TSL 2009 349
TSL 2009 349
TSL 2009 349
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FIRST INTERNATIONAL CONGRESS «NON-FERROUS METALS OF SIBERIA – 2009» • PART III • NON-FERROUS AND RARE METALS PRODUCTION
ore deposit (Krasnoyarsk Province) and battery paste for a new lead smelter currently under construction
in Khakasia. The proposed flow-sheet comprises smelting of ore concentrates in an Ausmelt furnace and
processing of rich smelting slag in an electgrothermal furnace to produce crude lead-antimony alloy and
secondary slag containing 1.0–1.5 Pb and 7–9 % Zn. It is planned that in the future the secondary slag will
be subjected to fuming in an Ausmelt furnace to recover zinc and lead. The use of the Ausmelt technology
has been agreed upon with the developer company.
Lead and zinc are recovered in most cases by Waelz process in drum-type furnaces and by fuming in
furnaces having lateral tuyeres and external firing chambers or a submersible vertical lance. In addition,
until now cleaning of solid slags has been performed in some cases in shaft-type furnaces, which are not
sealed properly and which require expensive metallurgical-grade coke [2, 3].
All above technologies use solid, liquid or gaseous fuel, the combustion of which even when using
oxygen-enriched blowing air results in generation of large volumes of off-gas entailing serious environ-
mental problems.
In this respect, electric smelting furnaces (ore smelting furnaces) for slag treatment have substantial
advantages, because the volume of generated off-gas is much lower.
Electric furnaces of round or rectangular configuration with three-phase feeding (Figure 2) have
found extensive use in the nonferrous metals industry, in the iron-and-steel sector, as well as in the chemi-
cal industry due to a number of advantages associated with the basic energy, technological and design
features of such furnaces [2, 3, 4, 5].
First of all it should be pointed out that transformation of electric energy to thermal energy takes place
directly in molten slag, into which graphite or self-baking electrodes are submersed. At the same time, vir-
tually all physicochemical interaction and conversions in the process of exchange or reduction processes
aimed at metal recovery proceed within the slag volume. As a result, the energy required for maintaining
the processes is used to a maximum extent when the heat and mass exchange conditions in the slag agitated
by convective streams are as close to the ideal conditions as possible. At the same time, due to good contact
between reacting compounds, the conditions for heterogeneous processes for production of commercial-
grade products (matte, slag, crude metal) from molten bath are rather favorable. The entire energy for
the process is provided due to use of electricity and it is not required to burn any type of fuel with air or
technical-grade oxygen blowing.
As a consequence, only gaseous products formed as a result of reactions between sulfides and oxides
or reduction processes are emitted from an electric smelting furnace. The unique opportunity to create
a sealed unit for electric smelting eliminates or minimizes any air infiltration and the electric smelting
process itself is conducted in the furnace under a slight negative pressure to avoid release of toxic process
gases to the ambient air. As a result, the quantity of off-gas leaving the smelting furnace in the process
of reaction or reduction smelting will be smaller by 3 to 5 times in comparison with smelting of the same
amount of feed charge in any other type of smelting furnace using carbonaceous fuel (even if oxygen
blowing is used for combustion). This means that the cost of dust recovery and off-gas treatment will be
much lower in case of electric smelting processes.
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FIRST INTERNATIONAL CONGRESS «NON-FERROUS METALS OF SIBERIA – 2009» • PART III • NON-FERROUS AND RARE METALS PRODUCTION
An electric smelting process is easy to start up; process conditions can be maintained using appropri-
ate automation means within a narrow range of values; and it is permissible to shut down the operation for
a relatively long periods of time without freezing the melt. Provided that advanced equipment is used, the
operating personnel can easily control the process and ensure the required performance values.
Due to the small off-gas volume and possibility to ensure satisfactory thermal insulation of the walls,
the heat balance of electric smelting furnaces is quite positive permitting a high heat efficiency; and the
lack of turbulent mixing of the molten slag bath (intensive agitation of the melt with convective streams
is observed only within the zone close to the electrodes) makes it possible to avoid significant wear of the
lining because the zone of active charge melting is determined by heat emission within a range of about
1.5 m to 2 m around the electrodes. Within that zone the turbulence of the slag due to convection is maxi-
mal and attenuates toward the furnace walls [4].
At the same time, it is possible to control the excessive accretion formation in electric furnaces by
adjusting the process conditions (by controlling the depth of electrodes submersion into the slag), as well
as adjust the thickness of the protective accretion layer on the lateral wall lining.
It is possible to perform slag cleaning inside electric furnaces (reducing the lead content down to
<1 %) by discrete feeding of reducing agent and simultaneous rapid one-time increase in the temperature
of the melt, which is difficult or virtually impossible in furnaces of other designs [3].
Electric smelting processes, and first of all fuming furnaces, provide some additional options when
fed with direct current with polarization of the metallized bottom phase, which permits not only preven-
tion of accretion formation on the furnace bottom (under the metal or matte layer), but also an increase in
metal recoveries from slags and improvement of the thermal efficiency of the electric furnace. In such a
furnace, graphite or self-baking electrodes are combined in heteropolar groups, one of which is submersed
into the liquid metallized bottom phase and the other one into the molten slag. In this way it is possible to
(1) realize the idea of a furnace bottom electrode, without disturbing the sealing of the furnace bottom;
(2) concentrate energy introduced to the furnace mainly in the vicinity of the electrodes submersed into
the slag with virtually constant temperatures at the periphery of the melt (i.e. at the walls); (3) by cathodic
polarization of the bottom phase in the area of anodes in the molten slag, superimpose the local overheat-
ing and sparging zones formed as a result of carbon monoxide formation due to electrolysis phenomenon,
intensifying thereby metals reduction and sublimation of volatile components [4, 6]. Although the electro-
thermy using direct current has not found so far extensive use in the nonferrous metals industry, its pros-
pects in the foreseeable future do not cause any doubts (this refers also to secondary lead production).
Physicochemical characteristics of produced slags (and mattes) are important for any pyrometallur-
gical technology applied in the nonferrous metals industry, and especially for electrothermal smelting,
where mass and heat exchange processes proceed within the molten slag.
Iron-calcium-silicate slags used in electrothermal smelting furnaces should not only meet the require-
ments set to slags generated at lead smelters, but also have sufficient electrical conductivity to ensure the
best electrothermal conditions and completion of the processes taking place in the furnace [7]. Slags with
high conductivity require that the smelting process be conducted under a low voltage and a high amper-
age. In case of lower conductivity it is necessary to increase the voltage, which results in electric arc forma-
tion, local overheating and requires serious precaution measures in the process of the furnace operation.
The process parameters of the electric smelting process are also dependent on the viscosity of slag.
An increase in the silica content and a reduction in the calcium oxide content in slags cause an increase
in the slag viscosity and hinders slag discharge from the furnace. Furthermore, an elevated silica content
affects the specific conductance of slag.
Some data is given below to demonstrate the effect of temperature on viscosity and conductance of
molten slag (31.0 % SiO2, 35.25 % Na2O, 8.75 % CaO, 29 % FeO) [7]:
An essential factor having an effect on the physicochemical properties of lead smelting slags is the
content of soluble lead oxide in the slag, and first of all lead silicates having low melting temperature.
Reduction cleaning of slags down to a residual lead content of 0.8 % to 1.2 % is performed using car-
bonaceous reducing agent in an electric slag cleaning furnace of special design. The rate of carbothermal
lead reduction from solid oxides and silicates with solid carbon is higher than the rate of reduction with
gaseous carbon monoxide. This is also true for lead reduction from silicate melts [3, 5, 7–9]. Due to this
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FIRST INTERNATIONAL CONGRESS «NON-FERROUS METALS OF SIBERIA – 2009» • PART III • NON-FERROUS AND RARE METALS PRODUCTION
reason it is reasonable to feed additional solid carbon over the melt (or better into the melt) even if gaseous
carbon monoxide is used for slag cleaning.
Processing of secondary lead-containing raw materials, such as waste generated in the process of copper
and zinc production or smelting of spent lead batteries (paste) jointly with ore concentrates, is accompanied
by formation of iron-silicate slags, which are collector for zinc and some other impurities, with subsequent
recovery of zinc by fuming. Accumulation of zinc in slags necessitates adjustment of their composition to en-
sure fusibility of zinc-containing slags, e.g. by increasing the iron content of slag to facilitate better dissolu-
tion of ZnO and reduce the CaO content, which affects the solubility of zinc. It is recommendable to keep the
CaO content in slag below 16 % to permit concentration of zinc in slag; in case of a CaO content of 24 % zinc
oxide in slags becomes virtually insoluble. Similarly, the lower is the SiO2 content of slag, the easier proceeds
the dissolution of ZnO in slag [10, 11].
However, the issue of obtaining fluid and electrically conductive slags has not been studied to a suf-
ficient degree so far, and the selection of a suitable slag for electrothermal smelting process in case of
smelting of secondary lead-containing raw materials under specific conditions and for specific feed charge
requires empirical assessment. For example, when the operating conditions were being developed for the
electrothermal process for smelting of industrial waste (lead-containing residue from a zinc plant and gas
treatment sludge from the copper smelter) at the Almalyk mining and metallurgical complex (Uzbekistan),
an appropriate composition of zinc-containing slags was selected to ensure optimal conditions for opera-
tion of a round three-electrode electric furnace with a bottom area of 8.7 m3 operating at 1050–1150 oC and
discharging slag with a content of 9–16 % ZnO. Table 1 below contains the ratios of oxidized components
selected on the basis of practical experience to ensure slag fluidity and required electric conductivity for
different ZnO contents of slag.
Table 1.
Ratios of FeO, SiO2 and CaO in slags with different ZnO contents
Ratio ZnO content, %
5 10 15 20
FeO
1.25 1.43 1.7 2.01
SiO2
FeO
2.37 2.72 3.2 3.77
CaO
SiO2
1.9 1.9 1.9 1.86
CaO
In the presence of Al2O3 in slag, the permissible zinc oxide content is limited. It is recommended that
based on the practical experience of lead smelting the sum of ZnO + Al2O3 in slag does not exceed 20 %.
In [11] it was maintained that the slag viscosity increases with an increase in the SiO2 content from
30.3 % up to 44.9 %. If lead smelting slag contains approximately 20 % ZnO, it is recommended to keep the
FeO content of 39.64 %; in case of a ZnO content of 25 % the FeO content should be 40.1 %. In [12] some
empirical data is given for selection of an optimal lead smelting slag composition: Σ ZnO + SiO2 in slag
should be ≤ 40 %, and Σ ZnO + CaO ≤ 29 %.
The above data indicates that the selection of an optimal slag composition not only improves the eco-
nomics of secondary lead production process with the use of electrothermal technology, but also provides
an opportunity to obtain environmentally sound slags, which can be utilized in the construction industry
and for road construction.
The gained operating experience shows that in case of electric furnaces it is especially important to
maintain a constant volume of the slag bath (reaction bath) and lead bullion (bottom phase). The constant
slag and lead volumes in the furnace permit stabilization of the energy performance of the furnace due to
its thermal inertia, a reduction in non-productive electricity consumption and avoid waste of graphite elec-
trodes (burning of open areas of electrodes), because the electrodes are constantly submersed in the slag.
Furthermore, the constant (irreducible) operating volume of slag permits more efficient response of
compounds in the process of reactions within the operating temperature zone.
In electric furnaces the constant operating slag volume is maintained by discharge only of excessive
quantity of the formed molten slag (above the slag tap hole level), and the irreducible lead bottom phase vol-
ume is maintained either by using a lead discharge siphon or by discharge of excessive lead via the operating
tap hole. The bottom (emergency) tap hole is used only if it is required to completely discharge the molten
bath from the furnace.
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FIRST INTERNATIONAL CONGRESS «NON-FERROUS METALS OF SIBERIA – 2009» • PART III • NON-FERROUS AND RARE METALS PRODUCTION
The electrothermal technology for slag cleaning at the plant in Khakasia was selected due to the fol-
lowing factors:
• Availability of cheap electricity in the region and lack of natural gas, as well as possibility to use
inexpensive rejected coke fines as reducing agent. Furthermore, up to one third of the reducing
agent quantity required for slag cleaning will be provided by electrode burning;
• Possibility for use of a sealed unit for slag cleaning with low dust entrainment and small off-gas
volume, which permits to use economically efficient standard-type bag filters to ensure compliance
with the sanitary norms for lead release to the atmosphere;
• Possibility for ensuring process conditions in the electric furnace with minimal lead and zinc fum-
ing, permitting concentrating of zinc in slag (up to a zinc content of 9–12 %) with a residual lead
content in slag of maximum 1.0–1.5 %. Such slag can be used then for zinc recovery by slag fum-
ing;
• It is easy to control the slag cleaning process by controlled feeding of both molten and solid smelting
slag;
• When using an Ausmelt furnace in the process flow-sheet it is easy to obtain slag of an optimal com-
position for treatment in an electric slag cleaning furnace virtually without adjustment of the final
slag.
All above factors, as well as availability of a Russian manufacturer of high-quality electric furnaces
permitted the Customer to decide to use an electric slag cleaning furnace for treating slag from the Aus-
melt furnace.
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FIRST INTERNATIONAL CONGRESS «NON-FERROUS METALS OF SIBERIA – 2009» • PART III • NON-FERROUS AND RARE METALS PRODUCTION
SUMMARY
Based on a review of the modern status of technology and equipment used for lead production world-
wide the Gintsvetmet Institute developed and agreed with the Customer («Carat-CM» LLC.) upon the pro-
cess flow-sheet for treatment of a mixture of Russian lead concentrates and battery paste obtained from
spent lead batteries comprising the following steps:
• Oxidizing smelting of feed charge in an Ausmelt furnace to produce low-antimony lead bullion ac-
cumulating precious metals, as well as smelting slag concentrating part of the lead and virtually all
impurity metals and off-gas with a high SO2 content to be used for sulfuric acid manufacture;
• Treatment of smelting slag in electrothermal furnace to reduce the lead content in final slag down
to 1.2–1.7 %;
• Production of high-grade lead (mainly S-1 Grade) in refining and cupellation furnaces, as well as
lead-antimony alloys and master alloys and Doré metal.
The overall lead, sulfur and precious metals recoveries in the given flow-sheet are over 98 %, and
recycling of alloying metals for battery alloys is in the order of 95–97 %.
The use of advanced dust recovery and off-gas treatment methods and equipment will ensure compli-
ance of the lead smelter under construction with the applicable Russian sanitary norms.
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