PRODUCTION OF HIGH QUALITY ELECTROWON NICKEL AT

RUSTENBURG BASE METALS REFINERS (PTY.) LTD.

Z.Hofirek andP.Halton
Rustenburg Base Metals Refiners (Pty.) Ltd.,
P.O. Box 483, Rustenburg, Republic of South Africa 0300

ABSTRACT
A decision was taken in 1978 to increase the base metal production capacity at Rustenburg
Base Metals Refiners (Pty.) Ltd. (RBMR). Seventeen different options were proposed and
after full evaluation a new refinery was built and conmiissioned towards the end of 1981. The
original basic process, with nickel and copper cathodes, and cobalt and sodium sulphate crystals
as the products, was chosen, which also allowed the continued use of the operatmg, technical
and marketing experience and skills that had been developed over the previous twelve years.
This paper discusses the attainment of a high quality electrowon nickel that was required to
raise the metallurgical operation from a base metal recovery plant of a platinum mine to a
refinery on a par with other base metal producers.

KEYWORDS
Electrowinning, nickel, cathodes, impurity, removal.

INTRODUCTION
Rustenburg Base Metals Refiners (Pty.) Ltd. (RBMR) comprises a platinum group metal
(PGM) enrichment plant and base metal refineiy serving many mine shafts, eight concentrators
and two smelters, positioned on the Bushveld Igneous Complex over a distance of some 300
km. The enriched PGM concentrate from RBMK is refined to pure metals by Precious Metals
Refiners (Pty.) Ltd. (PMR^; both refineries are situated near Rustenburg, about 120 km west of
Johannesburg. The whole integrated mining and metallurgical complex, being the world's
largest producer of platinum group metals, is controlled by Johannesburg Consolidated
Investment Company.
RBMR is a medium sized nickel producer with a nominal plant capacity of 20,000 tpa. The
nickel is ultimately electrowon from a Ni-Cu converter matte and is sold, due to its high
chemical quality, under its own name, "Matthey Nickel" on the London Metal Exchange.
Electrolytic nickel metal was first produced at RBMR in the early fifties using the Orford
process for Ni-Cu separation. The nickel concentrate was converted into nickel metal anodes
and electrorefined. Hydrometallurgical operations, in principle identical to the present
process, commenced in 1966. Since Rustenburg is primanly a PGM producer, no particular

233
234 ELECTROMETALLURGICAL PLANT PRACTICE

concern was given at that time to the quality of electrowon nickel, which generally satisfied the
ASTM specincation.
The introduction of exhaust catalysts in the US in the mid-seventies significantly increased the
world demand for platinum, and an expansion of the smelting and refining operations was
planned. It also became evident that nickel was a very large contributor to the company's
revenue, and therefore a top quality product would have to be produced in order to ensure
premium prices in the volatile metal markets.
An integral part of the new refinery design phase was an extensive study of impurities
behaviour in the existing refinery circuits. Sherritt Gordon was commissioned to conduct a
study into the efficiency of pressure leaching in order to improve the primary bulk separation of
major metals. Also, novel processes for copper, iron and selenium removal were piloted and
then successfully incorporated into the new design. The refinery was built and commissioned in
1980-8L The major process changes were:
the replacement of vertical air agitated pressure leach columns with horizontal
mechanically agitated Sherritt Gordon autoclaves,
the introduction of a non-oxidizing leach period to the terminal phase of the
nickel leach (primary leaching stage),
the substitution of solvent extraction for copper and iron removal from the nickel
solution by precipitation with matte,
the incoφoration of a selenium removal stage.
These changes resulted in improvements of nickel cathode quality, in some instances by an
order of magnitude, and the new quality standard "Matthey Nickel" was created for nickel sales
on the international market. Further optimization of the purification stages led to the creation
of an improved refinery internal standard, "High Grade". Oinenüy about 90% of nickel
cathode is produced within this high grade specincation. The various nickel specifications and
typical RBMR cathode impurity contents are shown in Table I.

PROCESS DESCRIPTI0N(^'2)

Underground mined ore is treated at Rustenburg Platinum Mines by conventional techniques,

i.e., crushing, milling, flotation, electric furnace smelting and converting to produce a matte
containing 47% Ni, 27% Cu, 2.5 % Fe and 22.5% S. The converter matte is cast into ingots and
slow cooled for a period of 3 days to facilitate the crystallization of a metallic Ni-Cu-Fe alloy
containing - 9 9 % of the platinum group metals (PGM).
Crushed matte is transported to RBMR where, after fine milling, it is subjected to magnetic
separation. The PGM-containing magnetic alloy fraction then undergoes hydrometallurgical
treatment, in order to produce a PGM-enriched concentrate as a feedstock for the Precious
Metals Refinery. The resulting leach solution, as well as the non-magnetic sulphide fraction
containing large quantities of nickel and copper with cobalt, is fed to the Base Metal Refinery
(BMR) to accomplish recovery of the valuable metals.
A simplified flowsheet of the BMR is shown in Figure 1. The refinery comprises five major
process sections, all of which are fully integrated:
a^ leaching: primary and secondary leach stages.
b) purification: Cu, Fe, Co, Pb, Se removal stages.
c) electrowinning of nickel and copper,
d^ cobalt sulphate production.
e) sodium sulphate production.
 ELECTROMETALLURGICAL PLANT PRACOCE 235

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236 ELECTROMETALLURGICAL PLANT PRACTICE

TABLE 1. International nickel cathode speciflcations and typical impurity contents in

Rustenburg cathodes.

ASTM ISO MATTHEY NICKEL TYPICAL VALUES

9990 9995 LME H.G. OLD REFY. NEW Rl
Antimony <50 <20 <10 <5 <1
Arsenic <50 <10 <5 <1
Bismuth <50 <20 <5 <5 <1
Carbon 300 300 150 100 150 50 25
Cobalt 1500 5000 1000 1000 500 250 90
Copper 200 300 50 180 50 120 8
Iron 200 300 200 150 50 100 15
Lead <50 <50 <10 30 10 25 3
Manganese <50 <5 <1
Oxygen 40
Phosphorus <50 <20 <5 <1
Selenium <10 50 10 60 7
Silicon <50 20
Silver <5 <5 <1
Sulphur 100 300 <25 50 30 35 10
Tellurium <5 <5 <1
Tin <50 <5 <5 <1
Zinc <50 <20 30 30 20 15
Nickel 99.80 > 99.90 > 99.97

Fresh matte initially enters the purification section, into the copper removal stage, where it is
contacted with the primary leach discharge solution in a series of 4 continuous, stirred tank
reactors. All the dissolved copper and iron is rejected into the residue producing a virtually
acid-, Cu- and Fe-free solution, while stoichiometrically equivalent amounts of nickel are
dissolved. The reaction slurry is then discharged into a large thickener, with the underflow
being fed to the primary leach whilst the nickel rich overflow solution undergoes further
purification.
The copper removal residue is subiected to a pressure leach at 135°C and 1000 kPa in Sherritt
Gordon horizontal autoclaves divided into 4 compartnlents by vertical weirs. Each
compartment is agitated by a top mounted agitator. Copper spent electrolyte is used as a
source of acid. Only the leading 2 compartments are aerated at a controlled rate to ensure
maximum nickel dissolution; the last 2 compartments are operated without air in order to
re-precipitate part of the copper, which was either dissolved in the oxidizing phase or supplied
with the spent electrolyte. Primary solid-liquid separation is carried out in thickeners and the
overflow is filtered and washed on a belt filter. About 80-85% nickel extraction is achieved in
the combined copper removal and primary leach stages.
The primary leach residue then undergoes secondary copper leaching at 145°C and 1000 kPa in
autoclaves similar in construction to the primary autoclaves. Copper spent electrolyte is again
used as a source of acid. All compartments are aerated to ensure almost complete dissolution
of copper (98%) and the residual nickel (to 99%), whilst a large proportion of iron is
re-precipitated in the form of jarosite or hematite. The discharge slurry is then filtered and the
residue re-pulped and re-filtered, before treatment in a small pyrometallurgical section for the
recovery of the residual PGMs which are recycled as Cu bullion into the converters. The
copper-rich filtrate is then treated with sodium sulphite solution (generated in the
jjyrometallurgical operation) to remove a large proportion of the dissolved selenium. The
iltered selenium-rich cake is combined with the secondary leach residue.
 ELECTROMETALLURGICAL PLANT PRACTICE 237

No further purification other than solution clarification is required in the copper circuit and the
solution, now containing 75 g/L Cu, 30 g/L Ni and 60 g/L acid, enters copper electrowinning.
About 40 g/L Cu is deposited on starter sheets in each pass at a current density of 190 A/m".
Copper anolyte is recycled to both leach stages where it supplies all the acid necessary for base
metals dissolution.
The copper removal thickener overflow requires further purification prior to nickel
electrowinning:
lead removal by barium hydroxide,
cobalt removal by nickelic hydroxide,
fine fihration of feed electrolyte.
The detailed description of these stages is given in the following chapters.
The oxidation of sulphides in the pressure leach stages generates an excess of acid which is
removed as sodium sulphate in the "sulphur remova" stage. For this purpose, nickel spent
electrolyte is split in stoichiometric proportions into 2 streams: one part is neutralized to pH 9
with caustic soda, and the precipitated nickelous hydroxide is filtered on drum filters and
re-dissolved in the remaining part. Since the dissolved cake solution contains some lead (from
anodes) and copper (from bus bars) generated during Ni electrowinning, it is recycled to the
copper removal stage. The filtrate is processed in the sodium sulphate plant into saleable
anhydrous crystals.
Whilst the lead removal cake is recycled to the smelter, the cobalt removal cake is further
processed for cobalt recovery. Initially the cobalt cake is leached at a controlled pH in nickel
spent electrolyte to dissolve nickel hydroxides. The filtered cake is subjected to a reducing
leach in sulphuric acid to dissolve the remaining nickel with the cobalt; the resulting solution is
then purified (Cu, Fe and Pb removal) and the cobalt is separated from the nickel by solvent
extraction with D2EHPA. Pure cobalt solution is crystallized to saleable C0SO4.7H2O whilst
the nickel-containing raffinate is recycled to the sulphur removal stage.

NICKEL ELECTROWINNING
General Considerations
Although the nickel standard electrode potential is very low at -0.25V, the actual
electrowinning cell voltage usually exceeds 3.5V even under ideal conditions. This large
voltage increase is caused by cathodic and anodic overvoltages due to flowing current (l.OV),
high anodic water decomposition potential ( + 1.25 V) and ohmic losses through the electrolyte,
cathode bags and contacts (1.2V). Excessive cathode hydrogen evolution is prevented by
maintaining a very low H"*" concentration in the catholyte through the relatively high pH of the
feed solution and the use of a buffering agent. Back migration of H"*" ions, and to some extent
Pb"'" ions generated at the anode, is minimized by maintaining a positive solution head in the
cathodic compartment created by the use of cathode bags with a fixed permeability. In the
absence of acid in catholyte, ohmic losses are reduced by maintaining a nigh concentration of
other mobile ions, sodium being the most commonly used.
At the high cell voltage with an almost neutral catholyte, there are many elements in the
periodic system which would be reduced at the cathodic surface to the elemental form and
co-deposited with nickel. This fact clearly implies that the art of high quality cathode
production is rooted to a very large degree in extensive catholyte purification. A study of
impurities behaviour in the electrowinning cell has shown that under the operating conditions
of the RBMR tankhouse, impurity deposition is governed by the following approximation:
Impurity content in cathode (ppm) = 20 χ impurity concentration in cell feed (mg/L).
238 ELECTROMETALLURGICAL PLANT PRACTICE

Therefore, with the exception of cobalt, an impurity concentration in the cell feed must be
maintained well below 1 mg/L^ which in many instances is at the limit of commonly employed
analytical techniques.
Further contamination of cathodes results from electrolyte inclusion, or occlusion, in the
deposited metal. For this reason the metal deposit must be dense with a smooth surface. Any
agents or phenomena leading to porous cathodes, splitting, nodularity or pitting must thus be
strictly controlled.
TankhQus^ practic^P)
The filtrate from the oxidizing conditions of the cobalt precipitation process is first clarified,
and then undergoes pH adjustment using concentrated sulphuric acid and temperature
adjustment, before being fed into header tanks for gravimetric feed to the individual cathode
compartments of the nickel electrowinning cells. The fiow to each cathode is kept at a constant
rate with the use of glass orifices, and a head of - 3 0 mm is maintained in the compartment
using woven bags of a selected permeability.
No surface smoothing agents are used, the only additive being boric acid, which was originally
added as a pH buffer. The use of this reagent is presently under review.
The starter sheets grown on titanium blanks are prepared manually. Immediately prior to use
they are anodically depassivated at 90 A/m^ for 20 minutes and then temporarily stored in
boric acid solution.
The cathode product, after sampling and analysis, is sold as whole or half cathodes, or 100-mm
or 25-nim squares depending on the consumers' requirements.
The nickel tankhouse operating parameters are summarized in Table II.

GENERAL IMPURITY MANAGEMENT

The operating philosophy of a PGM-producing integrated metallurgical complex puts RBMR
nickel production at a considerable disadvantage with respect to good impurity management:
to prevent losses of volatile PGMs (Ru, Os), the extent of oxidation in the
converters is limited to a minimum sulphur (22.5-23%) and iron (2.5-3%)
content, at which good PGM collection onto metallic alloy can be managed.
to prevent any further PGM losses, there are no other impurity outlets other than
the products (Cu, Ni, Au, individual PGM, C0SO4, Na2S04) with their own tight
specifications, and electric furnace slag.
Blowing furnace matte to a relatively high sulphur content also minimizes rejection of many
volatile impurities which tend to concentrate in the converter matte. Each plant of the
metallurgical complex, but particularly the PGM refinery, operates with numerous internal
recycles accumulating impurities within the circuits. These impurities are finally rejected in
residues reverted back to the smelter. Many reverts, due to their small quantity, are recycled
on a campaign basis, which results in extreme variation of impurity levels in the RBMR matte
input, in some instances by an order of magnitude (Table III).
In the Base Metal Refinery, the secondary leach residue is the major collection point for many
impurities, particularly non-metallic and residual precious metals. In the past, its recycle to the
smelter, combined with high recycles of PMR reverts, caused occasional problems with quality
of both nickel and copper cathodes. In the late seventies, Johnson Matthey undertook an
investigation into a separation of the precious metals and non-metallic impurities contained in
 ELECTROMETALLURGICAL PLANT PRACTICE 239

the secondary leach residue. A pyrometallurgical process, based on the collection of residual
PGMs in molten copper (copper bullion) and rejection of silver and impurities into a copper
matte, was developed^ and installed at RBMR in 1983. The PGM-containing copper bulhon
is recycled to the converters whilst the silver-containing copper matte is sold to an overseas
refiner. Starter sheet trimmings are used as a source of copper. The incoφoration of this
orocess has considerably alleviated the problem with many of the impurity accumulations in
)oth the base and precious metals refineries.
Impurity movements through the metallurgical complex are closely monitored by analyzing
residues and solutions going forwards or backwards. Major impurities are analyzed on a shift
or daily basis, whilst monthly composites assays are used for minor elements. Impurity
distribution reports are issued on a monthly basis. The approximate element distribution in
major RBMR streams is shown in Table IV.
TABLE II. Nickel tankhouse parameters

T^nkhpyse C^H Nymbgr

Production 122
Starter Sheet 30
Cell Construction Anodes <fe Cathpdes
Shell Precast concrete Anodes: Pb-Sr-Sn
Liner GRPAtlac 4010 No. per Cell 41
Thickness 6mm Cathodes:
Length 6560 mm Production Ni starter sheets
Breadth 1150 mm Starter sheets Ti blanks
Depth 1170 mm No. per cell 40
live volume 5.5 m^ Spacing 160 mm
Frames Oregon pine
Bags Woven terylene
El^Ctrplyte Fe^d Spent Electrolyte
Cell flow rate 0.55 m^/h Sulphuric acid 50 g/L
3.5 Nickel 50 g/L
nickel 80 g/L
Na sulphate 120 g/L
Boric acid 6 g/L
Operating Parameters Pulling cyci^

Cell current 14-15 kA Starter sheets 2 days

Cell voltage 3.6-3.9 V ^ Production 6 days
Current density 205-230 A / m 2
Current efficiency 96-98 %
Electrolyte temp. 60-65 OC
240 ELECTROMETALLURGICAL PLANT PRACTICE

TABLE III. Compositional ranges of the converter matte and its non-magnetic fraction

Converter Matte Non-magnetic

Ni-Cu matte
% %

Nickel 45.0 - 7.5 41.0 - 44.0

Copper 26.0 - 28.0 27.0 - 30.0
Cobalt 0.55 - 0.70 0.45 - 0.65
Iron 2.5 - 3.0 1.5 - 2.0
Sulphur 21.5 - 23.0 23.0 - 24.5
ppm ppm
Antimony 10 150
Arsenic 10 150
Bismuth 10 100
Chromium 10 100 No signif
Lead 100 500 changes
Manganese 5 15
Selenium 250 750
Silica 150 300
Silver 100 300
Tellurium 100 250
Tin 10 50
Zinc 5 15

TABLE rV. Approximate elements distribution (%) in streams exiting RBMR

Products Feed to Recycle Cu matte

PMR to Smelter exit
Nickel 98.8 0.1 1.0 0.1
Copper 93.0 0.1 3.4 3.5
Cobalt 98.8 0.1 1.0 0.1
Iron 0.1 0.5 98.0 1.4
Antimony 25 65 10
Arsenic 25 60 15
Bismuth 20 60 15
Lead 0.5 10 64.5 25
Manganese 100
Selenium 1.5 5 10 83.5
Silver 15 25 60
Tellurium 5 10 85
Tin 10 80 10
Zinc 90 10
 ELECTROMETALLURGICAL PLANT PRACTICE 241

BEHAVIOUR AND CONTROL OF METALLIC IMPURITIES

Copper ^nd Iron
Since copper and iron removal is accomplished in identical stages, both of these metals are
addressed in this section.
Copper is the second most abundant element in the matte, at 27%. The major copper
constituent is the non-stoichiometric sulphide djurleite (Cu^ ggS). Iron is also present in
significant quantities (1.5%), although the mode of occurrence is not well defined. A large
proportion of iron appears to be dissolved in the major sulphides of nickel (NÍ3S2) and copper
(^1.96^)·

Bulk separation of nickel from copper and iron is performed in the primary leach autoclaves,
utilizing the high copper affinity for the sulphur and the low iron solubility in sulphate solutions
at elevated temperatures. The process chemistry has been described^^'^'. Ni-Cu separation is
further enhanced by the non-oxidative mode of leaching carried out in the last 2 compartments
of the primary autoclaves. In fact, due to the use of copper-containing solutions as a source of
acid, a negative overall copper extraction (i.e. precipitation) is aimed for at 75-80% nickel
extraction.
Primary leach discharge solution typically contains 5 g/L Cu and 1 g/L Fe. In the old refinery,
both metals were removed in a solvent extraction stage using versatic acid. As the assay of
nickel cathodes in Table I indicates, the efficiency of removal was rather poor. In the new
refinery, metals are removed to levels less than 10 mg/L using a new process involving contact
with fresh matte.
The ability of Ni-Cu matte to precipitate copper ions from solution is a well known
phenomenon, comniercially employed in the Outokumpu process^^'®^ and previously used in the
AMAX process^^'^^'. This ability was originally ascribed to direct cementation onto a nickel
alloy present in the matte (c.f. Outokumpu). However, it was soon recognized that sulphur
deficient nickel sulphide, heazlewoodite (NÍ3S2), is similarly efficient in copper precipitation.
RBMR commenced testwork on the use of alloy-free matte for copper removal in the early
seventies, following successful work carried out at Johnson Matthey in the mid-sbcties. The
process chemistry has been described^°'^'. It appears that copper is precipitated by two
different routes:
A) by metathesis with heazlewoodite at a solution pH below 3 according to the
generally accepted overall reaction:
2 Cu-' ^ + NÍ3S2 = CugS + NiS + 2NÍ-' (1)
B) by hydrolysis at a solution pH above 3
3 Cu^ ^ + SO4-- + 4H2O = Cu3(OH)4S04 + 4H^ (2)
Free acid or any generated H"*" ions are simultaneously removed by reaction with
heazlewoodite:
2H+ + N Í 3 S 2 + Í/2O2 = Ni+^ + 2 N Í S + H2O (3)

resulting in a gradual pH increase above the stability of cupric and ferric ions, which begin to
hydrolyze forming insoluble basic sulphates, antlerite (Cu3(OH)4S04) and parabutlerite
(Fe(OH)SO^). Precipitation is completed at pH 6 with discharge solution now containing less
than 10 mg/L Cu and Fe. The terminal concentration is obviously a function of the solubility
product of hydrolytic species at a given temperature and pH.
242 ELECTROMETALLURGICAL PLANT PRACTICE

Extensive pilot plant testwork was carried out at RBMR in order to establish the optimal
conditions and the limitations of the proposed process. Work has shown that the rate of iron
precipitation is a limiting factor. In order to nunimize additional iron dissolution from matte,
slightly acidic primary leach discharge solution is pre-neutralized to pH 2.5-3 with caustic soda.
This also eliminates excessive frothing which generally accompanies the acidic phase of
removal. The testwork has also shown that the presence of cupric ion in the feed solution is
essential for efficient iron removal. In the absence of copper or at a low copper concentration,
the copper-free discharge solution isproduced at pH 6, but containing sigmncant quantities of
iron, obviously in the ferrous state. Tne catalytic effect of cupric ion on ferrous ion oxidation is
well documented^^^'. In practice an optimal copper/iron ratio in the feed is ensured by
operating the non-oxidizing phase of the primary pressure leach at temperatures not exceeding

The pilot plant testwork culminated in the design of a full scale plant. The removal stage
comprises a series of 4 continuous stirred tank reactors, each having a height/diameter ratio of
4:1, with an overall residence time of 12 hours. Each reactor is agitated with a system of 3
impellers on one shaft, and aerated at a rate of Im^ air/lm*^ reactor volume/hr. The
temperature of the system is maintained at 80°C., i.e. optimal temperature for iron
precipitation. Slurry from the last reactor is discharged into a large thickener (mean residence
time - 2 0 hours), with the underflow being fed into the primary leach whilst the overflow is
diverted to the lead removal stage.
The thickener has a considerable moderating influence on any copper breakthrough in the
reactor discharge. The effect is twofold: partially by dilution with a large solution volume but
more so by further hydrolysis of cupric ions. The thickener is capable of accommodating
reactor discharge copper concentrations of up to 100 mg/L for several days, and as high as 1000
mg/L for several hours with no copper breakthrough in the overflow.
Residual iron and copper in the copper removal discharge solution pass the lead removal stage
to the cobalt removal stage which acts as a very efficient final scavenger. Provided that feed
concentrations do not significantly exceed 10 mg/L, discharge iron and copper concentrations
well below 1 mg/L are obtained. The residual iron is oxidized to the hydrolysable ferric form,
whereas the mechanism of copper removal is obscure. This described purification of nickel
electrolyte results in the production of nickel cathodes typically containing 8 ppm Cu and 15
ppm Fe.
Cobalt
Cobalt is not generally considered a harmful impurity and international nickel cathode
specifications allow contents between 1000-5000 ppm. Since cobalt metal or compounds
historically commanded prices several times higher than those for an equivalent mass of nickel,
effort has been made at RBMR to recover cobalt separately. The process for cobalt removal
from the nickel electrolyte was licensed from Outokumpu and installed in the old refinery in
1974. The process is based on the oxidation of the cobaltous ion to an insoluble cobaltic
hydroxide by electrolytically generated nickelic hydroxide Ni03_4.xH20.
The cobalt content of incoming matte varies between 0.45-0.65% depending mainly on the
severity of oxidation in the converters. No specific cobalt compound has been identified in the
matte. Electron scanning microscopy points to cobalt dissolution in the nickel sulphide lattice.
Possibly for this reason, cobalt behavior in the leaching stages is similar to nickel.
During the new refinery design phase, a large effort was devoted to optimization of the existing
process and data generation for reactor design. The target for the cobalt discharge
concentration was originally set at less than 3 mg/L, corresponding to nickel cathodes content
less than 50 ppm. The new stage was designed with 5 continuous stirred tank reactors in series
and a residence time of 10 hours. Each reactor was equipped with a draft tube to ensure good
mixing at minimum power requirement. However, it became evident during operation that
 ELECTROMETALLURGICAL PLANT PRACTICE 243

cobalt removal to very low concentrations is costly in reagent consumption and reactor
maintenance and later an economic compromise was chosen.
In the current operation, i
reactors in series at 80°C.
added to the first reactor in a quantity corresponding to a Ni'^^'^^/Co^
Discharged slurry is filtered with the filtrate containing less than 10 mg/L Co, typically 4-6
mg/L, and nickel cathodes with 80-110 ppm Co are produced.
Cobalt cake, having a Co:Ni ratio of 1:5, is leached under controlled pH in the nickel spent
electrolyte producing a residue with a Co:Ni ratio of 3:1. The leachate, containing about 10%
of the cobalt originally present in the cake, is recycled to the copper removal thickener for
reasons to be discussed m the section on zinc. The enriched cobalt residue is processed in the
cobalt sulphate production plant. The final separation of cobalt and nickel is accomplished by
solvent extraction in a sulohate medium, using the process jointly developed by RBMR and
Warren Spring Laboratory^^»''^).
The study of impurity behavior has pointed out enormous advantages of using nickelic
hydroxide as the reagent for cobalt removal. These are:
efficient scavenging of metallic impurities (Cu, Fe, Pb, Zn), passing at low
concentrations through preceding removal stages, to levels generally below 1
mg/L,
complete removal of manganese,
partial removal of magnesium and calcium which would otherwise accumulate in
the closed refinery circuits, and finally exit in the sodium sulphate solution,
almost total destruction of solvent extraction organics recycled from the cobalt
sulphate plant in the raffinate,
oxidation of the sulphide ion present in low concentrations in electrolyte when
barium sulphide was used as reagent for lead removal.
For these reasons the cobalt removal stage was positioned as the last purification stage prior to
the nickel electrowinning.
Lead
A low lead content in nickel cathodes was historically required and lead precipitation by
barium sulphide was practiced in the old refinery.
The content of lead in the incoming matte normally varied between 100-500 ppm, but during
excessive recycling of anode sludges and PGM refinery residues to the smelter, values as hign
as 4000 ppm have been recorded. Lead in matte is present as discrete species of PbS (galena),
identified by electron scanning microscopy.
Matte is subjected to an oxidizing atmosphere in the copper removal reactors causing oxidation
of PbS, initially to solid PbSO^ which is then dissolved under intensive agitation. A further
source of soluble lead is neutralized nickel spent electrolyte recycled from the sulphur removal
stage. Part of this lead originates from the slow dissolution of lead anodes; however during
periodical cell cleaning and cell sludge filtration, an appreciable quantity of very fine PbS04
passes to the filtrate and is also re-dissolved. Thus any cell cleaning campaign is usually
accompanied by high lead peaks in the lead removal feed solution. Values as high as 80 mg/L
have been recorded in the lead removal feed, although typical concentrations lie between 10-20
mg/L.
244 ELECTROMETALLURGICAL PLANT PRACTICE

Lead removal by barium sulphide is attributed to two different reactions:

a) isomorphic co-precipitation of PbS04 with BaS04
b) precipitation of Pb"^ as PbS
Precipitation of trace metals in solution as insoluble sulphides generally requires a long
induction period'^"*'. It is thus believed that isomorphic co-precipitation plays the major role in
lead removal. This in fact allows efficient use of non sulphidic reagents such as barium
hydroxide or carbonate.
Two draft tube reactors in series with a mean residence time of 40 minutes were designed for
the new refinery. Although this system operated reasonably well under normal circumstances,
high lead peaks in the feed required disproportionately high use of reagent and occasionally
resulted in cathodes outside the specification. A hypothesis was formulated to explain this
behavior: PbSO. is incorporated with BaS04 only during BaS04 precipitate formation or
crystal growth. Since precipitation is almost instantaneous, the efficient use of reagent can only
be ensured by its rapid distribution through the bulk of solution. Rapid and uniform
distribution can be achieved by injection of the reagent into a highly turbulent system which can
be realized with a pipe reactor. Tlie proposal was successfully tested by reagent injection into a
transfer pipe from the storage tank to the reactor. A p ^ e residence time of 5 seconds was
shown to be as efficient as 40 minutes in the reactors. This allowed greatly reduced reagent
addition rates, which were then proportional to the feed lead concentrations. The system was
incorporated into the plant operation leaving the reactors in position in order to age the fine
precipitate and facilitate better filtration.
The correctness of this hypothesis has never been rigorously tested, but whether it is true or not
is beside the point: the system operates extremely well and has resulted in further reductions in
the discharge lead concentrations down to 0.1-0.3 mg/L at half of the previous average reagent
consumption. Also in 1987 barium sulphide, a health hazard, was replaced by barium
hydroxide with no apparent change in lead removal efficiency.
Due to the application of Rustenburg residue policy, nickel cell sludge was recycled to the
smelter and significantly contributed to the lead levels in matte. This sludge is now washed to
remove entrained nickel and sold periodically as lead residue on a tender basis. Also the "fast
corroding" Pb-Sb anodes (life 3-4 years) are now being replaced at the end of their life by "slow
corroding" Pb-Sr-Sn anodes (life 6-8 years). The overall effect of such plant modifications and
policies has demonstrated itself in the reduction of the nickel cathode lead content from 15-20
ppm during the initial years of the new refining operation to the current values of 2-5 ppm.
Zinc
The zinc content of matte varies between 5-15 ppm. Since the relative quantity of zinc in matte
at 20 g/t of contained nickel is lower than the acceptable quantity of zinc in cathodes at 30 g/t
Ni, no zinc removal stage was considered in the design of the new refinery. However, soon
after commissioning, an unexpected behavior of zinc in the refinery circuits necessitated the
development of specific control strategies.
More than 90% of the zinc in the matte is dissolved in the primary leach and enters the copper
removal stage. In the terminal phases of the copper removal at pH 5.4, zinc begins to hydrolyze
forming a Zn(OH)2 precipitate. The precipitate is recycled with copper removal residue to the
primary leach and is entirely re-dissolved. The repetition of this process leads to permanent
zinc accumulation in the closed circuit, primary leach - copper removal - primary leach. This
zinc accumulation is counteracted by periodic zinc release achieved by lowering the pH of the
copper removal discharge to about 5. Small quantities of copper and iron released at the same
time are collected in the following purification stages.
 ELECTROMETALLURGICAL PLANT PRACTICE 245

This arrangement operated well when BaS was used as the reagent for lead removal, since a
significant proportion of released zinc and copper were co-precipitated. The introduction of
Ba(OH)2 resulted in a rapid accumulation of copper in the closed circuit, lead removal - cobalt
removal - cobalt cake treatment - lead removal, finally leading to copper breakthrough into the
nickel cathodes. Thus, recycling of the filtrate to the copper removal stage was used to
eliminate the copper accumulation, but this action seriously aggravated the zinc accumulation
in the primary circuit. The solution, based on detailed knowledge of metal hydrolytic
equilibna, was found in the recycling of the filtrate to the copper removal thickener. The
slightly acidic treatment filtrate at pH 2.5 lowers the solution pH in the thickener to levels
sufficient to prevent zinc precipitation, but not low enough to stop the copper precipitation.
The current average zinc content in nickel cathodes is 15 ppm. However with the periodical
character of zinc release from the copper removal stage, zinc values oscillate between 5-25
ppm. Due to this precarious situation of zinc distribution in the refinery circuits, RBMR
extensively investigated various methods of zinc removal. Ion exchange resins saturated with
phosphorus based organic acids were shown to be enable of selectively removing zinc in the
presence of large excesses of Ni, Co, Cu and Fe^^". The process was piloted on various
refinery streams producing raffinate well below 1 mg/L Zn and cathodes with less than 5 ppm.
Thus, if required, either due to increased zinc content of matte or lowered cathode
specification, a zinc removal stage can be installed in a relatively short time.
MinQr Metallic Impurities

Many of these impurities do not co-deposit with nickel, but they may accumulate in the closed
refinery circuits to unacceptable levels.
Manganese
The matte content varies between 5-15 ppm. Manganese is almost entirely dissolved in the
primary leach and re-precipitated as MnO^ in the cobalt removal stage. Manganese then
enters the cobalt sulphate production plant where it is periodically removed from strip solution
as MnOg by persulphate oxidation. The nickel cathode content is below 1 ppm.
Chrpmiym
Levels in the matte vary considerably from 10-100 ppm depending on the smelter operation and
the slag contamination of matte. Chromium is present in the form of leach resistant spinel
structures, NiCr204 and FeCrgO^, which pass through the process unchanged to the secondary
leach residue. TTie nickel cathode content is below 1 ppm.
lin
The content in matte varies between 10-50 ppm. Very little is known about its behavior in the
refinery circuits, but similar to chromium, it is almost totally rejected in the secondary leach
residue. The Ni cathode content is below 1 ppm.
Magnesium and Calcium
The major source of both metals is industrial water (5-15mg/L Mg, 20-25 mg/L Ca) from the
area distribution system (Rand Water Board). A large proportion of both metals appears to
follow cobalt to the cobalt sulphate production plant. They tend to form mbced sulphate
deposits in the solvent extraction cells and are periodically removed during cell cleaning. A
significant proportion of the magnesium and calcium also exits the refinery as a contaminant of
the sodium sulphate crystal. The magnesium and calcium content in nickel cathodes are not
specified or measured.
246 ELECTROMETALLURGICAL PLANT PRACTICE

PrggÍQUS Metais

About 1% of the PGMs contained in the converter matte enters the Base Metal Refinery in the
non-magnetic concentrate. Some dissolution of rhodium and ruthenium occurs in the
secondary leach, but these metals are re-predpitated in the selenium removal stage and
recovered in the pyrometallurgical section. The nickel cathode content of the individual
platinum group metals and gold is below the detection limit of 0.05 ppm.
B^hftvipr and Cpntrpl pf Npn-Metalliy Impuriti^g
Selenium
Selenium is one of the most obnoxious impurities affecting not only the chemical but also the
physical quality of nickel cathodes. Concentrations above 50 ppm make electrowon nickel hard
and brittle which commonly results in cathode splitting during deposition.
The selenium content of incoming matte varies between 250-750 ppm depending on campaigns
of residue recycles to the smelter. No specific selenium compound has been identified in the
matte and it is believed that selenium freely substitutes sulphur in the copper sulphide crystal
lattice. This is supported by electron scanning microscopy and leaching behavior.
In the primary leach, none of the sulphur associated with copper is oxidized and the extent of
selenium dissolution is beyond the accuracy of analytical techniques. In the secondary leach,
more than 95% of the sulphur is oxidized to the sulphate resulting in an intermediate selenium
concentration of several hundred mg/L. Initially selenium is oxidized to the selenite anion
SeOg^" (SelV), this species being further oxidized to selenate anion SeO/" (SeVI) as the redox
potential of solution increases above 400 mV in the terminal phases of the leach.
Simultaneously, the ferric ion begins to precipitate as jarosite or hematite, effectively collecting
the Se(IV) species. The complex and dynamic reaction sequence results in discharge selenium
concentrations between 50-100 mg/L of total Se with a variable ratio of Se(IV):Se(VI), this
variation being dependent upon the temperature, acidity, terminal redox potential and the
extent of iron precipitation.
In copper electrowinning, only Se(IV) is co-deposited whilst Se(VI) passes to the anolyte.
Furthermore, according to the literature^^°', some Se(IV) might be anodically oxidized to
Se(VI).
About 20-30% of the copper spent electrolyte is bled to the primary leach to maintain a sulphur
balance within the copper circuit. This stream also provides the acid for nickel primary
leaching whilst maintaining low nickel concentration in the copper circuit. A large proportion
of both selenium species appears to pass the primary leach without change. However Se(IV) is
effectively collected in the copper removal stage, possibly with hydrotytic iron species, thus
leaving Se(VI) as the only form entering further purification stages. Extensive sampling has
shown that Se(VI) is not affected to any measurable extent in the lead or cobalt removal stages,
and enters nickel electrowinning where it is co-deposited.
The fact that soluble selenium in both nickel and copper circuits is generated in the secondary
leach fixed the position of a selenium removal stage to directly after the secondary leach. The
target for the Se (total) discharge concentration was set at less than 1 mg/L. Sherritt Gordon
carried out laboratory screening of various selenium precipitation reagents and concluded that
only SOg containing reagents at 170^C are capable of meeting the recmired selenium discharge
concentration^^^'. The process was successmlly piloted at RBMR^^^'. Based on pilot plant
data, a full scale plant, comprising 4 vertical columns in series (redundant leach columns from
the old refinery) with a mean residence time of 40 minutes, was built and commissioned. Plant
operation confirmed the design data and nickel cathodes with less than 1 ppm Se were
produced. Due to faults in the mechanical design (FEP instead of the recommended PTFE
pipe lining), frequent failures of the interconnecting pipes were experienced. After a short
 ELECTROMETALLURGICAL PLANT PRACHCE 247

period, the column operating temperature was reduced to 90-110°C which led to an increase of
nickel cathode selenium content to 15-20 ppm, i.e. still within Matthey Nickel specification (30
ppm). Further optimization of the process resulted in significant improvements and currently
the typical nickel cathode selenium content is 7 ppm.
An excess of SO^ is required for efficient selenium precipitation, which at temperatures above
9QPC rapidly reduces cupric to cuprous ions. The cuprous ion is unstable in sulphate medium,
and on cooling disproportionates to metallic copper and cupric ion. Metallic copper tends to
form hard and compact crystalline deposits in the pipes and valves causing frequent blockages.
Thus, from the start of the operation, two oxidation columns in series were an integral part of
the selenium removal stage. Reduction column discharge solution was oxidized to a redox
potential above 300 mV by air at a pressure of 1000 kPa. Contrary to expectation, the oxidation
columns rather than the reduction columns were subjected to severe corrosion. These columns
were all 316L stainless steel.
Ourine 1985 the expensive oxidation colunms were replaced by a pipe reactor of 60m length (20
second residence time) at an enormous maintenance cost saving. The success of the pipe
reactor operation was ensured by a specific design of pipe internal gas distributor (bubble
breaker) enabling the maximum oxygen mass transfer from the gas to the liquid phase.
Minor Npn-M^tallig Elgm^ntg (Τφ, A$, Sb. Bi)
Similar to selenium, there is a large variability in the matte content of these elements:
Te 100 - 250 ppm
As 10 - 150 ppm
Sb 10 - 150 ppm
Bi 10 - 100 ppm
caused by periodic recycling of PGM and Base Metal Refinery residues to the smelter.
These elements again appear to be predominantly associated with copper sulphides and thus
very low dissolution occurs in the primary leach. This was also the general case in the old
refinery. The introduction of the non-oxidative mode of primary leaching further suppressed
their dissolution. Currently, the extent of their concentration in the primary leach solution is
below the limits of analytical detection (0.5 mg/L).
The attack of copper sulphides in the secondary leach stage initially releases a significant
proportion of these elements into solution. However, contrary to selenium, they are very
efficiently collected by the iron precipitates, and the secondary leach discharge solutions
commonly contain less than 1 mg/L
Prior to the introduction of the RBMR pyrometallurgical stajge, the recycle of non-metallic
impurities in the secondary leach residue to the smelter was significantly contributing to their
levels in the converter matte. Massive rejection of non-metallic impurities in the copper matte
(Table IV) reduced their content in the converter matte close to the lower limits (Se, Te) or
mid-values (As, Sb, Bi) of the quoted ranges.

OTHER IMPURITIES
Organics
There are three major sources of organic materials in the refinery circuits:
flocculation agents used in the primary leach and copper removal thickeners.
248 ELECTROMETALLURGICAL PLANT PRACTICE

antifoaming agents used in the primary leach and secondary leach autoclaves and
occasionally on the copper removal reactors.
extractant (D2EHPA: di-(2-ethylhexyl) phosphoric acid), modifier (TBP:
tributylphosphate) and diluent (ESCAID - a paraffin solvent) used in the cobah
solvent extraction circuit and entrained in the recycled raffinate.
The fate of flocculating and antifoaming agents in the refinery circuits is largely unknown.
Whether they contribute to the carbon level in nickel cathodes is a matter of speculation.
The effects of solvent extraction organics are well defined:
a) diluents cause severe pitting of nickel cathodes
b) D2EHPA and TBP contribute to the phosphorus level of nickel cathodes.
The raffinate, routinely analyzed by gas chromatography, contains 5-20 mg/L D2EHPA, 5-10
me/L TBP and 5-30 mg/L ÉSCAID. The metal content of the raffinate is precipitated in the
sulphur removal stage. However, the precipitated hydroxides collect most of the organics,
which, after redissolution in the nickel spent electrolyte are recycled to the copper removal
stage. Organics are partially collected with the lead precipitate and then totally rejected from
the nickel solution in the cobdt removal stage. Whether they are destroyed by the powerful
oxidant or physically absorbed onto cobalt cake in not known. The concentration of the solvent
extraction organics in the nickel electrowinning feed is below the limit of chromotographic
detection (1 mg/L). Nickel cathodes contain less than 1 ppm of phosphorus and typically 25
ppm of carbon.
Chlorides
Although chlorides do not affect the chemical or physical quality of nickel cathodes, they are a
cause of several unwanted phenomena in the refinery circuits. Long term operating experience
has shown that the refinery carmot tolerate more than 50 mg/L Cl in the circuit. Higher
concentrations result in:
increased corrosion of 316L stainless steel tanks, pipes and valves.
increased corrosion of lead anodes.
increased evolution of chlorine gas, now nasally detectable in the tankhouse
atmosphere.
The major source of chlorides are caustic soda solution (100-150 g Cl/t NaOH) and industrial
water (normally 15-25 mg/L Cl). Tlie only outlet from the refinery is in the sodium sulphate
solution from the sulphur removal stage. Since a very large proportion of caustic soda is used
in this stage, caustic soda chlorides leave the circuit at once. The sodium sulphate volume
generated is approximately equal to the industrial water usage, which, under normal
circumstances maintains an equilibrium chloride concentration in the refinery circuits at 20-30
mg/L. However during periods of prolonged drought, the chloride concentration in industrial
water may increase to levels as high as iSd mg/L resulting in the negative effects mentioned
above. In the existing operations, no water pretreatment is carried out.
Silica
Concentrations of soluble silica in the refinery circuits are surprisingly high, in the range of
0.3-0.5 g/L. The term soluble silica is applied here to colloidal silica in addition to truly soluble
silicate anions. Silica is, or is suspected to be, a cause of numerous problems such as poor
filtration, blinding of cathode bags, deposition and restriction of fiows in pipes and valves, and
 ELECTROMETALLURGICAL PLANT PRACTICE 249

cathode nodular growth, supported by finding silica crystals at the roots of nodules. Most of
these are fortunately restricted to the copper arcuit.
The source of silica is matte contaminated with slag at 0.1-0.2%. Laboratory pressure leach
experiments have shown that the maior component of slag, fayalite FcgSiO^, is totally
decomposed in acidic medium to soluble iron, silicate anion and a residue of pure SiOg.
Dissolution of fayalite proceeds predominantly in the secondary leach with solubilized silica
entering copper electrowinning. High acid concentration in the copper spent electrolyte (125
g/L) tends to precipitate soluble or colloidal silica in the form of silica gel. Gel formation can
be indirectly observed on filtration rates through a 5-micron laboratory filter: with very fast
rates for electrolyte feed (100 mL/30 seconds) and very slow rates for spent electrolyte (100
mL/30 minutes). The control of silica in the circuit is facilitated by addition of some spent
electrolyte to the secondary leach discharge slurry, where gel is collected onto the iron
precipitates and rejected with the secondary leach residue.
Due to the relatively high pH of the nickel circuit solutions (3-6), silica appears to be present in
the form of anionic species. The nickel spent electrolyte acid concentration (50 g/L) is not
sufficiently high to promote excessivegel formation and most of the silica exits the nickel circuit
in the sodium sulphate solution. The solubility of silica is enhanced by the high pH 9 of
hydroxides precipitation. Nickel cathodes typically contain 20 ppm silicon.
Matte contamination with slag is minimized at the smelter by ingot casting using ladles with a
bottom discharge.
PaniPMiat<? gQiid?
Particulate solids in the electrolyte feed are a notorious cause of cathode nodular growths.
Solids originate from two sources:
a) fine solids passing through the final filtration stage.
b) airborne solids.
Final filtration of the nickel electrolyte feed is carried out on pre-coated disc filters (FUNDA
type). Filtrate is continuously monitored by turbidity meters. If the solids concentration
exceeds 5 mg/L the filtrate stream is automatically put on recycle. The typical particulate
solids concentration in the electrolyte feed is 2 mg/L.
Airborne solids can be a source of serious problems, particularly during dry and windy
conditions in the August - October period. Since the tankhouse is not totally isolated from the
outside atmosphere, a considerable amount of dust can enter the building. Investigations
carried out at RBMR have shown that coal dust from the coal yard is particularly harmful,
while silicate soil particles have negligible effect on the promotion of nodular growths. For this
reason the tankhouse and the boiler house were built some 100 metres apart on the line of the
prevailing wind.

SUMMARY
The development of the refining process at Rustenburg has been successful in producing the
desired quality of base metals. After commissioning, the initial five years were spent in
achieving this objective. Over the last four years, efforts have been centered on optimization of
the process. At the same time, a good understanding of impurity behaviour and control has
been realized.
250 ELECTROMETALLURGICAL PLANT PRACTICE

It is considered that this process can economically treat matte of differing, but not too
dissimilar, composition for the refining of nickel, copper and cobalt. To this end RBMR toll
refined a quantity of matte in 1985 and 1986.

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 ELECTROMETALLURGICAL PLANT PRACTICE 251

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