibration using two different elemental analysis
techniques has been performed, comparing values received by
XRF and Inductively coupled plasma—optical emission spec-
trometry (ICP-OES). Referring to the samples before dissolu-
Fig. 6  PGMs kinetic behavior for 0.5–3 h leaching time (Color figure tion, calibration curve covers PGMs concentration ranges of
online) 614–2760 ppm, 1270–2730 ppm, 237–322 ppm for Pt, Pd, Rh
respectively. Another calibration has been obtained for lower
PGM concentrations, namely 50–600 ppm, 50–1000 ppm,
Discussion 50–250 ppm for Pt, Pd, Rh, respectively, referring to solid
residues received after leaching.
The present leaching method, is based on the Harjanto et al.
[9] study, focusing on industrialization and further optimiza- Conclusion
tion. Harjanto et al. claimed, that promising leaching yields,
namely 95.5%, 100% and 85.6% for Pt, Pd and Rh, respec- In this work, an optimized single-step leaching process
tively, have been received via HCl–H2O2–NaClO system. for PGMs has been developed, following the well-tested
Harjanto’s one-step leaching refers to one leaching solution, HCl–H2O2–NaCl system. Comparing with previous studies
which consists of HCl, ­H2O2 and partial substitution of HCl on the same system, pretreatments, such as reduction or pre-
by NaClO. Nevertheless, hydrogen treatment (350 °C, 3 h) concentration, have been avoided in this novel approach. The
is included, affecting the dissolution rate of Rh (77%). In the leaching yields obtained are 100%, 92% and 61% for Pt, Pd
present leaching system, no pre-concentration or reduction and Rh, respectively, using low acidity reagents, namely 3 M
stage has been preceded. It is suggested that the described HCl, 4.5 M NaCl, 1% v/v ­H2O2, under mild temperature con-
leaching process, will reduce process cost (OPEX), as less ditions (70 °C). Furthermore, the highest S/L ratio achieved
energy is consumed, and green reagents in low-acidity (S/L = 0.7) leads to high catalyst mass dissolution, thus sig-
environment are used. Moreover, in terms of industrializa- nificant PGMs dissolution by direct leaching. The high S/L
tion, high S/L ratio assists in smaller industrial installations ratio of the proposed process offers significant advantages in
affecting the investment cost (CAPEX). However, leachates’ industrial design, as smaller plant installation may be required.
waste management should be considered referring to the Undoubtedly, improvements in liquid waste management
cost efficiency of this method. As for environmental aspect, should be proposed to minimize waste treatment expenses.
milder acidity reagents may prevent waste generation in a Both mild acidity and leaching temperature of the proposed
significant extent. leaching system lead to the presumption that an environmen-
In terms of catalyst’s samples preparation, the requirement tally friendly approach has been implemented. Further leachate
of a large homogenized batch has been fulfilled. Aiming to analysis must be performed to evaluate the sustainability of the
receive a large batch of PGMs secondary resource, 25 com- process design followed by PGM separation studies.
mercial spent catalysts have been collected, sorted, preproc-
essed, milled, and analyzed for their noble metal content. Acknowledgements Special thanks to Centre of Research & Technol-
ogy Hellas (EKETA) for their contribution to characterization tech-
Moreover, the spent catalyst batch has been characterized niques SEM/EDS, XRD.
using XRD, SEM_EDS and XRF techniques. Almost 20 cata-
lyst samples were used, which derived from the catalysts batch,
and have been leached, following at least one repetition for References
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Affiliations

Iakovos Yakoumis1 · Anastasia Moschovi1 · Marianna Panou1 · Dimitris Panias2

1 2
MONOLITHOS Catalysts and Recycling Ltd, Athens, Laboratory of Metallurgy, School of Mining
Greece and Metallurgical Engineering, National Technical University
of Athens, Athens, Greece

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