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Bildiriler Kitabı TMMOB Metalurji ve Malzeme Mühendisleri Odası

Production of Pure Platinum and Palladium from Dore Yasemin Kılıç, Güldem Kartal Şireli, Servet Timur
Metals via Hydrometallurgical Methods İstanbul Technical University - Türkiye

Abstract PGMs resemble to each other in terms of their chemical


properties. The basic chemical characteristic of them is
The primary objective of this research is to investigate the their low electron affinity [4]. These PGMs with low
dissolution and precipitation characteristics of platinum and electron affinity form some various complex salts [3]. The
palladium in order to determine the best parameters for complex salts formed by PGMs are one of the most
their refining. Pure platinum and palladium plaques were important eigen value of this study. Platinum group metals
used for examining the dissolution parameters. As for their that are malleable with high corrosion resistance have a
precipitation parameters, Dore metals supplied from a high catalytic capability. Platinum and palladium are
silver refining slime and resin PGM’s-recovery system of a capable of absorbing very large volumes of hydrogen gas
gold refinery were dissolved and these solutions were and due to this property of them they are widely used in
utilized. Dissolution experiments were performed in aqua automobile catalysts. PGMs with high thermodynamic
regia. Test parameters were defined as a dissolution time stability show great resistance to corrosion by becoming
and a HCl/Me(Pt-Pd) ratio. After determining the optimum passive due to the thin oxide film which form in anodic or
HCl amount in aqua regia, additional studies were oxidizing atmosphere by oxygen absorption. Therefore, in
performed to reduce the amount of HNO3 in aqua regia. In the absence of complex ions, PGMs are resistant to alkali,
the precipitation stage, platinum and palladium ammonium salt and acidic solutions [3,5,4].
salts; time, temperature, amount of NH4Cl addition and pH
values of the solution were examined. As a result of the The most remarkable characteristic of PGMs is their
dissolving experiments, the ideal time was determined as 6 nobility when their separation chemistry is considered. This
hours with the HCl/HNO3 ratio of 4.25. The optimum represents their resistivity against aqueous solutions which
precipitation parameters were determined as 4 hours, room dissolve almost all base metals. Chloro-complexes are the
temperature and pH 4. In order to obtain the most efficient most significant area of PGM chemistry. The reason for
precipitation, NH4Cl was used 4 times as the stoichiometric that is chloride solution is the only cost-effective option for
amount. performing enrichment. All PGMs except ruthenium form
hexa-chloro complexes in chloride solutions by having +4
1. Introduction state. This hexa-chloro species can be precipitated from
their aqueous chloride solutions as ammonium salts.
With the improving technology and new environmental Forming volatile tetra-oxides is another option that is being
regulations, the area of use of PGMs are increasing. The used in PGM separation. Other than these, oxidation states
recycling of precious metals is of capital importance due to and redox potentials are one of the most distinct
their distinctive characteristics, their rarity and their high characteristics of PGMs both for this study and for general
price. Being in the 8B group in the periodic table, PGMs application [6].
include platinum, palladium, rhodium, ruthenium, osmium
and iridium. PGMs, which are very similar in terms of There are two basic methods for the refining of precious
physical and chemical properties and exist together in the metals from wastes and scraps: hydrometallurgy and
nature, are rarer than other metals and of capital importance pyrometallurgy. However, pyrometallurgical method is not
technologically [1,2]. mostly preferred due to high melting points of PGMs that
result in excessive amounts of energy consumption with
PGMs are elements generally with high atomic mass, high cost as well as non-environmental friendly. Within the
density, melting point and boiling point. PGMs also have scope of hydrometallurgical method, hydrolysis,
high thermal and electrical conductivity. The EMF values distillation, organic precipitation, solvent extraction, liquid
of PGMs clearly show that the ions of these metals are membrane extraction, solid-liquid extraction, ion-
reduced easily and they tend to be at the metallic state [3]. exchanger resins and selective precipitation are the mostly
used refining methods for PGMs. Hydrometallurgy was

587
18. Uluslararası Metalurji ve Malzeme Kongresi | IMMC 2016
UCTEA Chamber of Metallurgical & Materials Engineers Proceedings Book

preferred in this study too and after dissolving step refining 2.4. Evaporation of HNO3
of platinum and palladium was implemented by selective
precipitation. In this regard, refining process is started with Before moving on to platinum and palladium precipitation,
silver precipitation after the dissolution treatment in aqua the excess amount of HNO3 was evaporated in order to
regia is finished. After silver, in order to remove the gold provide a good oxidation.
from the solution, gold precipitation is achieved by Fe + or
NaHSO3 solutions. Following to this step, in order to 2.5. Oxidation of Pt(II) to Pt(IV)
discard the existence of excess amount of oxidant, the
evaporation of redundant nitric acid is performed. Once In order to precipitate platinum as (NH4)2PtCl6 salt,
precipitation of platinum as (NH4)2PtCl6 salt with NH4Cl platinum should be in +4 state. When pH<1, it is already in
addition, palladium is oxidized from Pd+2 to Pd+4 state and the form of +4 ion state, so there was no need for oxidation
is precipitated as (NH4)2PdCl6 salt with NH4Cl [4,8]. since precipitation was accomplished in acidic conditions.

2. Experimental Procedure 2.6. Precipitation of (NH4)2PtCl6

In this study, pure platinum and palladium plaques are used Precipitation of (NH4)2PtCl6 salt was realized with NH4Cl
for examining dissolution parameters. For precipitation addition. In this step, precipitation time, NH4Cl amount and
parameters, alloys from a silver refining mud and resin temperature were determined as the parameters to be
recovery system of a plant were dissolved and these optimized.
solutions were used.
2.7. Oxidation of Pd(II) to Pd(IV)
After dissolution, silver precipitation step started. Once
silver was precipitated, gold also was precipitated and Steady state for palladium is +2. However, In order to
HNO3 evaporation step completed. Afterward, oxidant precipitate platinum as (NH4)2PdCl6 salt, palladium should
addition was done in order to precipitate platinum and be in +4 state. Therefore, a strong oxidant (perchlorate) was
palladium as chloro-complex salts. Finally, platinum and used.
palladium were precipitated respectively.
2.7. pH adjustment
2.1. Dissolution
In order to precipitate (NH4)2PdCl6 salt, pH value is very
Dissolution experiments were performed in aqua regia. Test significant. For the ideal precipitation, pH value was
parameters are dissolution time and HCl/Me(Pt-Pd) rate. determined as a parameter and precipitation yield was
After determining the optimum HCl amount in aqua regia, calculate for different pH values.
some studies were performed intended to reduce the
amount of HNO3 in aqua regia. The related equations are 2.8. (NH4)2PdCl6 precipitation
shown below.
After oxidation and pH adjustment steps, (NH4)2PdCl6
Pd + 3HCl + HNO3 ļ PdCl2 + 2H2O + NaCl (1) precipitation was actualized by addition of NH4Cl. Time,
temperature and amount of NH4Cl were determined as the
Pt + 4HCl + 4HNO3 ļ PtCl4 + 4H2O + 4NO + 2O2 (2) parameters to be optimized.

2.2. Silver (Ag) precipitation 3. Results and Discussion

The silver included in the raw material was separated from In order to determine the acid mix proportion, a series of
the solution via cementation according to Eq.3 experiments were executed reliant to HCl/HNO3 rate and it
was observed that the mixing proportion should be
Cl- + Ag+ ļ AgCl (3) HCl/HNO3•4 (please see Fig.1). It is significant to have
this rate higher for avoiding the unnecessary boiling for the
2.3. Separation of gold (Au) evaporation of HNO3 in the precipitation step.

Fe+2 and NaHSO3 can be used for gold separation. Gold Other than this, the necessary amount of HCl in aqua regia
was removed from the solution by precipitating as gold was defined according to HCl/Pt=12 rate (cannot be
powders according to Eq. 4. The amount of chemicals used explained due to commercial reasons) and experiments
in this step was not examined as a parameter. were done also for HCl/Pt=24 and HCl/Pt=36 rates (Figure
2). HCl/Pt=12 is recognized sufficient for dissolution when
Au++Fe2+ļ Au+Fe3+ (4) environmental and economic factors and human health are

588 IMMC 2016 | 18 th International Metallurgy & Materials Congress


Bildiriler Kitabı TMMOB Metalurji ve Malzeme Mühendisleri Odası

considered, hence this value was accepted as the optimum Table 1. Concentration of the solution at the beginning
value. Element Concentration[ppm]
Platinum (Pt) 2046.24
Palladium (Pd) 1990.66
Gold (Au) 1411.2
Silver (Ag) 0
Iron (Fe) 1538.4
Copper (Cu) 23685.6
Nickel (Ni) 52.4
Zinc (Zn) 838.8

Before starting precipitation experiments, the selective


precipitation of gold was performed with the addition of
sodium metabisulphite since it is not possible to precipitate
platinum and palladium as amine compounds in the
Figure 1. Dissolved Pt variation with respect to HCl/HNO3 presence of gold. After the elimination of gold,
precipitation experiments was started. First, a series of
experiments (1 min., 3 min., 5 min., 10 min., 15 min., 20
min., 25 min., 30 min., 1 h., 2 h., 4 h., 24 h.) were executed
in order to define the optimum time for precipitation. When
the analysis results were examined, it was observed that
there is not a remarkable change in the amount of precious
metal in the solution after 4 hours, Thus 4 hours is accepted
as the optimum precipitation time (Figure 3).

Figure 2. Variation precipitation yield vs time at different


HCl/Pt ratios

From the experiments carried out by keeping the other


parameters same except HCl/Pt, it was seen that dissolution
was completed in 6 hours and this time is accepted as the
optimum time for the experiments. However, for the
industrial applications, 4 hours is recommended by Figure 3. Optimization of the necessary time for
considering granule or popcorn shape material are probably completion of Pt-precipitation
used instead of plaques as we utilized in our experiments
and because of the increase in the surface area, materials In order to examine the effect of temperature to
act more reactive which most likely result in a shorter precipitation, experiments were done at room temperature
dissolution time. (25 °C), 50 °C and 80 °C by using optimum amount of
NH4Cl for 4 hours. Maximum yield was achieved at the
For palladium dissolution tests, the amount of HCl in aqua room temperature (see Figure 4) and this is correlated with
regia is accepted as HCl/Pd=12 (same rate with the the increasing solubility of platinum complexes with the
platinum) but for the experimental integrity HCl/Pd•18 rate increasing temperature.
were also tested and the correction of the HCl/Pd=12 rate
was practiced.

Within the scope of precipitation of platinum and palladium


ammonium salts experiments; time, temperature, amount of
NH4Cl added and pH value of the solution were examined
as the test parameters. The concentration of the solution can
be seen in Table 1.

589
18. Uluslararası Metalurji ve Malzeme Kongresi | IMMC 2016
UCTEA Chamber of Metallurgical & Materials Engineers Proceedings Book

Figure 4. Effect of temperature on precipitation yield Figure 6. Effect of pH on precipitation yield


For the precipitation process, saturated NH4Cl solution was 4. Conclusion
added to aqua regia solution containing platinum and
palladium. Platinum was precipitated as (NH4)2PtCl6 Within the scope of the study, the parameters related to
(ammonium hexa-chloro-platinate) salt and palladium was platinum and palladium refining were optimized and it was
precipitated as (NH4)2PdCl6 (ammonium hexa-chloro- confirmed that this will be a more promising method. As a
palladate) salt. In these treatments, amount of NH4Cl was result of the dissolving experiments, the ideal time was
examined as a test parameter and in the analysis results, it determined as 6 hours with the HCl/HNO3 ratio of 4.25.
was observed that precipitation yield is increasing The optimum precipitation parameters were determined as
proportionally with the amount of NH4Cl added. In this 4 hours, room temperature and pH 4. In order to obtain the
case the ideal conditions for platinum were determined as most efficient precipitation, NH4Cl was used 4 times as the
room temperature, pH<1, CPt=2.7 g/L, t•4 h, and the stoichiometric amount.
optimum NH4Cl amount was accepted as the 4 times of the
stoichiometric amount of NH4Cl. References

[1] Lyon, S. B. (2010). Corrosion of Noble Metals. Elsevier


B.V., 3-27, UK.
[2] Brits, J. H. (2007). Palladium Stripping Rates in PGM
Refining, Hydrometallurgy, 89, 253-259, South Africa.
[3] Steel, M.C.F., (1991). Supply and demand of precious
metals for automotive and other uses, Catalysis and
Automotive Pollution Control II, Johnson Matthey PLC,
London, United Kingdom.
[4] Rao, C.R.K, Trivedi, D.C. (2004). Chemical and
electrochemical depositions of platinum group metals and
their applications, Coordination Chemistry Reviews, 249,
711-734.
[5] Hisar, R. (1964). Metal KimyasÕ Dersleri Bölüm II,
Figure 5. Effect of temperature on precipitation yield
Platin Grubu Metaller, 266-274, østanbul.
[6] Bernardis, F.L., Grant, R.A., Sherrington, D.C. (2005).
Once platinum precipitation was completed, palladium
A review of methods of seperation of the platinum-group
precipitation process was started. The defined optimum
metals through their chloro-complexes,
values for time, temperature and NH4Cl amount are valid
Reactive&Functional Polymers, 65, 205-217.
for palladium, too. However, different than the platinum,
[7] Cui, J., Zhang, L. (2007). Metallurgical recovery of
palladium was oxidized from Pd+2 to Pd4+ state and pH
metals from electronic waste: A review, Journal of
adjustment was carried out. In order to prevent the
Hazardous Metals, 158, 228-256, Norway.
oxidization of palladium, perchlorate solution was used. As
a result of the experiments performed for pH 4, pH 8 and
Acknowledgement
pH 12 values, the maximum yield was received at pH 12
(see Figure 6). However, due to excess formation of metal
The samples used in this study were provided by Onsa
hydroxides and difficulty of achieving a clean precipitate in
Mücevherat ømalatÕ ve DÕú Tic. A.ù. We wish to gratefully
laboratory conditions, the second best result which is pH 4
acknowledge them for their help and generosity.
was chosen as the optimum value.

590 IMMC 2016 | 18 th International Metallurgy & Materials Congress