DOI 10.

1007/s11015-017-0403-2
Metallurgist, Vol. 60, Nos. 9–10, January, 2017 (Russian Original Nos. 9–10, Sept.–Oct., 2016)

IMPROVEMENT OF THE WAELZ PROCESS FOR

SLAG COMPONENTS BASED ON SOLID-FUEL
COMBUSTION MECHANISMS

V. I. Matyukhin, O. V. Matyukhin, V. V. Shatsillo, UDC 669.531.66

A. V. Matyukhina, and O. S. Koshcheeva

Drying, heating, and combustion of lumps of coke in a Waelz kiln produces gases released with active
combustion of carbon in the oxidizing zone in a counterflow regime with air blast entering through the kiln
discharge end. Under conditions of a charged layer of lumps of coke and materials with occurrence of them
at a surface from the direction of air stream supply, there is initially development of oxidation processes
with significant release of heat and an increase in charge temperature. After charging, particles of solid
components descend into a lower layer and a new portion of movable material is charged. There is almost
no gas movement, and oxygen concentration is close to zero. As a result of this, oxidation processes within
a layer slow down considerably with a reduction in heat liberated, and under conditions of a steady-state
temperature regime, there is temperature equalization throughout the cross section of lumps of charge. With
a limited capacity for pelletizing starting materials due to a shortage of factions less than 0.4 mm, the
pelletizing time under conditions of a drum pelletizer 3 m in diameter and 6 m long is 7.4 min, with an
overall path covered by particles of 103 m, and the degree of development of this process does not exceed
17.41% with a change in average granule diameter from 10.64 to 11.06 mm. With introduction into a charge
composition of peat, there is an improvement of material pelletizing capacity with increased intensity of
heat transfer to fired granules within a kiln and an improvement in strength properties. There is an increase
in intensity of heat exchange processes in a charge layer with improvement of contacts between ore and
carbon particles. On heating of ore-peat briquettes to 1000–1050ºC, there is internal heating and there is
an excess concentration of CO within exhaust gases in the range up to 300–320ºC. The presence within the
composition of heated materials of metal oxides provides development of reduction in a stream of carbon
monoxide followed by oxidation (after burning carbon with gas phase oxygen). The use of these measures
in implementing the Waelz process will make it possible to increase the yield of zinc oxide by 5–10% with
an increase in unit productivity by 10–15% and a reduction in specific coke consumption by 5–7%.
Keywords: Waelz process, carbon oxidation, peat additive, pelletizing, granule strength, internal heating.

In order to extract zinc and lead from solid metallurgical waste, there is extensive use of reduction roasting in rotary
kilns given the name Waelz process. During its implementation, original cake in the form of lumps of ore or slag materials
5–10 mm in diameter in the presence of excess coke carbon, fed together with a charge, burns in the presence of oxygen from
an air blast at a temperature not above that for the start of melting original components [1]. Under conditions of a charged
layer in sloping drum kilns, charge components move from the cold end of the heating unit to towards the discharge area with
successive heating in zones of drying, warm-up, reduction and oxidation by gaseous products of a layer of burning solid fuel,
moving in an opposite direction. The limited nature of gas mass flow through a weakly blown layer of charge materials

Ural Federal University, Ekaterinburg, Russia; e-mail: matyhin53@mail.ru, ozzi89@mail.ru. Translated from Metallurg, No. 10, pp. 26–32,
October, 2016. Original article submitted December 4, 2015.

0026-0894/17/0910-1025 ©2017 Springer Science+Business Media New York 1025

 Fig. 1. Change in burning coke surface layer temperature 100 mm thick of lumps with a size of 10 mm (4)
and gas composition close to layer surface with air stream movement rate of 0.2 m/sec: 1) oxygen; 2) carbon
monoxide; 3) carbon dioxide.

provides preferential diffusion regime for development within it of coke carbon oxidation, metal oxide reduction, and zinc
compound sublimation. Liberation from a layer of volatile metal zinc and lead vapor on contact of the increased temperature
region with kiln atmosphere oxygen are oxidized and form a dust fraction that is removed from the workspace in the form
finished product (Waelz-oxide). The diffusion mechanism of development of layer processes in a rotary kiln limits the inten-
sity of mass transfer phenomena and unit productivity with a specific coke consumption not below 160–200 kg/ton of original
charge and chemical yield of Waelz oxide not above 92–94%. The preferred convective method of heat transfer between kiln gas
atmosphere and heated materials is accompanied by significant dust entrainment from the furnace workspace (up to 200 g/m3),
which requires effective organization of heat and mass transfer processes in a layer and capture of dust particles.
According to theoretical ideas [2], combustion of individual lumps of solid fuel is a collection of complex physico-
chemical processes, occurring in several stages: fuel preparation, combustion of gaseous products and coke residue. With the
layer method of solid fuel combustion under conditions of a charged layer of the Waelz process its oxidation is accomplished
in a charge surface layer with not more than 2–3 lump diameters, washed by a stream of furnace atmosphere gases. In order
to study the mechanism of surface combustion of carbon in a coke layer 100 mm thick, a laboratory study was made of the
temperature and gas regimes for oxidation of previously heated material in a neutral atmosphere to 1200ºC in nonoxidizing
conditions of a coke charge, formed from individual lumps with diameter of 10 mm, with surface washing by an air stream at
a temperature of about 20ºC at a rate of 0.2 m/sec, providing a preferential laminar gas atmosphere movement regime. In
conducting research, the surface layer temperature was monitored by means of low-inertia high-temperature pyrometer of
type Termoskop-100-VT, and gas samples were also collected at a distance of 10 mm from the layer surface with subsequent
analysis by means of an automatic Testo type gas analyzer (Fig. 1).
According to the data obtained, combustion of a surface layer of coke with formation of a burning zone proceeds at a
distance of about 5 mm from the place of supply of air blast and is accompanied by an increase in its temperature (see Fig. 1,
line 1). As gas is fed along a surface layer, oxygen content within it is reduced, and at a distance of about 22.5 mm, it almost
equals zero. Simultaneously, there is an increase in carbon dioxide concentration (see Fig. 1, line 3), whose maximum content
reaches 16.8% at a distance of 9 mm from contact of gas with a coke charge, which determines the extent of the oxidation
zone. CO content increases steadily (see Fig. 1, line 2), mainly, as a result of reduction of CO2 by coke carbon. The greatest
change in carbon monoxide concentration in gases occurs at a distance from the surface of about up to 16 mm and determines
the extent of the zone of active combustion of solid fuel within a layer. With further gas movement along a surface layer, there

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TABLE 1. Charge Grain Size Composition
Moisture Fraction content, % Average
Sample area content, diameter,
% +10 mm –10+5 mm –5+2 mm –2+1 mm –1+0.5 mm 0.5–0.2 mm –0.2 mm total mm

Before PD 24.21 61.91 7.36 8.75 3.88 7.36 5.16 5.57 100 10.64
After PD 24.05 57.21 14.24 16.17 5.78 5.02 1.11 0.47 100 11.06

is reduction of carbon dioxide on contact with coke carbon and formation of excess CO. The process of coke carbon oxidation
ceases at a distance of about 22.5 mm from the place of gas supply as a result of a lack of excess oxygen in the gas phase.
In a rotary kiln, the flow of fuel components, formed with oxidation of solid fuel particles by oxygen of the gas phase,
enters into contact with oxygen molecules of the gas atmosphere with formation of a layer of combustion zone limited over the
height to an extent not more than 10–15 mm. The process ceases after combustion of coke residue. The intensity of heat liber-
ation from this zone is determined by the rate of oxygen supplied to the fuel surface from the kiln atmosphere and temperature
of the layer. Stable combustion of fresh portions of coke entering into movement of a charge layer proceeds in a previously
ignited fuel particle in the heated zone of a kiln. Oxygen entering with the air blast (see Fig. 1, line 1) initially is consumed in
forming CO2 and CO. Heat liberated from flame combustion of CO creates a thermodynamic basis for forming the subsequent
flow of carbon monoxide. The CO2 content (see Fig. 1, line 3) with excess oxygen initially increases and reaches a maximum
at a distance equal to 3–4 lump diameters, and this corresponds to the maximum temperature (see Fig. 1, line 4). The region of
a layer characterized by presence of excess oxygen is called the oxidation region, and is determined by an increase in CO and
CO2 content. Subsequent movement of kiln gas atmosphere over the surface of a layer of particles creates conditions for reduc-
tion of carbon dioxide from coke surface particles with an increase in CO concentration, which intensifies reducing processes
within a layer. However, the amount of heat liberated is reduced with a lowering of material temperature.
Under conditions of cyclic movement of lumps of coke and materials in a charged kiln layer on their arrival at its
surface, there is preferential development of oxidation processes with significant heat liberation and an increase in charge
temperature. After particles roll over a surface layer, they fall into the lower part of a charge where there is almost no gas
movement, and oxygen concentration is close to zero. As a result of this, development of oxidation processes and heat liber-
ation in a layer slows down, and there is levelling of the temperature through the cross section of heated lumps of charge.
Lumps of solid fuel hardly participate in thermal work of the layer as a result of limited contact between coke charge and kiln
gas atmosphere. Under laboratory conditions, it was noted that the temperature of coke lumps at a depth of 10 mm with sur-
face flushing of layer by an air stream is almost unchanged. In a kiln, active chemical processes in materials develop for about
30% of the time of thermal treatment on arrival close to a charge surface. In the rest of time, lumps within a charge in a kiln
workspace are in a holding regime at relatively high temperature.
Thus, with use of solid fuel in the Waelz process initially it is used as a heat source, which subsequently creates
conditions for reduction in a carbon dioxide layer with CO formation in the gas atmosphere and metal phase in solid charge
components. The rate of chemical reaction in treated solid materials of a certain size is made difficult as a result of kinetic
limitations of the process of gas reduction of CO2 and metal oxides.
One method for intensifying heat transfer is improvement of contact between ore and carbon-containing particles [3].
For this, it is desirable to provide constant contact by pelletizing in the charge preparation stage.
At the Chelyabinsk Zinc Plant (ChTsZ), the stage of charge preparation, including crushing and sorting components with
respect to grain size composition, ends with pelletizing in a cylindrical drum 3.0 m in diameter and 6.0 m long. However, its pa-
rameters are far from rational values, primarily with respect to size of original charge lumps over a wide range, i.e., to 100 mm. In
order to reduce energy expended on heating charge particles, it is expedient to provide conditions for their heat treatment in a
regime of heating thermally thin bodies with values of Biot criterion less 0.3 [4]. For this, under continuous charging conditions
for materials, it is necessary to limit the range of change in particle size of starting materials to not more than 5–10 mm by
stabilizing the grain size composition of a whole stream of charge with additional crushing in a roller crusher.

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TABLE 2. Average Peat Composition

Working mix composition, wt.% Volatile yield, %

Peat sort QiP, kJ/kg
СР
Н Р
S P
O P
N P
A P
W P to fuel weight

Lumpy 30.9 3.2 0.2 17.8 1.3 6.6 40 10718 70

Shredded 25.7 2.7 0.1 14.9 1.1 5.5 50 8499 70

Experimental data are provided in Table 1 for grain size composition of a charge before and after and after a drum-pel-
letizer (DP) for existing ChTsZ technology. Analysis of the data obtained shows that charge pelletizing in drum proceeds
under unfavorable conditions. The average charge lump diameter increases from 1.64 to 11.06 mm, i.e., 3.94% in all. This
condition of the pelletizing process is mainly connected with inadequate amount of charge lump particles of fraction –0.4 mm
[5], which ahead of a drum- pelletizer comprises about 10% of the overall weight of materials treated, and pelletized aprticle
(class +1.6 mm) is more than 78%.
The potential capacity of original charge components for pelletizing was determined by a granulation rate coeffi-
cient, representing the overall area of pelletizable fractions to volume of pelletized fractions (fine) in accordance with an
expression

where ρrol is rolled layer density, kg/cm3; ρap is nucleus apparent density, kg/m3; mi is weight of charge pelletizable monof-
raction +1.6 mm, kg; mm is weight of pelletized fractions –0.4 mm, kg; and di is average diameter of charge pelletizable
monofraction, mm.
Then, the granulation rate coefficient before a drum-pelletizer will equal

The granulation rate coefficient after pelletizing comprises

Their values indicate that before granulation there are significant possibilities for pelletizing an original charge, but
after granulation these possibilities are reduced by more than a factor of 270 with an insignificant change in average size of
pelletized material. The degree of charge pelletizing, equal to the fraction of fine particles participating in granule formation,
comprises in all

where is amount of class 0–0.4 mm in an original charge, kg; is amount of class 0–0.4 mm in lumps, kg.
Calculation of material movement kinetics in a drum by a well-known procedure [5] showed that with a total weight
of material in a drum of about 3100 kg the pelletizing time is about 7.4 min. This is entirely satisfactory for completion of
charge granulation (3–5 min), and the overall path of individual lumps of material in a drum with a reciprocating path of
movement in a layer is about 103 m.
In order to stabilize the grain size composition of a pelletized charge, it is expedient to introduce into its original
composition elements containing an increased amount of pelletizable particles fraction –0.4 mm facilitating granulation.
These conditions are most completely satisfied by adding peat [6], which improves the Waelz process for ore components
(Table 2) due to an insignificant ash content (not more than 5–7%), presence of up to 30% active carbon in a finely dispersed

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TABLE 3. Effect of Added Peat on Fired Granule Strength

Granule strength (N/pel.) after roasting at 1300ºC and solid fuel content, %
Area of sample selection at kiln outlet
0.5 2.0

Layer surface 2800 1100

Layer center 2490 1250
Along drum generating line 2490 1300

Fig. 2. Change in temperature drop through inert sample cross section with addition of 12%
peat to original charge with roasting in a gas atmosphere containing 13% CO2 and 14% O2.

condition (amount of pieces <0.4 mm up to 80%), developed specific surface (more than 1200 m2/m3), low cost, and general
availability. The use of peat additive in the charge preparation stage in a BP will make it possible to stabilize the grain size
composition of original components at the level of not lower to 11.5–12.0 mm, to increase the potential capacity of charge
materials for pelletizing by more than a factor of 3.6 with an increase in the degree of pelletizing up to 20.1%. The crushing
strength of individual raw ore material-peat granules reaches 50–100 N.
The appearance within an original charge composition of an internal heat source in the form of added peat [5], ex-
hibiting a developed surface, will facilitate intensification of heat exchange and kinetic processes in a layer on heating as a
result of improvement of oxidation reactions both of coke carbon and also a number of chemical elements participating in
developing the Waelz process. With increase in amount of peat, there is an increase in amount of heat liberated within a mass
of heated materials, which improves conditions for heating with an increase in strength of granules formed, collected on un-
loading a fired charge in a rotary kiln (Table 3). Pelletized materials prepared during roasting are distinguished by high poros-
ity, which reduces diffusion difficulties on subsequent heat treatment.
On heating ore-peat materials under oxidizing conditions of a rotary kiln atmosphere, a considerable internal heat
source is rolled finely dispersed solid fuel, which is relatively uniformly distributed between individual ore particles in the
stage of charge preparation. Since in this case fuel particles do not experience a steady wearing effect of elements of a charge
layer, then there are no special requirements for their strength properties.
In order to study features of fuel carbon oxidation in pelletized material without considering conditions for develop-
ment of oxidation-reduction reactions within a mass of fired material, test specimens were used with a diameter and thickness
of 15 mm prepared from a mixture of chamotte powder class –0.1 mm inert with respect to oxygen of a gas atmosphere and
12% peat under conditions of increasing ambient temperature at a rate of 10 deg/min with an air supply rate of 0.2 m/sec.
Their temperature-time condition was evaluated during heating from readings of calibrated thermocouples with electrode

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 Fig. 3. Change in gas atmosphere composition at outlet from reaction vessel during
inert material roasting: 1) oxygen; 2) carbon dioxide; 3) carbon monoxide.

diameter of 0.15 mm, whose bead was installed at a specimen surface and within its central part. It was shown by experiments
for analyzing the temperature drop through a specimen cross section that solid fuel carbon burning within them does not pro-
ceed uniformly from the surface. With a uniform heating rate regime up to 150–200ºC, there is a steady increase in material
temperature with an increased value at its surface compared with the a central region (Fig. 2). The maximum temperature drop
through a specimen cross section is 4ºC with a temperature of about 200ºC.
A further increase in gas atmosphere temperature in a workspace facilitates the start of development of exothermic
processes of peat carbon oxidation within specimen inner layers. In this case, the temperature drop between the surface and
its center starts to decrease, but with gases reaching a temperature of 320–350ºC there comes a point when there is thermal
equilibrium (tte) when the temperature level throughout the whole specimen cross section becomes uniform.
Subsequent external heating of materials in an oxidizing atmosphere facilitates rapid burning of solid fuel carbon and
liberation of a considerable amount of heat. This leads to an increase in temperature of specimen central layers, and the drop
in temperature over its cross section changes sign. Internal heating of material continues up to 1000–1050ºC (temperature of
maximum heat liberation of tmax). With a high gas atmosphere temperature, the intensity of heat liberation decreases, and the
temperature drop through a specimen cross section is reduced. During this heating period, the temperature at the center strives
to reach the surface temperature, and after 1170ºC it starts to lag behind the latter.
The combustion mechanism described above for additions of solid fuel is confirmed by data the change in chemical
composition of waste gases (Fig. 3) during experimental; specimen heating in an air atmosphere under the same conditions
obtained by means of a Testo automatic gas analyzer.
It should be noted that in the initial heating section (up to 300–320ºC) a change in oxygen concentration is hardly
observed, which points to the slow rate of peat carbon oxidation. At a temperature of about 320ºC, excess concentration of
carbon monoxide arises in waste gases (see Fig. 3, curve 3) as a result of development of secondary fuel oxidation reactions,
which reach a maximum value (τmax is time for reaching the maximum gasification) with a gas atmosphere temperature of
about 600ºC. A subsequent increase in roasting temperature reduces waste gas CO concentration due to more complete oxi-
dation of peat carbon and reaches a zero value at about 880ºC.
With the use of ore and slag components containing metal oxides within the composition of heated materials, in the
oxidizing atmosphere of a rotary kiln, the nature of change in their temperature is retained. However, apart from solid fuel
oxidation processes, oxidation and reduction of metal oxides starts to develop, which is accompanied by a corresponding ther-
mal effect. It has been established by experiment that with an increase in heating temperature for all materials to 500–600ºC
preferential development applies to processes of metal oxide reduction, accompanied by heat absorption. In the range up to

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880–900ºC, the intensity of reduction processes is reduced, and with a higher heating temperature up to that of complete peat
carbon oxidation (1000–1050°C), there is simultaneous development of metal oxide oxidation and reduction reactions with a
predominant effect of the latter. Above this temperature in an oxidizing atmosphere, there is marked development of oxidation
reactions for metal oxides, reduced in the preceding heating stage.
Thus, in order implement more efficient development of reduction processes in a layer during the Waelz process
introduction of peat additive should be used in the pelletizing stage as both an internal and external heat source. According to
preliminary test data, this measure under conditions close to rotary kiln operation showed that the chemical yield of zinc with
treatment of ore-peat briquettes in a coke “bed” with temperature around 1300ºC for 1 h comprises 96–98%, which makes it
possible to expect an increase in zinc oxide yield under industrial condition by 5–10% with an improvement in unit produc-
tivity by 10–15% and reduction in specific coke consumption by 5–7%.
Conclusion. In order to improve the efficiency of the Waelz process under conditions of a charged layer, it is
expedient:
1) to stabilize grain size composition of an original charge using a roller crusher before pelletizing;
2) to introduce into the original charge composition finely dispersed peat as an internal heat source under oxidizing
conditions for roasting granules, which will make it possible to increase the chemical yield of zinc by 5–10% with an increase
improvement in Waelz kiln productivity by 10–15%, and a reduction in specific coke consumption by 5–7%.

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