Advanced Materials Research Vols 311-313 (2011) pp 891-897 Online: 2011-08-16

© (2011) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/AMR.311-313.891

Experimental research on the novel process of iron ore direct reduction

by coal gas

YI Ling-Yun 1,a, HUANG Zhu-Cheng 1,b, PENG Hu2, JIANG Tao1

1
School of Minerals Processing and Bioengineering, Central South University, Changsha, China.
2
Changsha Syno-Therm Co., Ltd. ,Changsha, China
a
email: [email protected], bemail: [email protected]

Keywords: iron ore pellets, coal gas, gas-based direct reduction, reduction kinetics
Abstract: In this paper, the direct reduction of iron ore pellets was carried out by simulating the
typical gas composition in coal gasification process, Midrex and Hyl Ⅲ process, the influence of
gas composition and temperature on reduction was studied. Results show that the proportion of H2
increasing is helpful to improve the reduction rate, while when H2/CO>1.6, changes of H2 content
will have very little influence on it. Appropriate reduction temperature is about 950℃, higher
temperature(1000℃) may unfavorably slowed the reduction rate. From the kinetics analysis at 950℃
and 1000℃, when H2/CO=0.4 the prophase of reduction course (~90%) is likely controlled by
interfacial chemical reaction mechanism and in the later controlled by gaseous diffusion
mechanisms. However, when H2/CO>0.4 the whole reduction course is likely controlled by
interfacial chemical reaction mechanism. The reaction rate constant (k) and effective diffusion
coefficient (De) at 950℃ are both better than those at 1000℃. Research also shows that the
coal-water slurry gasification based on Texaco furnace is more suitable for iron ore direct reduction
than other coal gasification processes.

Introduction
Compared with “blast furnace-converter-continuous casting” process, the “electric arc
furnace-continuous casting” process with advantages of lower investment and energy consumption,
higher productivity and better environmental protection is concerned by more and more steel
enterprises. Due to the pure and stable composition, direct reduction iron (DRI) is considered to be
the perfect material for electric arc furnace (EAF) steelmaking. [1] As EAF steel output growing and
the high quality scrap supply is seriously insufficient, the demand for DRI will grow continuously
in the world.
The gas-based reduction process with advantages of mature technology and high productivity is
the main one in direct reduction process. But using natural gas as reductant makes its development
restricted by gas and region.[2] So developing the coal-gas reduction process is significant for the
promotion of steel industry in China. In recent years, researches of using coke oven gas (COG),
Corex furnace gas as reductant in iron ore reduction are studied widely. The process using COG as
reductant in Hyl-Ⅲ has been carried out in Mexico. The process using Corex gas in Midrex
furnace has also been carried out in Saldanha, South Africa, with production of 650000 tons per
year.[3] However, research on using coal gas in direct reduction is rare. In this paper the direct
reduction of iron ore pellets was carried out by simulating the typical gas composition in coal
gasification process, Midrex and Hyl Ⅲ process, the influence of gas composition and temperature
on reduction was studied.

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892 Advanced Materials and Processes: ADME 2011

Experimental
The chemical composition of iron ore pellets investigated in the present study is shown in Table 1.
The majority of the charged pellets were in the size range 12.5-16 mm, the crushing strength of the
pellets was 2973 N. The schematic diagram of experimental apparatus is shown in Fig.1.

Table 1. Chemical composition of the iron ore pellets

Composition TFe FeO SiO2 Al2O3 MgO CuO V2O5

Mass% 64.24 0.24 5.31 1.55 0.61 0.05 0.02

Fig. 1. Schematic diagram of the apparatus.

1-Cylinder,2-Gas flowmeter,3-Mixer,4-Elevator,5-Electronic balance,
6-Silica tube,7-Sharft furnace,8-Pellets,9-Gas outlet

The temperature of reducing gas in Midrex process is 850~900℃, and 930~950℃ in Hyl-Ⅲ
process. Gas composition in the two processes is shown in Table 2. Typical gas composition in coal
gasification process is shown in Table 3.[4,5]

Table 2. Gas composition in MIDREX and HYL-Ⅲ processes

Composition CO CO2 H2 H2O CH4 N2
MIDREX 34~37 1.5~2.5 55~58 3~4 0.5~3 0.5~1
HYL-Ⅲ 23.5 3.0 61.8 0.6 4.0 7.1
Table 3. Gas composition in coal gasification process
Composition CO CO2 H2 H2O CH4 N2
Texaco 45~55 ~10 30~40 - 0.06 0.3
Shell 63.3 1.5 26.7 2.0 0 4.1
BGL 54.23 3.03 32.6 - 6.13 3.35
Table 4. Composition of the reducing gas
Composition H2 CO CO2 N2
25.7 64.3 2 8
33.8 56.2 2 8
Ratio% 45 45 2 8
55.4 34.6 2 8
65 25 2 8
 Advanced Materials Research Vols. 311-313 893

In Texaco and Shell process, as in Midrex and Hyl process, the total content of H2 and CO is
about 90%, but the ratio of each differs widely. In Shell, BGL and Texaco processes, the proportion
reaches about 0.4, 0.6 and 1.0 respectively. In Midrex and Hyl processes the proportion reaches 1.6
and 2.6. So, compositions of the five reducing gases investigated in the present study are shown in
Table 4, the proportion of H2:CO is 0.4,0.6, 1.0, 1.6 and 2.6 respectively.

Results and Discussion

Effect of Reducing Gas Composition. Iron ore pellets were reduced at 850~1000℃ with H2:CO
varying from 0.4 to 2.6 in the reducing gas. Changes of the reduction degree of the pellets with time
during the reduction are shown in Figs. 2. In general, the increase in hydrogen content caused a
obvious increase in reduction rate. As shown in Fig. 2, when the proportion of H2:CO increases
from 0.4 to 1.6, reduction rate will increase significantly. In proportion range from 1.6 to 2.6, the
reduction curves are almost coincident, which indicates that change of H2 content has little effect on
the reduction rate. Due to the superior diffusion coefficient and adsorption capacity, H2 can improve
the reduction rate.[6] However, in actual reduction process, reduction rate is also influenced by many
other factors, such as temperature, ore size, porosity and reaction pressure. Reduction rate does not
increase infinitely along with the raise of H2 content, so choose an appropriate composition of
reducing gas is important in optimization of reduction process.

Fig.2. Reduction ratio of pellets by reducing gases with various proportion of H2:CO
at 850℃(a), 900℃(b), 950℃(c), 1000℃(d).

Effect of Temperature. The isothermal reduction curves at 850~1000℃ are given in Fig. 3. It was
found that for each reduction curve, the rate of reduction was highest at the early stages and
decreased as reduction proceeds. In general, reduction rate increases with temperature. However,
with temperature raise to 1000℃, reduction rate significantly slows to the same level as 850~900℃.
894 Advanced Materials and Processes: ADME 2011

Normally, rise of temperature can improve reduction reaction rate, but the porosity of iron ore in
reduction process is constantly changing. At lower temperature the change is very small, but at
higher temperature, as the mineralogical transformation, sintering and softening occur in the pellets.
Thereby, reduction rate vs. temperature curves appear special changes. Li Yongquan[7] also found
that pellets began to softening around 1000℃, which hindered the reducing gas diffusion. On the
other hand, the equilibrium constant of reaction: H2+CO2=CO+H2O(g)+△H(1) increases with
temperature. So concentration of H2 in the reaction system decreases, while that of CO and H2O
increase, which results in reduction rate slowing. Tateo USUI[8] also proved the influence of
reaction(1) that reduction rate at 900℃ was higher than that at 1000℃.

Fig. 3. Reduction ratio of pellets at 850~1000℃ by reducing gases

with various proportion of H2:CO, H2:CO=0.4(a), 0.6(b), 1.0(c), 1.6(d), 2.6(e).
Reaction Kinetics. Based on the observed results, it can be concluded that the reduction of the
pellet proceeded topochemically. This kind of reaction included the process of diffusion of gaseous
species and that of intrinsic chemical reaction. The total reduction time is expressed by Eq.(2),
which is valid under the conditions of solid sphere being reacted with gas phase, the effect of gas
phase mass transfer being negligible and the reaction rate being controlled by intrinsic interfacial
chemical reaction and the diffusion of reactant and product gas species through solid product
layer.[9,10]
r0 ρ 0  1
 r0 2 ρ 0  2R 2

t= 1 − (1 − R ) 3
 + 1 − − (1 − R ) 3
 (2)
k (C0 − Cq )   De (C0 − Cq )  3 
Where t is reduction time (min), C0 and Cq are reduction gas concentration at granule surface
and in equilibrium, respectively (mol/cm3), k is reaction rate constant (cm/min), De is effective
diffusion coefficient (cm2/min), r0 is characteristic initial radius of pellets (cm), ρ0 is initial oxygen
concentration in the pellet (mol/cm3), and R is reduction degree.
Based on the results shown in Figs.5~6, the reduction at 950℃ was optimum, while reduction
rate significantly slows at 1000℃. So applying Eq.(2), three cases for rate controlling step at 950℃
and 1000℃ with various proportion of H2:CO were examined, namely, (i) chemical reaction
control, (ii) diffusion control and (iii) mixed control. The relationship between 1-(1-R)1/3and time at
950℃ is shown in Fig. 4.
 Advanced Materials Research Vols. 311-313 895

1.0 0.29

0.9
0.28
0.8

0.7

g(x)=1-2x/3-(1-x)2/3
0.27
f(x)=1-(1-x)1/3

0.6 g(x)=0.03+0.0052t
R=0.98271
0.5
0.26
0.4

0.3 H2/CO=0.4 f(x)=0.01723t

H2/CO=0.6 f(x)=0.02509t 0.25
0.2 H2/CO=1.0 f(x)=0.02985t
H2/CO=1.6 f(x)=0.03007t
0.1 0.24
H2/CO=2.6 f(x)=0.03108t
0.0
0 5 10 15 20 25 30 35 40 45 50 39 40 41 42 43 44 45 46 47 48

Time,min Time,min

Fig. 4. Relationship between 1-(1-R)1/3 and Fig. 5. Relationship between 1-2R/3-(1-R)2/3

time at 950℃. and time in later phase for H2/CO=0.4.

It was found that, when H2/CO=0.4 the prophase of reduction course (R=0~91.36%) is likely
controlled by interfacial chemical reaction mechanism, as shown in Fig.4, and the later controlled
by gaseous diffusion mechanisms, shown in Fig.5. However, when H2/CO>0.4 the whole reduction
course is likely controlled by interfacial chemical reaction mechanism, shown in Fig.4. Obviously,
H2 decrease the diffusion resistance due to the smaller molecule diameter, so with the increase of H2
content the diffusion control step in the last stage was effectively avoided.
The relationship between 1-(1-R)1/3and time at 1000℃ is shown in Fig. 6. Similar with that at
950℃, when H2/CO=0.4 the prophase of reduction course (R=0~90.95%) is likely controlled by
interfacial chemical reaction mechanism, as shown in Fig.6, and the later controlled by gaseous
diffusion mechanisms, shown in Fig.7. However, when H2/CO>0.4 the whole reduction course is
likely controlled by interfacial chemical reaction mechanism, shown in Fig.6.

0.9 0.28

0.8
0.27
0.7
0.26
g(x)=1-2x/3-(1-x)2/3

0.6 g(x)=0.06+0.004t
f(x)=1-(1-x)1/3

0.5 0.25 R=0.99809

0.4 0.24
0.3 H2/CO=0.4 f(x)=0.0159t
0.23
H2/CO=0.6 f(x)=0.01808t
0.2 H2/CO=1.0 f(x)=0.01979t
H2/CO=1.6 f(x)=0.02583t 0.22
0.1
H2/CO=2.6 f(x)=0.02681t
0.0 0.21
0 5 10 15 20 25 30 35 40 45 50 40 42 44 46 48 50
Time,min Time,min

Fig. 6. Relationship between 1-(1-R)1/3 and Fig.7.Relationship between 1-2R/3-(1-R)2/3 and

time at 1000℃. time in later phase for H2/CO=0.4.
896 Advanced Materials and Processes: ADME 2011

The slopes of lines in the figure were obtained from linear regression analysis, and the reaction
rate constant was calculated at each experimental condition, showing in Table 5. The effective
diffusion coefficient in later phase for H2/CO=0.4 was calculated, showing in Table 6.

Table 5. Reaction rate constant at 950℃ with various proportion of H2:CO.

Reaction rate Gas compositon（H2:CO）
constant, cm/min 0.4 0.6 1.0 1.6 2.6
950℃ 0.01732 0.02509 0.02985 0.03007 0.03108
1000℃ 0.01590 0.01808 0.01979 0.02583 0.02681

As can be seen, interface reaction rate constant increases with the proportion rise of H2 in
reducing gas. So raising the proportion of H2, can effectively improve the reduction process.
Compared with 1000℃, the reaction rate constant(k) and effective diffusion coefficient(De) at
950℃ are obviously superior.
Table 6. Effective diffusion coefficient in later phase for H2/CO=0.4

Effective diffusion coefficient, 950℃ 1000℃

cm2/min 0.0052 0.004

Conclusions
The direct reduction of the iron pellets by the typical gas composition in coal gasification process,
Midrex and Hyl Ⅲ process were investigated from 850℃ to 1000℃. The results can be
summarized as follows:
(1) Generally, the increase of hydrogen content in reducing gas leads to an obvious increase in
reduction rate. When the proportion of H2:CO increases from 0.4 to 1.6, reduction rate will
increase significantly. In the proportion range from 1.6 to 2.6, the reduction rate keeps invariant.
(2) Raising temperature can effectively improve the reduction rate. However, with temperature raise
to 1000℃, reduction rate significantly slows. So the optimum reduction temperature is about
950℃.
(3) From the kinetics analysis at 950℃ and 1000℃, when H2/CO=0.4 the prophase of reduction
course (~90%) is likely controlled by interfacial chemical reaction mechanism and in the later
controlled by gaseous diffusion mechanisms. However, when H2/CO>0.4 the whole reduction
course is likely controlled by interfacial chemical reaction mechanism. The reaction rate
constant (k) and effective diffusion coefficient (De) at 950℃ are obviously superior.
(4) According to research, the coal-water slurry gasification based on Texaco furnace is more
suitable for iron ore direct reduction than other coal gasification processes.

Acknowledgements
This work was financially supported by the National science fund for distinguished young scholars
(50725416).
 Advanced Materials Research Vols. 311-313 897

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Advanced Materials and Processes: ADME 2011
10.4028/www.scientific.net/AMR.311-313

Experimental Research on the Novel Process of Iron Ore Direct Reduction by Coal Gas
10.4028/www.scientific.net/AMR.311-313.891