JOM

https://doi.org/10.1007/s11837-018-2927-8
 2018 The Minerals, Metals & Materials Society

MANUFACTURING WITH RECYCLED MATERIALS

Nonisothermal Carbothermal Reduction Kinetics

of Titanium-Bearing Blast Furnace Slag

MENGJUN HU,1 RUIRUI WEI,1,2 MEILONG HU,1,3 LIANGYING WEN,1

and FANGQING YING1

1.—College of Materials Science and Engineering, Chongqing University, Chongqing 400044,

People’s Republic of China. 2.—e-mail: wrui1990@outlook.com. 3.—e-mail: hml@cqu.edu.cn

The kinetics of carbothermal reduction of titanium-bearing blast furnace (BF)

slag has been studied by thermogravimetric analysis and quadrupole mass
spectrometry. The kinetic parameters (activation energy, preexponential fac-
tor, and reaction model function) were determined using the Flynn–Wall–
Ozawa and Šatava–Šesták methods. The results indicated that reduction of
titanium-bearing BF slag can be divided into two stages, namely reduction of
phases containing iron and gasification of carbon (< 1095C), followed by
reduction of phases containing titanium (> 1095C). CO2 was the main off-gas
in the temperature range of 530–700C, whereas CO became the main off-gas
when the temperature was greater than 900C. The activation energy calcu-
lated using the Flynn–Wall–Ozawa method was 221.2 kJ/mol. D4 is the
mechanism function for carbothermal reduction of titanium-bearing BF slag.
Meanwhile, a nonisothermal reduction model is proposed based on the ob-
tained kinetic parameters.

et al.3 proposed preparation of TiC in vacuum using

INTRODUCTION
Titanium carbide (TiC), as the main ingredient of
cemented carbide, is widely used in the machine
manufacturing, metallurgy, and aerospace fields,
due to its high melting point, high hardness, and
high chemical resistance. Carbothermal reduction
of TiO2 is currently the main method to produce TiC
powder.1 However, this process has the disadvan-
tages of high cost and heavy pollution.1–3
Titanium-bearing blast furnace (BF) slag, con-
taining about 23–29% TiO2, is a byproduct of the
iron-making process in the Panzhihua–Xichang
area of China.2,4 More than 70 million tons of
titanium-bearing BF slag has been accumulated,
increasing at the rate of about 3.5 million tons per
year.5 Such an enormous amount of stored tita-
nium-bearing BF slag may cause significant envi-
ronmental pollution and represents resource waste.
However, there are currently no energy-efficient,
cheap ways to use the titanium in such slag.
Therefore, many researchers have focused on uti-
lization of titanium-bearing BF slag,3,5–9 particu-
larly secondary utilization of titanium. In recent
years, some researchers have proposed a method to
prepare TiC from titanium-bearing BF slag. Hu
a method based on carbothermal reduction and acid
leaching. The influence of the carbon content,
reduction time, and vacuum degree on such forma-
tion of TiC was investigated. Zhen et al.10 studied
synthesis of TiC by carbothermal reduction of
titanium-bearing BF slag in a tube furnace,11 and
subsequently investigated the effect of the reduction
time and carbon particle size on such preparation of
TiC. The proposed process offers lower-cost prepa-
ration of TiC with increased utilization efficiency of
titanium-bearing BF slag.
To complete the process and improve the effi-
ciency of preparation of TiC by carbothermal reduc-
tion of titanium-bearing BF slag, thermogravi-
metric analysis (TGA) and quadrupole mass spec-
trometry (QMS) were used in this work to investi-
gate the reduction kinetics of titanium-bearing BF
slag.
EXPERIMENTAL PROCEDURES
Materials
The chemical composition of the Ti-bearing slag
used in these experiments is presented in Supple-
mentary Table SI. Before the experiments, milled
 Mengjun Hu, Wei, Meilong Hu, Wen, and Ying

slag ( 74 lm) was homogeneously mixed with

carbon powder ( 50 lm, 99.9% commercial purity)
at mass ratio of 1:0.38.3

Thermogravimetric Analysis
TGA experiments were carried out using a Setsys
Evo 1750 TGA apparatus (Setaram, France). Slag–
carbon mixture was heated from ambient tempera-
ture to 1450C in the furnace at predetermined
heating rate of 4C/min, 6C/min or 8C/min. The
flow rate of argon was determined to be 20 mL/min.
When the temperature reached 1450C, the samples
were held for several hours to complete the reduction
process. The final mass of samples was recorded.
During reduction, the quantitative composition of
the off-gas was simultaneously monitored by con-
necting the TGA apparatus to a QMS with LC-D200
(Tilon, UK) apparatus, previously calibrated, until
the temperature reached 1450C. The phase trans-
formations during reduction were investigated by x-
ray diffraction (XRD) analysis using a D/Max2500/
PC apparatus (Rigaku Corporation, Japan).

Rate Law and Kinetic Analysis12–15

For details, see the Supplementary Material
section ‘‘Rate law and kinetic analysis.’’

RESULTS AND DISCUSSION

Carbothermal Reduction Behavior
Titanium-bearing BF slag, considered to be a mix-
ture of the main oxides TiO2, Al2O3, CaO, SiO2, Fe2O3,
and FeO, was investigated using thermodynamics
calculations with FactSage6.2 (Thermfact and GTT-
Technologies, Germany). The relationship between
the Gibbs free energy of reduction of oxides and
temperature was obtained and is shown in Fig. 1a.
The results indicated that iron oxide can be reduced to
Fe at 700C, whereas the titanium oxide can be
reduced at temperatures > 1050C. The other oxides
(Al2O3, CaO, and SiO2) cannot be reduced below
1450C. It is inferred that iron oxide is easier to reduce
than titanium oxide. The iron oxide is first reduced
to low-valence-state oxides then to Fe (Fe2O3 fi
Fe3O4 fi FeO fi Fe).16–18 Similarly, TiO2 is first
reduced to a low-valence-state oxide then to TiC at
higher temperature (TiO2 fi TinO2n–1 fi TiC).19–21
It is worth noting that several low-valence-state tita-
nium oxides will be produced during the reduction.
Ti-bearing BF slag was reduced using carbon
powder at three different heating rates. As a result
of the limitations of the experimental equipment, in
this study, only the experimental TGA data
obtained from room temperature to 1450C were
used to calculate the nonisothermal reduction kinet-
ics of the titanium-bearing BF slag.
The XRD patterns of the original sample, and
samples obtained at 1100C and after the complete
reduction experiments are shown in Fig. 1b. The
results indicate that phases containing iron were
Fig. 1. (a) Changes of Gibbs free energy with temperature at 1 atm
and (b) XRD patterns of samples in the experiments.
reduced to Fe at 1100C, whereas phases containing
titanium were reduced to TiC after the complete
reduction experiments.
The weight loss, reduction degree, and reduction
rate are shown as functions of temperature in
Fig. 2a, b, and c, respectively, revealing that the
heating rate clearly affected all three. The slag was
reduced until the temperature reached 595C.
When the temperature exceeded 670C, the mass
loss from the sample slowed due to a lower reduc-
tion rate. However, the weight loss changed again
when the temperature reached 800C. For the
different heating rates, the weight loss, reduction
degree, and reduction rate clearly increased with
increase of the temperature > 800C. The reduction
degree in this study reached 0.93, 0.88, and 0.81 for
heating rate of 4C/min, 6C/min, and 8C/min.
Figure 2d shows the results of analysis of the off-gas
from the reduction experiments carried out at differ-
ent heating rates. Three obvious CO2 peaks are
observed at temperatures ranging from 530C to
700C for the different heating rates, whereas CO
was not detected. This may be due to reduction of
phases containing iron in the slag (Fe2O3 fi Fe3O4).
When the temperature exceeded 900C, CO and CO2
appeared simultaneously. The contents of CO and CO2
Nonisothermal Carbothermal Reduction Kinetics

Table I. Selected possible reaction models based on Šatava–Šesták method

A1 A2 A3/2

b (C/min) Es (kJ/mol) lg A (/min) |r| Es (kJ/mol) lg A (/min) |r| Es (kJ/mol) lg A (/min) |r|
4 162.6 1.82 0.971 81.3 – 0.63 0.987 108.4 0.17 0.971
6 155.6 1.65 0.979 77.8 – 0.62 0.972 103.8 0.11 0.975
8 182.1 2.64 0.986 91.0 – 0.05 0.999 121.4 0.83 0.991

A1/2 D2 D3

b (C/min) Es (kJ/mol) lg A (/min) |r| Es (kJ/mol) lg A (/min) |r| Es (kJ/mol) lg A (/min) |r|
4 325.3 7.04 0.974 268.1 4.58 0.988 282.1 4.80 0.985
6 311.3 6.49 0.979 267.7 4.54 0.987 278.5 4.65 0.985
8 364.1 14.14 0.982 309.9 5.52 0.994 309.9 6.23 0.997

D4 D8 C1

b (C/min) Es (kJ/mol) lg A (/min) |r| Es (kJ/mol) lg A (/min) |r| Es (kJ/mol) lg A (/min) |r|
4 223.1 2.26 0.996 277.2 4.26 0.986 216.6 3.81 0.946
6 227.9 2.45 0.994 274.7 4.16 0.986 194.2 3.06 0.962
8 234.8 2.81 0.994 318.7 5.71 0.997 230.3 4.36 0.994
The bold font is to point out the difference between the calculated data using D4 model and the others, the calculated data with bold font is
the reaction activation energy

increased with increasing temperature, and the CO
concentration was much higher than that of CO2. It is
worth noting that two distinct dips can be observed
from 800C to 1095C, consistent with the results for
da
. This may reflect the reaction of Fe3O4 fi FeO and
dt
FeO fi Fe. When the temperature exceeded 1095C,
based on the results of the thermodynamics calcula-
tions, phases containing titanium should start to be
reduced. With increase of the temperature, the con-
tent of CO first increased then decreased, and then
again, particularly for the rate of 4C/min. It can be
inferred that the reduction reactions TiO2 fi
TinO2n 1 and TinO2n 1 fi TiC occurred at this
stage. When the temperature exceeded 900C, the
CO content increased greatly. Meanwhile, the reduc-
tion degree significantly increased, indicating the
main reduction stage of the slag.
Therefore, combining the results in Figs. 1 and 2,
the reduction process of titanium-bearing BF slag
can be divided into two stages. The first stage
mainly corresponds to reduction of phases contain-
ing iron (from iron oxide to Fe) and gasification
reaction of carbon (CO2 + C = 2CO) at temperatures
< 1095C. In the second stage, the reaction is
mainly reduction of phases containing titanium at
temperatures > 1095C.
Calculation of Activation Energy Using
Flynn–Wall–Ozawa Method
Reduction of iron oxide mainly occurs at lower
temperature and lower reduction degree. Figure 2b
indicates that the reduction degree was less than 0.10
at 1100C. Therefore, to completely exclude the influ-
ence of reduction of iron oxide, the reduction degree
values from 0.15 to 0.80 in steps of 0.05 were used to
calculate the activation energy using Eq. 7 (see
supplementary material). The relationships between
lg b and 1/T corresponding to the selected reduction
degrees are plotted in Supplementary Fig. S1, show-
ing a linear relationship. The activation energy for
reduction of titanium-bearing BF slag was calculated
from the slopes using the Flynn–Wall–Ozawa method.
The activation energy values are presented in Sup-
plementary Table SIII. Note that the activation
energy at different reduction degrees first increased,
then decreased to 194.8 kJ/mol, then increased to
253.45 kJ/mol when the reduction degree reached
0.80, indicating that the samples were more difficult to
reduce in the latter stage. The activation energy value
for the entire reduction process was s 221.2 kJ/mol.
This TGA–QMS method provides an alternative
approach to calculate the reduction kinetics of tita-
nium-bearing BF slag.
Most Probable Mechanism Function
To determine the most probable mechanism func-
tion for nonisothermal reduction of titanium-bear-
ing BF slag, the Šatava–Šesták method was applied.
According to previous works,13,18,19,21 the Avrami–
Erofeev model, diffusion model, and chemical reac-
tion model are the most probable mechanism func-
tions for the carbothermal reduction experiments.
The Šatava–Šesták method can be used to obtain
the differential and integral expressions for the
common reaction mechanisms.

Fig. 2. (a) Weight loss, (b) reduction degree, (c) reduction rate, and (d) off-gas content recorded by QMS for titanium-bearing BF slag versus
temperature at different heating rates.
For different heating rates, linear fit results for lg
b versus 1/T are shown in Fig. 3. The calculated
results for the activation energy, preexponential
factor, and correlation coefficients are presented in
Table I. Note that the linearity of g(a) for D2, D3, D4,
and D8 is excellent, with the activation energies of
the D4 reaction model at different heating rates
being closer than the others. Moreover, the activa-
tion energies of the D4 reaction model calculated
using the Flynn–Wall–Ozawa method (Table SII)
Mengjun Hu, Wei, Meilong Hu, Wen, and Ying
and Flynn–Wall–Ozawa method (221.2 kJ/mol)
agree well with each other. Therefore, the D4
reaction model, namely, g(a) = [(1 + a)1/3 1]2 and
f(a) = 3/2(1 + a)2/3[(1 + a)1/3 1] 1, is the most prob-
able mechanism function for nonisothermal reduc-
tion of titanium-bearing BF slag. The reaction
mechanism identified in this study is in agreement
with the reaction mechanisms proposed for TiO2 in
previous studies.22 Meanwhile, according to the
Nonisothermal Carbothermal Reduction Kinetics

Kinetics Model
The kinetics model for nonisothermal reduction of
titanium-bearing BF slag can be obtained by sub-
stituting the activation energy and preexponential
factor into the D4 reaction model. The nonisother-
mal kinetic models at different heating rates are
presented in Table II.

CONCLUSIONS
The reduction kinetics of titanium-bearing BF
slag was studied by TGA–QMS method. The follow-
ing conclusions can be obtained:
1. Carbothermal reduction of titanium-bearing BF
slag can be divided into two stages. The first
stage is reduction of phases containing iron
and gasification of carbon at temperatures
< 1095C, and the second stage is reduc-
tion of phases containing titanium at temper-
atures > 1095C. The reduction degree
increased with increase of temperature, and
CO 2 was the main off-gas at temperatures
< 700C whereas CO became the main off-gas
at temperatures > 900C. With increasing
heating rate, the weight loss and reduction
degree decreased, especially when the temper-
ature was higher than 800C.
2. The activation energy estimated by the Flynn–
Wall–Ozawa method was 221.2 kJ/mol, and
the activation energies estimated using the
Šatava–Šesták method were 223.1 kJ/mol,
227.9 kJ/mol, and 234.8 kJ/mol at heating rate
of 4C/min, 6C/min, and 8C/min, respec-
tively.
3. The most probable mechanism function for the
nonisothermal reduction of titanium-bearing BF
slag is the D4 reaction model with integral and
differential forms of g(a) = [(1 + a)1/3 1]2 and
Fig. 3. Relationship between g(a) and 1/T at (a) 4C/min, (b) 6C/ f(a) = 3/2(1 + a)2/3[(1 + a)1/3 1] 1, respectively.
min, and (c) 8C/min.
Kinetic models for nonisothermal carbothermal
reduction of titanium-bearing BF slag were
obtained.

Table II. Kinetic model of reduction of titanium- ACKNOWLEDGEMENTS

bearing slag in slag–carbon mixture
The authors are grateful to the National Natural
b (C/min) Kinetics model Science Foundation of China (Project 51674054) and
the Open Foundation of the State Key Laboratory of
4 da/dT = 183exp( 27,076/T) (3/2) Vanadium and Titanium Resources Comprehensive
(1 + a)2/3[(1 + a)1/3 1] 1 Utilization of China for support. R.W. thanks the
6 da/dT = 280exp( 27,578/T) (3/2) China Scholarship Council for financial support.
(1 + a)2/3[(1 + a)1/3 1] 1
8 da/dT = 645exp( 28,401/T) (3/2)
(1 + a)2/3[(1 + a)1/3 1] 1
ELECTRONIC SUPPLEMENTARY
MATERIAL
results in Table I, the activation energy (Es) and
preexponential factor (lg A) increased from The online version of this article (https://doi.org/
223.1 kJ/mol to 234.8 kJ/mol and 2.26/min to 2.81/ 10.1007/s11837-018-2927-8) contains supplemen-
min as the heating rate was increased from 4C/min tary material, which is available to authorized
to 8C/min. users.

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