Extraction and Refining

of the Platinum Metals

A COMPLEX CYCLE OF SMELTING, ELECTROLYTIC
AND CHEMICAL OPERATIONS

By A. F. S. Gouldsmith, A.R.s.M., B . s ~ . ,and B. Wilson, B.s~.,F.R.I.C.

Platinum Refineries, Johnson Matthey & Co Limited

The earlier stages of the mining and

A major development in the world’s recovery of the platinum metals from the
platinum industry took place in the Rustenburg Platinum Mines have been
early nineteen twenties when large reviewed in some detail in this journal (I),
deposits of p l a t i n u m bearing ore were while the geology of the Bushveld Igneous
discovered in the Transvaal in South Complex and the platinum reefs-constituting
Africa. T h i s led to the formation in an enormous reserve of platinum metals-
1931 of Rustenburg Platinum Mines which are mined by the Rustenburg company
Limited to work these deposits, and has also been described (2). This article
this company remains to this day the deals with the succeeding stages of extraction
only platinum producer in South Africa and refining carried out in the smelting works
and the only major producer in the and refineries of Johnson Matthey & Co
world whose prime activity is the Limited in order to bring the concentrates
extraction of the p l a t i n u m metals. received from the mining company into
From the outset Johnson Matthey marketable forms.
has been associated with Rustenburg, Operations conducted at the mine result
$rst in developing methods f o r the in two products-a rich gravity concentrate
extraction of the platinum metals f r o m which is passed directly to the wet process
these OTCS, and thereafter as smelters refinery of Johnson Matthey, and a converter
and rejners of the output f r o m the matte that has been worked up from the
mines. flotation concentrate. This matte is cast and
T h i s article describes the complex either prepared for shipment to the Johnson
and lengthy cycle of operations required Matthey smelter at Brimsdown in the United
to effect complete recovery of the s i x Kingdom or sent to Matte Smelters (Pty.)
platinum metals and to yield at the Limited, a company formed in South Africa
same time electrolytically rejned copper in 1952 as a joint subsidiary of Rustenburg
and nickel. Platinum Mines and Johnson Matthey in
Today the joint activities of Rusten- order to cope with the increasing output
burg and Johnson Matthey constitute from the mines. The process operated at
the world’s largest source of the platinum this plant, which is adjacent to the Rustenburg
metals in all forms. Together they mine, is essentially the same as the primary
ensure to industry throughout the world stages of the Brimsdown process.
adequate and continuing supplies of During the past thirty years the quantities
these metals. of matte received at the Brimsdown refinery
have increased, and in 1950 a new plant was

Platinum Metals Rev., 1963, 7 , (41,136-143 136

 The Johnson Matthey smeZting works at Brimsdown. Here the nickel-copper matte, carrying
the platinum metals at about$fty ounces to the ton, arriuesfrom South _Africa and is smelted
to yield metallic nickel and copper and the platinum metals i n the form of a concentrate

added, bringing the site for treating Rusten- anode slime containing the precious
burg matte at Brimsdown up to a total area of metals.
ten acres. 3. Chemical operations, for the separation
Improved techniques and more modern and refining of the individual metals.
equipment are always under review, but the
basic process for extraction of the platinum Smelting Operations
metals has remained essentially the same. Converter matte from Rustenburg arrives
Rustenburg converter matte contains about at the Brimsdown smelter in bags of about
46 per cent of nickel and 28 per cent copper, 150 pounds each. It has been crushed to
together with some other base metals and three-inch size. After weighing and sampling
sulphur. The platinum group metals, the first operation is to separate the nickel
together with some gold, total about fifty and copper sulphides. This is done by
ounces to the ton. The complete process of making use of the fact that molten sodium
extraction consists essentially of enriching sulphide is completely miscible with copper
this matte to approximately 65 per cent sulphidc and completely immiscible with
content of platinum metals and then treating nickel sulphide, so that if the converter matte
this concentrate with acids to separate the is melted with sodium sulphide two fractions
individual platinum group metals from each separate out-a sodium sulphide/copper
other, followed by final refining. sulphide layer floating on a nickel sulphide
Operations to achieve this can roughly be layer. Furthermore, a nickel matte with a
divided under three headings : deficiency of sulphur is an excellent collector
I. Smelting operations, where the original of the platinum group metals; therefore
matte is broken down to yield metallic under suitable conditions a nickel matte can
nickel and copper anodes. be produced that is low in copper and will
2. Electro-refining operations, where these contain the platinum group metals. At
anodes are dissolved electrolytically to Brimsdown this operation is mainly carried
produce pure nickel and copper and an out in a blast furnace, although six-ton

Platinum Metals Rev., 1963, 7 , (41, 137

 The$rst stage of the smelting operations
is a blast furnace treatment to separate
nickel matte containing very small
amounts of copper and practically all of
the platinum metals

The copper tops are then either

poured into a five-ton reverberatory
holding furnace or directly into a
horizontal-type copper converter.
The converter is lined with mag-
nesite brick and capable of taking
charges up to five tons. By blowing
air through the molten top consider-
able heat is generated and sodium
sulphate is first formed. This is
tapped off as a watery liquid and
used again in the blast furnace.
Silica is then added to the converter
to flux iron oxide and any excess
soda; this slag is also poured off
and the residual copper sulphide
reverberatory furnaces are also used. The blown down to blister copper in the normal
blast furnace is water-jacketed for its full way. The blister copper is tapped into a ladle
height and has a rectangular hearth measuring and poured directly into one of three small
72 x36 inches. Converter matte, salt cake reverberatory furnaces. T h e copper is
(sodium sulphate) and coke are fed in and the then further refined and cast into moulds
molten materials run into a settler
where the sodium sulphide/copper
sulphide top layer flows con-
tinuously into a ladle, while the
bottom layer of nickel matte is
tapped intermittently. By careful
control of temperature and sulphur
content a nickel matte can be
obtained containing little copper
and all the platinum metals,
whereas any gold will have followed
the copper sulphide into the
“tops” layer.

Casting the enrichd nickel matte into

pigs. These are then crushed, ground
and roasted

Platinum Metals Rev., 1963, 7 , (41, 138

 The ground nickel matte is roasted i n this battery of [Link]. The nickel oxide
produced is then reduced to metal and cast into anodes

to make anodes for the electro-refinery. may contain gold and small quantities of the
In the meantime, nickel matte from the platinum group metals.
blast furnace operation is broken, crushed The cells are constructed of rubber-lined
and ground in ball mills to 20 mesh. This concrete. Internal measurements are approxi-
material is then roasted to nickel oxide in mately 84 x 2 x 3 feet. The warmed elec-
oil-fired 17-feet diameter Herreschoff type trolyte is fed in at one end and overflows
furnaces with two hearths separated by an from the other into a launder running
air gap. Ground nickel matte is fed through abetween the lines of cells. From the launder
hopper on to the top hearth which is kept the liquid is pumped to overhead tanks
where its heat is maintained, and by gravity
at a low temperature; it then falls through to
the lower hearth which is kept at 900' to flows to a manifold which feeds it back to
950°C. After cooling, the resultant nickel the cells. During electrolysis the electrolyte
oxide is briquetted with anthracite coal and tends to accumulate nickel and quantities
sand. These briquettes are next charged into have to be bled off occasionally and replaced
by pure copper sulphate.
an oil-fired reverberatory type furnace, where The impure
the oxide is reduced to metal and tapped intoelectrolyte is treated for recovery of the
anode moulds. These anodes, which contain copper sulphate and the nickel sulphate is
practically all the platinum metals, are thenpassed to the nickel refinery. There are 21
passed into the electrolytic nickel [Link] and 20 cathodes in each cell and a
current of 15; amp per square foot is main-
Electro-Refining Operations tained. The quantity of anode slime formed
Copper anodes from the converter process by the dissolving of these anodes is small and
are dissolved electrolytically using an acid falls to the bottom of the cells, where it is
copper sulphate solution as an electrolyte. periodically recovered.
The products of this operation are pure The dissolving of the nickel anodes
copper cathodes and an anode slime which follows the same general pattern, the products

Platinum Metals Rev., 1963, 7 , (41, 139

The electrolytic nickel refinery at Brimsdown. Here pure nickel cathodes are produced, while the platinum
metals accumulate in the anode residues and are removed f o r the separation and refining of the individual
metals

being pure nickel cathodes and an anode The filtered liquor is stored in overhead
slime containing the bulk of the platinum tanks ready for feeding back to the cells.
group metals. In this case the electrolyte As in the copper refinery, the cells are
is a neutral solution of nickel sulphate constructed of rubber-lined concrete and
containing boric acid as a buffer and has to 24 cells make up one unit. Internal dimen-
be continually purified to produce a pure sions of the cells are about I I & x 2 x 29 feet.
cathode. Copper and iron are present in the There are ZI anodes and 20 cathodes in each
anodes and being more electro-negative than cell and the current density is 12; amp per
nickel must be removed from the electrolyte square foot. Anodes and cathodes in each
or they will deposit on the cathode as cell are in parallel.
impurities. To achieve this each cathode is The quantity of slime produced by the
placed in a calico bag with purified electrolyte nickel anodes is far greater than from the
flowing into it, so that the cathode will grow copper anodes and although a little falls to
in clean liquor. The stripped liquor flows the bottom of the cells the majority adheres to
out of the bag laterally and picks up the the anode and has to be scraped off. This
impurities from the solution of the anode. is normally done every IOO running hours,
This liquor flows out of each cell into a both to bring the platinum metals forward
launder and is pumped across to large and to stop the anodes becoming passive.
circular treatment tanks where it is heated to During all the processes that have been
approximately 70°C. An emulsion of nickel described so far slag, residues and flue dust
carbonate is added to adjust the pH and air have been produced. Normally these are
is blown through to hydrolyse out the iron. worked into a previous stage of the process,
After this any copper present is precipitated but in primary work several products result
and the contents pumped through a filter which although poor in values compared with
press to separate out the solid impurities. the initial matte are far too valuable to be

Platinum Metals Rev., 1963, 7 , (41, 140

thrown away. These are collected, blended by employing the simplest possible methods,
with suitable fluxes and smelted in a blast including siphoning and gravity draining,
furnace to a matte which is blended in with and use is made of glass-lined vessels, glass
the original matte at the beginning of the pipelines and glandless pumps of chemically
process. resistant materials.
The complete cycle of treatment is very
Chemical Operations complex and can only be briefly outlined here.
From this stage onwards the concentration Basically the separation and refining of these
of the platinum group metals is more rapid six closely allied metals involves their
and the processes entirely chemical. First precipitation as complex salts followed by
the slime is subjected to roasting and leaching successive stages of recrystallisation and then
attacks to remove the last of the copper, by calcination, under carefully controlled
nickel, iron and sulphur. This produces an conditions in electrically heated muffle
enriched slime running approximately 65 furnaces, to produce the metals in the form
per cent of the platinum group metals and of sponges or powders suitable for melting and
gold. working.
At this point the platinum-bearing gravity Initial treatment comprises digesting with
concentrates shipped from South Africa join aqua regia to produce a solution containing
those produced in the Johnson Matthey the major portion of the gold, platinum and
smelting plant, and together enter the wet palladium as chlorides, the residue comprising
process refinery. Here they are treated for the more insoluble metals, iridium, rhodium,
complete elimination of base metals, and the ruthenium and osmium. The solution is
platinum metals are brought into solution reduced by adding ferrous chloride to remove
for their separation and individual refining. the gold. The addition of ammonium chloride
The solutions handled are usually highly to the filtrate precipitates impure ammonium
concentrated, extremely valuable and very chloroplatinate, which is calcined to a crude
corrosive. Handling is therefore carried out platinum sponge, redissolved, reprecipitated

The initial step i n the wet process rejinery comprises digestion with aqua regia to dissolve the platinum and
palladium, leaving the other four metals as an insoluble residue

Platinum Metals Rev., 1963, 7 , (41, 141

This sertion of the wet process re$ner,y - the largest of its kind in the world - handles the precipitation,
redissolving and reprecipitntion of platinum and palladiam. Jt is arranged on the cascade system to
facilitate the movement of solutions

as pure ammonium chloroplatinate and chloride, which on acidification precipitates

calcined again to give pure platinum sponge. palladium diammino &chloride. This salt
The filtrate from the ammonium chloro- is then calcined to pure palladium sponge.
platinate is oxidised, and excess of ammonium The other four metals are extracted from
chloride added to precipitate the palladium as the original insoluble residue, first by fusion
a crude ammonium salt. This is redissolved with alkaline and oxidising fluxes, followed by
in ammonia to form a tetrammino palladium dissolution in water and then by distillation

In this part of the rejinery the four “insoluble” metals - rutl~enium,rhodium, iridium und osmium - are
extrarted and separated as their complex ammonium salts

Platinum Metals Rev., 1963, 7 , (41, 142

 Thefcnal stage in the refcning operations -platinum sponge i s being melted in a highfrequency
induction furnace for casting into ingot form

of ruthenium and osmium as volatile oxides. metal required for special purposes give a
These distillates are then treated in a similar product totalling only a few parts per million
way to the solutions of the soluble metals, of impurities.
by precipitation of their complex salts and In every case the metals produced are
calcination to metal. subjected to chemical and spectrographic
The solution remaining after distillation analysis. After meeting the specified require-
contains the iridium and rhodium, which are ments, the sponges are converted to solid
recovered as sodium salts, followed again by metal-or to alloys-either by melting in
precipitation of their complex ammonium high frequency induction furnaces or by the
compounds and calcination. method of powder metallurgy, followed by
The whole of the plant, the largest of its forging and rolling.
kind in the world, is arranged on the cascade From this refinery the six platinum metals
system, so that all movement of liquids is by are supplied in pure form to independent
gravity. The methods employed achieve an fabricators and users throughout the world,
extremely high degree of purity in each of to Johnson Matthey associated companies in
the metals. For example, routine production the United States, Canada, South Africa,
of platinum yields a metal of 99.99 per cent Australia, Belgium and Italy, and to the
purity, while additional steps in refining company’s London manufacturing centre.

References
I C. B. Beath, R. J. Westwood and C. A. Platinum Mining at Rustenburg, Platinum Metals
Cousins .. . . .. .. Rev., 1 9 6 1 , s ~102-108
2 C.A. Cousins . . .. .. .. The Bushveld Igneous Complex, Platinum Metals
Rev., 1959, 3,94-99

Platinum Metals Rev., 1963, 7 , (41, 143