Hydrometallurgy 68 (2003) 69 – 75

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Separation of Ir, Pd and Rh from secondary Pt scrap

by precipitation and calcination
G. Schreier, C. Edtmaier *
Institute for Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164-CT, 1060 Vienna, Austria

Received 19 February 2002; received in revised form 21 October 2002; accepted 22 October 2002

Abstract

Secondary platinum scrap from the glass industry with iridium, rhodium and palladium additions arising from alloys or
enrichment due to multiple recycling of the construction elements was used to study the refining behavior and to define and
control parameters influencing the selectivity and yield. Dissolving this material in boiling aqua regia, diluting with water or
hydrochloric acid and precipitating with ammonium chloride (NH4Cl), then separating the mother liquor gives a precipitate,
where the accompanying platinum group metals (PGMs) iridium, rhodium and palladium are separated from the platinum matrix.
Calcination of the precipitate gives a sponge of high purity (>99.90%). The influence of the dilution of the solution with water
and/or hydrochloric acid, as well as the temperature of the precipitation, has been investigated.
D 2003 Elsevier Science B.V. All rights reserved.

Keywords: Precious metal separation; Precipitation; Hydrolysis

1. Introduction used. Depending on the temperature in the glass

The separation of additions of iridium, palladium
and rhodium from a platinum matrix has been inves-
tigated. The material used is a typical secondary scrap
arising from the glass industry and is less polluted with
base metals such as Fe, Ni or/and Cu. The concen-
trations for iridium, rhodium and palladium of the
investigated scrap were 8636 mg/kg Ir, 5455 mg/kg
Rh and 168 mg/kg Pd; the one of iron, nickel and
copper below 100 mg/kg per element. Construction
components in the glass industry are commonly pure
platinum, but PtIr1 and PtRh10 are also extensively
* Corresponding author. Tel.: +43-1-58801-16135; fax: +43-1-
58801-16199.
E-mail address: cedtmaie@mail.zserv.tuwien.ac.at
(C. Edtmaier).
process, Pt is used for lower, PtIr1 for higher and
PtRh10 for highest process temperatures up to 1650
jC. As these materials are not always ‘‘separated’’
completely due to their composition before refining,
the scrap for refining has a composition as described
above. The investigations were made to prove the
quality of a separation by precipitation with ammo-
nium chloride, as example for a simple process.
2. Experimental procedure
A solution was prepared by dissolving the scrap in
boiling aqua regia.
18HCl þ 4HNO3 þ 3Pt ! 3H2 ½PtCl6  þ 4NO þ 8H2 O
ð1Þ

0304-386X/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X ( 0 2 ) 0 0 1 9 4 - 9
70 G. Schreier, C. Edtmaier / Hydrometallurgy 68 (2003) 69–75

Table 1 accompanying elements iridium, rhodium and palla-

Solubility of PGM complexes in water at different NH4Cl dium in the investigated scrap were 8636 mg/kg Ir,
concentrations (Beck et al., 1995)
5455 mg/kg Rh and 168 mg/kg Pd.
NH4Cl (NH4)3 (NH4)3 (NH4)2 (NH4)2
The preparation of the solution comprised further-
(mol/l) [Rhl6] [PdCl6] [IrCl6] [PtCl6]
(g/l) (g/l) (g/l) (g/l) more the step of destroying the nitric compounds and
driving off nitric gases from the solution, distilling of
0 40 3 1 1
0.5 20 7e  2 5e  2 3e  2 the residue HCl and diluting with water and/or HCl.
1 12 2e  2 2e  2 1e  2 The precipitation was done by adding ammonium
1.5 8 1e  2 1e  2 8e  3 chloride to the metal solution. The mother liquor was
filtered off and the precipitate was calcined under inert
The experiments showed an optimum dissolution time gas atmosphere, washed with pure water, separated and
of 4 h, above which the dissolvable amount of metal dried (Disam et al., 1997; Ullmann’s Encyclopedia of
was less and the efficiency decreased rapidly. The Industrial Chemistry; Schreier, 1993; Gmelin, 1951).
optimum proportion of HCl (32 wt.%)/HNO3 (53 After the dissolution process has reached its opti-
wt.%) was 3:1. The experiments were carried out in mum (time), the metal solution was heated to 453 K,
a 2-l glass balloon flask with return-flow coolers and then cooled to 403 K for adding hydrochloric acid to
electric heating caps charged with 1500 g precious destroy any nitric compounds and drive off nitric gases.
metal cuttings (with about 4.5 times the stoichiometric This was repeated several times, until no nitric gas was
amount). Hot aqua regia was charged into the flask, formed and seen in the waste-gas stream. Residues of
as then the dissolution reaction starts much faster. nitric gases will reduce the yield of precipitation. The
This scrap consisted of cuttings from sheets and solution was then evaporated in order to reduce the
facings from castings and had a specific surface of volume and to distil any HCl remaining from the
about 150 – 200 mm2/g. The concentrations for the dissolution process. The distillation temperature was

Fig. 1. Influence of HCl concentration on yield and remaining PGM contents in calcined platinum powder (distillation temperature = 453 K,
precipitation temperature = 353 K).
 G. Schreier, C. Edtmaier / Hydrometallurgy 68 (2003) 69–75
varied between 453 and 463 K in order to study its
influence on purity and yield during precipitation. The
hot solution was diluted with water to a concentration
of about 600 g Pt/l to obtain a platinum concentrate
which can be stored. The solution was filtered to
separate etching products from the glass balloon flasks
and PtClx compounds. Just before the precipitation
process, the metal solution was diluted a second time
to a suitable precipitation concentration, which is in the
range of 180 – 250 g/l. The influence of the added
hydrochloric acid and/or water on yield and purity
was then investigated.
The precipitation process was carried out by adding
an ammonium chloride solution (NH4Cl (p.a.)) to the
precious metal solution under vigorous stirring. The
influence of the temperature of the solutions on purity
and yield was investigated and therefore varied be-
tween 293 and 353 K. A concentration of 300 g/l NH4
Cl was chosen. This gave the yellowish Pt precipitate
(NH4)2[PtCl6], which was washed with a dilute NH4Cl
solution (150 g/l) to remove the reaction solution com-
pletely. In the mother liquor, all desired base metals and
the platinum group metals Ir, Rh and Pd which should
Fig. 2. Influence of HCl concentration on yield and remaining PGM contents in calcined platinum powder (distillation temperature = 463 K,
precipitation temperature = 353 K).
71
be separated were dissolved, as well as Pt to a certain
extent. To ensure a high product purity, it is essential
that the contact time between the mother liquor and the
precipitate is kept small; otherwise, a coprecipitation of
the impurities will contaminate the precipitate.
Calcination of the precipitate was carried out at a
temperature of 693 K in a furnace with a fused silica
muffle. This gave a metallic sponge of platinum of
high purity (>99.90%) and particle sizes in the range of
1– 10 Am. The sponge was washed several times with
hot distilled water in order to remove any residues of
reaction products. In this process the sponge disinte-
grated into a fine powder. The platinum powder was
then dried to constant weight.
The sponge was characterized by SEM and ana-
lyzed with ICP/AES for residue concentrations of base
metals and iridium, rhodium and palladium.
3. Results and discussion
The process step of precipitation has the main
influence on the purity and yield. For the refining
72 G. Schreier, C. Edtmaier / Hydrometallurgy 68 (2003) 69–75
effect, the different solubilities of the metal complexes
in the HCl and NH4Cl solutions are essential (Beck et
al., 1995) (Table 1).
With increasing NH4Cl concentration, the solubility
of the platinum complex decreases. The platinum
complex precipitates because of its lower solubility.
Meanwhile, the other PGM complexes remain dis-
solved in the mother liquor. A higher temperature
has the reverse effect: the higher the temperature, the
higher the solubility and, therefore, the refining effect
is less. Because of the precipitation reaction
H2 PtCl6 þ 2NH4 Cl ! ðNH4 Þ2 ½PtCl6  þ 2HCl
there is always HCl in the mother liquor. This primar-
ily causes a decrease in solubility—e.g. of the rhodium
complex—and, therefore, decreases the selectivity of
the precipitation. It is furthermore known from Beck et
al. (1995) that more or less all PGM – chlorine com-
plexes are susceptible to hydrolysis, especially at
higher temperatures, and can influence the complete-
ness of the reaction and the separation effect consid-
Fig. 3. Solution diluted with water, distillation temperature = 453 K, influence of precipitation temperature on yield and Rh, Ir, Pd concentration
in calcined Pt powders.
erably. Dilution of the solutions and acid concentration
also play an important role.
In an optimum process, the platinum precipitates
completely; the base metals and the PGMs are in the
mother liquor. But in reality, yield and purity are
competitive: the higher the yield, the lower the avail-
able purity of the platinum precipitate and the subse-
quent platinum powder. But yield and purity are
essential for the economic efficiency of an industrial
process. The following experiments demonstrate the
parameters controlling the process.
ð2Þ 3.1. Influence of HCl concentration in the metal
solution (before precipitation) on refining effect and
yield
The separation of PGMs—rather than base met-
als—is more complicated because of their noble con-
dition, the atomic and chemical similarity between
platinum and PGMs. The preparation for the precip-
itation was investigated—diluting with water or HCl—
to assess influence on yield and the remaining PGM
 G. Schreier, C. Edtmaier / Hydrometallurgy 68 (2003) 69–75
content in the precipitate and calcined powders. The
distillation temperature in Fig. 1 was 453 K, and 463 K
in Fig. 2. The precipitation temperature was 353 K for
both cases, and the starting solution had a metal
concentration of 594 g Pt/l. No base metals such as
Ni, Cu or Fe were found in the resulting platinum
powders described in the following experiments.
The experiments show clearly the dependence of
the separation effect of rhodium, iridium and palla-
dium from the HCl concentration in the metal solu-
tions. Diluting with water (HCl concentration = 0 in
Figs. 1 and 2) gives lowest PGM concentrations in the
calcined platinum powders. The increasing HCl con-
centration results in higher values, especially for
iridium. Simultaneously, with a higher HCl concen-
tration, an increase in yield of precipitation can be
noticed. Increasing the distillation temperature from
453 to 463 K has the effect of reduced iridium and
rhodium concentrations, as the palladium concentra-
tion is almost the same for both experiments.
It can be noticed that during the dilution of the
distilled solution with water a reaction occurs, which
Fig. 4. Solution diluted with water, distillation temperature = 463 K, influence of precipitation temperature on yield and Rh, Ir, Pd concentration
in calcined Pt powders.
73
causes the enormous refining effect during the follow-
ing precipitation step. The reaction can only be the
hydrolysis reaction (Cl ions of the complex are
changed through OH ions). The resulting complexes
do not form a precipitate of low solubility and remain
dissolved in the mother liquor during the precipitation
(Ullmann’s Encyclopedia, 5th ed.). The willingness for
hydrolysis seems to be much higher for iridium,
rhodium and palladium than for the platinum, which
is the reason for their complete separation at the
precipitation process. The impairment of the yield
can be explained by that part of the platinum which
also exists as hydrolysis complex. Therefore, during
the distilling of the remaining HCl from the dissolution
process, less and less HCl is available with increasing
temperature. Hydrolysis complexes can be formed by
reaction with the water if the distillation temperature is
high enough. At a lower distillation temperature of 453
K, too much HCl is available. When diluting such
solutions with water no hydrolysis complexes can be
formed and increasing PGM concentrations can be
observed.
74 G. Schreier, C. Edtmaier / Hydrometallurgy 68 (2003) 69–75
3.2. Influence of precipitation temperature on refining
effect and yield
It can be anticipated that both yield and degree of
purity can be also influenced by the precipitation
temperature. Because of the better solubility of the
precious metal salts in the mother liquor at higher
temperatures, a prevention of a coprecipitation of
iridium, rhodium and palladium, as well as a reduction
of the platinum yield can be expected. The solution
was the same as used in the above experiments.
Minimum values for iridium and rhodium can be
achieved with precipitation temperatures from 313 to
333 K and diluting with water (Figs. 3 and 4).
Temperatures below 313 K show increasing values
for iridium and palladium. Lower values of palladium
are obviously influenced by higher precipitation tem-
peratures. A higher distillation temperature again
reduces the content of iridium, rhodium and palladium.
The results shown in Figs. 3– 5 confirm the expected
influence of the precipitation temperature on the yield:
at higher temperatures, the yield is generally higher;
Fig. 5. Solution diluted with 2M HCl, distillation temperature = 453 K, influence of precipitation temperature on yield and Rh, Ir, Pd
concentration in calcined Pt powders.
for a precipitation at 313 K, the yield is worst. Diluting
the metal solution with 2 M HCl results in an overall
increase of PGM concentration, as well as in a general
increase of yield (Fig. 5).
A higher precipitation temperature reduces the iri-
dium, rhodium and palladium concentrations slightly
for the case of diluting with 2 M HCl. Such platinum
powders would not fulfill the general industrial re-
quirements on purity (>99.90%). The dependence of
yield and purity of all experiments on the precipitation
temperature can be explained by a superimposition of
the solubility temperature dependence by an inversion
of the Pt complex hydrolysis. Due to the precipitation
HCl is released (Eq. (2)) and the inversion of the
hydrolysis will start by this HCl. The higher the
precipitation temperature, the faster this reaction must
proceed. Therefore, at a precipitation temperature of
353 K, the contact time during the precipitation and the
separation of the mother liquor is sufficient for the
inversion of the hydrolysis to result in an increase of
yield and iridium, rhodium and palladium concentra-
tion. The precipitation can, therefore, be described as a
 G. Schreier, C. Edtmaier / Hydrometallurgy 68 (2003) 69–75
process where at low temperatures (e.g. 293 K), the
solubility of the complexes is so low that the concen-
tration of iridium, rhodium and palladium increases.
At temperatures between 313 and 333 K, and for
diluting with water, medium yield and lowest PGM
contents can be achieved because of the hydrolysis,
whereas the separation of iridium, rhodium and pal-
ladium from platinum at higher temperatures is de-
termined by the kinetics of the inversion of the
hydrolysis.
4. Conclusion
With the described procedure, 8636 mg/kg Ir, 5455
mg/kg Rh and 168 mg/kg Pd can be separated in one
refining step to form platinum powders with a purity of
>99.90%. The influences of temperatures and the
preparation of the solutions for the precipitation have
been investigated. This preparation for the precipita-
tion influences both yield and degree of purity
immensely. In order to distil the remaining HCl from
the dissolution process, the solution has to be reduced
in volume until a temperature of about 453 K is
reached. Otherwise, the refining degree will be low,
especially in the presence of iridium. If the HCl is
removed completely, hydroxide complexes of the pre-
cious metals are formed while diluting the solutions
with water. This hydrolysis reaction takes place pri-
marily with iridium, rhodium and palladium. This
yields very pure precipitates but also decreases the
yield because also a part of the platinum exists as
hydroxide complex. As the efficiency of a process is
important, the precipitation has to be optimized for
high yields and high purity. For highest purity, the
distilled solutions should be free from remaining HCl
and should be diluted with water before the precip-
itation. Although yield is low with this procedure,
industrial applications require a compromise between
purity and yield. Acceptable values can be achieved by
adjusting a low HCl concentration in the solution, an
optimal concentration is about 1 M HCl. In this case,
the inversion of the hydrolysis of the Pt complex
75
during the precipitation occurs and the precipitate
has an acceptable low concentration of iridium, rho-
dium and palladium.
Increasing precipitation temperatures increase the
yield, but decrease the separation of iridium, rhodium
and palladium, even when the solutions are diluted
with water. This phenomenon can also be explained
by the inversion of the hydrolysis effect because HCl
is released during the precipitation. The HCl starts the
inversion of the hydrolysis of the precious metal
complexes. The higher the precipitation temperature,
the faster this reaction proceeds, so that the contact
time during the precipitation and the separation of the
mother liquor is sufficient for the inversion. This
results in an overall increase of yield and iridium,
rhodium and palladium concentrations in the calcined
powders. The content of iridium and rhodium is
lowest for precipitation temperatures between 313
and 333 K. Above and below, the precipitate has
higher concentrations. It can be supposed that at
higher temperatures the iridium, rhodium and palla-
dium concentration is determined by the kinetics of
the inversion of the hydrolysis reaction, whereas at
lower temperatures, the solubility of all complexes is
so small that the iridium, rhodium and palladium
concentrations in the precipitate and subsequent pow-
ders decrease.
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