Solvent extraction in the primary and

secondary processing of zinc

by P.M. Cole* and K.C. Sole†

stringent requirements for produciton of high-

purity zinc by electrowinning (EW)2. Zinc EW
Synopsis from sulphate medium is extremely sensitive
to the presence of trace impurities and requires
An unprecedented expansion of the global zinc industry is currently a highly purified electrolyte. The selectivity of
under way. While most new projects and plant upgrades remain modern solvent extractants, an improved
committed to traditional processing technologies, recent advances understanding of the process chemistry, and
in zinc solvent extraction (SX) have created opportunities for new
engineering innovations, have today enabled
process routes for both primary and secondary materials. The first
SX to provide unique advantages as a purifi-
commercial plant to use zinc SX for the mainstream processing of a
low-grade ore is under construction and promises to become one of cation step ahead of the EW circuit in
the lowest cost zinc producers. Several other oxide and sulphide hydrometallurgical process flowsheets.
projects in various stages of feasibility are considering the In most of the new applications involving
inclusion of SX in their process flowsheet. Zinc SX has also proved SX processing in sulphate media, di(2-
advantageous in the reprocessing of secondary materials, partic- ethylhexyl)-phosphoric acid (D2EHPA) is
ularly for the treatment of zinc residues and furnace dusts. This used. This extractant is selective for zinc over
review focuses on recent installations and projects under most of the species deleterious to EW (Cu, Cd,
development that feature zinc SZ as the key separation step. Co, Ni, and the halides) and is readily stripped
by acid concentrations typical of the spent
tankhouse electrolyte (~180 g/l H2SO4). Circuit
configurations generally include an organic-
phase scrub to further ensure electrolyte
Introduction purity. Iron build up in the organic phase is
controlled by a concentrated HCI treatment.
The traditional roast-leach-electrowin(RLE) The selectivity of D2EHPA for zinc over
zinc production route was developed for the selected base metal and alkali cations is
processing of sulphide ores. It can prove illustrated in Figure 1.
inefficient for some complex sulphides and is In contrast to the zinc industry itself, zinc
not readily applicable to the treatment of other SX has found wider application in the refining
ore types. Inherent to this route is the of other base metals, providing an efficient
generation of SO2 gas that has to be fixed for means for the removal of zinc as an impurity
environmental reasons, usually resulting in species. These applications are surveyed
the production of sulphuric acid. These elsewhere4. This review focuses on recent
limitations have encouraged the search for installations and developmental projects
alternative processing routes for both featuring zinc SX. Some historical perspective
sulphides and other ores. is provided by brief descriptions of earlier
Approximately 30% of global zinc processes.
production arises from recycled zinc. With
increasing awareness of secondary zinc Primary processing of zinc
materials as a valuable resource and stricter
environmental legislation that restricts Flowsheets involving zinc SX for the primary
dumping of these hazardous materials, interest processing of zinc sulphides have been the
in their recycling has increased1. Direct
retreatment of such materials via the process
* Anglo American Research Laboratories (Pty) Ltd,
of origin is not always cost effective and can
Johannesburg, South Africa.
deleteriously affect the operation of the † Hatch, Pvt Bag X20, Gallo Manor, 2052.
primary plant due to high levels of impurity
© The South African Institute of Mining and
species. Metallurgy, 2002. SA ISSN 0038–223X/3.00 +
The development of process routes for the 0.00. This paper was first presented at: ISEC
treatment of both primary and secondary 2002, International Solvent Extraction Conference,
sources of zinc has been hindered by the very Cape Town, South Africa, 17–21 Mar. 2002.
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The Journal of The South African Institute of Mining and Metallurgy NOVEMBER/DECEMBER 2002 451
Solvent extraction in the primary and secondary processing of zinc
Brunswick ore was reported7. The process featured zinc SX
using the zinc-selective bisbenzimidazole extraction, ZNX
50, developed by Zeneca (now Avecia). Zinc metal was
electrowon in a divided cell in which chlorine gas was also
generated for recycle. Interestingly, this process route was
reported to be more cost effective for treating the whole ore
than for treating the concentrate, generating approximately
10% more revenue.

Sulphate routes
Pressure leaching for the hydrometallurgical processing of
zinc sulphides has been applied commercially for many years
but purification of these liquors has, to date, relied on a
series of precipitation steps to achieve the electrolyte purifi-
cation required for the production of high-purity zinc.
Indications are, however, that SX may be used in future
installations, with pilot-plant studies having been carried out
by TR on pressure leach liquors using D2EHPA1.
Figure 1—pH dependence of the extraction of selected cations by An alternative approach to the hydrometallurgical
D2EHPA3 treatment of sulphides is the use of bacterial leaching for
solubilizing the valuable metals. Following a bulk iron-
removal step (typically by precipitation), SX has been shown
subject of investigation for some time. Interestingly,
to be successful in producing ultrapure electrolytes suitable
however, the first commercial application of zinc SX on the
for the production of special high-grade (SHG) zinc metal
mainstream process liquor will be for the exploitation of an
(>99.995% purity) from a variety of bioleach liquors. In
oxide orebody.
pilot-plant studies, MIM Holdings of Australia have proved
Sulphide ores and concentrates the feasibility of this route for treating concentrate,
demonstrating that the simplified zinc-recovery flowsheet
Most zinc ores occur as sulphides and, as such, are amenable
can provide low capital and operating costs with high overall
to upgrading by flotation. The traditional treatment route
zinc recoveries (96%)8. For the development of the Lanping
includes smelting of the concentrates, followed by hydromet-
deposit in China, BHP Billiton have proposed bacterial
allurgical processing to produce electrolytic zinc metal. Direct
leaching of the sulphide concentrate, an atmospheric leach of
ore processing via a hydrometallurgical route could enable
the oxide material, and the treatment of the combined leach
the economic exploitation of complex ores that yield low
liquor by SX for the recovery of zinc9. A process for the
upgrading recoveries, while hydrometallurgical processing of
treatment of Mexican polymetallic (Cu/Zn) and chalcopyrite
concentrates would avoid the generation of SO2 and would be
copper concentrates, developed by BacTech and Mintek,
more flexible with respect to the grade of feed material that
includes bioleaching, copper recovery by SX/EW, and zinc
can be treated. The inclusion of an SX separation step in
recovery by SX/EW10.
potential process flowsheets could also accommodate
difficult-to-treat concentrates, such as those with high lead Non-sulphide zinc ores
or halide contents.
Extensive feasibility studies have shown that oxide, silicate,
Chloride routes and carbonate-based zinc ores, not amenable to conventional
Chloride routes for the treatment of sulphides have been processing, can be viably treated using zinc SX technology in
known for over a century, however, few have been commer- a purely hydrometallurgical processing route9. A key feature
cialized because of the associated corrosion problems. that contributes significant economic advantage to these
Although modern materials of construction have improved projects is that SHG zinc cathode is produced at the mine site.
this situation considerably, there are currently no known This is rarely seen for the processing of sulphide ores. Use of
plants that use this technology for zinc. There have, SX enables the entire process stream to be treated for the
however, been several process developments that have made selective recovery of zinc, with a single SX circuit capable of
use of SX for the treatment of zinc sulphides. processing in excess of 150 000 t/a zinc1. This means that
The Zinclor Process was developed by Técnicas Reunidas the impurity-removal operations are small, treating only a
(TR), for the treatment of concentrates5. Leaching with ferric bleed stream of the main circuit, rather than the entire
chloride was followed by SX with pentylphosphonate and EW process stream as in traditional flowsheets.
in their patented Metclor cell. Another process for the
Skorpion project
treatment of concentrates proposed leaching in concentrated
ammonium chloride, followed by zinc SX using D2EHPA Anglo American’s Skorpion project wil be the first
modified with isodecanol6. The ammonia fixed in the metal- commercial application of zinc SX for primary zinc
ammine complex provided neutralization of the acid released processing, involving a capital investment of US$ 454 million
during extraction. to develop the mine and refinery near Rosh Pinah in
More recently, a detailed engineering design for a plant southern Namibia11. A simplified flowsheet of the proposed
based on ferric chloride leaching of a complex sulphide New process is given in Figure 212.
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452 NOVEMBER/DECEMBER 2002 The Journal of The South African Institute of Mining and Metallurgy
Solvent extraction in the primary and secondary processing of zinc

Figure 2—Simplified flowsheet for the Skorpion zinc project12

Following atmospheric leaching in sulphuric acid, iron, scrubbing circuit use demineralized water to wash out
aluminium, and silica are removed from solution by precipi- physically entrained impurity species; spent electrolyte is
tation. Zinc is then selectively extracted by SX with D2EHPA, employed as the scrub liquor in the third wash stage to
enabling the electrowinning of SHG zinc. The selection of SX ‘crowd off’ co-extracted impurity species from the loaded
as the purification step serves several purposes. The ore is a organic phase. Treating a bleed stream with 6 M HCI controls
low-grade oxidized silicate containing soluble chloride and iron build up in the organic phase. Residual HCI is removed
fluoride minerals. The choice of D2EHPA as the extractant from the regenerant solution by distillation, producing
and the inclusion of a scrubbing circuit ensure the rejection concentrated FeCI3 liquor, which is neutralized prior to
of the halides, as well as the base metals that are deleterious disposal to tailings.
to zinc EW. SX also successfully upgrades the rather dilute Construction of the full-scale plant commenced in May
leach liquor (30 g/l Zn) (produced as a consequence of the 2001, and the first metal is expected in December 2002. The
leach conditions dictated by the elevated silica content feasibility study conducted for the planned capacity of
(~26%) of the ore) to an advance electrolyte containing 90 150 000 t/a zinc showed that the Skorpion project will be the
g/l Zn that is suitable for EW. Soluble losses of zinc in the most profitable zinc facility in the world9, with an expected
filtration step are minimized by employing a dilute leach production cost of US$ 0.25/lb.
liquor, and the problematic formation of silica gel is avoided.
Projects under development
Operation with a high extractant concentration ensures
minimal calcium co-extraction and allows high zinc transfer Several non-sulphide ore projects in various stages of
in the extraction circuit without the need for neutralization. development and feasibility studies intend to use zinc SX for
The acid generated by the extraction reaction is then primary ore processing (Table I).
available for leaching on recycle of the raffinate.
Zinc recovery from geothermal brines
TR was responsible for providing the SX technology11
and the plant will be the largest yet built for zinc SX. The A process originally developed by BHP for the recovery of
circuit comprises three extraction, three scrubbing, and two zinc from geothermal brine that has been used for power
stripping stages, and an organic regeneration stage. Zinc generation is currently being commissioned by Kvaerner
transfer of 20 g/l across the extraction circuit is achieved, Metals for CalEnergy Minerals in the Imperial Valley of
yielding a raffinate of 10 g/l Zn. The first two stages of the California. High-temperature underground brine is brought to
▲

The Journal of The South African Institute of Mining and Metallurgy NOVEMBER/DECEMBER 2002 453
Solvent extraction in the primary and secondary processing of zinc

Table I
Non-sulphide primary ore processing projects under development that use zinc SX
Project Capacity (t/a Zn) Ore type Process route

Shairmerden, Kazakstan13 100 000 Oxide, silicate, carbonate Sulphate leach, zinc SX
Angouran, Iran14 100 000 Carbonate, silicate Sulphate leach, zinc SX
Sierra Mojada, Mexico15 - Oxide Sulphate leach, zinc SX
Accha, Peru16 - Oxide, carbonate Chloride leach, zinc SX

Table II
Composition of furnace dusts and upgraded zinc solution produced by SX at Met-Mex Peñoles22
Element Blast furnace dust% Reverbatory furnace dust (%) Upgraded zinc SX solution (mg/l)

Zn 10.6 15.6 95 000

Cd 23.8 1.1 128
As 1.1 8.8 <1
Pb 39.1 30.2 <2
Fe 0.1 0.1 <2
CI 4.3 0.4 7
F 0.5 0.3 2

the surface and flashed down in pressure vessels to produce materials. Advantages claimed for the MZP include the high
steam to drive electricity-generating turbines. Zinc is selectivity over species such as halides and magnesium, the
recovered from the brine before it is pumped back production of an electrolyte from which SHG zinc can be
underground. Very hot geothermal brine (19 t/h) is passed produced, high zinc recoveries, and safe and environmentally
through an ion-exchange column to adsorb zinc. A conven- friendly operation. Gypsum precipitation in the SX circuits
tional anion-exchange resin (DOWEX 21K XLT) selectively remains a problem, with the production of 80 to 150 kg per
complexes zinc, as it is unique among the species present in tonne of material treated. However, by using a source of pure
forming multivalent anionic complexes in brine solution; lime for neutralization in the SX circuit, ‘white gypsum’ can
other elements remain in solution as cations. The resin is be produced, which may be sold for certain applications in
eluted with water. The application of reverse osmosis to the the plasterboard industry.
eluate produces a concentrated zinc solution that is purified
Re-processing of furnace dusts
by SX using D2EHPA, prior to EW to produce zinc cathode.
The operation is expected to yield 30 000 t/a zinc17 in one of Electric arc furnaces produce 10 to 15 kg of dust per tonne of
the cleanest zinc-recovery operations ever undertaken. steel produced, representing one of the more contaminated
zinc residues. The steel industry has approved the MZP as
Secondary processing of zinc ‘technically, economically and environmentally suitable for
the solution of the EAFD problem’21. A project for the
Several pyrometallurgical processes have been implemented treatment of 82 000 t/a EAFD in Spain has been proposed,
for the treatment of secondary materials, however, these are but to date this has not been implemented, despite several
generally only efficient for a constant composition feed and successful pilot-plant trials on different EAFD compositions.
need to have a high production capacity to be economically Dust generated from blast and reverberatory furnaces at
viable18. Some materials are not amenable to treatment by the Met-Mex Peñoles lead smelter in Torreón, Mexico, has
these routes, and environmentally acceptable discharges are since 1998 been treated in a zinc SX plant built at the site22.
not always assured. Hydrometallurgical processes are The material was previously recycled, causing saturation of
potentially less sensitive to these constraints; the most undesirable species such as cadmium, arsenic, and halides in
successful of these include an SX step to purify and upgrade the main circuit. Installation of the SX plant is reported to
the zinc. offer operating, economic, and environmental advantages:
TR has been at the forefront of developments in the greater flexibility now allows the treatment of ‘dirty’ lead
processing of secondary zinc materials. Recycling plants, now concentrates; increased revenues are realized from the sale of
closed, were built in Spain and Portugal based on their impurity species recovered; and airborne dust generation has
Zincex process19,20. This was superseded by the Modified decreased. Production is 5000 t/a zinc cathode of 99.99%
Zincex Process (MZP), which has found application and is purity. Table II compares the composition of the high-
the instrument of numerous new investigations into the impurity feed material with an assay of the upgraded zinc
treatment of secondaries such as Waelz oxides, galvanizing solution produced by SX.
residues, and electric arc furnace dusts (EAFD)18,21. The Italian trials to recover zinc from EAFD by SX have also
process uses D2EHPA for the selective extraction of zinc from been reported23. In this process, iron was not removed from
the acidic sulphate liquor produced on the leaching of these the leach liquor prior to SX. Zinc and iron were co-extracted
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454 NOVEMBER/DECEMBER 2002 The Journal of The South African Institute of Mining and Metallurgy
Solvent extraction in the primary and secondary processing of zinc
using D2EHPA; zinc was stripped with 1 M H2SO4 and iron The BATENUS process, which also used D2EHPA Sx for the
was periodically removed from the organic phase by recovery of zinc, was fully piloted and commercialization was
treatment with HCI. It was reported, however, that HCI expected in 1995; the reason why this did not go ahead is
stripping introduced partial degradation of the extractant, unknown.
and a reductive stripping process for iron was under
development. Conclusions
Fluor Daniel Wright has also carried out development of
an SX process to recover zinc from EAFD. The extraction of The advantages afforded by hydrometallurgical processes
zinc chloride by ZNX 50 was evaluated24. that feature SX have only recently been realized in the zinc
recovery industry. The commissioning of the Skorpion
Process residues and tailings
refinery, as the first plant to use SX for the recovery of zinc
In 1988, Española del Zinc in Cartagena, Spain, integrated from a primary source, will add further impetus to this
SX into a conventional zinc refinery flowsheet for the development. An increase in the application of zinc SX
recovery of water-soluble zinc from stockpiled and fresh technology can be expected during the next decade, partic-
leach residues25,26. The main refinery treats a mixed sulphide ularly in the processing of non-sulphide primary materials
concentrate to produce 40 000 t/a zinc via a RLE circuit. The and for the treatment of an increasing variety of secondary
iron hydroxide precipitate exiting the primary leach circuit materials.
contains about 20% zinc. These solids are leached, along
with previously dumped material, in a secondary leach using Acknowledgements
sulphuric acid and the loaded strip liquor generated in the SX
plant. Iron is removed as ammonium jarosite. The secondary Appreciation is extended to Dr Doug Flett for this thoughtful
filtrate from the washing of the jarosite solids (containing 14 comments on this manuscript. This review is published by
g/l Zn, 0.03 g/l Fe, 0.7 g/l Cu, 0.3 g/l Cd, pH 3) is not permission of Anglo American Research Laboratories (Pty)
suitable for EW and is treated by SX to upgrade and purify Ltd.
the zinc into a concentrated (120 g/l Zn) strip liquor for
recycle. References
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Most operating zinc refineries use precipitation methods for Metallurgy, Johannesburg, 2002. pp. 1045–1051.
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magnesium and manganese. Since zinc EW is extremely 3. SOLE, K.C. and COLE, P.M. Ion Exchange and Solvent Extraction, vol. 15,
Y. Marcus and A. SenGupta (eds.), Marcel Dekker, New York, 2001.
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▲

456 NOVEMBER/DECEMBER 2002 The Journal of The South African Institute of Mining and Metallurgy