Scandinavian Journal of Metallurgy 2001; 30: 292–296 Copyright C Munksgaard 2001

Printed in Denmark. All rights reserved

SCANDINAVIAN
JOURNAL OF METALLURGY
ISSN 0371-0459

Kinetic study on the carbothermic reduction of zinc oxide

Hsi-Kuei Chen
Department of Chemical Engineering, Hwa Hsia College of Technology and Commerce, Chungho, Taiwan 235, ROC

This study investigated the carbothermic reduction of zinc ox- rate of zinc were determined from the regression of the ex-
ide with carbon powder under a nitrogen atmosphere (at 1 perimental data.
atm). The experimental results indicated that the reduction
rate could be increased by increasing the molar ratio of C/ Key words: zinc oxide, carbothermic reduction, EAF dust, zinc
ZnO, height of solid sample, density of solid sample or reac- metal, carbon
tion temperature. The rate was also found to be increased
by reducing the grain size of zinc oxide and carbon or the c Munksgaard, 2001
nitrogen gas flow rate. The empirical expressions of conver-
sion rates of zinc oxide and carbon as well as the production Accepted for publication 15 September 2000

A large amount of dust containing toxic zinc is gener-

Experimental procedures
ated in the steel production process by the electric arc
furnace (EAF). Dumping the EAF dust in a landfill is Nitrogen with minimum purity of 99.999% was em-
hazardous to the environment. Therefore, recovery of ployed. Carbon and zinc oxide powder were supplied
zinc metal from the EAF dust is worthy of investiga- by the Cerac corporation with a purity of over 97%.
tion from the viewpoint of environmental protection Carbon and zinc oxide were ground separately and
and economic benefits. then screened. Solid reactants in the predetermined
A large amount of zinc metal can be recovered from proportions were then mixed in a V blender and then
the EAF dust by the carbothermic reduction method. transferred to a cylindrical quartz crucible and loaded
This method has 2 advantages: (1) simplicity of the in a thermogravimetrical analysis system (TGA), sen-
process and (2) ease for large-scale operation. sitivity ∫0.001 g. Nitrogen was flowed over the solid
Sufficient literature is not found on this subject. Ex- sample and the conversions of zinc oxide and carbon
traction of zinc metal from pure zinc oxide or EAF as well as the yield of zinc were determined. The
dusts through the carbothermic reduction was found weights of solid samples were in the range of 5¿10ª4
to be feasible by [1–6]. A mathematical model of the to 1.5¿10ª3 kg. The operating variables studied are
carbothermic reduction of zinc oxide has been derived listed in Table 1. The italicized values are the standard
by Guger & Manning [7] and an analysis of EAF dust operating variables; i.e., when the effect of that vari-
has been studied [8–11]. However, a quantitative rate able is not studied, its value is held at the italicized
equation has not yet been proposed. value in that series of experiments.
Although there are many reactions involved in the
reduction of ZnO, the main reactions are:
Table 1. Values of the operating variables
ZnO(s)πCO(g) » Zn(g)πCO2(g) , (1)
Variable Valuea)
C(s)πCO2(g) » 2CO(g) . (2) C/ZnO molar ratio 1.0, 1.5, 2.0, 2.5
carbon grain size (¿107 m) 5, 39, 414
zinc oxide grain size (¿107 m) 5, 39, 414
The purpose of this investigation is to study the kinet-
solid sample height (m) 0.005, 0.01, 0.015, 0.02
ics of the carbothermic reduction of pure zinc oxide initial bulk density (kg/m3) 216.7, 336.5, 454.3, 570.4
with carbon powder. Moreover, this study aims at reaction temperature (K) 1073, 1173, 1273, 1373, 1423
N2 flow rate (¿105 m3/s) 0.167, 0.833, 1.25, 1.67
finding the optimal operating conditions which may
help setting up a plant for zinc recovery. a)
The italicized values indicate the standard operating conditions.

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 Reduction of zinc oxide

Results and discussion

Calculation of conversion and yield
The results of the reduction experiments are presented
as plots of the conversions of zinc oxide and carbon,
XZnO and XC, and the yield of zinc, YZn, versus time.
They are defined as follows:

DW
XZnO Ω o
, (3)
(93¿CZnO)

DW
XC Ω o
, (4)
(93¿CC )

W1
YZn Ω o
, (5)
(65¿CZnO)

where

o
CZnO Ω initial concentration of zinc oxide (kmol/m3)
o
CC Ω initial concentration of carbon (kmol/m3)
W1 Ω weight of zinc metal obtained by
water condensation method (kg) Fig. 1. Plot of the conversion of ZnO against reaction time. The effect
DW Ω weight loss of solid sample (kg) of gas flow rate.

Effect of gas flow rate

The effect of flow rate of inert gas (nitrogen) outside
the solid sample is shown in Figs. 1, 2. From Fig. 1, it
can be seen that the higher the gas flow, the slower
the reaction, the reason being that when the nitrogen
flow rate is increased, more CO and CO2 are carried
off by the inert gas. This reduces the concentrations
of CO and CO2 in the solid matrix, the overall reaction
thus being decelerated.
If all zinc oxide is converted to zinc metal, the con-
version of zinc oxide should be equal to the zinc yield.
However, according to Figs. 1, 2, the fraction of zinc
oxide converted was, under all conditions, higher
than the yield of zinc.
According to eqs. (1)–(2), zinc oxide is converted to
zinc metal gas, which would be collected by a con-
denser; the conversion of zinc oxide may then be
equal to the yield of zinc. However, in each of the
experiments, a small amount of zinc metal gas will
condense on the surface of the crucible and the quartz
wires. Thus, the yield of zinc is smaller than the con-
version of zinc oxide.

Effect of grain size

In this study, 2 series of experiments were preformed. Fig. 2. Plot of the yield of Zn against reaction time. The effect of gas
In one series, the grain size of zinc oxide was fixed at flow rate.

293
Chen

5¿10ª7 m and the grain size of carbon was varied:

5¿10ª7, 3.9¿10ª6, 4.14¿10ª5 m. In the other series,
the carbon grain size was held constant at 5¿10ª7 m,
and the zinc oxide grain size varied: 5¿10ª7,
3.9¿10ª6, 4.14¿10ª5 m. The results, as shown in Figs.
3–4, indicate that the smaller the grain size of either
zinc oxide or carbon, the faster the reaction.

Effect of molar ratio of C/ZnO

The results of this series of experiments are shown in
Fig. 5. A high carbon content in the solid sample pro-
vides more CO gas and accelerates the reaction rate.
Consequently, more zinc oxide is converted, produc-
ing more zinc metal. This explains the results shown
in Fig. 5: the higher the molar ratio of C/ZnO, the
faster the reaction.

Effect of solid sample height

Fig. 6 shows the effect of the solid sample height on
the conversions of zinc oxide and carbon. It is clear
that the higher the solid sample height, the higher the
conversions of zinc oxide and carbon. When the solid
sample height is large, the holding time of the CO gas
in the solid matrix is long. Hence, the resulting high Fig. 4. Plot of the conversion of ZnO against reaction time. The effect
concentration of CO gas in the solid sample increases of zinc oxide grain size.
the reaction rate.

Fig. 3. Plot of the conversion of ZnO against reaction time. The effect Fig. 5. Plot of the conversion of ZnO against reaction time. The effect
of carbon grain size. of molar ratio of ZnO/C.

294
 Reduction of zinc oxide

Fig. 6. Plot of the conversion of ZnO against reaction time. The effect Fig. 7. Plot of the conversion of ZnO against reaction time. The effect
of solid sample height. of initial bulk density.

Effect of initial bulk density

In this series of experiments, 4 experimental runs with
different initial bulk density were carried out: 216.7,
336.5, 454.3 and 570.4 kg/m3. When the initial bulk
density of the solid sample is increased, the contact
area between zinc oxide and carbon is increased, and
more importantly, the inter-particle gas diffusion path
decreased. Hence, the reaction rate is increased. The
higher initial bulk density may also reduce the po-
rosity of the solid matrix impeding the diffusion of
CO and CO2 from the solid matrix to solid surface.
Consequently, the overall reaction is accelerated as
evidenced in the results shown in Fig. 7.

Effect of reaction temperature

Experiments were conducted at 5 temperatures within
the range 1073 to 1423 K, and the results shown in
Fig. 8. It can be seen that an increase in reaction tem-
perature accelerates the reaction. When the reaction
temperature is below 1173 K, the conversion of zinc
oxide is very low.

Reaction rate expressions

From the data obtained, the following empirical rate Fig. 8. Plot of the conversion of ZnO against reaction time. The effect
expressions for the conversions of zinc oxide and of reaction temperature.

295
Chen

carbon and the yield of zinc were determined by the drawn for Figs. 1, 2 and 6, since the resistance due to
regression method: the gas film mass transfer and inter-grain gas dif-
fusion is substantial in these 2 cases.
dXXnO
rZnO Ω Ω 5.763¿109 exp(ª248,210/RT)
dt Conclusions
ª0.25 ª0.33 0.98 0.61
dC d ZnO |o X ZnOX 0.72 0.23
C Y Zn , (6) The rate of carbothermic reduction could be increased
by increasing the reaction temperature, initial bulk
dXC density, solid sample height or molar ratio of C/ZnO,
rC Ω Ω 4.831¿109 exp(ª321,540/RT)
dt and by decreasing the grain size or nitrogen flow rate.
ª0.36 ª0.57 0.95 0.49
dC d ZnO |o X ZnOX 0.57 0.12
C Y Zn , (7)
Acknowledgements
dYZn
rZn Ω Ω8.176¿108 exp(ª232,150/RT) The author thanks the National Science Council of
dt
Taiwan for its financial support for this investigation
ª0.17 ª0.35 0.52 0.61
dC d ZnO |o X ZnOX 0.78 0.24
C Y Zn , (8) under Grant no. NSC88–2214-E-146–002.

where dC is the grain size of carbon(m), dZnO the grain

size of zinc oxide (m), R the gas constant (8.314 J/mol),
T reaction temperature (K), XZnO the conversion of zinc
oxide, XC the conversion of carbon, Yzn the yield of zinc
and |o the initial bulk density of solid sample (kg/m3).
That the higher the temperature, the higher the re-
action rate, is fully represented by the exponential
terms; that the smaller the grain sizes of zinc oxide or
carbon, the faster the reaction, is presented by the
minus exponents of dZnO and dC in the rate expres-
sions. When the value of the initial bulk density is
larger, the faster the reaction is presented by the ex-
ponents of |o in the rate expressions.
The conversions of zinc oxide and the yield of zinc
calculated by integrating eqs. (6)–(8) are represented
by solid lines in Figs. 3–5 and 7, 8 (the experimental
conditions coincide with the symbol). Good agree-
ment is found between the calculations and actual
measurements. The calculated curves have not been
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