UNIT 1: PGMS
Study Unit 1
Extraction of PGMs
• Concentration
• Pyro-and hydrometallurgical extraction of
PGMs
• Extraction of Platinum from UG-2 ores
PGMS
• Platinum, palladium, and rhodium, with ruthenium,
iridium, and osmium being less prevalent and less in
demand.
• Gold, it is a precious metal and not one of the PGMs
It is often lumped together with the PGM content
when talking about the valuable products from PGM
smelting.
• The base metals nickel, copper, and cobalt
commonly occur together with the PGMs and are
produced as co-products in the smelters and
refineries.
PGM DEPOSITS IN AFRICA
• The primary PGM-rich deposits include the
Bushveld Complex in South Africa (the largest
known layered igneous complex of its type in
the world, extending some 350 km from west
to east, and some 250 km from north to
south, containing more than two thirds of the
world’s reserves of PGMs),
• The Great Dyke in Zimbabwe (the second
largest known deposit of platinum in the
world
RESERVES
Exploitable South African reserves of platinum-group
metals are concentrated in narrow but extensive
strata known as the
• Merensky Reef_ base metal sulphides
• Platreef(Anglo)_ greater quantity of base metal
sulphides present,with more palladium than
Merensky
• UG2 chromitite layer_ has a high chromite content
• They require different approaches to metallurgical
processing
PGM CONTENT
• The Merensky Reef _4 - 10 g/t,
• UG2 reef _4.4 - 10.6 g/t.
• UG2 ore is by far the richest source of
rhodium, which is currently the highest-priced
PGM and an important constituent of the
catalysts used in motor car exhaust systems.
• The currently exploitable South African reserves of platinum-group metals are
concentrated in narrow but extensive strata known as
• Merensky Reef,
• Platreef, and
• UG2 chromitite layer.
• These three layers in the Bushveld Complex each have their own distinctive
associated mineralogy, and have been well described mineralogically.
• The Merensky Reef has the PGMs occurring in conjunction with base metal
sulphides;
• The Platreef has an even greater quantity of base metal sulphides present; and
• The UG2 chromitite layer has a high chromite content together with relatively
low quantities of base metal sulphides. Platreef is currently smelted only by
Anglo Platinum, but Merensky and UG2 ores are processed by all the
producers.
Merensky Reef ores
• Contains up to 3% base-metal sulphide minerals, distributed as follows:
pyrrhotite (45%), pentlandite (32%), chalcopyrite (16%), and pyrite (2 to 4%).
• The majority of the PGMs in the Merensky ore are associated with
pentlandite, occurring either in pentlandite grains or at the
pentlandite-gangue grain boundaries.
• To a lesser extent, the PGMs are associated with other base-metal
sulphides or
occur in the form of minerals such as braggite, cooperite, laurite, or
ferroplatinum.
• The major gangue minerals are pyroxene, plagioclase feldspar, and biotite.
UG2 Ore
• The principal constituents of UG2 ore are chromitite (60-90%),
orthopyroxene, and plagioclase, together with minor amounts of talc,
chlorite, and phlogopite, as well as smaller amounts of base-metal and
other sulphides and platinum-group minerals.
• The base-metal sulphides are predominantly pentlandite, chalcopyrite,
pyrrhotite,
pyrite, and to a lesser extent millerite.
• The sulphide grains of UG2 ore are generally finer than those of the
Merensky Reef.
• These ores are quite different from each other, and require different
approaches to metallurgical processing. For example, UG2 ore has
a much lower content of nickel and copper sulphides, and contains
much more chromite than Merensky ore.
• The Platreef can be considered as metallurgically similar to Merensky
ore, although somewhat enriched in palladium.
• The extent to which UG2 ore is processed has a major influence on
the smelting behaviour, as traditional six-in-line furnaces are
susceptible to build- ups of high-melting chromite spinels if the Cr2O3
content of the feed is too high.
• Merensky ore contains much more sulphide than does the UG2 ore,
and the minerals are found in a silicate substrate, while UG2 ore has
a chromite matrix. The Cr2O3 content of the UG2 ore presents
major challenges in processing.
• In Merensky ores, the ratio of nickel to copper is fairly constant at
about 1.7, but the PGM to base metals ratio is not constant.
• Merensky ore contains much more sulphide than does the UG2 ore,
and the minerals are found in a silicate substrate, while UG2 ore has
a chromite matrix. The Cr2O3 content of the UG2 ore presents
major challenges in processing.
• In Merensky ores, the ratio of nickel to copper is fairly constant at
about 1.7, but the PGM to base metals ratio is not constant.
• The Merensky and UG2 reefs are situated in close proximity to each
other.
• The UG2 reef lies anywhere between 20 and 330 metres below the
Merensky horizon, and varies in thickness between 0.15 to 2.5
metres.
• Reserves of PGMs plus gold are estimated (20) at 547 million ounces
in the Merensky Reef, and more than 1000 million ounces in the UG2
reef.
• The PGM content of the UG2 reef is comparable with, and sometimes
higher than, that of the Merensky Reef. The PGM content in the
Merensky Reef ranges between about 4 and 10 g/t, whereas the UG2
reef contains between 4.4 and 10.6 g/t.
• UG2 ore is by far the richest source of rhodium, which is currently the
highest- priced PGM and an important constituent of the catalysts used
in motor car exhaust systems.
• The copper and nickel contents of UG2 ore are generally less than a tenth
of those found in the Merensky Reef.
• The Cr2O3 content of UG2 ore is about 30%, as opposed to about
0.1% for Merensky ore. The low-grade chromite produced as a by-
product during the treatment of UG2 ore is also sold, and there is no
reason why it could not be used for the production of ferrochromium.
• The high demand for palladium also makes the processing of UG2
concentrates very attractive.
PGMs minerals
• Typical ores for PGMs contains 10g PGM/ton ore, thus the identity of the
particular mineral is unknown.
Mineral Formula
Sulphide minerals
Chalcopyrite CuFeS2
Pentlandite (Fe, Ni, Co)9S8
Pyrite FeS2
Pyrrhotite Fe1 − xSx
Gangue minerals
Alteration silicates Hydrated minerals
Chromite spinel FeCr2O4
(Mg, Fe)SiO3 – Ca(Mg,
Pyroxenes
Fe)Si2O6
Olivine (Mg, Fe)2SiO4
Plagioclase/feldspar NaAlSi3O8 – CaAl2Si2O8
Quartz SiO2
Haematite
PGM contents during the various stages
Ore 0,0005% (5g/t)
Flotation concentrate 0,0150% (100-
400g/t)
Converter matte 0.20%
PGM concentrate 30 – 65%
Refined metals 99.90% for Rh, Ru,
Os
99.95% for Pt, Pd,
Au
BENEFICIATION PROCESS
• During each separation stage of the process, there is an increase in the
concentration of PGMs –
• about 30:1 in the concentrator,
• about 10:1 in the furnace, about 3:1 in the converter, and
• about 200:1 in the base-metals refinery.
• For South African producers, the approximate distribution of the operating
costs for each stage is as follows (28):
• Mining: 72%, Concentrating: 10%, Smelting: 9%, Refining: 9%.
• PGM recovery is typically about 85% in the concentration stage, 95 to 98%
in smelting, and 99% in refining.
• By far the greatest loss of PGMs occurs during crushing, milling, and
flotation, and research into these operations could prove very rewarding, as
could the development of new processes that remove some of the
constraints on the various concentration stages.
BENEFICIATION PROCESS
• Comminution, and a gravity concentrate is
extracted.
• The sulphides are concentrated by flotation.
Smelting and converting, to produce a PGM-
containing nickel-copper matte.
• The matte is treated hydrometallurgically to
separate the base metals from the precious
metals.
• Finally, the PGM concentrate is refined to
separate the individual precious metals into
their pure forms.
Concentrator
The MF2 circuit derives its name from the terminology Mill, Float, Mill, Float, i.e. MFMF or MF2.
The principal behind the MF2 circuit is two-fold: first, to prevent over-grinding of the sulphides, in
particular pentlandite which is prone to “sliming”. Secondly, to prevent over grinding of actively
floating gangue material such as talc.
Reagents
Reagent suite consists of four chemicals. (Stilwater case)
The collectors used are potassium amyl xanthate, at a rate of 47 g/t and dithiophosphate
(Cytec 3477), at a rate of 35 g/t.
No frother is used as the ore is “naturally frothy” and 3477 is a mildly frothing collector.
The original design did not use any 3477 but it was found to increase PGE recovery by
2-4% (Hodges, Clifford, 1998). The collectors are added to the flash flotation cell, the
rougher conditioner and the middlings feed (Turk, 2001).
Carboxylmethyl - cellulose (CMC) is used for talc control and is added at a total rate of
450 g/t (Hodges, Clifford, 1998). The CMC is added to the flash flotation cell, the
rougher conditioner, the cleaner conditioner, the second cleaner feed and the middlings
feed (Turk, 2001).
Sulphuric acid is used in the rougher conditioner and middlings feed to control the pH to
about 7.8. It has been noted that the recovery of PGE drops off dramatically at the
natural pH of the milled ore. CuSO4 (used as an activator) which was part of the original
reagent suite but was removed as it did not contribute any apparent benefits in terms of
recovery.
It should be noted that the reagent dosage rates will in all likeliness change over the
years in response to varying ore compositions
SMELTER
Smelting:
• Temps: 1350°C & 1600°C
• Tapping: Slag 1350°C 2.7 to 3.3
Matte 1200°C 4.8 to 5.3
Converting: For removal of S and FeS
Silica is added for fluxing
(2FeO.SiO2), with some dissolved magnetite
Ox rxn is exothermic: 1250°C
the matte is poured out only once it has
attained the desired iron content.
• During smelting, some magnetite (and other
spinels such as chromite) that is not reduced and
fluxed, dissolves in the matte and slag.
Magnetite sometimes forms an intermediate
viscous zone between the matte and slag
layers, causing an increase in entrainment.
A build-up of magnetite or other spinels causes a
reduction in operational furnace volume.
HYDROMETALLURGICAL PROCESSING
• South African PGM smelters are under pressure
to accept concentrate blends containing greater
proportions of concentrates arising from the
high-chromite UG2 and the lower-grade Platreef
ores, and less from the traditional Merensky
Reef, which is historically the backbone
concentrate feed to PGM smelters.
• The impact of higher chromite contents and
lower PGM grades on smelter furnace efficiency
and operating costs is of prime importance to
the ongoing sustainability of the PGM industry.
REFINING
The next step is to separate base metals from the pgm. The final
stage is the separation and purification of the six pgm, plus gold
and small amounts of silver. The soluble metals - gold, palladium
and platinum, which dissolve in hydrochloric acid and chlorine
gas - are generally the first to be extracted, in that order. The
insoluble pgm come out next, with rhodium usually last.
The refined pgm have a purity of over 99.95 per cent, and can be
produced in a number of forms: ingot, grain or a fine powder
known as "sponge". The time between mining of the ore and
production of pure metal typically ranges from around 6 weeks
for palladium to up to 20 weeks for rhodium.
HYDROMETALLURGICAL PROCESSING
• The Kell Process has been developed for the
extraction of platinum group metals
(PGMs)and base metals from sulphide
flotation concentrates
• Particular interest is the hydrometallurgical
treatment of low-grade concentrates and
middling streams produced at some
operations
BENEFITS
• Reduced power costs,
• Ease of processing,
• Environmental benefits, e.g 70% less of CO2
emissions.
• It allows for the treatment of high-chromium low-
grade ‘dirty’ concentrates e.g secondary concentrates
from the platinum industry’s ‘ (MF2) and
concentrates from retreatment of tailings.
• It allows greater concentrate mass pulls,
• Has higher tolerance to gangue intergrowths in
concentrates, and its use can provide substantial
increases in overall PGM recovery.
Compared with smelting and refining these reductions
are calculated for Kell for this comparison with
smelting as:
• Total energy consumption – 50% reduction.
• Electrical energy consumption – 84% reduction.
• Energy consumption costs – 76% reduction.
• CO2 emissions – 70% reduction.
• Installed power requirement – 92% reduction
POX
• Sulphur, Ni, Co, and Cu are first selectively removed
by use of a modified pressure oxidation (POX) step.
– partially or completely oxidizes sulphides to metal
sulphates in solution
• The residue from this step is subjected to a thermal
treatment to render PGM phases readily amenable to
recovery by chlorination
– to remove sulphate and elemental sulphur from
the solid residue as disulphide, sulphur dioxide
and/or hydrogen sulphide gas
THERMOLYSIS
• At 300 - 750 °C for up to 120 minutes, typically
400 - 650 °C for 10 to 30 minutes, under
oxidizing, neutral or reducing conditions, to
remove sulphate and elemental sulphur from
the solid residue as disulphide, sulphur
dioxide and/or hydrogen sulphide gas,
• At 500 - 1000 °C for up to 120 minutes,
typically 700 - 1000 °C for 30 to 120 minutes,
under oxidizing, neutral or reducing
conditions, to condition the PGMs to be
soluble in chloride medium.
CHLORINATION
• Leaching of PGMs requires the high oxidation-reduction
potentials (ORPs) and complexing ligand provided by
chlorination leaching .
• The following indicative reactions are present under the
chlorination leach conditions:
• 2HCl + Pt (s) + 2Cl2 (g) -> H2PtCl6 (aq)
• 2HCl + Pd (s) + Cl2 (g) -> H2PdCl4 (aq)
• When chlorine gas is dissolved in water, it is rapidly
hydrolysed and a reversible redox reaction
• takes place as a disproportion reaction with water as follows,
dictating chlorine solubility in water:
• Cl2 + H2O <-/-> H+ + Cl− + HOCl
•
