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RHODIUM RECOVERY AND RECYCLING FROM SPENT MATERIALS

Conference Paper · June 2011

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9th European Symposium on Electrochemical Engineering (9th ESEE) 

Rhodium recovery and recycling from spent materials

V. Stankovića, C. Comninellisb
a
University of Belgrade, Technical Faculty Bor, VJ12 19210 Bor, Serbia;
Tel.: +381 30 424555; Fax: +381 30 421078; E-mail: vstankovic@tf.bor.ac.rs
b
FSB, EPFL,1015 Lausanne, Switzerland; E-mail: christos.comninellis@epfl.ch

Abstract
Rhodium has currently twice higher price than platinum and approximately seven
times higher than palladium on the world market. Its price has had a very turbulent
motion within last five years, going up and dawn following the world metal market
instability. Currently, its price is rising slowly reaching at the end of 2010 the price of
around 106.000 $US/kg.
In this article a review on rhodium recycling processes from spent catalytic materials
will be considered. Particular attention is paid to the solvent extraction and
cementation of rhodium from acidic solutions. In this regard, the case-study will be
presented, considering a solution containing rhodium, palladium and platinum ions in a
real leach solution. Some experimental results on separation of these ions by solvent
extraction with calixarenes and cementation with copper powder are also given and
discussed. A new technology scheme for rhodium recycling is proposed.
Keywords rhodium recycling; solvent extraction; PGMs; cementation
1. Introduction and rhodium market consideration
1.1 Price fluctuation of rhodium on the world market
Rhodium, belonging to PGMs, is a rare and the most expensive precious metal, having currently
twice higher price than platinum and approximately seven times higher than palladium on the
world market. As is illustrated in Fig. 1, its price has had a very turbulent motion within last ten
years, going up from 70500 $US/kg in 2005 and on, reaching finally an absolute maximum of
353.000 $US/kg in the middle of 2008; than dropping suddenly dawn during the second half of
that year to a less than 28000 $US/kg due to the world economy crisis. After that, the rhodium
price has came in a calm period through two last years, rising slowly and reaching at the end of
2010 the price of around 106.000 $US/kg, what was its price in early two-thousandth .

Fig. 1 Rhodium price fluctuation in the period 2000 – 2010 [1]

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1.2 World rhodium production

The main amount of rhodium produces from primary sources as a by-product in the precious
metals production. In the last five years the total rhodium production does not exceed 24 t/year as
it is shown in Fig. 2 (a). In Fig. 3 (b), are given the major producers and their share in the total
world production. South Africa is the biggest producer producing approximately 82 %. The
other, even more significant producers are far below South Africa, sharing the remaining 18% of
total world production.

(a) (b)

Fig. 2 Recent rhodium world production (a) and the main producers (b) [2]

1.3. World rhodium consumption

Gross rhodium demand was decreased throughout 2008 and ‘09 due to the world economic crisis,
following a significant dropping of automotive car production. The current situation is that the
rhodium demand is around 24 to 25 t/year. Rhodium is mostly used for automotive catalysts
(>80%) and, in a much less extent for the other industries as: jewellery; glass industry;
electroplating; electronics and so on, as is illustrated in Fig. 3 and specified by branches in Table
1. As metal, it uses rarely in its pure form rather as an alloy with palladium and platinum.
Obviously, an increase in rhodium demand could be a good indicator that the economy
automotive crisis is behind us. The other industries - rhodium consumers, are also recovering
slowly themselves.

Table 1 Rhodium consumption specified by industrial branches

Year/Industry 2008 2009 2010
Consumption %
Autocatalyst 85,6 86,4 83
Chem. Ind. 7,6 7,5 7,6
Glass 3,8 3,4 2,8
Other 3 2,7 6,6

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Fig. 3 Rhodium world demand and major industrial consumers [2]

2. Recycling of rhodium
It is clear from Fig. 2(a) and Fig. 3, that there is a significant gap of approximately 25% between
rhodium supply and demand on the world market. This deficiency is replenished by an amount of
rhodium recycled mainly from spent auto-catalysts. As it is known, metallic layer on ceramic
carrier contains, in average, 1.5 g of Pt and Pd and 0.3 g of Rh per autocatalyst. This is why the
recycling of rhodium cannot be considered independently of platinum and palladium recycling.
Recycling of rhodium is in expansion, as is shown in Fig. 4, not only because of an increased
metal market demand but also with an aim to save the primary sources, what is the world trend in
every way.

Fig. 4 The amount of recycled rhodium through five years

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In this study only wet processes for rhodium recycling will be discussed. The recycling of
rhodium from spent/waste materials means the recycling of rhodium from spent catalysts because
the amount of rhodium spent in automotive industry and captured in waste automotive catalytic
converters is the most significant source for recycling. Recycling of valuable metals from such
materials is carried out by dissolving catalytic layer containing PGMs from a ceramic carrier by
means of mineral acids in the presence of a proper oxidant [3]. Removal and recovery of PGMs
from such leach liquors, as well as from similar PGMs bearing streams comprises a very complex
technology, which follows an overall technology scheme that is usually employed for PGMs
production from primary sources, i.e.: leaching of rhodium from rhodium bearing materials;
separation of rhodium ions from other leach liquor constituents, its concentration and purification
by using an appropriate technology, finally producing either pure metal or salts or some other
commercial product. This also includes the use of many various and aggressive chemicals and
production different mainly harmful effluents and/or by-products that have to be further managed
making them either commercially viable or environmentally acceptable. Due to an extremely
high price of rhodium and its complex production, many recycling processes for rhodium and
other associated PGMs are under research and development in order to make the existing
processes more efficient and less complex, or to establish qualitatively new technology, for
rhodium recycling and reuse, by employing modern processes and operations.
2.1. Solvent extraction (SX)
As rhodium ions usually exists in leach liquors associated with some common heavy metals ions
(Fe2+/Fe3+, Cr3+, Mn2+, Ni2+, ...), depending on the leached rhodium bearing materials, as well as
the other PGMs, and a surplus of acid as leaching agent, solvent extraction (SX) is most
frequently employed to separate, in the first step, common metals ions from precious ones and
then to treat separately both streams for stepwise removal some of targeted ions. For this purpose
some collective extractants are used, as: DEHPA, TOPO, Aliquot, LIX (series 54 to 65N), etc. In
the second step, PGMs are separated each other by using some more specified extractants, as: tri-
iso-octylamine (Alamine), N-n-octylamine, TBP, di-octilsulphite, or some other commercial
extractant selective against a particular PGM ion. The main drawback of SX technique is a poor
selectivity of used extractants i.e., difficulty to separate quantitatively one ionic specie from the
other ones from aqueous phase, particularly if the present ions have similar features, i.e.
belonging to the same group of metals. This disadvantage leads in lowering the extraction
efficiency and the purity of produced extracts, requesting their further separation, having as a
ultimate result certain losses of targeted metal and higher production costs. Also, using SX a
certain amount of metal is always being captured by the organic phase, circulating in the process
[4,5].
Considerably high interest of scientists has been paid, during the past two decades, to study
some new processes based on solvent extraction and membrane technologies. Liquid membrane
(LM) processes, particularly supported liquid membrane (SLM) processes are a new direction in
developing more efficient separation and concentration techniques for removal and recovery not
only PGMs but also hazardous ions from various aqueous streams [6,7]. The second approach
consists in synthesizing new, more powerful, more selective and less harmful extractants.
Recently, new oligo-molecules based on different calix-arene derivatives have been
developed and tested as a particularly suitable for solvent extraction of precious metals. Some of
these derivatives are able to complex and extract metal ions from very acidic media equally
efficiently as from weakly acidic solutions [8,9]. Working with calixarene[4]- tetramide, oxygen

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donor extractant (LBC), we found that it is very effective to complex Ag+-ions separating them
from Pd-ions, as is reported in Fig. 5. Kinetics of metal complexation is fast and equilibrium is
achieved after 10 minutes.

Fig. 5 Extraction of Ag+ and Pd2+ with LBC-calixarene [9]

Calixarene[4]-thio-tetramide (THIO), acting as S-donor extractant, is able to extracts both

silver and palladium achieving high extraction percentage. Using these two calixarenes
consecutively it is possible to separate firstly silver and then platinum and palladium from a
mixture, from nitrate media. Using LBC dissolved in CH2Cl2, in a concentration of 1 mM and an
acidic aqueous solution of Pt-, Pd- and Rh-ions as a mixture in an acidic media (pH< 1), we
found that Pd-ions are slightly extracted achieving the distribution coefficient 2.3 in a significant
surplus of LBC. Working with THIO, under similar experimental condition, both Pt- and Pd-ions
were completely transferred from chloride solution into organic phase (extraction percentage >
99%), while Rh-ions remain in the aqueous phase. It may be pointed out that THIO separates Pt-
and Pd-ions efficiently, while Rh-ions remain in the raffinate. These two extractants could have a
great potential in separation Pt4+ and Pd2+ from Rh3+-ions and should be considered more
intensively, particularly for the purpose to be employed in developing a new process for recycling
and recovery of PGMs from chloride and nitrate leach liquors. Moreover, the considered
calixarenes do not complex neither Cu2+ and Pb2+, nor other heavy metal ions at all, they could be
used for selective removal of precious metal ions from leach solutions in which they are
associated with non-noble heavy metal ions. Indeed, most of calixarenes extract alkali and
alkaline earth metal ions, some of them in a considerable amount [8], and that can be recognized
in many cases as a disadvantage because a pre-treatment of such solutions is needed. So far, the
price of calixarenes could be a barrier for an industrial application but not for precious metals
whose price can many times cover the production costs. Dichloromethane is usually used as a
solvent as well as few others, mainly hazardous organic compounds, what also could reduce their
implementation as extractants. These solvents dissolve calixarenes quite well; these extractants
have low viscosity and reasonably higher density than the aqueous phase, ensuring fast and
efficient phase separation and could be acceptable in some especial cases as it is SX of precious
metals. Recently, ionic liquids have been considered as diluents for some calixarene derivatives
[10], what opens a new possibility to apply a direct electrowinning of extracted metals from
organic phase [11].

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9th European Symposium on Electrochemical Engineering (9th ESEE) 

2.2. Ion exchange processes

Ion exchange and adsorption processes are in use for years in industrial production of precious
metals. Carbon or resin in pulp as well as carbon or resin in column, are old and well known
technologies in gold production from primary ores. As these technologies are more convenient
for more diluted solutions they found their position in treating leach solutions and effluents for
collective or selective removal of precious metal ions. Some of them are also employed in
precious metal recycling technologies, including rhodium recycling. Rhodium separation from
other metal ions present in chloride media can be successfully carried out by using ion exchange
resin, as Amberlite IRA900, achieving an adsorption percentage > 95%, starting from an initial
concentration of approximately 10 ppm. Indeed, the process kinetics is very slow and almost 10
to 12 (in some cases 24) hours is needed to achieve desired concentration in the outlet stream
[12]. Here is, similarly as it is with SX technique, the problem of selectivity. Namely, IX resins
rather adsorb PGMs collectively so that this technique is more applicable for separation PGM
ions from the others present in a solution [13]. In this respect, IX technique is more suitable for
rinse waters from precious metals production and electroplating plants. Such waters, having
different composition but, as a rule, with a very low concentration of metal ions and lower acid
content, appear in considerably high amounts in PGMs recycling technologies.
2.3. Cementation
Cementation of metal ions by a metal, less noble than that one in ionic form, can be described by
an overall stoichiometric equation:

mMen+ + nMe1 = mMe + nMe1m+ (1)

where: Me, Me1 are metal to be reduced and oxidized, respectively; m, n are the stoichiometric
coefficients and number of electrons exchanged in the reaction. Cementation is an old but
efficient process still in use on industrial scale. Cementation is used in some cases for the
reduction of PGMs, either collectively or selectively from leach solutions or wastewaters
containing PGMs ions [14]. As an electro-reducing agent, Zn-powder is usually used but, in some
cases, Al-, Fe- or Cu-powder, having considerably higher standard potentials than Zn has, but
still lower than standard potentials of here considered PGMs.
Since the standard potential of each PGM is quite high: Rh3+/Rh = 0.8 V; Pd2+/Pd = 0.987 V;
PtCl42-/Pt = 0.758 V, every mentioned metal for cementation, having standard potentials as
follows: Zn2+/Zn = - 0.763 V; Fe2+/Fe = - 0.44V; Cu2+/Cu = 0.337 V could be used for reducing
PGMs.
The cementation technique is simple and easily controllable, giving the reduced metal in its
elemental form and achieving a very low concentration of its ions in the outlet stream. The
process can be considered as irreversible because the corresponding equilibrium constant may
achieve very high value. The main drawback is that the cemented metal is not pure enough (in the
best case < 95%), containing a certain amount of metal for cementation and must be further
refined to a desired purity. This needs an additional step either pyro- or hydrometallurgical route
to purify the cemented metal. In case of hydrometallurgical way the cemented metal can be
treated by a proper acid solution to dissolve the residual cementing metal and, after phase
separation, rinsing and drying. Another lack is that the consumption of oxidized metal is
sometimes several times higher than the stoichiometric one, particularly if cementation is carried
out from more acidic solutions and if standard potential is negative when hydrogen evolution

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9th European Symposium on Electrochemical Engineering (9th ESEE) 

takes place as a secondary reaction. In such cases the acid is almost fully neutralized and
produced metal salt must be then removed from the aqueous phase in order to prevent an
environmental pollution of surface or ground waters with ions formed in the cementation process.
If the cementation occurs from a mixture of ions the composition of produced solid phase will
be similar to that one of the aqueous phase. In such cases the cementation percentage of metal
ions are different and, as a rule, less than those ones when cementation occurs from single ion
solutions. Obtained cemented metal mixture is then usually added to a similar but larger metal
amount and must be further processed in order to separate metals each other getting a requested
purity.
Working with acidic chloride solution (pH<1), containing Rh3+, Pd2+ and Pt4+ and using Cu-
powder as a reducing agent, in a surplus of that stoichiometry needed, the following results were
achieved, as reported in Table 2.

Table 2 Cementation of PGMs with copper powder

Metal ion Rh3+ Pd2+ Pt4+
Initial conc., ppm 240 140 75
Final conc., ppm 56 2 9
% of cementation 76 98.6 88
Potential difference, V 0.463 0.65 0.421

Cementation percentage of rhodium is the lowest in spite of its highest inlet concentration
because it has the lowest potential difference between Rh3+/Rh and Cu/Cu2+. When the
cementation occurs from single ion solution the percentage of cemented rhodium can reach >
99% as reported by S. Aktas [14]. Indeed, the kinetics of PGMs cementation by copper powder is
reasonably slower due to a lower potential difference, so that longer process time is needed to
reach the desired cementation percent.
2.4. Other reducing methods
2.4.1. Chemical reduction
Palladium ions can be easily reduced by ascorbic acid from less acidic solutions (free acid
concentration< 4 M), achieving a very high precipitation percentage > 99% [6]. The reduction
process is fully selective against Rh3+-ions which remain in the solution. This method can be
employed for quantitative separation palladium from rhodium ions from leach solutions. Both
Pd2+ and Rh3+-ions can be effectively reduced to metallic form by means of formic acid. In nitrate
systems that happens at pH =2. Very few reports are available in the relevant literature on
chemical reduction of Rh3+-ions as those ones existing for platinum and palladium electroless
plating. Rh3+-ions can be deposited by using sodium borohydride in alkaline media [15], so that it
will not be considered here anymore.
2.4.2. Electrochemical reduction
Electrodeposition of rhodium is widely investigated and explored in the frame of electroplating
rather than electrowinning processes. Electroplating baths contains strong acids in a surplus and
only in this view they are similar to the PGMs leach solutions. Electrowinning of rhodium could
be carried from pretreated leach solutions purified from Pt- and Pd-ions but with very low current
efficiencies. Electrodeposition of rhodium occurs simultaneously with hydrogen evolution
reaction for which a freshly deposited rhodium layer acts as a catalyst [16]. Since at the recycling
of rhodium palladium exist in leach liquors, an electro-separation between Pd2+ and Rh3+ could

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 9th European Symposium on Electrochemical Engineering (9th ESEE) 

be carried out by electrodeposition of palladium at a very controlled deposition potential.

Namely, palladium can be reduced to metal by electrolytic deposition onto platinum cathode at a
relatively low reducing potential of -0.2 V vs. SCE. Deposition rate is fast comparing to rhodium
electrodeposition and a separation factor 10 can be achieved [17]. Going towards more negative
potentials separation factor decreases due to a certain co-deposition of rhodium giving an impure
deposit and lessening the current efficiency due to an enhanced hydrogen evolution reaction. An
interesting approach has recently been reported by M. Jayakumur et al [18], who studied the
electrodeposition of rhodium from 1-butil-3-methil imidiazolium chloride at – 1.7 V and 100oC,
producing pure powdery rhodium metal deposited on stainless steel cathode. This process can be
considered, so far as am attempt which could potentially be viable for rhodium electrowinning in
the future.

3. Conclusions
Recycling of PGMs from spent automotive catalysts is a very complex technology comprising
many sophisticated operations and expensive chemicals in order to split PGMs ions each other
producing pure commercially acceptable products. Instead of metal, it is more convenient to
produce salts that would be used in production of new catalytic converters.

References
1. Kitco Precious metal Charts, www. kitco.com/charts, (2011).
2. J. Butler, Platinum 2010, Interim Review, Published by Johnson Matthey, (2010).
3. D.J. Aberasturi, R.Pinedo, I. Larranand, T. Rojo, Minerals Engineering, in press (2011).
4. B.R.Reddy, B. Raju, J.Y. Lee, H.K. Park, J. Hazard. Materials 180 (2010) 253.
5. K.C. Sole, A.M. Feather, P.M. Cole, Hydrometallurgy 78 (2005) 52.
6. Z. Kolarik, E. Renard, Platinum Metals Review 47(2) (2003) 74.
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9. V. Stankovic and V. Fajnisevic, Electrochem. Engng. Symp. CHISA, Prague, August, 2008.
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11. V. Stankovic, I. Duo, C. Comninellis, F. Zonnevijlle, J. Appl. Electrochem. 37 (2007) 1279
12. S.Shen, T. Pan, X. Lin, L. Yuan, J. Wang, Y. Zhang, Z. Guo, J. Hazard. Mater. 179 (2010) 104.
13. ibidem; J. Col. Interface. Sci. 345 (2010 ) 12.
14. S. Aktas, Hydrometallurgy, in press (2011).
15. C.R.K. Rao and D.C. Trivedi; Coord. Chem. Rev. 249 (2005) 631.
16. D. Pletcher and R.I. Urbina; J. Electroanal. Chem. 421 (1997) 137.
17. M. Jayakumur, K.A.Venkatesan, T.G. Srinivasan, Electrochim. Acta 54 (2009) 1083.
18. M. Jayakumur, K.A.Venkatesan, T.G. Srinivasan, P.R.V. Rao, Electrochim. Acta 53 (2008) 2794.

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