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A leaching process was established Cyanide pressure leaching was potentials for the half reactions are:13
based on the ability of platinum-group examined for recycling PGM from
metals to form stable chloro-complexes spent catalysts where substantial care Pt2+(a) + 2 e– = Pt (s) (E° = 1.19 V)
in acidic chloride solutions. Industrial is needed to prevent evolution of the PtCl42–(a) + 2 e– = Pt (s) + 4 Cl–(a)
catalyst losses were examined for the hazardous HCN gas and destruction (E° = 0.73 V)
recovery of platinum, palladium, and of the remaining cyanide in waste
rhodium by leaching with a mixture of solutions.6–8 On the other hand, halide PtCl62–(a) + 2 e– = PtCl42–(a) + 2 Cl–(a)
sulfuric acid and sodium chloride to processes were established after several (E° = 0.74 V)
avoid using aqua regia or autoclave modifications proved efficient and safe Pd2+(a) + 2 e– = Pd (s) (E° = 0.92 V)
conditions. Extraction of platinum particularly with secondary recovery
and rhodium in 60% H2SO4 at 135°C by pressure leaching with iodine/iodide PdCl42–(a) + 2 e– = Pd (s) + 4 Cl–(a)
steadily increased with increasing NaCl solutions. However, pressure leaching (E° = 0.62 V)
concentrations reaching 95% and 85%, is expensive and can render the process PdCl62–(a) + 2 e– = PdCl4 (s) + 2 Cl–(a)
respectively, at 0.1 M NaCl after complicated with respect to materials (E° = 1.29 V)
two hours. By comparison, palladium and handling.9,10 F. Solomon has patented
was dissolved more quickly but also a process based on treating PGM residue Rh3+ (a) + 3 e– = Rh (s) (E° = 0.70 V)
reached 85% under the same conditions. with a polar organic solvent where RhCl63–(a) + 3 e– = Rh (s) + 6 Cl–(a)
Extraction of each metal increased with bromine is dissolved to form a non- (E° = 0.44V)
temperatures up to 125°C but plateaued aqueous PGM complex.11 The organic
at higher temperatures. Similar behavior solvent is subjected to electrolysis to According to these potentials, dissolu-
was observed with increasing H2SO4 recover the PGM. A mixture of bromide tion reactions are rather difficult.
concentrations up to 60%. More than salt and bromine was also used for However, the presence of chloride ions
99% extraction of each metal was leaching of PGM.12 for the formation of stable complex
obtained after ten hours using 0.1 M ions and the resulting increase in the
HYPOTHESIS
NaCl and 60% H2SO4 at 125°C. reduction strength of the metal is the
For solubilization of platinum, pal- reason it works.14
INTRODUCTION
ladium, and rhodium metals in aqueous The Eh-pH diagrams of Pt-Cl-H2O
Platinum group metals (PGM) are chloride media, the standard electrode and Pd-Cl-H 2O systems were con-
barely soluble in mineral acids, and
traditional aqua regia (mixture of
concentrated hydrochloric and nitric
acids) or hydrochloric acid/chlorine
2 2
gas processes suffer from high reagent PdCl62–
consumption, corrosion problems, Pt(Cl)62– PdO3
1 1
and the need for scrubbing emitted Pt(OH)2
PdCl42– Pd(OH)4
hazardous gases.1 Several attempts have
Eh (V)
Eh (V)
0 Pt(Cl)42– 0 Pd(OH)2
been made to find alternative processes
to overcome these drawbacks and Pt
–1 –1
Pd
increase PGM extraction efficiency.2–4
Complexation/oxidation leaching is a –2 –2
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
favorable approach regarding economi-
pH pH
cal and environmental purposes. This a b
technique is based on the ability of PGM Figure 1. Eh-pH diagrams of (a) Pt-Cl-H2O and (b) Pd-Cl-H2O systems, metal concentration
to form stable aqueous complexes with 10-5 M, Cl- concentration 10-1 M, 25 °C.
ligands such as cyanide, halide, sulfite,
and thiosulfate ions (Table I).5
Pt Dissolution (%)
Leaching Procedures
–200 mesh 38.767 4.32 0.323 60
Whole sample 16.76 1.87 0.14 Leaching experiments were per-
formed in a 250 ml Pyrex round- 40 —Un-Washed
structed using Stabcal software devel- bottomed flask placed in a thermostati- —Washed
20
oped by Hsin H. Huang, Department of cally controlled water bath. The flask
Metallurgical and Materials Engineer- was fitted with a Pyrex condenser 0
ing, Montana Tech of the University of 0 30 60 90 120 150
and a thermometer. Sodium chloride
Time (min.)
Montana, Butte, Montana. As shown was dissolved in sulfuric acid and the
Figure 2. The leaching of platinum from
in Figure 1a and b, most of the chloro- mixture was poured into the flask. Once washed and un-washed catalyst losses.
complexes of platinum and palladium the specified temperature was reached, 0.1 M NaCl, 125 °C, 60% H2SO4, S/L =
ions lie within the water stability region. a 1 g sample of the catalyst losses was 1:100 g/ml.
The PtCl62– predominates at a wide area added and the slurry was heated and
100
of acidic and high potential regions and stirred. After reacting for a set period of
the PdCl42– in acidic and less potential time, the leaching residue was filtered 80
Metal Extracted (%)
regions. This confirms the possible and washed with bi-distilled water 60
dissolution of platinum and palladium acidified with 5% aqua regia. Contents 40 —Pt
as chloro-complexes in chloride media. of platinum, palladium, and rhodium in —Pd
20 —Rh
In general, the dissolution of PGM is filtrate solutions were measured using
based on providing a high oxidation an inductively coupled plasma-atomic 0
0
0.02 0.04 0.06 0.08 0.1 0.12
potential and effective complexing emission spectrometer (ICP-AES). NaCl Concentration (M)
ions in solution. For instance, in case Standard solutions [1,000 ppm from Figure 3. The effect of NaCl concentration
of PGM dissolution with aqua regia, SPEX (Metuchen, New Jersey)] of each on the extraction of platinum, palladium,
and rhodium. 60% H2SO4, 2 h, 135 °C,
the formed nascent chlorine (Cl2) and metal were diluted with bi-distilled water S/L = 1:100 g/ml.
nitrosyl chloride (NOCl) provide the and used for calibration of the ICP-
high oxidation potential, and the high AES. The PGM dissolution efficiency
100
chloride-ion concentration acts as the was estimated from the weight of the
complexing agent. A PGM dissolution dissolved metal and the initial weight 80
Metal Extracted (%)
system comparable to aqua regia can be of the same metal in the sample. All 60
created by using a mixture of a proper reagents were chemical grade and
40 —Pt
oxidizing agent, a chloride salt, and obtained from Fisher Scientific. —Rh
an acidic solution such as sulfuric 20 —Pd
Sample Evaluation and
acid. The sulfuric acid by itself cannot 0
Preliminary Investigation
dissolve platinum, but partially dissolves 0 20 40 60 80
palladium and hardly dissolves rhodium The precious metals contents in the H2SO4 Concentration (%)
only at highly concentrated boiling catalyst losses were detected using Figure 4. The effect of H2SO4 concentration
on the extraction of platinum, palladium,
acid. The addition of a chloride salt fire-assay technique facilities of the and rhodium. 0.1 M NaCl, 2 h, boiling
to a moderate H2SO4 concentration StillWater Mining Company, Montana; temperature, S/L = 1:100 g/ml.
would stabilize the PGM ions in the results are presented in Table II.
of platinum with 60% H2SO4 and 0.1 M while about 30% of palladium was
60
NaCl at 125°C. The unwashed sample simultaneously extracted.
showed a continuous increase of dis- 40 —Pt Maximum extraction occurred for
solved platinum with time, while the —Rh each metal at 60% H2SO4, with platinum
20 —Pd
washed sample showed very poor and at 95% and rhodium and palladium
slow dissolution of platinum. After 0 each at 85%. The extraction was
0 20 40 60 80 100 120 140
two hours, <10% and >90% platinum Temperature (°C) on the order of Pd>Pt>Rh at low
were dissolved from the washed and Figure 5. The effect of temperature on acid concentration (<50% H2SO4) but
unwashed samples, respectively. This the extraction of platinum, palladium, and at higher acid concentrations was
indicates that the PGM sample has a rhodium. 0.1M NaCl, 2 h, 60% H2SO4, somewhat reversed and on the order
S/L = 1:100 g/ml.
self-oxidizing agent that was lost during of Pt>Rh>Pd. Subsequent experiments
washing in water. Thus, a leaching were therefore performed using 60%
process in a mixture of H2SO4 and NaCl H2SO4 and 0.1 M NaCl in order to
100
can be established depending on the maintain extraction of platinum, pal-
self-oxidation of the sample. ladium, and rhodium at a maximum.
Metal Extracted (%)
80