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Article history: Direct reduction of iron ore pellets (DRI) with and without biomass was studied using
Received 26 December 2014 hydrogen as the reducing agent. The influences of temperature and time on the reduction rate
Received in revised form of pellets were investigated. X-ray diffraction (XRD), scanning electron microscopy (SEM) and
13 February 2015 BET (Bet specific surface area) tests were adopted to interpret the mechanism of Fe2O3
Accepted 14 February 2015 reduction with H2, as well as explore the role of biomass in pellets during the reduction
Available online 12 March 2015 process. Results show that the biomass not only improve the reduction extent of the pellets,
but also increase the reduction velocity index (RVI) of the pellets by 1.12%/min. The BET test
Keywords: indicates that the existence of biomass can create porosity in pellets by dehydration and
Biomass combustion/pyrolysis, which increases the contact area between iron oxide and reducing gas
Ironmaking during reduction process, and decreases the apparent activation energy of pellets from
Direct reduction 122 kJ mol1 (without biomass) to 111 kJ mol1 (with biomass). For the DRI process, the crucial
Kinetics reduction step FeO / Fe is controlled by the intrinsic interfacial chemical reaction.
Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
* Corresponding author. School of Environmental Science & Engineering, Huazhong University of Science and Technology, 1037 Luoyu
Road, Wuhan, Hubei 430074, China. Tel.: 86 13247178429. .
E-mail address: xiaobo_hust@163.com (B. Xiao).
http://dx.doi.org/10.1016/j.ijhydene.2015.02.065
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
4734 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 4 7 3 3 e4 7 4 0
energy candidate in the direct reduction ironmaking to alle- The reactions of CO and H2 with iron oxide are endothermic,
viate the environmental pollution. which is in favor of the reduction of the pellets due to the
Recently, a number of studies have been conducted to effect of temperature field. Both CO and H2 are ideal reducing
introduce biomass into metallurgical industries [4e10]. Stre- agents for the process. However, compared to H2, the reduc-
zov [4] investigated the fundamental mechanisms of iron ore tion kinetics of CO is relatively poorer. Moreover, the genera-
reduction with biomass wood waste. Reduction tests were tion of a large amount of greenhouse gas CO2 from CO results
conducted using mixtures with different weight ratios of in the oxidation of metallic iron in the porous surface to form
biomass and iron ore. The iron ore was successfully reduced nFeO$SiO2 slag phase, subsequently leading to the decrease of
to predominantly metallic iron phase when 30 wt.% of direct reduction iron (DRI) quality.
biomass was introduced into the mixture. Katyal et al. [5] and In order to identify the optimal addition amount of
Emmerich et al. [6] investigated the possibility of metal biomass in pellets, a roasting process was conducted with
smelting operations with charcoal produced from wood or biomass addition amount varying from 0.5% to 10% in an
other biomass materials. The results showed that the charcoal increment of 0.5%. It was found that the pellets with a 2%e3%
can substitute for coke successfully in the blast furnace. In weight fraction of biomass exhibited the properties that meet
these studies the reduction of metallic oxides was performed the industrial requirements. Therefore, all the samples used
either using biomass in their natural form or char from in the present study have a weight fraction of 2% biomass.
biomass pyrolysis. The reduction process was driven by the In order to explore the kinetics and mechanism of direct
carbonthermic Boudouard reaction: reduction process of ironmaking with bio-gas, the direct reduc-
tion of iron ore pellets with and without biomass to metallic
Fex Oy s yCOs xFes yCO2 g (1) iron was studied with H2 as the reducing agent over a wide
range of temperatures. The effect of temperature and time on
xCs xCO2 g 2xCOg (2) the reduction rate of pellets was investigated. XRD, SEM and BET
tests were used to analyze the reduction mechanism. The effect
Fex Oy s xCs xFes y xCO2 g 2x yCOg (3) of biomass in pellets was also discussed in the present study.
Table 1 e Chemical compositions of iron ore and bentonite and the proximate and elemental analyses of the biomass.
Sample Chemical composition (%)
Fe Si Al Mn Ca Mg Ti S K
Iron ore 67.72 5.39 2.02 0.30 9.39 14.49 0.33 0.27 e
Bentonite 3.25 68.41 18.37 0.04 3.77 3.88 0.69 e 1.55
Biomass Ultimate analysis (wt.%)
C H O N S
48.21 6.54 44.39 0.77 0.09
Proximate analysis
Higher heating value (MJ/kg) Moisture content (wt.%) Volatile matter (wt.%) Fixed carbon (wt.%) Ash (wt.%)
16.83 7.78 73.06 16.33 2.83
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 4 7 3 3 e4 7 4 0 4735
The green balls were firstly dried in an oven at 378 K for Determination of the extent of reduction
24 h, then pre-sintered to 1173 K for 30 min and roasted at
1523 K for 25 min to afford oxidizing roasting pellets. At last, The reduction extent (f wt.%) is calculated by the following
the roasted pellets were reduced by hydrogen and nitrogen equation [11]:
(both the concentration of H2 and N2 use was 99.999%, pro- f 0:111W1 =0:430W2 m0 mi =m0 0:430W2 100% (4)
vided by Wuhan Xiangyun Industry CO., Ltd) in a specially
where m0 is the mass of the pellet before reduction, mi is the
designed experimental apparatus, which is presented in Fig. 1.
mass of the pellet in reduction process, W1 and W2 are the
mass of FeO and TFe in the pellet before and after the reduc-
tion respectively, 0.11 represents the oxygen demand con-
Experimental procedure and characterization
version coefficient when converting FeO to Fe2O3, 0.43
Fig. 1 e Schematic diagram of reduction experimental Fig. 2 e Reduction curves of oxidized pellets with
equipment: 1, Electronic balance; 2, reduction chamber; 3, temperature and time. (a). Oxidized pellets with 96 wt.%
composite pellet; 4, electric furnace; 5, Al2O3 particles; 6, N2 iron ore power, 2 wt.% biomass and 2 wt.% bentonite; (b).
reservoir; 7, H2 reservoir; 8, flow controller; 9, control Oxidized pellets with 98 wt.% iron ore power and 2 wt.%
cabinet; 10, computer. bentonite.
4736 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 4 7 3 3 e4 7 4 0
represents the oxygen demand conversion coefficient when which happens mainly in the later stage [12,13]. Secondly, the
converting Fe to Fe2O3. reduction process is commonly controlled by gas diffusion
and chemical reaction, and the contact area is the key factor.
In the initial reduction stage, the hydrogen can be easily
Results and discussion diffused to the reaction surface and the reaction area is larger
than that in the later stage, which can be described by the
Reduction behavior of pellets kinetics model e contracting unreduced nucleus model
[14e17].
The roasted pellets were isothermally reduced in the range of It can be seen from Fig. 2, reduction temperature has a
temperature from 1123 K to 1323 K with pure hydrogen and significant effect on the reduction ratedthe higher the tem-
the results are shown in Fig. 2. perature, the faster the reduction rate. Actually, the main
At the initial stage of reduction (0e5 min), the reduction reduction reactions (1e3, 5, 6) during DRI process are endo-
extent of pellets with biomass increased from 44.12% at 1123 K thermic, which are strengthened by increasing the
to 68.45% at 1323 K, while the value changed from 40.23% to temperature.
65.23% for the pellets without biomass. Afterward, the variation It can also be seen from Fig. 2, the addition of biomass has a
of reduction extent with time (10e20 min) became less pro- positive effect on the reaction extent. The time needed for the
nounced, which can be explained with two ways: Firstly, the reduction extent of 99% is shorter when adding biomass into
main reduction reactions in the initial stage were as follows: pellets under the same reduction temperature, reflecting an
accelerated reduction reaction rate.
3Fe2 O3 H2 2Fe3 O4 H2 O (5) In order to discuss the effect of porosity on the reduction
behaviors of the pellets, the pore volume and BET tests were
Fe3 O4 H2 3FeO H2 O (6) conducted. The results showed that the surface area of the
pellets with and without biomass were 6.03 m2/g and
At T > 843 K, The transformation of Fe2O3 to FeO is much
easier to take place compared to the reduction of FeO to Fe,
Fig. 5 e SEM images of pellets samples with different components before and after reduction. a. Pellets with biomass before
reduction; b. Pellets with biomass reduced for 5 min; c. Pellets with biomass reduced for 15 min; d. Pellets without biomass
before reduction; e. Pellets without biomass reduced for 5 min; f. Pellets without biomass reduced for 15 min.
16.26 m2/g, respectively. Fig. 3 displayed the nitrogen generally higher than that of pure iron ore. This reflects that
adsorption curve measured by automated gas adsorption adding biomass in pellets can improve the reduction extent of
system, using BJH (BarretteJoynereHalenda) method to illus- the pellets.
trate the pore volume distribution. The ordinate (dV/dD) is the The scanning electron micrographs of the reduced pellets
pore volume distribution function which represents the pore were examined to detect the surface changes of pellets with
volume during this range. biomass at different reduction time, 0 min, 5 min and 15 min
It can be seen from Fig. 3a that the pore distribution was (as shown in Fig. 5aec), and Fig. 5def shows the surface
non-uniform. In the pellets containing biomass, the pore changes of pellets without biomass. The internal average pore
diameter less than 95 nm mainly concentrated in the range size and porosity of pellets with biomass are larger than those
3e5 nm and 13e22 nm with pore volume pore (dV/dD) of about of pellets without biomass. Besides, the size distribution is
0.007 cm3/nm.g and 0.009 cm3/nm.g, respectively. Conversely more uniform for pellets with biomass due to the higher
the pore distribution showed in Fig. 3b was relatively uniform. conductivity for reduction reaction.
The pore diameter less than 95 nm mainly concentrated in the From Fig. 5b and e, it can be found that the small iron
range 2.5e92 nm, mostly in the range of 3e10 nm and the pore particles and large magnetite particles in pellets periphery are
volume (dV/dD) were between 0.0008 cm3/nm g and reduced to the wustite. The core iron ore particles are not
0.0009 cm3/nm g. reduced. But the reduction degree of pellets in Fig. 5b is higher
By comparison, the main difference is that when the pore than that of the reduced the pellets in Fig. 5e. The reasons can
size was 4 nm, the pore volume of pellets containing biomass be interpreted as follows: Firstly, after adding biomass pellets,
was 8 times higher than that of pellets without biomass, and the biomass that contacts with the iron ore was burned off in
when the pore size was 16 nm, this value was 15 times. In the roasting process. So the pellets with biomass inside would
other stages, pore volume of the pellets with biomass were form more pores. Accordingly the specific surface area and the
slightly higher than the pellets without biomass. reaction interface increased. However, for the pellets with no
For the gasesolid reduction reactions, high porosity facili- biomass, the pore between the iron ore didn't increase after
tates the gas molecules diffusion, and further promotes the roast. Secondly, after adding biomass, the porosity of the
reduction reactions. Thus the reduction performances of the pellets was increased and reducing gas is easier to diffuse and
pellets with the addition of biomass were better than the contact with the iron ore. Meanwhile, the gas generated is also
pellets without biomass. easier to flowing out. Therefore, under the condition of 1173 K
XRD analysis of samples before and after reduction at of temperature and 5 min of reducing time, adding biomass
1173 K under different reduction time was carried out and the into pellets reduced the resistance of interfacial chemical re-
results are shown in Fig. 4. It was observed that both kinds of action, resulting in the enhancement of reduction degree.
pellets can be reduced to metallic iron at 1173 K after some- When the reduction time lasted up to 15 min, both kinds of
where within 10e20 min. Under the same reduction condition, the pellets are almost reduced to metallic iron (Fig. 5c and f).
the peak value of products from pellets containing biomass is Compared with the pellets reduced for 5 min, metallic iron
4738 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 4 7 3 3 e4 7 4 0
grains have obvious aggregation and growth. However, the where kG is gas phase boundary mass transfer coefficient (cm/
final characteristics of the two reduced pellets are basically s); r0 is characteristic initial radius of pellets (cm); De is
the same. This shows that the addition of biomass has no effective diffusion coefficient (cm2/s) and given by:
influence on the quality of DRI products, but it greatly im- .
proves the pellets reduction rate and saves energy De r0 r20 6tD C0AH2 CAH2 ; (11)
consumption.
k is reaction rate constant (cm/s) and can be estimated by:
Analysis of the reduction velocity index .
k Kr0 r0 tC 1 K C0AH2 CAH2 ; (12)
The reduction velocity index (RVI) [11,17] was proposed to K is reaction equilibrium constant; r0 is initial oxygen
evaluate reduction behavior of the pellet. A higher RVI value concentration in the pellet (mol/cm3); C0AH2 and C*AH2 are the
indicates a higher reducibility of the pellets. The RVI equation concentration of H2 at granule surface and in equilibrium
is presented as below: (mol/cm3), respectively; t is reduction time (min).
According to un-reacted core model, the reduction time t
RVI dRt =dt 40 33:6=t60 t30 (7)
and reduction extent f functions were selected to do curve
where t30 and t60 are the consuming time of reduction extent fitting work. If the reduction process was controlled by inter-
arriving to 30% and 60%, respectively. Under the same facial chemical reaction, the kinetic equation obtained is as
reduction condition, the reducibility index RVI of the pellets follows:
with biomass was 1.12%/min higher than that of pellets " #
MFeO $k$C0AH2
without biomass. 1 1 f
1=3
t; (13)
rFeO $r0
Reduction kinetics analysis
formations of Fe2O3 / Fe3O4 and Fe3O4 / FeO are more rapid Experiment(1123 K): R2=0.9838
0.8
than that of FeO / Fe, thus the former two reactions can be diffusion control
ignored in the kinetics analysis [19e21]. The step of FeO / Fe chemical control
0.6 Fitting line:
under hydrogen atmosphere can be expressed as follows:
diffusion control
chemical control [1-(1-f)1/3]/t
FeO H2 Fe H2 Og DrGqm 23430 16:16T J=mol (8)
0.4 R2=0.9954
lnK DGq RT 1:943 2818=T (9)
0.2
The reaction (FeO / Fe) equilibrium constant K under
different reduction temperature can be calculated by (9) and
the results are shown in Table 3. 0.0
To study the kinetics of the pellet reduction process, a weight 0 5 10 15 20 25
change detection method was adopted under isothermal con- Time, min
ditions and the experimental apparatus is shown in Fig. 1. In the
reaction process, the gas flow rate was set at 7 cm/s. The effect of (b)
0.8 [1+2(1-f)-3(1-f)2/3]/t
external diffusion can be negligible as the gas flow rate is above Experiment(1123 K):
[1-(1-f)1/3] or [1+2(1-f)-3(1-f)2/3]
R2=0.9781
5 cm/s. Therefore, it is presumed that the reaction rate might be diffusion control
controlled by three mechanisms: 1) the intrinsic interfacial chemical control
0.6
chemical reaction, 2) the diffusion including internal diffusion Fitting line:
diffusion control [1-(1-f)1/3]/t
of reactant and product gas species through solid product layer, R2=0.9995
chemical control
and 3) the mix of 1) and 2). The pellet reduction process is a 0.4
typical gas solid reaction, which can be described by the reaction
rate equation (10) presented by Szekely [18].
h i . h i 0.2
2=3 1=3
f=3kG 11f 21f $r0 6De 11f $K=k1K
MFeO $k$C0AH2
Suppose x1 ;
rFeO $r0
1=3
1 1 f x1 t; (14)
3
where r(FeO) represents the density of FeO (kg/m ); M(FeO) is the
FeO molecular weight.
The relationships between 1(1f)1/3 and reaction time
t were calculated, fitted and typical results were shown in
Fig. 6a and b. The correlation coefficients of R2 for the reduc-
tion of the pellets with and without addition of biomass were
0.9954 and 0.9995, respectively.
When the reduction process was controlled by diffusion,
the kinetic equation obtained is as follows:
2=3
1 2f=3 1 f x2 t (16)
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