Chemical Engineering Journal 327 (2017) 822–830

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Chemical Engineering Journal

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Direct reduction of iron ore/biomass composite pellets using simulated

biomass-derived syngas: Experimental analysis and kinetic modelling
Dabin Guo a, Yubiao Li b, Baihui Cui a,c, Zhihua Chen d, Shipeng Luo e, Bo Xiao a, Hongping Zhu a,
Mian Hu a,⇑
a
School of Civil Engineering and Mechanics, Huazhong University of Science and Technology, Wuhan 430074, China
b
School of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, China
c
Wuhan Botanical Garden, Chinese Academy of Sciences, Wuhan 430074, China
d
School of Environment, Henan Normal University, Xinxiang 453007, China
e
School of Chemical and Environmental Engineering, Jiangsu University of Technology, Changzhou 213001, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

An environmentally friendly DRI

technology using biomass as additive
agent in pellet was studied.

The reduction process followed the
interfacial chemical reaction
mechanism.

The pellets added of biomass
decreases the DE from 97.53 kJmol1
to 86.05 kJmol1.

A novel approach to produce direct
reduced iron using biomass syngas
was developed.

The DRI production process can be
carried out with no net CO2 emission.

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents a novel and environmentally friendly production of direct reduced iron (DRI) technol-
Received 12 February 2017 ogy using biomass as an additive agent in iron ore pellets and simulated biomass-derived syngas as the
Received in revised form 1 June 2017 reducing agent. The effects of biomass addition on iron ore pellets reduction and consequent reduction
Accepted 20 June 2017
kinetics in simulated biomass-derived syngas atmosphere were investigated. The results demonstrated
Available online 23 June 2017
that the biomass addition improved the pellet porosity and specific surface area, thus increasing both
the reducibility and reduction rate and decreasing the apparent activation energy for pellet reduction.
Keywords:
Mathematical modelling of experimental data indicated an interfacial chemical reaction mechanism with
Biomass
Ironmaking
FeO ? Fe as the rate controlling step. The simulated biomass syngas is an alternative gas-based reductant
Direct reduced iron to natural gas, coal gas, more than 99.5% reduction degree of the oxidized pellets was reduced at 1323 K
Simulated biomass-derived syngas within 20 min. The apparent activation energies were 86.05 kJmol1, 97.53 kJmol1 for the pellets with
Kinetics and without biomass addition. The proposed iron ore reduction process therefore would be a potential to
reduce iron directly using biomass with high efficiency and real environmental benefits.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction

The global warming concerned recently worldwide has con-

⇑ Corresponding author at: School of Civil Engineering and Mechanics, Huazhong
tributed to many disaster, resulting in the loss of properties and
University of Science and Technology, Wuhan 430074, China
human life. This phenomenon has been commonly regarded due
E-mail address: mianhu_hust@[Link] (M. Hu).

[Link]
1385-8947/Ó 2017 Elsevier B.V. All rights reserved.
 D. Guo et al. / Chemical Engineering Journal 327 (2017) 822–830 823

to the release CO2, methane and nitrous oxides from human amount of fluxing agent or additive is added to the iron ore-coal
actions, especially in the industrialization process. The accumula- pellets to improve the reduction efficiency. Fan et al. [24], for
tive of these gas in the atmosphere gave rise to the greenhouse instance, revealed that the flux additives can improve the reduc-
effect. Therefore, many countries have established associations tion efficiency. However, no studies have been carried out investi-
and laws to reduce the greenhouse gas emission. Ironmaking is gating the effects of additives on the reduction performance of the
an energy intensive industrial process mainly using coal as heat iron ore pellet in the gas-based direct reduction process, which is
source and reducing agent, accounting significantly for the anthro- however equally important for the development of new emerging
pogenic CO2 emissions in the world [1–3]. With the rapid growth DRI technology.
of world steel production, coking coal also known as metallurgical Compared with the additives mentioned above, lignocellulosic
coal is becoming scarce worldwide, it is extremely necessary to biomass has some advantages: firstly, it is mainly composed of cel-
find the substitute for traditional fossil energy to reduce carbon lulose, hemicellulose and lignin, which can be burnt completely
release. The fossil fuel based technologies widely applied in most with very little residue left to affect the quality of the pellet. In
of iron and steel industries are responsible the greenhouse gases the previous paper, it was confirmed that the vast majority of bio-
(GHG) emissions [4–6], e.g. steel industries accounts for 19% CO2 mass fuel can be burnt, when it is crushed to a particle size of about
emission in all the industrial sectors [7]. The scarcity of conven- 10 lm at a temperature of 1437 K [25,26]. Secondly, biomass is an
tional energy such as fossil fuels and the ever-increasing demands environmentally friendly renewable source of energy and is glob-
for new energy sources have resulted in the world moving into an ally available. In addition, abundant biomass is available in China,
era of renewable energy [8]. The efficient utilization of biomass the straw, other agricultural residues and forest residues
plays a very positive role in solving problems on energy resources accounted for 87% of all the biomass [27,28].
and ecological environment [9–11]. The utilization of biomass in The present work therefore is to develop an environmentally
ironmaking process increased the drop strength of green pellets, friendly strategy to form DRI efficiently using biomass as an addi-
which is beneficial to the transformation of the materials. In addi- tive agent in iron ore pellet and using simulated biomass-derived
tion, the addition of biomass can increase the burst temperature, syngas as a reducing agent. The effects of biomass addition on
reduce the breakage rate during roasting process. Furthermore, the reduction performance and consequent reaction process and
syngas belongs to fossil fuel while the biomass is considered as reduction kinetics in simulated biomass-derived syngas atmo-
renewable fuel [12]. Therefore, the application of biomass reduces sphere will be investigated. Particularly, the understanding of the
the emission of CO2. If biomass could be reasonably applied to reduction behavior of iron ore/biomass composite pellets in the
direct reduced iron (DRI) production processes, it is of great signif- DRI route would be beneficial to the industrial implementation
icance in energy saving and emission reduction. However, up to in producing DRI by using biomass including the biomass additive
date, only a few studies were conducted using the biomass for agents and simulated biomass-derived syngas.
ironmaking. Wang et al. [13] have successfully applied biomass
rather than pulverized coal into blast furnaces to reduce the on-
site emissions by 28.1%. Hata et al. [14] studied the possibility of 2. Materials and methods
mixing biomass tar with goethite ore for ironmaking, however this
process resulted in a relatively complicated procedure and pro- 2.1. Materials
duced harmful Fe-C. Gan et al. [15] investigated the biomass fuels
such as charcoal, charred-straw and molded-sawdust as an alter- The iron ore samples were provided by Wuhan Iron and Steel
native to traditional sintering fuels. The results showed that the (Group) Corp. and bentonite from the Wuhan Iron and Steel
increasing substitution rate of biomass for coke breeze resulted Group Ezhou Iron and Steel Co., Ltd. The chemical compositions
in rising vertical sintering speed, but decreasing yield and tumble of iron ore powder and bentonite were shown in Table 1. The
index of sinter. Therefore, appropriate substitution rate should be pine sawdust collected from a furniture factory in HUST was
made to satisfy the productivity and quality of sinter. Isothermal crushed before mixing with iron ore powder. The results of ulti-
reduction of Fe2O3 briquettes by biomass-generated syngas (mix- mate analyses of biomass samples were C, 48.21%; H, 6.54%; O,
ture of H2 and CO) at various temperatures was investigated by 44.39%; N, 0.77%; S, 0.09%. In our previous research [29], the drop
Luo et al.[16], who found that H2 was essential for high quality and compressive strengths of green pellets were increased signif-
pig iron under reducing condition, achieving a maximum 94.7% icantly when the percentage of biomass was controlled at 2% in
Fe under 1100 °C for 60 min. However, the gas producing from bio- the pelletizing process. Therefore, iron ore with biomass compos-
mass gasification usually included not only H2 and CO, but also CH4 ite green pellets were made of 96 wt.% of iron ore powder, 2 wt.%
and CO2. Using such gas to reduce briquettes has not been studied of biomass, and 2 wt.% of bentonite. As a control, iron ore com-
by researchers. Carvalho et al. [17] suggested that in the iron ore posite green pellets without biomass were produced with 98
pelletizing industry, the bio-synthetic gas can be regarded as an wt.% of iron ore powder and 2 wt.% of bentonite. The composite
alternative to natural gas. Biomass gasification, as one of the most green pellets with or without biomass were rolled and pelletized
promising strategies among all the technologies for bio-synthetic on a disc balling machine, with the outer diameter being of 1 m.
gas producing, has attracted much attention recently, e.g. circulat- After pelleting, the moisture of green pellets with a particle size
ing fluidized bed was regarded as the most potential gasification of 1.0–1.5 cm were removed through heating in an oven con-
model for large-scale producing as it can deal with a various fuels trolled at 378 K for 24 h and pre-sintered to 1173 K for 30 min.
under differing gasification [Link] authors also reported that Subsequently, the pellets were roasted to oxidized pellets after
dual fluidized bed steam gasification followed by methanation heating under 1523 K for 25 min, in an oxygen-enriched atmo-
was most favorable to form bio-synthetic natural gas. As the iron sphere in an electric furnace. The specific surface area of the oxi-
reduction using either conventional blast furnace or new emerging dized pellets with and without biomass addition was 6.03 m2/g
direct reduction technology is driven by carbothermic Boudouard and 16.26 m2/g, respectively.
reaction, coal could be substituted by the woody biomass to pro- Table 2 shows the chemical compositions and pellet compo-
vide both carbon and energy [18]. nents of oxidized pellets with and without added biomass. The
Iron ore direct reduction in the industry can be mainly divided reducing gas was a mixture of high purity (99.999%) H2, CO, CO2
roughly into two categories: gas-based and coal-based [19–23]. In and CH4 with various proportions by simulating the syngas compo-
some coal-based direct reduction (CBDR) processes, a small sition generated from steam catalytic gasification of biomass. The
824 D. Guo et al. / Chemical Engineering Journal 327 (2017) 822–830

Table 1
Chemical compositions (%) of iron ore and bentonite.

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 –
Bentonite 3.25 68.41 18.37 0.04 3.77 3.88 0.69 – 1.55

Table 2
Chemical composition and pellet components of oxidizing roasting pellets.

Pellet samples Pellet components, % Chemical composition, mass percent, %

Iron ore Bentonite Biomass TFe FeO SiO2 Al2O3 MnO CaO MgO TiO2 K2O
With biomass 96 2 2 57.56 0.28 7.78 2.99 0.22 1.66 4.78 0.19 0.14
Without biomass 98 2 0 57.68 0.26 7.63 2.93 0.22 1.63 4.69 0.19 0.14

resultant gas composition was H2, 45.6%; CO, 36.2%; CH4, 5.9%; cross section prior to being loaded in the metallographic machine,
CO2, 12.3%. processed via grinding, polishing and cleaning the surface. The
mineral morphology of the pellets before and after reduction treat-
ments were characterized by a metallographic microscope. The
2.2. Experimental apparatus and methods
mineral phases of the pellets were analyzed by powder X-ray
diffraction (XRD), using an X’Pert Pro XRD with Cu Ka radiation
Fig. 1 shows the schematic diagram of experimental apparatus
and k = 1.5418 Å, operated at 30 mA, 40 kV with a scanning rate
used to reduce pellet samples. Overall, the lab-scaled ironmaking
of 10° min1 within a 2h from 15° to 90°. In addition, scanning elec-
system was mainly composed of electronic balance, reduction
tron microscopy (SEM) operated at 10 kV was also applied to char-
chamber, electric furnace, temperature controller, gas flow control
acterize the change of the pellets before and after reduction.
and computer recording system.
At the start-up of each test, 50 pellets of known mass were
2.3. Determination of reduction rate
placed in the middle of the hanging cages. They were heated up
to the desired temperature in the electric heating oven under N2
The reduction degree, f (%) of the pellets was calculated accord-
atmosphere. Then, the reducing gas replaced N2 for the whole
ing to Eq. (1) [30]:
reduction process. After 30 min, the reducing gas was switched

off while the N2 was applied again until the reactor was cooled 0:111W1 m0  mi
f¼ þ  100% ð1Þ
to room temperature to avoid re-oxidation of products. During 0:430W2 m0 þ 0:430W2
the reduction process, the pellets weight was recorded automati-
where m0 is the mass of pellet before reduction; mi is the mass of
cally by an electronic weight balance and the computer. It should
pellet in reduction process; W1 and W2 are the contents of FeO
be noted that the pellet samples were loaded and the reducing
and TFe in the pellet before and after reduction, respectively.
gas was kept at a flow rate of 6–10 cm s1.
The pellet samples with different components before and after
reduction were cut fixed within the thermosetting resin to make 3. Results and discussion

3.1. Effects of temperature and time

Oxidized pellets with and without added biomass were isother-

mally reduced from 1123 K to 1323 K with simulated biomass-

Fig. 1. The schematic diagram of experimental apparatus for the direct reduction of Fig. 2. Reduction curves of oxidized pellets with temperature and time: (a) with
pellet samples. biomass, (b) without biomass.
 D. Guo et al. / Chemical Engineering Journal 327 (2017) 822–830 825

Fig. 3. Cross-section micrographs of pellet samples: (a) before reduction, (b) reduced for 5 min, (c) reduced for 20 min and without biomass (d) before reduction, (e) reduced
for 5 min, (f) reduced for 20 min.

1
derived syngas. As can be observed from Fig. 2, there was no signif- C þ CO2 ! 2CO DGh ¼ 162600  167:62 T; J  mol ð9Þ
icant difference in the reduction rates with and without biomass
addition when the temperature was controlled at 1123 K and The combination of Eqs. (2)(4) and Eqs. (5)(7) gave a negative
1173 K. However, when the temperature was increased to over enthalpy DH when temperature is over 1123 K, indicating the
1223 K, the addition of biomass increased the reduction rate of pel- reduction of Fe2O3 by H2 and CO follows an endothermic reaction
lets apparently, indicating a faster reduction rate in the presence of under the temperature range examined. This also means any eleva-
biomass. Specifically, the reaction time was 18.3 min to reach a tion of temperature can increase the reducing rate of iron ore to
90% reduction degree without biomass addition, which was element iron. In addition, Eqs. (8) and (9) indicated that CH4 added
reduced to 15 min when biomass was added at 1223 K. In addition, in the simulated biomass syngas will be decomposed into C and H2
then temperature was at 1323 K, the reaction time was declined at temperature 1123 K. The formed C will continuity react with
from 13.1 min to 10 min. Therefore, the addition of biomass CO2 to form CO, following the Eqs. (5)(7).
reduced energy consumption within a shorter time. It is worth noting that under the same condition, the reduction
Usually, the reduction of iron ore by syngas proceeds in a series degree of oxidized pellets with biomass were always higher than
of interrelated reactions as given in the chemical equations below: those of ordinary oxidized pellets without biomass addition during
the whole reduction process. The reasons will be discussed in
3Fe2 O3 þ H2 ! 2Fe3 O4 þ H2 O DGh detail in the following sections.
1
¼ 15547  74:40 T; J  mol ð2Þ
3.2. Effects of biomass addition
Fe3 O4 þ H2 ! 3FeO þ H2 O DGh
1
¼ 71940  73:62 T; J  mol ð3Þ 3.2.1. Metallographic changes
The metallographic structure of the pellets with and without
1 biomass was shown in Fig. 3 when the reduction temperature
FeO þ H2 ! Fe þ H2 O DGh ¼ 23430  16:16 T; J  mol ð4Þ
was set at 1323 K. It is clearly seen that before reduction, the oxi-
dized pellets with biomass addition was more porous compared to
3Fe2 O3 þ CO ! 2Fe3 O4 þ CO2 DGh
the pellets without biomass addition (Fig. 3a, d) probably due to:
1
¼ 52131  41:0 T; J  mol ð5Þ Firstly, the gas generated from the gasification or combustion pro-
cess emitted from the pellet, resulting in micro channels and
Fe3 O4 þ CO ! 3FeO þ CO2 DGh increasing the porosity level of the pellet. Secondly, the original
1 position of the biomass was free after gasification and combustion
¼ 35380  41:16 T; J  mol ð6Þ processes, which further increases the porosity level of the pellet.
In addition, Fig. 3e shows that most of the pellets were not
1
FeO þ CO ! Fe þ CO2 DGh ¼ 22800 þ 24:26 T; J  mol ð7Þ reduced (dark) while the silvery white metallic luster indicated
the reduced parts but still with a low level of porosity. The reduc-
1
CH4 ! 2H2 þ C DGh ¼ 91044  110:67 T; J  mol ð8Þ tion product was in the outer layer and the unreacted portion was
wrapped within this layer, indicating a retract model. In contrast,
826 D. Guo et al. / Chemical Engineering Journal 327 (2017) 822–830

species for the pellets with biomass addition was greater than that
without, indicating that the addition of biomass increased the crys-
tallinity of the products.

3.2.3. Scanning electron microscopic analysis

The SEM image shown in Fig. 5 indicated the pellet samples
made by the simulated biomass-derived syngas at a reduction tem-
perature of 1173 K under different reduction time. Obviously, the
average pore size and porosity of the oxidized pellets (Fig. 5a, d)
with biomass addition were much greater than those of the con-
trol. The evenly distributed big pore in the biomass added compos-
ite pellets were beneficial to improve the reduction rate. After
reducing for 5 min, the small mineral particles in the edge of both
oxidized pellets were reduced to wustite and the reduction degree
of biomass added composite pellet was higher than that of the con-
trol (Fig. 5b, e). There are probably two reasons for the difference
between the pellets with and without biomass. Firstly, the biomass
itself helps to improve the porosity of the pellet, the reaction inter-
face area of mineral particles with biomass added was greater than
that of the control. Secondly, as higher porosity resulted in easier
enter and discharge of the reducing gas and the gaseous reduction
products, which is beneficial to the reduction between the pellets
and simulated biomass syngas. After 20 min, the two pellets were
mainly reduced to metallic iron and/or metallic iron grains that
tended to agglomerate and formed larger particles (Fig. 5c, f).
Finally, there was no difference between the reduction product of
biomass added pellets and the control, suggesting that the addition
of biomass had no effects on the quality of the final product in DRI
processes.

3.2.4. Reduction velocity index analysis

The reduction velocity index (RVI, Eq. (10)) was used to evaluate
the reduction behavior of the pellets, e.g. higher RVI values indi-
cated higher reducibilities and faster reduction rates.

Fig. 4. XRD pattern of pellet samples before and after reduction at 1173 K under dRt 33:6
RVI ¼ ¼ ð10Þ
different reduction time: (a) with biomass, (b) without biomass. dt40 t60  t30

where t60 is the time reducing 60% of the pellet while t30 is the time
reducing 30% of the pellet. The results showed that the RVI of the
no distinct boundary between the reduced and unreduced portions
pellet with biomass was 0.179%min1 greater than that of the con-
in the iron ore/biomass composite pellet (Fig. 3b). While, for the
trol, indicating that the biomass enhanced the reducibility of the
control pellet, there was existed an evident boundary. As the iron
pellet.
ore was gradually reduced from high valence to low valence from
5 min to 20 min (Fig. 3e, f), greater silvery portion was observed.
When a certain degree of reduction was achieved, the porously 3.3. Kinetics analysis
reduced product iron shell was formed in the external part of the
pellet but there still existed an unreacted core in the interior area The reduction of oxidized pellets follows the unreacted core
of the pellet. With the reaction progressed, the unreacted core was model shown in Fig. 6. Such kinetics follows the classical gas-
gradually reduced until it was completely disappeared (Fig. 3c, f). solid reactions equation (Eq. (11)) derived by Szekely et al. [31]:

r0 h i
Eventually, the entire cut surfaces would be silvery white metallic
f 2=3
luster. þ 1  ð1  fÞ þ 2ð1  fÞ
3kG 6De
Kc h i
1=3
3.2.2. XRD results þ 1  ð1  fÞ
kð1 þ KcÞ
Fig. 4 shows the XRD patterns of pellet samples made by the
simulated biomass-derived syngas at reduction temperature of C0A  CA
¼ t ð11Þ
1173 K under different reduction time. It can be seen that the oxi- q0 r0
dized pellets were mainly Fe2O3 before reduction. The peak of
Fe2O3 disappeared at 1173 K after a reaction with simulated where t denotes reaction time, min; C 0A denotes initial concentration
biomass-derived syngas for 2.5 min. Meanwhile, the peaks repre- of reducing gas (RG), molcm3; C A denotes gas concentration of
senting FeO and Fe appeared, suggesting that Fe2O3 were trans- pellet once reaction reach equilibrium with an equilibrium constant
formed into FeO and Fe. At a reaction time of 25 min, FeO peaks of Kc, molcm3; r denotes the radius of oxidized pellet with an ini-
disappeared but the peak intensity of Fe was enhanced, indicating tial value of r0, cm; q0 denotes initial oxygen concentration in the
that almost all the FeO was reduced into Fe. These further sug- pellet, molcm3; Kc is the reaction equilibrium constant; kG
gested that 1173 K could be the temperature for Fe2O3 reduction. denotes mass transfer coefficient between gas boundary layer and
It should also be noted that the peak intensity of the reduced Fe pellets surface, cms1. The reaction rate constant, k (cm2s1) and
 D. Guo et al. / Chemical Engineering Journal 327 (2017) 822–830 827

Fig. 5. SEM photos for pellet samples before and after reduction: (a) before reduction, (b) reduced for 5 min, (c) reduced for 20 min and without biomass (d) before reduction,
(e) reduced for 5 min, (f) reduced for 20 min.

effective diffusion coefficient De (cm2s1) can be expressed as Eqs.

(12) and (13), respectively.
KC q0 r0
k¼   ð12Þ
tC ð1 þ KC Þ C0A  CA

q r2 
 0 0
De ¼ ð13Þ
6tD C0A  CA

The left hand side of Eq. (11) represents reaction resistance con-
trolled by external diffusion, internal diffusion, and interfacial
chemical reaction respectively. It was recommended that the
external diffusion was negligible once the flow of RG was greater
than 5 cms1. Since such flow in our study was 6–10 cms1, Thus,
by eliminating the external diffusion item f/3kG. A series reaction
occurred in the reduction process (Fe2O3 ?Fe3O4 ?FeO ? Fe), with
the FeO ? Fe being as the control stage [32]. If the reduction pro-
cess was controlled by interfacial chemical reaction, reaction time Fig. 6. Unreacted core model with single interface.

equation of pellet can be solved as:

 
r0  qðFeOÞ r Namely, reaction time is obtained from Eqs. (14) and (17), as:
t¼ 1  ð14Þ
MðFeOÞ  k  C0A r0 qðFeOÞ  r0 h i
1=3
t¼ 1  ð1  fÞ ð18Þ
Furtherly, the weight of oxygen W(O) and weight loss (Wp) of MðFeOÞ  k  C0A
pellet at radius of r can be expressed as:
Taking the constants into consideration, Eq. (18) render as a lin-
4 ear equation of:
WðOÞ ¼ p  r30  qðFeOÞ  CðO2 Þ ð15Þ
3
a1 ¼ w1 t ð19Þ
4
Wp ¼ p  ðr30  r3 Þ  qðFeOÞ  CðO2 %Þ ð16Þ where
3
8
where q(FeO) is the density of FeO, kgm3; M(FeO) is molecular < w1 ¼
MðFeOÞ kC0A
qðFeOÞ r0
weight of FeO, gmol1 C ðO2 Þ denotes oxygen content (%) in pellet. ð20Þ
:
Then, reduction degree (f) can be calculated as: a1 ¼ 1  ð1  fÞ1=3

4
p  r30  r3  qðFeOÞ  CðO2 %Þ If the reduction of oxidized pellets was controlled by interfacial
f ¼3 ð17Þ chemical reaction, the plot of a1 = 1  (1  f)1/3 versus t will repre-
4
3
p  r30  qðFeOÞ  CðO2 %Þ
sent a straight line, fitted and typical results were shown in Fig. 7a.
828 D. Guo et al. / Chemical Engineering Journal 327 (2017) 822–830

where C0 is the gas film concentration of outer layer of the pellets,

molcm3. If the reduction of oxidized pellets was controlled by
internal diffusion, the plot of a2 = 1 + 2(1  f)  3(1  f)2/3 versus t
will represent a straight line. The fitted and typical results were
shown in Fig. 7b. Then, by plots a1 = 1  (1  f)1/3 (interfacial chem-
ical reaction control) and a2 = 1 + 2(1  f)  3(1  f)2/3 (internal dif-
fusion control) versus t, the correlation coefficient (R2) of linear
regression judge the kinetic control step of oxidized pellets reduc-
tion, namely that the possibly control step has a higher R2 value.
The a vs. t kinetic dependences of interfacial chemical and
internal diffusion control mechanisms were shown in Fig. 7. It is
evident that the corresponded coefficient (R2) of chemical control
was much greater than that of diffusion mechanism, indicating
that the kinetic of oxidized pellets reduction under biomass-
derived syngas atmosphere was a chemical controlled process.
Since the inner-diffusion was in a very slow rate, the interface of
ore sphere was reduced by simulated biomass-derived syngas via
contact. Thus, the reduction of oxidized pellets mainly manifested
a chemical control [Link] reaction time used for apparent
activation energy can be expressed as:
h i
1=3
t ¼ tC 1  ð1  fÞ ð24Þ

Kc q0 r0
tC ¼   ð25Þ
kð1 þ Kc Þ C0A  CA

where tC is reaction time once the reaction rate was controlled by

interfacial chemical reaction, respectively. The plot of
1=3 2=3
1 þ ð1  fÞ  2ð1  fÞ versus t/[1  (1  f)1/3] is a straight line,
from whose slope and intercept can be calculated the tD and tC
(Table 3). According to Eqs. (12), (13) and the tD and tC values,
The results of calculated k values were listed in Table 4.
According to Arrhenius equation, the reaction constant k is
expressed as:

DE
Fig. 7. Comparisons of reduction curve at 1123 K between chemical-controlled and
ln k ¼ þ ln A ð26Þ
RT
diffusion-controlled model for simulated biomass-derived syngas: (a) with
biomass, (b) without biomass. where DE is activation energy, Jmol1; R is ideal gas constant,
8.314 Jmol1K1; A is pre-exponential factor, s1; T is reaction
temperature, K. Activation energy and pre-exponential factor can
When the reduction process was controlled by diffusion, reac-
be calculated from the slope and intercept of linear regression of
tion time can be obtained as follows:
lnk vs. 1/T. The plots as well as corresponding linear regression of
qðFeOÞ  r20 h i lnk vs. 1/T was showed in Fig. 8. According to the fitting, the reac-
2=3
t¼ 1 þ 2ð1  fÞ  3ð1  fÞ ð21Þ tion activation energy of pellet mixed with biomass
2MðFeOÞ  De  C0
(DE = 86.05 kJmol1) was quite smaller than that without biomass
Eq. (21) also render as a linear equation of mixed (DE = 97.53 kJmol1). Such result indicated that biomass can
a2 ¼ w2 t ð22Þ reduce the reaction activation energy and improve the reaction rate
reduction of iron ore pellets. It was perorated above that the kinetic
with of pellet reduction was controlled by interfacial chemical reaction.
8 Once the iron ore was mixed with biomass, internal porosity and
< q r2
w2 ¼ 2MðFeOÞ
ðFeOÞ 0
De C0 reaction contact area of pellet were improved by biomass pyrolysis,
ð23Þ
:
a2 ¼ 1 þ 2ð1  fÞ  3ð1  fÞ2=3 this is consistent with the SEM and BET results. Moreover, the
pyrolysis of biomass generated reducing biochar and gases (such

Table 3
The intercept and slope of lines for t/[1-(1-f)1/3against 1 + (1-f)1/3-2(1-f)2/3 at 1123 K-1323 K.

T, K With biomass Without biomass

Intercept tC Slope tD Intercept tC Slope tD
1123 35.92 6.34 41.37 8.70
1173 28.45 5.05 32.20 6.08
1223 25.62 3.59 28.89 4.22
1273 20.74 3.32 22.82 4.14
1323 17.91 2.50 19.89 3.52
 D. Guo et al. / Chemical Engineering Journal 327 (2017) 822–830 829

Table 4
Reaction rate constant k of pellet with and without addition of biomass.

k, cm2s1 T, K
1123 1173 1223 1273 1323
With biomass 7.8 10.15 12.84 19.86 32.32
Without biomass 4.1 5.75 8.68 12.52 20.14

was shown in Fig. 9. Firstly, a small quantity (2–3.5 wt.%) of pulver-

ized biomass, iron ore and 1–4 wt.% of bentonite are mixed
together with assistant from water. Secondly, the well mixed blend
was introduced into a pelletizer to produce green pellets which
were dried and roasted under the oxygen-enriched atmosphere
to obtain oxidized pellets. These derived pellets with biomass
can be charged into the furnace. Finally, the reduction process
was initiated when the biomass-derived syngas made by steam
gasification of biomass were fed into the furnace and used as the
reducing agent. In this process, biomass instead of coke was intro-
duced to the pellet making process to provide a source of both car-
bon and energy and more importantly, to improve the reducibility
of the composite pellets. In addition, direct reduction of iron oxides
for high efficient production of DRI was obtained by using biomass-
derived syngas. Therefore, this proposed DRI process can provide
an alternative to the current metallurgical industries with various
environmental benefits.

Fig. 8. Arrhenius plot of chemical reaction rate under simulated biomass-derived 4. Conclusions
syngas atmosphere.
A novel approach using biomass with high reduction efficiency
and environmental benefits can be a useful solution to the issues of
as CO, CH4 and H2), possibly improving reducing free radicals DRI production. The biomass added in the pelletizing process
concentrations. increased the porosity and specific surface area, improved the
reduction rate of the oxidized pellets. Especially when temperature
3.4. Consideration of a new process for direct reduced iron production exceeded 1323 K, the addition of biomass in the pellets shorted
reaction time significantly, e.g. the reaction time was reduced from
Recently, an increasing interest has been paid in using biomass 13.1 min to 10 min to reach a 90% reduction degree with the addi-
as reductant and energy sources for clean ironmaking. A newly tion of biomass addition. In addition, the simulated biomass syngas
developed environmentally friendly production of DRI process is an alternative gas-based reductant to natural gas, coal gas, in

Fig. 9. Schematic of a CO2 emission-free DRI production process.

830 D. Guo et al. / Chemical Engineering Journal 327 (2017) 822–830

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