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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
a method based on carbothermal reduction and acid
Titanium carbide (TiC), as the main ingredient of leaching. The influence of the carbon content,
cemented carbide, is widely used in the machine reduction time, and vacuum degree on such forma-
manufacturing, metallurgy, and aerospace fields, tion of TiC was investigated. Zhen et al.10 studied
due to its high melting point, high hardness, and synthesis of TiC by carbothermal reduction of
high chemical resistance. Carbothermal reduction titanium-bearing BF slag in a tube furnace,11 and
of TiO2 is currently the main method to produce TiC subsequently investigated the effect of the reduction
powder.1 However, this process has the disadvan- time and carbon particle size on such preparation of
tages of high cost and heavy pollution.1–3 TiC. The proposed process offers lower-cost prepa-
Titanium-bearing blast furnace (BF) slag, con- ration of TiC with increased utilization efficiency of
taining about 23–29% TiO2, is a byproduct of the titanium-bearing BF slag.
iron-making process in the Panzhihua–Xichang To complete the process and improve the effi-
area of China.2,4 More than 70 million tons of ciency of preparation of TiC by carbothermal reduc-
titanium-bearing BF slag has been accumulated, tion of titanium-bearing BF slag, thermogravi-
increasing at the rate of about 3.5 million tons per metric analysis (TGA) and quadrupole mass spec-
year.5 Such an enormous amount of stored tita- trometry (QMS) were used in this work to investi-
nium-bearing BF slag may cause significant envi- gate the reduction kinetics of titanium-bearing BF
ronmental pollution and represents resource waste. slag.
However, there are currently no energy-efficient,
cheap ways to use the titanium in such slag. EXPERIMENTAL PROCEDURES
Therefore, many researchers have focused on uti-
Materials
lization of titanium-bearing BF slag,3,5–9 particu-
larly secondary utilization of titanium. In recent The chemical composition of the Ti-bearing slag
years, some researchers have proposed a method to used in these experiments is presented in Supple-
prepare TiC from titanium-bearing BF slag. Hu 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- Fig. 1. (a) Changes of Gibbs free energy with temperature at 1 atm
ture of the main oxides TiO2, Al2O3, CaO, SiO2, Fe2O3, and (b) XRD patterns of samples in the experiments.
and FeO, was investigated using thermodynamics
calculations with FactSage6.2 (Thermfact and GTT-
Technologies, Germany). The relationship between reduced to Fe at 1100C, whereas phases containing
the Gibbs free energy of reduction of oxides and titanium were reduced to TiC after the complete
temperature was obtained and is shown in Fig. 1a. reduction experiments.
The results indicated that iron oxide can be reduced to The weight loss, reduction degree, and reduction
Fe at 700C, whereas the titanium oxide can be rate are shown as functions of temperature in
reduced at temperatures > 1050C. The other oxides Fig. 2a, b, and c, respectively, revealing that the
(Al2O3, CaO, and SiO2) cannot be reduced below heating rate clearly affected all three. The slag was
1450C. It is inferred that iron oxide is easier to reduce reduced until the temperature reached 595C.
than titanium oxide. The iron oxide is first reduced When the temperature exceeded 670C, the mass
to low-valence-state oxides then to Fe (Fe2O3 fi loss from the sample slowed due to a lower reduc-
Fe3O4 fi FeO fi Fe).16–18 Similarly, TiO2 is first tion rate. However, the weight loss changed again
reduced to a low-valence-state oxide then to TiC at when the temperature reached 800C. For the
higher temperature (TiO2 fi TinO2n–1 fi TiC).19–21 different heating rates, the weight loss, reduction
It is worth noting that several low-valence-state tita- degree, and reduction rate clearly increased with
nium oxides will be produced during the reduction. increase of the temperature > 800C. The reduction
Ti-bearing BF slag was reduced using carbon degree in this study reached 0.93, 0.88, and 0.81 for
powder at three different heating rates. As a result heating rate of 4C/min, 6C/min, and 8C/min.
of the limitations of the experimental equipment, in Figure 2d shows the results of analysis of the off-gas
this study, only the experimental TGA data from the reduction experiments carried out at differ-
obtained from room temperature to 1450C were ent heating rates. Three obvious CO2 peaks are
used to calculate the nonisothermal reduction kinet- observed at temperatures ranging from 530C to
ics of the titanium-bearing BF slag. 700C for the different heating rates, whereas CO
The XRD patterns of the original sample, and was not detected. This may be due to reduction of
samples obtained at 1100C and after the complete phases containing iron in the slag (Fe2O3 fi Fe3O4).
reduction experiments are shown in Fig. 1b. The When the temperature exceeded 900C, CO and CO2
results indicate that phases containing iron were 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 at 1100C. Therefore, to completely exclude the influ-
concentration was much higher than that of CO2. It is ence of reduction of iron oxide, the reduction degree
worth noting that two distinct dips can be observed values from 0.15 to 0.80 in steps of 0.05 were used to
from 800C to 1095C, consistent with the results for calculate the activation energy using Eq. 7 (see
da supplementary material). The relationships between
. This may reflect the reaction of Fe3O4 fi FeO and
dt lg b and 1/T corresponding to the selected reduction
FeO fi Fe. When the temperature exceeded 1095C,
based on the results of the thermodynamics calcula- degrees are plotted in Supplementary Fig. S1, show-
tions, phases containing titanium should start to be ing a linear relationship. The activation energy for
reduced. With increase of the temperature, the con- reduction of titanium-bearing BF slag was calculated
tent of CO first increased then decreased, and then from the slopes using the Flynn–Wall–Ozawa method.
again, particularly for the rate of 4C/min. It can be The activation energy values are presented in Sup-
inferred that the reduction reactions TiO2 fi plementary Table SIII. Note that the activation
TinO2n 1 and TinO2n 1 fi TiC occurred at this energy at different reduction degrees first increased,
stage. When the temperature exceeded 900C, the then decreased to 194.8 kJ/mol, then increased to
CO content increased greatly. Meanwhile, the reduc- 253.45 kJ/mol when the reduction degree reached
tion degree significantly increased, indicating the 0.80, indicating that the samples were more difficult to
main reduction stage of the slag. reduce in the latter stage. The activation energy value
Therefore, combining the results in Figs. 1 and 2, for the entire reduction process was s 221.2 kJ/mol.
the reduction process of titanium-bearing BF slag This TGA–QMS method provides an alternative
can be divided into two stages. The first stage approach to calculate the reduction kinetics of tita-
mainly corresponds to reduction of phases contain- nium-bearing BF slag.
ing iron (from iron oxide to Fe) and gasification Most Probable Mechanism Function
reaction of carbon (CO2 + C = 2CO) at temperatures
< 1095C. In the second stage, the reaction is To determine the most probable mechanism func-
mainly reduction of phases containing titanium at tion for nonisothermal reduction of titanium-bear-
temperatures > 1095C. ing BF slag, the Šatava–Šesták method was applied.
According to previous works,13,18,19,21 the Avrami–
Calculation of Activation Energy Using Erofeev model, diffusion model, and chemical reac-
Flynn–Wall–Ozawa Method tion model are the most probable mechanism func-
tions for the carbothermal reduction experiments.
Reduction of iron oxide mainly occurs at lower The Šatava–Šesták method can be used to obtain
temperature and lower reduction degree. Figure 2b the differential and integral expressions for the
indicates that the reduction degree was less than 0.10 common reaction mechanisms.
Mengjun Hu, Wei, Meilong Hu, Wen, and Ying

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 and Flynn–Wall–Ozawa method (221.2 kJ/mol)
b versus 1/T are shown in Fig. 3. The calculated agree well with each other. Therefore, the D4
results for the activation energy, preexponential reaction model, namely, g(a) = [(1 + a)1/3 1]2 and
factor, and correlation coefficients are presented in
Table I. Note that the linearity of g(a) for D2, D3, D4, f(a) = 3/2(1 + a)2/3[(1 + a)1/3 1] 1, is the most prob-
and D8 is excellent, with the activation energies of able mechanism function for nonisothermal reduc-
the D4 reaction model at different heating rates tion of titanium-bearing BF slag. The reaction
being closer than the others. Moreover, the activa- mechanism identified in this study is in agreement
tion energies of the D4 reaction model calculated with the reaction mechanisms proposed for TiO2 in
using the Flynn–Wall–Ozawa method (Table SII) 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.
Mengjun Hu, Wei, Meilong Hu, Wen, and Ying

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