Minerals Engineering 22 (2009) 742–751

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Top submerged lance direct zinc smelting

J. Hoang a, M.A. Reuter a,*, R. Matusewicz a, S. Hughes a, N. Piret b
a
Ausmelt Ltd., 12 Kitchen Rd., Dandenong, Vic 3175, Australia
b
Piret & Stolberg Partners, Im Licht 12, D-47279 Duisburg, Germany

a r t i c l e i n f o a b s t r a c t

Article history: A long history of zinc processing starting with pilot plant studies in the 1980s has progressed to the treat-
Received 22 September 2008 ment of close to 800,000 tonnes a year of zinc bearing feeds in Top Submerged Lance (TSL) furnaces in the
Accepted 24 December 2008 form of residues and slags. Whereas these Ausmelt TSL applications are end-of-pipe applications treating
Available online 8 February 2009
residues from classical Roast-Leach-Electrowinning (RLE) process routes, this paper discusses Direct Zinc
Smelting (DZS) Process. In Stage 1 of this novel two stage TSL application the sulphide sulphur from the
Keywords: zinc concentrate is the energy carrier used to smelt the concentrate and fume 60–65% of the zinc content.
Non-ferrous metallic ores
Subsequently in Stage 2 zinc is fumed from the already molten Stage 1 slag to create a final discard slag
Pyrometallurgy
Mineral processing
with a total zinc recovery of 99%. The use of sulphide sulphur as fuel to smelt has economic advantage
Zinc over the present end-of-pipe TSL applications, that require two steps (for smelting and sulphur removal)
and then fuming using primary fuels. The slag product of the DZS process overcomes inherent environ-
mental liability and ever increasing economic burden associated with the traditional RLE processes by
eliminating the creation of large volumes of iron bearing residues (mainly jarosite and goethite) while
complementing high recoveries of Zn with those of the valuable elements e.g. Cu, Ag, Au, Pb, Ge, and
In. High levels of Fe, Mn, SiO2, and MgO in some concentrates render them unsuitable for processing
in RLE, however are elegantly directed by DZS to the benign slag. This paper will discuss Ausmelt’s appli-
cations in zinc processing with a focus on DZS to show how this process can extend the life of present RLE
sites.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction in close to 50 commercial Ausmelt TSL furnaces is testimony to this

technology’s flexibility to economically process both primary and/
With growing pressure on the margins for the processing of zinc or secondary feeds, while using varying fuels, oxygen and good
feeds as a result of increasing costs of energy and labour, the ever process control to produce high metal recoveries.
increasing drive for sustainable use of zinc resources, interest in Being environmentally compliant in regions for example such
the economical processing of secondary feed material sources has as Europe, Japan, and South Korea evidences TSL’s excellent envi-
surged. In addition the drivers for environmental conformity and ronmental performance by operating within all norms for offgas
stricter health regulations in an increasingly educated and environ- emissions and other environmental legislation.
mentally aware and active society will affect the future of metal This paper describes the technical and commercial aspects of
production. Intensifying the processes in metallurgy by maximiz- Ausmelt’s progress in the field of zinc processing. The discussion
ing mass and energy transfer in state-of-the-art furnace technology briefly provides an overview of Korea Zinc’s commercial applica-
will be a key. Since its invention, Top Submerged Lancing (TSL) tions for the treatment of zinc leaching residues (and other mate-
Technology has gained widespread commercial acceptance in rials) and subsequently focussing on the developments of Direct
non-ferrous metal production by doing exactly this. Zinc Smelting (DZS). The DZS process has the potential to make
The processing of among others copper, lead, tin, and zinc bear- an important contribution to treating lower grade unclean concen-
ing primary, secondary (residue) or recycled materials in TSL is trates in an innovative combination of the pyrometallurgical recov-
commercial reality. Close to 40% of Sn will be produced through ery of zinc as a ZnO fume and subsequent processing it in a
TSL furnaces in the next years, while an ever increasing amount simplified leach and electrowinning circuit while harnessing the
of copper is produced in TSLs while e-waste processes, lead battery sulphide sulphur as a fuel. This complements the success TSL al-
recycling and copper recycling are already commercial reality ready has in the processing of iron containing residues from the
(Matusewicz and Reuter, 2008). Producing these various metals classical Roast-Leach-Electrowinning (RLE) primary zinc industry,
fuming zinc from slags and treating secondary materials such as
* Corresponding author. Tel.: +61 3 9794 6200; fax: +61 3 9794 9411. Electric Arc Furnace (EAF) dusts to recover both the iron and zinc
E-mail address: [email protected] (M.A. Reuter). units.

0892-6875/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2008.12.014
 J. Hoang et al. / Minerals Engineering 22 (2009) 742–751 743

1.1. Zinc processing – current commercial solutions ing capacity of 925 kt/a. It is notable that this processing recovers
through its TSL technology (Fig. 2) 63.5 kt/a Zn, 39.0 kt/a Pb,
Traditional RLE processes are complex flow sheets that incorpo- 267 t/a Ag, 600 t/a Cd, and 75 t/a In (substantial amount on a global
rate a number of fundamentally simple steps to produce zinc sul- basis), adding considerably to the profit margin (Korea Zinc, 2008
phate liquor that undergoes electrolysis to produce the final zinc Annual Report). These fuming activities make Korea Zinc the only
metal product. The complexity in the flowsheet comes from the zinc smelter free from environmental pollution issues. While
need to purify the leach liquor to remove the iron, copper, cobalt, fuming recovers all the valuable metals from waste it also turns
nickel, and other elements such as arsenic and bismuth to prevent the leftovers into environmentally stable slag to be used as
them affecting the final product or reducing the efficiency of the construction materials.
electrowinning processes. The leach residue (usually jarosite or These fully commercialized TSL applications are complemented
goethite) is already a cost driver in terms of disposal and increasing by TSL flowsheets to process EAF dusts (Hughes et al., 2007; Lee
dumping costs, as well as negative publicity around them is contin- et al., 2006) as well as direct processing of zinc concentrates, which
uing to be a major concern as stricter environmental standards are is the topic of this paper.
enforced preventing the creation of ponds and other storage mech-
anisms for economically viable disposal. In addition, the RLE pro- 1.2. Direct zinc processing – future solutions
cess is less efficient in the recovery of valuable minor elements
such as Indium (In) or Germanium (Ge), which are commonly Over the past 25 years, fundamental investigations have been
found with zinc ores. conducted into the direct smelting of zinc sulphide concentrates
TSL zinc processing technology has been implemented in vari- with the objective of producing crude zinc metal directly by con-
ous commercial applications for the efficient recovery of zinc from densation of the zinc metal vapour from the SO2 bearing gas
these intermediate industrial products (residues, slags) in South stream or technologically best as oxidized ZnO fume.
Korea, Japan, and Australia (Hughes et al., 2008). Therefore, retro- Thermodynamic calculations by Yazawa (1979) on the volatil-
fitted to existing zinc smelting installations, the TSL furnace can ization of zinc as metal vapour from pure ZnS material during
treat primary leach residues to recover the zinc units and minor oxidation of sulphide showed that 99% of the Zn as sulphide is
valuable elements such as In and Ge to produce a discard saleable converted to zinc metal vapour. However, this tends to convert
slag low in zinc (<2%) enabling maximum zinc recovery from a to ZnO and ZnS during cooling, because of the presence of SO2
concentrate source. The zinc is returned in the form of zinc oxide and CO2, i.e. the pO2 is high enough for this to occur. These
fume can easily be treated in simplified existing zinc RLE works experiments were extended to industrial concentrates by Davey
for which only a neutral leach step is required (see Fig. 1). and Turnbull (1980), producing similar results, claiming as well
The Korea Zinc facility in Onsan (South Korea) is the most com- that the process is thermally autogenous. However, it has proven
prehensive evidence to date as to the success of TSL technology challenging and elusive to produce metal zinc by condensation
(Lee and Park, 2003; Kim and Lee, 2000; Lee et al., 2006). It com- from zinc vapour/gas mixtures other than for the Imperial Smelt-
prises an integrated flow sheet of seven interdependent projects ing Furnace. Test work has been conducted by Minproc (Foo
utilising twelve TSL furnaces (10 for the specific recovery of zinc) et al., 1992) for producing ZnO from Bolivian sulphide ores in a
that allows Korea Zinc to maximize the recovery of values from submerged combustion smelting process with zinc recoveries
these intermediate industrial residue products (e.g. goethite, QSL exceeding 92%.
slag, old residue ponds, indium, and germanium, etc.). This demon- In the late 1990s Ausmelt carried out extensive R&D resulting in
strates the flexibility of the TSL furnace and zinc technology in par- a two stage ZnS concentrate smelting–fuming process being pro-
ticular as depicted by Fig. 2. According to Korea Zinc’s 2008 annual posed and developed in conjunction with BUKA Minerals Ltd., Aus-
report the Korea Zinc Group (Korea Zinc, its wholly owned subsidi- tralia. In this process finely grained Zn–Pb bulk concentrate from
ary Sun Metals Corporation, and its sister company Young Poong) their existing operations were treated. The Buka Zinc Process
ranks second in the global zinc market and has refined zinc smelt- (BZP) was based on a two stage smelting process in the TSL furnace

Zn Metal

Traditional Roast-Leach- Electrowinning

Electrowinning Plant
Purified Zinc Traditional Residue
Solution
Leach Treatment
Solution
To further
Purification Haematite
Treatment or

Zinc Concentrates Roaster

Neutral
Recovered Zinc Solution

Primary Leach
Residue Strong Leach
(hot, acid)
Goethite
Jarosite
Electrolytic
(unknown)
} Dumping

Leach
Residues
Primary Leach Residue
(contains zinc-ferrite –ca.20%Zn)

Ausmelt TSL Residue Ausmelt ZnO Fume Ausmelt

Treatment Zn Fumer ZnO Fume Zn Fumer
Ausmelt TSL Residue
(alternate route) Benign Slag
Treatment
Disposal or (current route) Benign Slag
Sale (Disposal/Sale

Fig. 1. Commercialized TSL zinc technology solutions for processing zinc residues.
744 J. Hoang et al. / Minerals Engineering 22 (2009) 742–751

Pb Feeds

HIGH Pb
SLAG
Fume Leaching Zn/Pb Fume
Plant

Pb TSL
QSL FUME
Plant
Zn Plant Pb RESIDUE

SLAG
BULLION
GEOTHITE

Cu TSL Cu Pb Refinery
Plant DROSS

TSL Tailings
3 TSL Zn Fumers TSL QSL Fumers
Fumers

Discard Slag Cu Pb

Fig. 2. Korea Zinc’s integrated flowsheet using TSL Technology to recover zinc and lead from various slags and residues created during primary zinc and lead concentrate
processing producing benign discard slags while complying with all South Korean environmental legislation.

(Buckett and Sinclair, 1998). It was shown that high levels of zinc carbonate, whereas zinc dissolves as a zinc–amine complex. After
(>50%), lead (>90%) and silver (>90%) are recovered as fume in solution purification (by cementation using Zn-dust), the zinc is
the 1st Stage smelting process, with the majority of the balance recovered from solution by steam distillation of the ammonia
of the zinc (>40%), lead (<5%) and silver (<10%) recovered in the and precipitation of zinc in the form of a basic zinc carbonate.
2nd Stage reduction/fuming step. It was observed that in excess The distilled ammonia is absorbed and re-circulated.
of 5% of the sulphur input reported as sulphate to the Stage 1 fume, In order not to contaminate the closed ammonia solution circuit
principally due to sulphatisation of the lead present in the Stage 1 with sulphate, the ZnO fume is pre-leached in an alkaline Na2CO3-
fume in the gas handling system. solution in order to remove sulphate in the form of Na2SO4. While
In the BZP process the treatment of the lead-rich ZnO fumes was the selected treatment of the fume by the above method was ideal
conducted via a hydrometallurgical ammoniacal leaching process due to its small scale (i.e. pilot plant scale), it is disadvantageous
(ammonia–ammonium carbonate (AAC)-leach solution). The when used in large scale due to its economics and intermediate
advantage of this process is its good separation of the lead from residue streams etc. Due to renewed market interest coupled with
the zinc, as lead largely remains un-dissolved in the residue as lead the expected growth in the supply of concentrates that cannot be

Zn Metal
~103,000t/a
Fuel Coal Zinc Sulphide Concentrates (200,000t/a)
Lance Air Silica and Limestone Fluxes (according to Figure 4)
Lance Oxygen Reductant Coal Electrowinning
Shroud Air
Traditional Roast-
Ausmelt
Leach-Electrowinning
Sulphur
Smelting ca. 12% SO Capture Plant Solution
Furnace Purification
(1250 oC) Gases

Fuel Coal Liquid Slag

Offgas
Lance Air Washing/
Reductant Handling Fume (ZnO) Leach
Lance Oxygen Roasting
Coal System
Shroud Air
Optional

Ausmelt
Cu Matte/Metal Reduction ca. 0.3%SO2
Residue
(To Cu Smelter) Furnace (To Pb Smelter)
(1300 oC)
Recycle Diluent Slag
Discard Slag (~3% Zn)

Fig. 3. Conceptual flowsheet for zinc sulphide processing (the block on the right is the front end of a traditional zinc hydrometallurgical plant – hence the DZS process can run
parallel to a RLE route extending an old processing plant’s life with dumping issues).
 J. Hoang et al. / Minerals Engineering 22 (2009) 742–751 745

readily processed in the traditional RLE process, a process was according to Fig. 5 e.g. by slag recycle or zinc residues and oxy-
developed in which zinc is recovered from ZnS concentrate by gen partial pressure.
the direct ZnS concentrate smelting/volatilization in a Top Sub-  During the reductive Stage 2 the slag, which contains around
merged Lance (TSL) furnace process. The recovered zinc in the form 25% zinc, is fumed to produce ca. 3% zinc in slag producing zinc
of a crude zinc oxide product is suitable to be treated by the con- vapour. 40% of Stage 2 slag is recycled back to Stage 1 to dilute
ventional zinc RLE process. This will be discussed in more detail the zinc content in the smelting Stage 1 to 25%. The basic equa-
in the next section. tion is: ZnO þ C ¼ ZnðgÞ þ COðgÞðDG 1300  C ¼ 101:7 kJ=molÞ
controlled by the slag chemistry of Fig. 6.
2. Features of the Direct Zinc Smelting (DZS) Process  The zinc vapour is reoxidized according to ZnðgÞ þ 0:5O2 ðgÞ ¼
ZnOðDH 1750  C ¼ 455:5 kJ=molÞ, which is highly exothermic.
In this section the various main operating steps of the DZS pro- The dust is collected in a Bag-house or electrostatic precipitator
cess are presented and discussed in some detail based on a (ESP) optionally washed to remove halides/sulphate/lead and
200,000 t/a feed rate of concentrate. The main steps of the DZS pro- subsequently leached in a neutral leach leaching circuit (which
cess are depicted by Fig. 3 noting that the furnace details are de- could be an available RLE circuit).
picted in Fig. 4:  The created SO2 is converted to sulphuric acid, while all other
particulates are collected to environmentally acceptable levels.
 During Stage 1 the zinc concentrate is smelted and zinc fumed
directly as zinc metal. The basic reaction is: ZnS þ O2 ðgÞ ¼ To remove lead, halides and sulphur from the fume it can be co-
ZnðgÞ þ SO2 ðgÞ ðDG 1250  C ¼ 168:1 kJ=molÞ. Oxygen and air treated in the roaster of a RLE if this is operating parallel to the DZS
pass through the TSL lance, while the concentrate and fluxes process, otherwise a leaching step could be used to remove halides,
are fed through the roof of the furnace. Conditions are controlled sulphates, etc., which would however make Na2SO4 recovery (or

Fig. 4. A typical TSL furnace showing among others dimensions, architecture, lance structure, refractories, cooling panels, taphole, boiler system, and the basics of the lance
operation.
746 J. Hoang et al. / Minerals Engineering 22 (2009) 742–751

SiO2 - FeO - ZnO - CaO - Al2O3 - O2

o -8
1250 C, p(O2) = 10 atm, mass CaO/Z = 0.1,
mass Al 2O3/Z = 0.08, Z=(SiO2+FeO+ZnO)
SiO2
Slag-liquid + SiO2(s4) + CaAl 2Si2O8(s2)

0.9

0.1
0.8

0.2
0.7

0.3
Slag-liquid + SiO2(s4)

0.6

0.4
0.5

0.5
Slag-liquid
Willemite + Slag-liquid
0.4

0.6
Spinel + Willemite + Slag-liquid
0.3

0.7
Spinel + Slag-liquid + Willemite + Zincite Spinel + Slag-liquid
0.2

0.8
Spinel + Zincite + Slag-liquid
0.1

0.9
Spinel + Slag-liquid + Zincite + Ca2SiO4(s2)

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

ZnO FeO
mass fractions /(SiO2+FeO+ZnO)

Fig. 5. Simplified slag phase relationships for zinc direct smelting (Stage 1 at 1250 °C) in a TSL furnace showing the Slag-liquid area and typical operating point for smelting
conditions. Note that only a few major components were selected, i.e. FeOx, CaO, ZnO, Al2O3, and SiO2 (FeO must be read FeOx).

other means) from the leach solution necessary to control the sul- The reduction of the zinc level in Stage 1 slag is vital, since a
phur balance of the leaching circuit. high ZnO content increases the slag melting point and decreases
the fluidity. It has been demonstrated that by maintaining the suf-
2.1. Stage 1: smelting at 1250 °C ficiently low partial pressure of O2 during Smelting Stage 1 up to
25% Zn in slag can be tolerated with ease as shown by the large liq-
In the first stage, the concentrate is introduced to a starter slag uidus area in Fig. 5 for the given concentrations of lime and alu-
bath, whereby the smelting of ZnS concentrate under controlled mina in the slag. Furthermore, a low partial O2 pressure prevents
partial oxygen pressure conditions begins according to the theoret- the oxidation of ferrous oxide in the slag to ferric oxide the latter
ical considerations elaborated on by Yazawa (1979). A substantial combining with ZnO to form high melting zinc ferrite (bottom right
part of the zinc is eliminated by volatilization as metal vapour, corner in Fig. 5). In addition lime is added to the slag in order to
which is subsequently post-combusted to zinc oxide fume. From increase the activity coefficient of zinc.
our industrial experience the zinc content in the slag should in The process gas of Stage 1 Smelting is rich in SO2 (12 vol.%).
practice not exceed 25% to ensure that the liquidus temperature After heat recovery in a Waste Heat Boiler (WHB) and separation
is sufficiently low. Fig. 5 reflects (noting that the diagram simplifies of the fume by Bag-house or ESP, the process gas is wet-gas-
the industrial situation due to only considering the given slag com- cleaned, further treated if required, and then processed in an acid
ponents) that at the smelting conditions a maximum theoretical plant to produce sulphuric acid.
limit is around 37% as limited by the phase fields around the mol-
ten slag phase field at 1250 °C and pO2 = 108 atm (FactSageTM, 2.2. Stage 2: reduction at 1300 °C
1976–2007). However, this scenario can change sharply if much
higher Zn contents in the slag are achieved i.e. the operating point The Zn content of the Stage 1 slag is reduced from 25% to ca. 3%
moves into the adjacent fields that contain among others precipi- by volatilization reduction/fuming. The volatilized zinc is post-
tated phases. The pO2, which can be controlled well in a TSL fur- combusted and collected from the fume as ZnO dust. The bulk of
nace, must also ensure that the magnetite levels are controlled the remaining zinc is eliminated via the slag in Stage 2. This slag
well as shown in the phase field around FeOx (bottom right) to en- has a final zinc content of between 1% and 3% Zn, which represents
sure that the slag remains liquid. The Zn-content of the slag is also 1% of the original feed as the total zinc recovery is 99%.
controlled by the pO2 as well by the well-controlled internal recir- Fig. 6 gives only a thermodynamic indication of the reduction
culation of slag from Stage 2 containing only ca. 3% Zn. This dilutes step as it must be noted that fuming in a TSL furnace is also kinet-
the Zn content of the Stage 1 smelting slag. Note that about 60–65% ically driven due to the large volume of gas flowing through the
of the zinc input is eliminated during Stage 1. slag. This figure does show a large molten phase field in which zinc
 J. Hoang et al. / Minerals Engineering 22 (2009) 742–751 747

SiO2 - FeO - ZnO - CaO - Al 2O3 - O2

o -11
1300 C, p(O2) = 10 atm, mass CaO/Z = 0.2,
mass Al 2O3/Z = 0.08, Z=(SiO2+FeO+ZnO)
SiO2

0.9

0.1
Slag-liquid + SiO2(s4)

0.8

0.2
0.7

0.3
0.6

0.4
Slag-liquid
0.5

0.5
0.4

0.6
Slag-liquid + gas_ideal
0.3

0.7
Slag-liquid + Fe(s2)
0.2

0.8
Slag-liquid + gas_ideal + Fe(s2)

Slag-liquid + gas_ideal + Ca 2Al 2SiO7(s)

0.1

Slag-liquid + Spinel + gas_ideal + Fe(s2)

0.9
Slag-liquid + gas_ideal + Spinel

Slag-liquid + CaAl2O4(s) + gas_ideal

ZnO 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 FeO
mass fractions /(SiO2+FeO+ZnO)

Fig. 6. Simplified phase relationships for the reduction Stage 2 at 1300 °C in a TSL furnace for the components FeOx, CaO, ZnO, Al2O3, and SiO2 (FeO must be read FeOx) and the
typical operating point.

Concentrate (~52% Zn, ~7% Fe, 1-2% Pb) Ausmelt Smelting

Furnace
Recycle Diluent Slag to Control Slag Chemistry (~1250oC)

Liquid Slag
~25% Zn
Molten Slag
Optional
Holding Batch Ausmelt Reduction
Furnace Recycle Furnace
(single (~1300oC)
furnace)

Slag Heel
Discard Slag
Ladles ~3% Zn
Molten Slag
Optional Molten Transfer

Solid Granulated Slag

Granulation Final
Discard Slag
Fig. 7. Optional transfer methods for diluting the Zn in slag. (Slag recycle can be replaced by the use of zinc containing residues to control the slag chemistry.)
748 J. Hoang et al. / Minerals Engineering 22 (2009) 742–751

partially also exists as metal vapour at the simulated conditions at Table 1

1300 °C and pO2 = 1011 atm (FactSageTM, 1976–2007). Changes in consumptions using molten slag recycle instead of solid for 200,000 t/a
feed and 40% slag recycle.

2.2.1. Stage 2: slag recirculation Consumptions % Change

A proportion of the total slag that is generated is re-circulated to Lump coal 9.16
Stage 1 smelting in order to dilute the Stage 1 slag to achieve the Fuel coal 19.38
required zinc levels in the slag as dictated by the slag chemistry de- Lance air 10.57
Lance oxygen 11.59
picted by Fig. 5. The simplest way to perform the recirculation is, Shroud air 6.93
obviously, to granulate the second Stage 2 slag and to re-circulate
the required quantity to Stage 1 smelting. In order to ensure suffi-
cient Stage 1 slag dilution, the quantity of slag to be re-circulated leach residue) could be used as diluents for the Stage 1 slag, hence
can be high, i.e. about 40% of the concentrate feed based on a making slag recycling unnecessary. Their high iron content would
52% zinc containing concentrate of ZnS. be favourable the slag metallurgy of TSL. This would be the most
Obviously the granulated re-circulated slag needs to be re- attractive solution as it does process the old residue material with
melted consuming energy in the form of coal. An alternative would the advantage that it alleviates capacity issues as well is unlocks
be not to granulate the Stage 2 slag but to re-circulate it in the li- the metal value in it e.g. indium that left RLE route through this.
quid state to the Stage 1 Smelting, of which there are two options
available, either by ladle transfer or by batch operation keeping the 2.2.2. Metal phase generation during Stage 2
molten slag bath as a starter heel for the next cycle (see Fig. 7). Under the reducing conditions of Stage 2 as well as in the ab-
The benefits of using molten slag recycle (ca. 80,000 t/a) may sence of sulphur a metallic phase will be formed collecting the
present some engineering issues that need to be addressed and non-volatile reducible elements such as copper and (residual) sil-
weighed against the extra costs of solid slag recycle. Fig. 8 shows ver. In addition, gold, if present, would also be recovered to a large
the energy balance in a system with cold slag recycle and Table 1 extent in the metal phase as will (residual) arsenic.
shows the changes when changing to molten slag recycle to help The entrainment of non-volatile inert solids with the process
gauge the relative cost benefits of liquid slag recycle. It can be seen gas during the direct Smelting of ZnS concentrates amounts to
that as the coal fuel contribution to the energy balance is only min- about 1.6% of the non-volatile fraction of the total input, distrib-
or (4%) as compared to the contribution from the concentrates, and uted equally (50%) between Stages 1 and 2. As a consequence the
the enthalpy of reaction, there is only a marginal (10%) gain in dilution of the ZnO fumes by inert material will be quite low.
fuel and energy costs from using molten transfer as opposed to so- The fume is expected to contain 1–2% inert material (Fe2O3, SiO2,
lid slag transfer. This is however reflected in a 10% decrease in the Al2O3, MgO, etc.).
heat available for recovery in the offgas. Molten transfer may only
be of use where energy costs are extremely high, or the sulphur 2.3. Element distribution
content of the concentrates (the main source of energy) is lower
than usual. The distribution of various elements is summarized by Table 2,
Note as well that zinc containing residues such as jarosite (ca. which provides an overview of the degree of volatilization of
3% Zn), goethite (ca. 6% Zn), neutral leach residue (ca. 20% Zn), Elec- important elements in the feed. A more detailed discussion follows
tric Arc Furnace dust (>25% Zn) can be used to control the slag below as well as a general flow sheet for the leaching is depicted by
chemistry, as these also contain Fe. This has the advantage that res- Fig. 9. Various of these elements are recovered as sulphides under
idue ponds can be processed recovering e.g. In but also contained sulphide smelting conditions (e.g. AgS(g), SbS(g), InS(g), etc.) or un-
zinc and freeing up land. This would make slag recycling der reducing conditions fumed off as metals that re-oxidize and re-
unnecessary. port to the zinc fume as oxides (HSC, 1974–2007), while copper
Although molten slag transfer has its merits, it does detract will report to a metal phase during reduction.
from TSL’s commercially proven environmental track-record due
to it being a closed system, as zinc and other metals could fume 2.3.1. Non-volatile accompanying elements/compounds
from open ladles. Therefore, due to environmental reasons, granu- Non-volatile accompanying elements or substances are:
lated slag transfer would be recommended.
If DZS were operating parallel to an existing RLE plant, the iron  Fe, Cu, Ni, Co, Au, Mn, Cr, and
containing residues that are created (jarosite, goethite, neutral  SiO2, Al2O3, CaO, MgO, and TiO2.

Fig. 8. Indicative energy balance in the smelting furnace based on 200,000 t/a concentrate feed (52% Zn) in Figs. 3 and 7 and ca. 40% cold slag recycle as depicted by Fig. 7.
 J. Hoang et al. / Minerals Engineering 22 (2009) 742–751 749

Table 2
Approximate behaviour of elements during direct smelting of ZnS concentrates.

% of input with conc. Zn Pb Ag Cd As Sb Cl In Ge Hg S

Stage 1 62 93 87 68 72 24 100 63 59 100 7
Stage 2 37 6 12 27 17 62 0 31 35 0 0
Total volatilized 99 99 99 95 90 86 100 94 94 100 100
Reporting to Zn fume 99 99 99 95 90 86 100 94 94 0 7
Reporting to metal/speiss 0 0 0 0 6 5? 0 3 3 0 0
Reporting to discard slag 1 1 1 5 4 9 0 3 3 0 0

These elements will report either to the slag or to the metal al-  Bleed of solution: Cl, Na, and K (the latter two only present at
loy phase (Cu, Au). This means that their presence in the ZnS con- low concentration in ZnS concentrate).
centrate, even at more elevated concentrations, will not
significantly affect the Zn-winning process. Of the valuable ele- It must be noted that some sulphate is created in the zinc fume
ments only Cu and Au will be recovered, while Ni and Co are ex- e.g. insoluble lead sulphate but also soluble sulphates that do affect
pected to be lost with the slag as will be manganese and the sulphur balance in the leaching circuit, which will therefore
chromium. The fact that especially Fe and Mn (and some of the have to be bled from the system as gypsum. This does have a neg-
gangue oxides) are recovered to a benign slag makes this an extre- ative economic impact.
mely interesting process route as these are problematic during RLE.
2.4. Leach liquor purity affecting current efficiency
2.3.2. Volatile accompanying elements
Volatile accompanying elements are: The most critical issue for the ZnO fume leach process is the
ability to produce a purified solution at acceptable costs in order
 Zn, Pb, Ag, Cd, As, Sb, In, Ge, Tl, Se, (Te) and probably Sn, and to be able to achieve high current efficiencies during zinc electro-
 Cl, F, Na, K, and Hg. winning. The concentrations of very critical impurities such as Co,
Ni, In, Ge, As, Sb, and Tl must be sufficiently low in order to be able
With the exception of Hg, all of these elements will report to the to purify the neutral leach solution to the very low concentrations
ZnO fume in a more concentrated form. The degree of collection to required for electrowinning, all obviously at a reasonable or
the fume might vary due to the difference in volatility as a function acceptable cost.
of whether the dry gas cleaning is performed at a higher tempera-
ture ESP or at lower temperature in a bag-filter. This has an impact 2.5. Special considerations with regard to lead and tin
particularly on Cl and F, as well as possibly also Se.
All of these elements will dissolve up to their solubility level Since there is a high lead recovery in this process, high lead con-
during the sulphuric acid ZnO fume leaching process (Fig. 9), which taining ZnS concentrates could create a zinc fume with high sulph-
is low for Pb, Ag, Sb, and Sn, which will therefore mainly report to ated lead content (or rather partially sulphated lead) as well as
the Pb/Ag residue. The other elements are removed from the leach PbO. This would create a PbSO4 product that would need further
circuit by means of: processing as suitable separation of sulphur and lead may not have
been achieved. This would necessitate additional processing steps
 Selective precipitation from the (weak acid) leach solution in the which could be readily undertaken in a conventional TSL lead
case of As, In, Ge and residual dissolved Sn, smelter thereby realising the lead and silver credits.
 Cementation during the neutral leach solution purification: Cd, Tin is rarely present in ZnS concentrate. However, since tin can
traces of As, Sb, Se and Tl, and be volatilized as SnS(g) (as in the tin fuming process) or as SnO(g)

Fig. 9. Flowsheet for the sulphuric acid leaching of the ZnO fume from the DZS process with an optional dehalogenation leaching step shown.
750 J. Hoang et al. / Minerals Engineering 22 (2009) 742–751

(as in the converting process for black copper in the secondary cop- cessing of residues originating/slags from primary hydrometallurgi-
per smelting process) it may be assumed that tin will report to a cal and pyrometallurgical processing of zinc and lead concentrates.
large extent to the ZnO fume. During the sulphuric acid leaching The DZS process as proposed and discussed has the potential to
of the fume tin will dissolve in the leach solution up to its solubility provide excellent metallurgical performance that recovers 99% of
level. The removal of dissolved tin from sulphate leach liquors is the Zn to a high grade ZnO fume, which is better than any other
believed not to be without any problems. Since generally tin is known metallurgical process. The major economic benefits are
not present in ZnS concentrate information on the purification of the use of sulphide sulphur (instead of fossil fuel) as the energy
neutral leach solution with regard to tin is extremely scarce. A ded- carrier and the ability to fume the zinc from the Stage 1 slag, with-
icated process for tin removal may be required, particularly with out the need to remelt the slag. In addition, the DZS process en-
regard to the difficulty of separation of the hydrolyzed gelatinous ables the high recovery of Pb, Ag, Au, In, Ge, and Cu, which only
tin precipitate. As a similar condition would apply in the case of could be recovered up to a level of 50–70% by the conventional
the RLE process, it is not expected that the DZS process would pres- RLE process (including residue treatment). In excess of 99% of Pb
ent a particular disadvantage as compared to the RLE process with and Ag input will report to the fume, with Ge and In ranging from
respect to tin behaviour. 90% to 95%. This is superior to any other known process, including
the Waelz kiln process. It is subsequently relatively easy to recover
2.6. Economic and environmental advantages these values from the fume, provided their concentrations are suf-
ficiently high, ensuring that revenues exceed the cost of their
The cost of residue deposition has often been an argument in fa- extraction from the fume. The elements As and Sb will also concen-
vour of the implementation of processes which do not generate trate into to the fume. These two elements can be eliminated either
residues but valuable products. For example metallurgical slags with the Pb–Ag residue (when leaching the fume) or be separated
could be used as building materials or can safely be deposited as as a separate residue depending on whether or not the recovery of
they pass elution criteria in a much reduced volume than precipi- In/Ge is economically warranted. About 93% of the sulphur input
tates from hydrometallurgical processing. However, the cost of will be recovered as sulphuric acid, which is similar to the recovery
deposition of a wet solid residue (e.g. gypsum sludge, jarosite, of sulphur in the conventional RLE process.
etc.) in 2008 for Europe is assumed not to exceed €20/t of dry The DZS process provides distinct metallurgical and economic
material.1 If the residue is stabilized with cement at an addition of advantages with reference to the RLE process for the processing
about 15% by weight of dry residue, and the stabilized residue is of ZnS concentrates that have higher concentrations of non-volatile
stacked on a tailor-made pad area, the deposition costs are expected elements/compounds than the usual level encountered in ZnS con-
to be slightly higher but not to exceed €25/t of dry material.2 It may, centrates which are used in the RLE process. These refer in partic-
therefore, be concluded presently that the cheapest way of disposal ular to Fe, Mn, SiO2, MgO but also to Ni, and Co, which in the DZS
of wet solid residues is by ponding, or in a stabilized form. process report to a benign slag, making this extremely interesting
However, the real issue with regard to the deposition of resi- for processing of high manganese and iron containing zinc ores.
dues is not the cost of deposition itself, but the possibility of depo- Increasing dumping costs, the lack of dumping space and the
sition, i.e. this is affected by public opinion, public awareness and non-issue of dumping permits in certain parts of the world are
ever increasing education concerning issues around environment, likely scenarios that will and does already confront the zinc indus-
scarcity of land and past failures due to improper handling or solid try in an ever increasing environmentally conscious playing field.
waste mismanagement, just to name but a few issues. These issues This provides an interesting inclusion within the basis for compar-
have led the authorities to introduce legislative barriers, which are ison between the economics of the DZS vis-à-vis the RLE process,
a deterrent to the implementation of new residue ponding facilities especially also if the positive aspect of harnessing the sulphur as
and extending new licenses (e.g. Belgium) or prohibiting them in energy carrier is considered in the analysis.
total (e.g. The Netherlands). The introduction and application of In summary, the DZS process is a (virtually) residue-free process
eco-taxation for residue deposition is an example of a deterrent. that can be tailored to the needs of the zinc smelting industry, run-
It is expected that, in future, new operations generating wet solid ning possibly also parallel to classical RLE routes to clean up resi-
residues will not be granted permission to be erected in areas of due ponds and extend the life of well established RLE site. The
dense population, or suitable for agricultural and other industrial slag, which is generated as an environmentally friendly benign
applications. These issues will all increase these deposition costs slag, can be valorised to meet increasing strict environmental con-
and hence the industry does need to act now. Due to dynamic trol for the disposal of metallurgical intermediate residues.
change in zinc prices and changing treatment charges it is re- Potentially running RLE and DZS in parallel does increase the
frained from providing an exact analysis, but DZS does become flexibility of a present facility to process a wide variety of feeds
attractive at relatively low dumping costs. including residues and hence does lengthen the present life of well
established RLE sites by decreasing their reliance on jarosite/goe-
3. Conclusion thite ponds. In addition, a wealth of metals present in the residues
such as indium will be recovered.
Since the early 1980s Ausmelt has been developing novel pro-
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