Continuous Fuming of Zinc-Bearing Residues: Part II.

The Submerged-Plasma Zinc-Fuming Process

KAREL VERSCHEURE, MAURITS VAN CAMP, BART BLANPAIN, PATRICK
WOLLANTS, PETER HAYES, and EVGUENI JAK

A new high-temperature submerged plasma zinc-fuming process has been developed for the
treatment of zinc leach residues, electric arc furnace (EAF) dusts, and other zinc-containing
waste materials. Continuous operation of this process requires high zinc-fuming rates while
retaining vessel integrity through the formation of a stable freeze lining. A zinc-fuming process
model using the FactSage thermodynamic databases and ChemApp thermodynamic software
has been developed, which simultaneously describes chemical, thermal, and heat-transfer out-
comes of this process. The model has been used to systematically investigate the potential effects
of operating parameters such as feed composition, fuel/oxygen ratio, electrical power and
fluxing parameters on bath temperature, heat loss, Zn concentration and content in slag, Cu
concentration, and content in matte.

DOI: 10.1007/s11663-006-9010-5
 The Minerals, Metals & Materials Society and ASM International 2007

I. INTRODUCTION is required before the mixture can be fed in the shaft

THE disposal of zinc-containing wastes is a matter of
increasing concern to the metallurgical and wider
community as the environmental impact associated with
these materials is more clearly appreciated. Major
sources of these materials at present are zinc leach
residues and electric arc furnace (EAF) dusts. The
development of technologies that can provide technical
and economic solutions to the processing of these
materials remains an ongoing problem.[1,2,3] In the past,
several pyrometallurgical technologies have been devel-
oped to process these materials based on the reduction
and volatilization of heavy metals, such as Zn and Pb.
Waelz Kilns for the treatment of neutral zinc leach
residues and EAF dust are processes using a large rotary
kiln to fume Zn and other volatile species.[4,5] A dried
mixture of residue, coke, and fluxes is injected in the kiln
and progressively heated to 1200 C to 1300 C.[4] Zinc
oxide containing phases are thereby decomposed and
volatile species such as Zn (g), Pb (g), and PbS (g) are
fumed from the solid burden to the gas phase.
The shaft furnace process has been used for treating
zinc leach residues at several electrolytic plants, but is
nowadays rarely used in practice.[6] As with the Waelz
process, the residue has to be dried and mixed with
fluxes and coal, but an additional briquetting operation
KAREL VERSCHEURE, Research assistent, BART BLANPAIN,
and PATRICK WOLLANTS, Full Professors, are with the Depart-
ment Metaalkunde en Toegepaste Materiaalkunde (MTM), Kath-
olieke Universiteit Leuven, B-3001 Heverlee, Belgium. Contact e-mail:
karel.verscheure@mtm.kuleuven.be MAURITS VAN CAMP, Senior
Metallurgist, is with Umicore Research, B-2250 Olen, Belgium.
PETER HAYES, Professor, and EVGUENI JAK, Associate Profes-
sor, are with the Pyrometallurgy Research Centre, PYROSEARCH
School of Engineering, The University of Queensland, Brisbane, Qld
4072, Australia.
Manuscript submitted July 25, 2006.
furnace. As in other zinc-fuming processes, heavy metals
such as Zn and Pb are fumed and postcombusted.
Coke-packed bed reactors are another option to treat
zinc-containing residues.[7,8,9] In this technology, EAF
dust or oxidic waste in powder form along with coal
powder is injected at the tuyere level of a low-shaft
furnace together with a small quantity of preheated
gas.[7,8,9] The shaft of the furnace is filled with coke, and
in front of each tuyere in the lower part of the coke
column, a cavity is formed in which the reaction between
the injected oxide and reducing agent (carbon, CO)
occurs. Liquid metal and slag phases are formed. Zinc
and lead, in contrast, are reduced and evaporated and
leave the furnace with the off-gas.
Conventional zinc slag fuming processes for treatment
of lead blast furnace slags are batch operations in water-
cooled jackets involving tuyere injection of fine, pulver-
ized coal and air into molten slags. The zinc, lead, and
other elements are removed from the slag bath by the
generation of volatile metal species. Supplementary
(tertiary) air is introduced above the slag bath oxidizing
the zinc gas to fine particulate ZnO. The coal acts as
both a heat source, as a result of combustion with the
primary and secondary air, and as a reductant, through
the production of CO gas. This CO is then available to
reduce metal oxides dissolved in the slag phase. The
chemistries of these lead blast furnace slags may be
described by the simplified system CaO-FeO-Fe2O3-
SiO2-ZnO with CaO/SiO2 between 0.7 and 1.2.[10] The
initial zinc oxide concentrations in these slags are in the
range 15 to 20 wt pct ZnO, and the liquidus tempera-
tures are in the range 1150 C to 1250 C. The rates of
reduction of these slags progressively decrease with
decreasing zinc oxide concentration in the slag.[11,12]
Typical limits of the zinc concentrations in the output
are 1 to 3 wt pct.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 38B, FEBRUARY 2007—21

 The Ausmelt process is a technology in which zinc is
removed in one or two submerged lance fur-
naces.[13,14,15] Dried residue, coal, and fluxes are fed
into a first submerged lance furnace, the smelting
furnace, to fume part of the Zn and Pb from the slag
and to remove sulfur as SO2. The molten slag contin-
uously overflows into a second Ausmelt furnace, the
fuming furnace, where the remaining zinc is fumed to
levels down to 3 wt pct Zn in slag.
Various processes using electrical power have been
developed to treat zinc-containing residues.[16–20] In the
Primus process,[16] zinc and lead are first fumed in a
reducing roasting step, and an electric furnace is then
used to fume the remaining volatiles and to form a slag
and metallic iron phase. Other examples of processes
using electrical power are the slag resistance fur-
naces[17,18] and the DC arc furnaces.[19,20]
The variety of processes demonstrates that many
approaches to zinc fuming of zinc-containing residues
are possible and have been investigated. In any of these
processes, the challenge is to develop a continuous zinc-
fuming process that
(1) treats finely divided particulate materials;
(2) enables a well-mixed high-temperature slag bath to
be maintained and enables rapid reaction rates to
be achieved;
(3) maintains vessel integrity through the use of freeze
linings and limits heat losses through the reactor
wall;
(4) reduces the environmental impact, through reduced
greenhouse gas and other fugitive emissions, and
produces a benign disposable solid waste product;
and
(5) is an economically viable, industrial-scale process.
The present article describes a new, electricity-based
pyrometallurgical process that has the potential to meet
all of these objectives. The effects of key process
variables on the performance and outputs of the new
process are analyzed using the mathematical process
model presented in Part I of this series of articles.[21]
II. DEVELOPMENT OF THE SUBMERGED
PLASMA PROCESS
A new process for the treatment of Zn-containing
residues is the submerged plasma process. In the
submerged plasma zinc-fuming process (Figure 1), elec-
tric plasma torches supply process heat and good mixing
conditions to the slag bath. Inside the plasma torches,
the cold blast air is transformed into a high enthalpy
plasma gas. Plasma gas is then mixed with natural gas
(CH4) and injected into the slag bath. Parallel to this, a
mixture of leach residue, petroleum coke, and fluxes is
fed continuously into the slag bath. A small fraction of
Cu cement, a co-product of the hydrometallurgical
production of Zn, is also added to the residue. The solid
feed dissolves into the molten bath; blast gases react
with the slag and reductant; and Zn and other volatile
metals fume off. Above the bath, the fume is post-
combusted with a slightly understoichiometric amount
22—VOLUME 38B, FEBRUARY 2007
Fig. 1—Schematic of the submerged plasma process for the
high-temperature fuming of zinc from zinc-containing residues.
of secondary air, and the resulting off-gases and solid
ZnO particles are removed from the smelting vessel.
After the postcombustor, the off-gas is further oxidized
with air in a radiation chamber and treated in an
electrostatic precipitator to recover ZnO. Part of the
heat generated in the postcombustion is transferred back
to the slag bath, resulting in increased energy efficiency
of the process. The outputs of the process are a slag
phase, a matte phase, ZnO-powder, and off-gas.
In the submerged plasma process, as in conventional
zinc-fuming processes, solid carbon is the principal
reagent used to reduce the metal oxides from the slag
and to maintain a reducing gas atmosphere. The
generation of CO/CO2 gas mixtures results in the release
of heat energy into the bath. In the case of the
submerged plasma process, however, additional enthal-
py is available from the electrical energy introduced in
the plasma; this being the case, the carbon and heat
requirements of the process are separated, i.e., the C/O
and electrical power can be independently adjusted to
optimize the performance of the reactor.
The use of submerged plasmas also allows high slag
bath temperatures (approximately 1300 C to 1400 C)
to be generated; this facilitates high zinc-fuming rates. A
key feature of the new process is the use of high-
temperature freeze linings to contain this slag bath, with
particular emphasis on freeze lining design through the
control of bath chemistry. This ‘‘slag engineering’’
approach is critical in achieving the desired operating
temperatures. Highly superheated fayalite slags are
aggressive and readily dissolve conventional refractory
materials, thereby limiting the maximum operation
temperatures of conventional slag fumers. The use of
freeze linings that are formed on the reactor wall,
backed by the water-cooled steel furnace shell, contains
the slag bath. The downside of using such freeze linings
is the potential for increased enthalpy losses to the water
cooling system due to the high superheat of the slags.
The challenge is to engineer or select a slag chemistry
that will provide a stable protective furnace lining and
also minimize heat losses through the shell. The model
described in Part I of this series of articles[21] is a unique
tool to investigate the effect of slag chemistry on the
freeze lining and on the outcomes of the process.
METALLURGICAL AND MATERIALS TRANSACTIONS B
 The submerged plasma process can be used to treat
zinc leach residues and other zinc containing wastes such
as EAF dusts. Umicore[22] is licensing the submerged
plasma technology for treatment of EAF dust through
ScanArc.[23] The first industrial plant was built by
ScanArc for ERAS[24] and started operation in 2005 in
Høyanger, Norway.
III. KEY FEATURES OF THE SUBMERGED
PLASMA PROCESS
There are several features of the new submerged-
plasma process that should be emphasized. As in other
metallurgical zinc-fuming processes, a balance must be
maintained between the thermal and reductant require-
ments. In the submerged plasma, carbon is used. The
temperature attained by the smelting bath will depend
on the C/O ratio, where O in this context is defined as
the sum of the oxygen in the blast air and reducible O in
the feed.
The relationship between adiabatic flame temperature
and C/O ratio is shown schematically in Figure 2. For
C-O reaction only, the maximum bath temperature is
attained at a stoichiometric ratio of C/O = 0.5, i.e., all
of the carbon is combusted to form CO2. If excess
oxygen is provided, then the bath temperature decreases
because the excess oxygen (and associated nitrogen in
air) has also to be heated to temperature. If the C/O
ratio is greater than 0.5, the gas will contain mixtures of
CO and CO2; the enthalpy change associated with CO
production from carbon is significantly less than CO2, so
the maximum bath temperature and available enthalpy
for the fumer are decreased as the C/O molar ratio is
increased above 0.5. The benefit of using a high C/O
ratio is that the CO gas may be used to carry out
chemical reduction of metal oxides present in the slag.
Carbon then provides thermal energy and acts as a
reductant.
In the submerged plasma processes, an additional
heat source is available—electrical energy is converted
Fig. 2—Adiabatic flame temperature and PCO2 =ðPCO þ PCO2 Þ ratio vs
C/O molar ratio for combustion of solid carbon (graphite) in air
(calculated with FactSage).
METALLURGICAL AND MATERIALS TRANSACTIONS B
to thermal energy, with a relatively small amount of gas.
The electrical power of the plasma torches can be
increased up to the maximum energy input level, where a
further increase of electrical power should be accompa-
nied by an increase of blast air. The latter is due to the
technical limitations on the ‘‘energy density’’ in the
carrier gas. The availability of this additional source of
thermal energy effectively makes it possible to carry out
reduction of the metal oxides at higher bath tempera-
tures at more reducing conditions with smaller gas
volumes than can be achieved in conventional zinc
fuming using only carbon as fuel.
The principal mechanism of zinc removal from the
slag to gas phase is through the production of Zn gas
species; the reaction is expressed as
ZnO (slag) þ CO (g) ! Zn (g) þ CO2 (g) ½1
At equilibrium,
PCO
PZn ¼ K1   aZnO ½2
PCO2
where K1 is the equilibrium constant of Reaction [1].
For this endothermic reduction reaction, high zinc
vapor pressures are favored by high temperatures, high
(CO/CO2) ratio in the gas phase, and high activities of
zinc in the slag. The high PCO/ PCO2 ratio corresponds to
a low oxygen partial pressure in the gas phase.
Continuous operation of zinc-fuming processes
requires high fuming rates down to low zinc concentra-
tion in the slag. To achieve these objectives, high process
temperatures (about 1350 C), low oxygen partial pres-
sures, and good mixing of the bath are essential. High
temperatures, however, drastically shorten the lifetime
of the conventional furnace linings. In the new zinc-
fuming processes, this is overcome through the use of
water-cooled freeze linings on the smelting reactors. The
design of these freeze linings is crucial for the technical
and economic feasibility of the process; stable freeze
linings are obtained through the control of bath
chemistry.
IV. MODEL PREDICTIONS
In the following section, the submerged plasma zinc-
fuming process and its sensitivity to changing process
conditions are systematically investigated using the
model described in Part I of this series of articles.[21]
The present study includes the effects of fuel and power
input, bath chemistry, throughput, and bath level. For
the predictions, the reactor characteristics listed in
Table I were adopted. A summary of the symbols used
in Table I is given at the end of this article. The sidewalls
of the bath are freeze lined, and the bottom of the
furnace, which is in contact with the matte phase, is
protected with a thick refractory and insulation layer.
The refractory and insulation layers contribute to the
total thermal resistance Rbottom. The sidewalls and roof
of the postcombustor are covered with a layer of dust
VOLUME 38B, FEBRUARY 2007—23
 Table I. Reactor Characteristics for the Submerged Plasma Process*
Geometry (m) Thermal Conductivities (W m)1 K) Thermal Resistances (K W)1)
rrefr,sw 1.70 kfl 3.4 Rbottom 0.02080
rshell,in 1.75 kins,bottom 2 Rsw 0.00095
rshell,out 1.76 krefr,bottommmm 4 Rroof 0.00320
tins,bottom 0.2 krefr,roof 2
trefr,bottom 0.4 krefr,sw 2 Temperatures (K)
trefr,roof 0.05 kshell 60.5 Twater 313
tshell 0.01
zbath 2 Heat-Transfer Coefficients (W m)2 K)
zpc 3 hbath 1000
hpc fi roof 200
hpc fi sw 200
hpc fi zf 700
hwater 1500
*The dimensions and shape of the cylindrical model furnace do not correspond to the schematic representation of the submerged-plasma furnace
in Fig. 1. The term rrefr,sw applies to the entire postcombustor section.

and solidified bath material. The thermal resistance of
these deposits was modeled here as a refractory layer
referred to as Rsw and Rroof for the sidewalls and the
roof of the postcombustor, respectively.
A. Base Case Submerged Plasma
An important starting point in the modeling is
selection of the base case—a set of conditions close to
those planned for large-scale industrial operations. The
data collected during the submerged plasma zinc-
fuming pilot plant trials performed by Umicore on
the 750 kg/h reactor have been used as the basis for the
selection of the base case. The averaged process
parameters were scaled up to industrial proportions
and then used for preliminary predictions using the
new model. The parameters were then adjusted, based
on the outcomes of these preliminary predictions, to
achieve realistic operational parameters such as tem-
peratures, heat losses, zinc concentration of the slag,
Cu concentration in the matte, and slag composition.
The selected base case values for the submerged plasma
zinc-fuming process are outlined in Tables II and III.
Unless specified otherwise, all concentrations and
ratios repeated in the following analyses are on a
weight basis.
A key aspect of the process is the use of high bath
temperatures (1300 C to 1400 C) and slags with high
liquidus temperatures. The high liquidus temperatures
can be achieved in practice through targeted fluxing, for
example, in this case, by use of dolomite (Ca,Mg)CO3
flux. The addition of materials that increase the liquidus
temperatures is the reverse of fluxing practice in
convectional slag processing operations using refractory
linings and appears counterintuitive. It should be
remembered that the aim of this slag engineering
practice is to form a freeze lining, a layer of bath
material that protects the furnace wall.

Table II. Material and Energy Inputs for the Submerged Plasma Process in Elemental Form: Base Case; All Inputs Enter the
Process at 25 C and 1 Atm (Bath Size 71.2 t)*
Residue (Wt Pct) Flux (Wt Pct) Fuel (Nm3 h)1)
ZnFe2O4 52.96 CaCO3 54.29 CH4 693.06
ZnSO4 17.91 SiO2 0.57
PbSO4 9.53 MgCO3 39.77 Blast Air
SiO2 4.97 Al2O3 0.61 Nm3 7914
CaSO4 4.63 H2O 4.76
Cu2O 2.19 t h)1 4.99 Secondary Air
Al2O3 1.20 Nm3 11,086
Zn2SiO4 1.11 Reductant (Wt Pct)
MgCO3 0.44 C 95.24 Electric Energy
ZnO 0.16 H2O 4.76 MW 21.6
ZnS 0.09 t h)1 2.65
PbO 0.04
CaCO3 0.01
H2O 4.76
t h)1 22.14
*All energy supplied to the preheater is electrical energy Qel. The energy from other heat sources Qhs is zero. The term Nm3 h)1 refers to the
standard temperature of 273.15 K and pressure of 100 kPa. The density of CH4 at 273.15 K and 100 kPa was taken at 0.7076 kgÆNm)3.

24—VOLUME 38B, FEBRUARY 2007 METALLURGICAL AND MATERIALS TRANSACTIONS B

Table III. Output for Submerged Plasma process: base case.
Tbath = 1349 C, Tliquidus = 1277 C, Tpc = 1596 C, specific
heat loss freeze lining calculated at the water-cooled surface of
the furnace shell = 69.49 kWm)2, thickness freeze
lining = 5.65 cm, Zn fuming rate = 4.50 t h1,
PCO2 =ðPCO þ PCO2 Þ ¼ 0:62
Slag (Wt Pct) Matte (Wt Pct)
MgO 6.75 S 25.5
FeO 37.45 Fe 17.7
SiO2 9.74 Cu 42.9
CaO 13.16 Zn 9.2
Al2O3 2.41 Pb 4.7
MgS 1.90 total (t h)1) 0.89
CaS 3.41
FeS 9.22 Gas (Partial Press, Atm)
Fe2O3 11.43 H2 2.97 · 10)2
PbO 0.07 N2 3.51 · 10)1
ZnO 3.25 O2 1.75 · 10)9
Cu2O 0.35 CO 1.42 · 10)1
ZnS 0.78 CO2 2.30 · 10)1
PbS 0.01 S2 3.68 · 10)4
Cu2S 0.08 SO2 2.32 · 10)3
total (t h)1) 12.28 Zn 8.75 · 10)2
Pb 2.73 · 10)3
PbS 5.78 · 10)3

B. Effect of Fuel Sources

As indicated in the process description, heat energy
(enthalpy) can be introduced into the submerged plasma
zinc-fuming bath by the combustion of carbon in the
bath or by the use of electrical energy in the plasma.
Using the process model, the effects of using these
different sources of energy on the steady-state operation
of the submerged plasma process can be explored.
Figures 3(a) and (b) show how, for a fixed electrical
power input, the bath temperature and liquidus tem-
perature of the slag, respectively, vary with the C/O
molar ratio and the C/feed mass ratio in the zinc-fuming
stage of the process, where O is the sum of the oxygen in
the blast air and reducible oxygen in the feed. Reducible
oxygen in the feed is defined as the sum of all reducible
oxygen from Fe2O3 (i.e., 1 O oxygen atom per molecule
Fe2O3) and the oxygen in PbO, ZnO, Cu2O, and in their
corresponding compounds (e.g., spinels and sulfates).
Using the residue speciation in Table II, it can be
calculated that the total amount of reducible O in the
residue is equal to 135 kmol/h (i.e., 2 O in ZnFe2O4 and
Zn2SiO4, and 1 O in ZnSO4, PbSO4, Cu2O, ZnO, and
PbO). The total amount of O in the blast air is equal to
147 kmol/h, and the total amount of C in the feed is in
total 241 kmol/h. The C/O molar ratio is hence equal to
0.86. Although three extra oxygen atoms of the sulfate
groups are partly liberated through reduction to S, only
one O atom per sulfate group was included in the
definition of reducible oxygen in the present study.
Clearly, alternative definitions are possible. Near the
base case, an increase of C/O leads to a decrease in bath
temperature and an increase in liquidus temperature; at
high C/O ratios, the bath and liquidus temperatures
approach each other. Because this is a continuous
process, slag must be continuously tapped from the
furnace. Clearly, as the bath temperature approaches the
Fig. 3—Bath and liquidus temperatures as a function of C/O and C/
feed for the submerged plasma process. The base case is indicated by
the intersection of the two dashed lines. The primary phase field for
the investigated range of C/O and C/feed ratios is wüstite.
liquidus, one of the limits of operability of the process is
approached, because the freeze lining may become very
thick and reduce the available reactor volume. At the
same time, however, increasing the C/O ratio in the
process leads to lower heat losses through the bath side
wall and increased thickness of the freeze lining
(Figures 4(a) and (b)). From Figure 5(a), it can be seen
that the Zn concentration in the slag is largely deter-
mined by the C/feed mass ratio in the process. From
Figure 5(b), it can be seen that the submerged plasma
process is characterized by relatively high PCO2 =
ðPCO þ PCO2 Þ ratios in the bath; for the range of
investigated operating conditions, this value is in the
range 0.5 to 0.75. This indicates that C is well combusted
to CO2 and contributes substantially to the enthalpy
supply of the process. From Figure 5(b), it can be seen
that the C/feed ratio is also an important factor in
determining the combustion ratio.
Model predictions indicate that maintaining constant
C/O and C/feed ratios in the bath and increasing the
electrical power (enthalpy) input will increase the bath
temperature, and the liquidus temperature of the resul-

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 38B, FEBRUARY 2007—25

Fig. 4—(a) Heat loss freeze lining and (b) freeze lining thickness as a
function of C/O and C/feed ratios for the submerged plasma pro-
cess. The base case is indicated by the intersection of the two dashed
lines.
tant slag will decrease (Figure 6(a)). These changes are
reflected in an increase in heat loss and decrease in freeze
lining thickness with increasing electrical power
(Figure 6(b)).
C. Effects of Bath Chemistry
The effects of changing bath chemistry, through
adjustment of CaO/SiO2 and Fe/SiO2 in the feed to
the zinc-fuming stage, were also analyzed. These
changes in bath composition can be achieved by
changing the mass of CaCO3 in the flux and SiO2 and
Fe2O3 introduced in the residue, but keeping the total
mass of feed, C/feed mass ratio, C/O molar ratio, and
electrical power in the plasma constant.
The effects of increasing CaO/SiO2 on bath and
liquidus temperature, heat loss, and lining thickness are
shown in Figure 7 for base case Fe/SiO2 = 4.50.
Increasing CaO/SiO2 does not greatly change the bath
temperature but leads to modest increases in liquidus
temperatures. The heat losses through the freeze lining
decrease slightly with increasing CaO/SiO2 in the slag.
26—VOLUME 38B, FEBRUARY 2007
Fig. 5—The pct Zn in slag and PCO2 =ðPCO þ PCO2 Þ ratio in the bath
as a function of C/O and C/feed ratios for the submerged plasma
process. The base case is indicated by the intersection of the two
dashed lines.
The steady-state zinc concentration in the slag decreases
almost linearly from 4 to 3 pct with increasing CaO/
SiO2 from 0.5 to 2 (Figure 8). Although the higher Zn
fuming rates (lower final Zn concentrations in the slag)
at high CaO/SiO2 ratios would lead to a decrease of the
bath temperature, this effect is counteracted by the
decreasing heat losses at high CaO/SiO2 ratios. The
result is a modest increase in bath temperature
(Figure 7(a)). From Figure 8, it can also be seen that
copper in matte increases slightly from 39 to 45 pct Cu
with increasing CaO/SiO2 from 0.5 to 2. The Cu
concentrations of the matte, as calculated by FactSage,
are comparable to the Cu concentrations found in the
pilot experiment, although it should be noted that the
initial separation of the matte from slag observed in the
pilot tests was incomplete and an additional decantation
procedure was necessary.
The effects of increasing Fe/SiO2 on bath and liquidus
temperatures, heat loss, and lining thickness are shown
in Figure 9 for base case CaO/SiO2 = 1.61. Increasing
Fe/SiO2 does not greatly change the bath temperature
but leads to a modest increase in liquidus temperature in
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 6—(a) Bath and liquidus temperature and (b) heat loss through
the freeze lining and freeze lining thickness vs electrical power input
of the submerged plasma process. The base case is indicated by the
dashed line. The primary phase field for the investigated range of
electrical power input is wüstite.
moving from Fe/SiO2 3.5 to 5.5. As is the case with
CaO/SiO2, increasing the Fe/SiO2 ratio leads to slight
decreases in heat losses through the freeze lining and
increases in freeze lining thickness (Figure 9(b)). The
steady-state zinc concentration in the slag decreases
almost linearly from 3.3 to 3 with increasing Fe/SiO2
from 3.5 to 5.5, and the copper concentration in the
matte remains almost constant with Fe/SiO2 ratio
(Figure 10).
The effect of changing MgO/feed was also investi-
gated through adjustment of MgCO3 in the flux while
maintaining constant C/feed, C/O, CaO/SiO2, Fe/SiO2,
and Zn/feed ratios with respect to the base case.
Figure 11 shows the effects of MgO/feed on bath and
liquidus temperature, heat loss, and freeze lining thick-
ness. After an initial decrease in bath and liquidus
temperature for the MgO/feed ratio ranging from 0.5 to
1.5 wt pct, the bath and liquidus temperatures increase
significantly for MgO/feed ratios of 1.5 to 4 wt pct.
Similarly, an increase of MgO/feed ratio from 1.5 pct to
4 wt pct results in a sharp decrease of heat losses and
increase of the freeze lining thickness. From Fig-
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 7—(a) Bath and liquidus temperature and (b) heat loss freeze
lining and thickness freeze lining vs CaO/SiO2 ratio in the input of
the submerged plasma process. The base case is indicated by the
dashed line. The primary phase field for the investigated range of
CaO/SiO2 ratios in the input is wüstite.
ure 12(a), it can be seen that the remaining Zn in the
slag decreases from over 4 pct to less than 3 pct and the
concentration of Cu in the matte remains nearly
constant in the range 1.5 to 4 pct MgO/feed. From
Figure 12(b), it can be seen that the Zn fuming rate
increases for increasing MgO/feed rates of 1.5 to 4 pct,
while PCO2 =ðPCO þ PCO2 Þ remains nearly unaffected.
When comparing Figures 8 and 12(a), it can be seen
that an increase of CaO/SiO2 from 0.5 to approximately
1.8 and an increase of MgO/feed from 1.25 to approx-
imately 3.75 both lead to a change in wt pct Zn in the
slag from 4 to 3 wt pct. Increasing the CaO/SiO2 ratio
from 0.5 to 1.8 corresponds to an increase of CaO of
approximately 1356 kgÆh)1 or 24.17 kmolÆh)1, while
changing the MgO/feed ratio from 1.25 to 3.75 pct
corresponds to an increase of MgO of approximately
678 kgÆh)1 or 16.83 kmolÆh)1. From this calculation, it
can be concluded that MgO seems to be a more effective
fluxing agent per mole to promote Zn fuming.
To increase the MgO content of the feed in industrial
practice, dolomite (MgCO3ÆCaCO3) can be added to the
residue. The effects of dolomite flux additions were
VOLUME 38B, FEBRUARY 2007—27
Fig. 8—The wt pct Zn in slag and wt pct Cu in matte vs CaO/SiO2
ratio in input of the submerged plasma process. The base case is
indicated by the dashed line.
Fig. 9—(a) Bath and liquidus temperature and (b) heat loss freeze
lining and freeze lining thickness vs Fe/SiO2 ratio in the input of the
submerged plasma process. The base case is indicated by the dashed
line. The primary phase field for the investigated range of Fe/SiO2
ratios in the input is wüstite.
28—VOLUME 38B, FEBRUARY 2007
Fig. 10—The wt pct Zn in slag and wt pct Cu in matte vs Fe/SiO2
ratio in the input of the submerged plasma process. The base case is
indicated by the dashed line.
Fig. 11—(a) Bath and liquidus temperature and (b) heat loss freeze
lining and freeze lining thickness vs MgO/feed ratio in the input of
the submerged plasma process. The base case is indicated by the
dashed line. The primary phase field for the first three data points
is spinel, and the primary phase field for the other data points is
wüstite.
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 12—(a) The wt pct Zn in slag and wt pct Cu in matte and (b)
Zn fuming rate and PCO2/(PCO + PCO2) ratio vs MgO/feed ratio in
the input of the submerged plasma process. The base case is indi-
cated by the dashed line.
investigated by increasing the dolomite mass rate (t h)1)
at constant C/feed mass ratio, constant C/O molar ratio,
and constant electricity input per ton of feed. The
composition of dolomite taken for this study is listed in
Table II. The main difference compared to the predic-
tions for increasing MgO/feed (Figures 11 and 12) is the
simultaneous increase of CaO content in the feed when
dolomite is added to the process.
From Figure 13(a), it can be seen that an increase of
dolomite additions from 1 to 2 t h)1 results in a
simultaneous decrease of bath and slag liquidus tem-
perature. The minimum in liquidus temperature around
2 t h)1 dolomite additions is due to a transition in
primary phase field from spinel to wüstite when dolo-
mite input is increased. This is due to the stabilization of
the wüstite phase by MgO. A further increase of
dolomite additions between 2 and 5.5 t h)1 results in a
substantial increase of liquidus temperature from
1220 C to 1320 C. From Figure 13(b), it can be seen
that the heat losses through the freeze lining decrease
and the freeze lining thickness increases for increasing
dolomite additions. The most pronounced changes in
the heat loss and freeze lining thickness are observed in
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 13—(a) Bath and slag liquidus temperature and (b) heat loss
through the freeze lining and freeze lining thickness vs dolomite
additions of the submerged plasma process. The base case is indi-
cated with the dashed line. The slag primary phase changes from spi-
nel to wüstite when dolomite additions are higher than 2 t h)1.
the range of 2 to 5.5 t h)1 dolomite. From Figure 14(a),
it can be seen that the concentration of Zn in the slag
changes drastically by approximately 4 pct over the
investigated range of dolomite additions, whereas only
minor changes in Cu concentration in matte occur over
the same range. The Zn fuming rate increases contin-
uously over the investigated range of dolomite addi-
tions, whereas the PCO2 =ðPCO þ PCO2 Þ ratio remains
almost constant over the entire range (Figure 14(b)).
The model predictions lead to important conclusions
about the role of slag chemistry; contrary to conventional
hot face practice with the use of freeze linings, the use of
slags having high liquidus temperatures leads to stable
operation and low heat losses of the slag fumer.
D. Effect of Zinc in Feed
In plant practice, the concentrations of zinc in the
residues may vary. The sensitivity of the zinc-fuming
process to these variations may also be predicted using
the process model. The results of these predictions,
showing changes in liquidus temperature, heat loss, and
VOLUME 38B, FEBRUARY 2007—29
Fig. 14—(a) The wt pct Zn in the slag and wt pct Cu in the matte
and (b) Zn fuming rate and PCO2 =ðPCO þ PCO2 Þ ratio vs dolomite
additions of the submerged plasma process. The base case is indi-
cated with the dashed line.
lining thickness are shown in Figure 15 for the base case
conditions CaO/SiO2 = 1.61 and Fe/SiO2 = 4.50. It
can be seen that the zinc concentration in the feed can
decrease the steady-state bath temperature by as much
as 25 C in increasing the zinc/feed ratio from 9.5 to
20 pct by weight. Conversely, the liquidus temperature
of the slags is increased by approximately 50 C over the
same range, most of this increase occurring between 15
to 20 pct Zn/feed ratio.
The heat losses through the freeze lining decrease
significantly with increasing zinc in feed from
approximately 120 kWm)2 at 9.5 pct Zn/feed to
40 kWm)2 for 20 pct Zn/feed (Figure 15(b)). Over this
same range of conditions, the steady-state concentra-
tion of zinc in slag increases from 1.4 to 3.5 wt pct
and copper in matte decreases from approximately 52
to 40 wt pct Cu (Figure 16).
E. Effect of Throughput and Bath Level
In plant practice, flexibility in terms of residue
throughput is often required. The sensitivity of the
30—VOLUME 38B, FEBRUARY 2007
Fig. 15—(a) Bath and liquidus temperature and (b) heat loss freeze
lining and freeze lining thickness vs Zn/feed ratio in input of sub-
merged plasma process. The base case is indicated by the dashed
line. The primary phase field for the investigated range of Zn/feed
ratios is wüstite.
zinc-fuming process to these variations may also be
predicted using the process model. Figures 17 and 18
show the effect of changing throughput—expressed in
tonne residue per hour—for the base case conditions at
fixed C/feed, C/O, CaO/SiO2, Fe/SiO2, and Zn/feed, and
at fixed electrical power input of 21.6 MW. It can be
seen that a change in residue throughput from 18.5 to
23.5 t h)1 gives rise to a substantial decrease in bath
temperatures from 1440 C to 1330 C and a decrease of
the heat losses through the freeze lining from 150 to
20 kWm)2. The same increase in throughput causes Zn
in the slag to increase from 1.6 to 3.5 wt pct and the Cu
concentration in the matte to decrease from 50 to 40 wt
pct.
Similarly, the effect of changing bath level, this is the
height of the bath during operation at fixed furnace
geometry, was investigated using the zinc-fuming model.
The bath height is limited to a certain minimum level to
allow sufficient reaction of the blast air with the bath
and limited to a maximum level to prevent accretions in
the gas off-take due to splashing phenomena. As can be
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 16—The wt pct Zn in slag and wt pct Cu in matte vs Zn/feed Fig. 18—Effect of residue throughput on wt pct Zn in the slag and
ratio in the input of submerged plasma process. The base case is wt pct Cu in the matte. The base case is indicated by the dashed
indicated by the dashed line. line.

Fig. 17—Effect of residue throughput on (a) bath and liquidus tem- Fig. 19—Effect of bath level on (a) bath and liquidus temperature
perature and (b) heat loss through the freeze lining. The base case is and (b) on heat loss through the freeze lining and freeze lining thick-
indicated by the dashed line. The primary phase for the investigated ness. The base case is indicated by the dashed line. The primary
range of residue throughputs is wüstite. phase field for the investigated range of bath levels is wüstite.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 38B, FEBRUARY 2007—31


Fig. 20—Effect of bath level on (a) total heat loss through the freeze
lining and (b) wt pct Zn in slag and wt pct Cu in matte. The base
case is indicated by the dashed line.
seen in Figure 19(a), an increase in bath level from 0.5 to
3 m in a steady-state situation will result in a decrease of
bath temperature as the total area of the bath through
which heat is extracted also increases. From
Figure 19(b), it can be seen that the specific heat loss
through the freeze lining, this is the heat losses per
square meter, decreases from 120 to 50 kWm)2. The
total heat loss through the freeze lining, however,
increases because the total surface of the freeze lining
increases (Figure 20(a)). From Figure 20(b), it can be
seen that the concentration of Zn in the slag and Cu in
the matte are only slightly affected and remain nearly
constant. The bath level for the base case geometry and
bath containing 71.2 t is 2 m.
F. Comparison with Conventional Zinc-Fuming
Processes
The base case of the submerged-plasma zinc-fuming
process (Tables II and III) was compared with published
data from of a conventional zinc-fuming process.[25] As
shown in Tables II and III, the zinc-fuming rate of the
32—VOLUME 38B, FEBRUARY 2007
base case of the submerged plasma process is 4.50 t h)1,
the total amount of slag produced is 12.28 t h)1, and the
final Zn concentration in the slag is 3.13 wt pct. When
assuming a slag density of 3500 kg/m3, the relative zinc-
fuming rate per volume of slag for the submerged
plasma process is 1.28 (t Zn)Æ(m3 slag))1Æh)1. From
Table III in Reference 25, it can be seen that starting
from an initial amount of slag of 45.32 t, the time
required to obtain a final Zn concentration of 3.13 wt
pct in the batch process is approximately 65.3 minutes.
During this time interval, approximately 3.90 tonne Zn
was fumed off. The average zinc-fuming rate per volume
of slag for the conventional zinc-fuming process is thus
0.28 (t Zn)Æ(m3 slag))1Æh)1.
This comparison seems to indicate that the relative
zinc-fuming rate of the submerged plasma process is
higher by a factor 4.6 as compared to the fuming rates of
the conventional slag fuming process listed in Reference
25. The addition of the slag loading and tapping times
for the batch process will make the practical differences
even higher. This drastic difference may be explained by
the ability of the submerged-plasma process to simulta-
neously maintain reducing conditions that promote
faster fuming and higher operational temperatures
(1300 C to 1400 C) as compared to the conventional
zinc-fuming process (1200 C to 1250 C). Operating the
zinc-fuming process at these high temperatures while
maintaining low heat losses and increased vessel integ-
rity is made possible through the use of high-tempera-
ture freeze linings and ‘‘engineering’’ the slag toward
high liquidus temperatures.
V. CONCLUSIONS
A new pyrometallurgical process has been developed
for the processing of zinc-containing waste materials.
The submerged plasma furnace has been tested at pilot
scale, and the process data obtained from these trials
have been used to design a full-scale industrial plant for
the treatment of EAF dusts.
The new process represents a radically new approach
to the design of zinc-fuming processes—the use of
supplementary heat supplied by the plasma torches
enables high bath temperatures to be maintained, and
the use of high liquidus temperature slags provides
stable freeze linings with which to maintain bath wall
integrity. These features and the reactor design lead to
higher zinc-fuming rates than are achievable using
conventional zinc-fuming processes.
The use of this technology offers a means of contin-
uous operation at high bath temperatures leading to a
more economically viable treatment process. The use of
hydroelectric power in the plasma offers the opportunity
of lowering the environmental impact of the process
through reduced greenhouse gas emissions.
A steady-state process model has been developed and
has been used to identify the sensitivity of the process to
changes in key process variables. The model simulta-
neously describes the chemical and thermochemical
processes, as well as the steady-state heat-transfer
processes. This link between process and slag chemistry
METALLURGICAL AND MATERIALS TRANSACTIONS B
and the requirements to maintain furnace lining integ-
rity and low heat losses through the reactor walls
represents a significant step forward in modeling capa-
bility. An important aspect of the model development is
the possibility to simultaneously optimize slag compo-
sition and process performance while ensuring vessel
integrity providing support for further process develop-
ment and optimization.
The comparison of the model predictions with previ-
ously published data on conventional zinc-fuming
processes confirms that the relative fuming rates of the
high-temperature submerged plasma process are
substantially higher than the zinc-fuming rates achiev-
able with conventional zinc slag fuming processes.
Operating the submerged plasma process at high tem-
peratures is made possible through the use of high-
temperature freeze linings and slag with a high liquidus
temperature. Dolomite additions to the zinc fumer slag
are used to achieve both the high fuming rates and the
high liquidus temperatures.
LIST OF SYMBOLS
hbath convection coefficient from bath to freeze
lining (W m)2 K)1)
hpc fi roof total heat-transfer coefficient from
postcombustion gas to roof (W m)2 K)1)
hpc fi sw total heat-transfer coefficient from
postcombustion gas to vertical sidewalls
(W m)2 K)1)
hpc fi zf total heat-transfer coefficient from the
postcombustion gas to the bath (W m)2
K)1)
hwater convection coefficient from water to
furnace shell (W m)2 K)1)
K1 equilibrium constant for the reduction
reaction of ZnO in the slag as expressed in
Reaction [1] (atm)
kfl thermal conductivity of the freeze lining
(W m)1 K)1)
kins,bottom thermal conductivity of the insulation layer
of furnace bottom (W m)1 K)1)
krefr,bottom thermal conductivity of the refractory layer
of furnace bottom (W m)1 K)1)
krefr,roof thermal conductivity of refractory deposit
on postcombustor roof (W m)1 K)1)
krefr,sw thermal conductivity of refractory deposit
on postcombustor sidewalls (W m)1 K)1)
kshell thermal conductivity of furnace shell (W
m)1 K)1)
Qhs heat input from other heat sources in the
preheater (W)
rrefr,sw inner radius of refractory sidewalls of
postcombustor (m)
rshell,in inner radius of furnace shell (m)
rshell,out outer radius of furnace shell (m)
Rbottom total thermal resistance of the furnace
bottom (K W)1)
Rsidewalls total thermal resistance of the
postcombustor sidewalls (K W)1)
METALLURGICAL AND MATERIALS TRANSACTIONS B
Rroof total thermal resistance of the
postcombustor roof (K W)1)
Tbath bath temperature (K)
Tliquidus liquidus temperature of the bath (K)
Tpc Postcombustor temperature (K)
Twater water temperature in the furnace jackets
(K)
tins,bottom thickness of the insulation layer in furnace
bottom (m)
trefr,bottom thickness of the refractory layer in furnace
bottom (m)
trefr,roof thickness of the refractory layer in furnace
bottom (m)
tshell thickness of furnace shell (m)
zbath height of the slag bath (m)
zpc height of the postcombustor (m)
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