Fuel 304 (2021) 121465

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Fuel
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Study on the feasibility and co-combustion mechanism of mixed injection of

biomass hydrochar and anthracite in blast furnace
Jinhua Li a, b, Runsheng Xu b, *, Guangwei Wang a, b, *, Jianliang Zhang a, b, c, Bo Song a,
Wang Liang a, b, Chuan Wang d, e
a
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China
b
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
c
School of Chemical Engineering, The University of Queensland, Queensland 4072, Australia
d
Swerim AB, SE-971 25, Luleå, Sweden
e
Thermal and Flow Engineering Laboratory, Åbo Akademi University, Åbo FI-20500, Finland

A R T I C L E I N F O A B S T R A C T

Keywords: Under the energy saving and emission reduction pressure, biomass has attracted much attention from metal­
Biomass hydrochar lurgical workers because of the renewability and zero CO2 emission characteristics. In this paper, the physical
Anthracite and chemical properties of biomass residue hydrochar (BRC) and Yangjing pingding anthracite (YAC) were
Co-combustion
systematically studied by X-ray diffraction, scanning electron microscope and Raman spectroscopy. Moreover,
Thermogravimetric analysis
Synergy effect
the combustion characteristics and mechanism of biomass residue (BR), BRC, YAC, and the mixtures of BRC and
Kinetics YAC were studied by thermogravimetric analysis experiments. The results show that BR has a high volatile
content of 82.26% and contains a large amount of alkali metals, but BRC has a low alkali metal content. The
carbon atom sequence degree and graphitization degree of BRC are lower than that of YAC. The BRC particles
also have a well-developed pore structure, and the reactivity of BRC is higher than that of YAC. The addition of
BRC to YAC can improve the combustion performance of YAC. There is an obvious synergistic effect in the
combustion process of the mixed sample. The kinetic model was used to fit the combustion reaction, and it was
found that the random pore model (RPM) showed a more accurate fitting result. When the ratio of BRC is 60%,
the activation energy of the mixed sample is 38.5 kJ/mol, which has superior combustion characteristics in
raceway of blast furnace.

1. Introduction
Coal is main energy resource of China, and nearly 70% of its energy is
provided by coal [1]. The development and utilization of coal has played
important role in promoting China’s development [2]. However, with
the development of human society, the contradiction between the
increasing energy demand and the increasingly scarce fossil energy has
become more and more prominent. Iron and steel industry is a big
consumer of energy, and steel production in China accounts for about
11% of total energy consumption [3–6]. Blast furnace ironmaking is the
main method of hot metal production at present and even in the next few
decades. The energy consumption of internal ironmaking including
sintering, pelletizing, coking and hot metal production accounts for
73.5% of the total energy consumption of iron and steel production
process [7]. In addition, blast furnace coal injection is the use of
relatively abundant coal types to partially replace expensive coke for hot
metal production; within a certain range, as the coal ratio increases, the
energy consumption and cost of hot metal production can be reduced at
the same time [8–10]. For a long time, blast furnace ironmaking has
been dominated by injection of bituminous coal and anthracite [11].
With the continuous improvement of blast furnace operation technol­
ogy, the blast furnaces can accept more bituminous coal and anthracite
to replace valuable coke resources [12]. Therefore, more pulverized coal
can be consumed by blast furnace. Based on the growth of energy de­
mand and the deepening of the resources crisis, it is very important to
develop a renewable fuel that can replace pulverized coal for blast
furnace injection [13].
Biomass energy is the fourth largest energy source after coal, pe­
troleum, and natural gas [11]. It is the metabolic product in the growth
process of animals, plants, microorganisms and other living organisms

* Corresponding authors at: School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China (G. Wang).
E-mail addresses: xu_runsheng@163.com (R. Xu), wgw676@163.com (G. Wang).

https://doi.org/10.1016/j.fuel.2021.121465
Received 13 May 2021; Received in revised form 24 June 2021; Accepted 14 July 2021
Available online 26 July 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
J. Li et al.
[13]. Since the photosynthesis in the growth process of agricultural and
forestry biomass absorbs CO2 and releases CO2 during the combustion
process, the use of such biomass resources can achieve zero CO2 emis­
sions [14]. Biomass is known as renewable green energy [15].
In the production process of blast furnace, it is required that the fuel
has better grindability and combustibility, higher calorific value and
lower ash content [8]. However, compared with coal, biomass has the
shortcomings of lower calorific value, fixed carbon content, grindability
and energy density, and higher volume, moisture content and volatile
content [16,17]. At the same time, biomass also has the characteristics
of wide distribution, loose structure, high recovery cost, difficulty in
long-distance transportation, and high alkali metal content, which are
not conducive to the direct use of biomass in injection process of blast
furnace [18]. In order to realize the ironmaking of biomass energy, it is
necessary to pretreat the biomass to reduce alkali metal elements and
increase its energy density.
Biomass energy upgrading technologies mainly include pyrolysis,
biotransformation and hydrothermal processes. As the dehydration of
biomass pyrolysis process requires a large amount of energy. In addition,
the biochar produced by pyrolysis contains a high content of ash
composed of alkali metal oxides. The upgrading of biomass by pyrolysis
is limited due to these reasons [18,19]. Biotransformation mainly refers
to fermentation and anaerobic digestion. Although the energy con­
sumption is low, the biotransformation process takes a long time
[17,20]. It does not match the current fast-paced industrial production.
Hydrothermal carbonization (HTC) technology is a kind of heat treat­
ment technology. This technology uses subcritical water as the solvent
and reactant for the reaction, and realizes the transformation from
macromolecular organics to gas, solid and liquid three-phase small
molecular organic products under the saturated vapor pressure of water
[17,21,22]. Compared with other thermochemical conversion technol­
ogies, the reaction conditions of HTC are mild, the temperature required
is also lower, there’s no need for external pressure, and the raw mate­
rials do not need to be pretreated [18]. Many scholars have shown that
the calorific value of biomass hydrochar produced by HTC is equivalent
to that of bituminous coal used for blast furnace injection. Moreover, the
ash content is also very low [18,23–25]. In summary, the upgrading of
biomass through HTC is not only costly, but also has a significant
upgrading effect [22,26]. HTC has been regarded as one of the most
promising technologies in biochar production, it has a very significant
upgrading effect on biomass fuels and can effectively convert organic
matter into valuable chemicals or fuels [17].
Many scholars have conducted research on mixed injection of
biomass or biochar in blast furnace [27,28]. Wang et al. [26] conducted
a study on the performance characterization of straw char for blast
furnace injection. The research results show that compared with
anthracite, straw pyrolysis char has a lower ignition point, lower
burning temperature, faster burning rate, more stable combustion pro­
cess, and better comprehensive combustion performance, but straw char
has a high content of alkali metals and a low ash melting temperature. It
is easy to coke during the injection process, and the ratio of replacing
coal powder should not be too high. Wang [29] conducted a basic
research on the application of biomass pyrolysis semi-coke to blast
furnace injection. Wang mentioned that the application of biomass semi-
coke to blast furnace injection can reduce the consumption of coke and
coal mining. The results show that indirect reduction can be developed
by blast furnace injection of palm shell semi-coke, the amount of pul­
verized coal injection can be reduced and the stable operation of the
blast furnace can be ensured. Theoretically, it is feasible to partially
replace pulverized coal in blast furnace injection with palm shell semi-
coke. Li [2] carried out an experimental study on peanut shell biochar
used as blast furnace injection fuel, and the results show that the ash
content and sulfur content of peanut shell char produced at 550℃ meet
the requirements of blast furnace injection. Wang [15] conducted a basic
study on blast furnace injection of agricultural and forestry wastes, and
the study shows that the combustion performance of anthracite can be
2
Fuel 304 (2021) 121465
improved by adding straw powder to anthracite, which is conducive to
the complete combustion of pulverized coal. However, due to the high
content of alkali metals in biomass, the ash melting point of mixed coal
after the addition of biomass decreases. Although there are many re­
searches on blast furnace injection of biomass or biochar [30–32], there
are few reports of large-scale blast furnace injection using biomass. The
main reason is that the wide distribution range of biomass, low energy
density, high alkali metal content, and the current biomass upgrading
technology such as pyrolysis cannot solve the problem that the biochar
produced contains a large number of alkali metals. It is of great signif­
icance to develop a reasonable and effective biomass treatment tech­
nology for the application of biomass energy in industry [17,26]. HTC
technology can effectively convert biomass into biochar, improve the
energy density, and reduce the alkali metal content [18]. Unfortunately,
although the biomass hydrochar produced by HTC has the characteris­
tics of high calorific value, low ash content and good grindability, there
are few studies on the combustion performance of hydrochar. Moreover,
the mechanism and kinetics of the co-combustion of biomass hydrochar
and anthracite has not been fully studied. Therefore, it is necessary to
study the feasibility and co-combustion mechanism of biomass hydro­
char and anthracite mixed injection into blast furnace.
In this paper, biomass residue (BR) was used as biomass raw mate­
rial. The biomass residues hydrochar (BRC) and the Yangjing pingding
anthracite (YAC) was selected as the test sample. Considering that
thermogravimetric analysis is one of the most effective methods to
describe the thermal conversion performance of biomass and coal
[33,34], it has been widely used in the study of fuel combustion char­
acteristics by many researchers [35–37]. Moreover, the kinetic study
based on thermogravimetric analysis can be used to quantitatively study
the combustion or gasification characteristics of fuels from the
perspective of activation energy and evolution of fuel structural pa­
rameters, it can provide optimization information for fuel combustion
process [16,38,39]. Therefore, the co-combustion characteristics of the
mixed coal formed by the mixing of BRC and YAC in different pro­
portions and the interaction between them during combustion were
studied by thermogravimetric analysis and kinetic analysis. The effect of
BRC on the combustion process of YAC was found. The feasibility of
using BRC as fuel for blast furnace injection is analyzed. In addition, the
work done by Wang [16] et al. would be referenced to find out the
significant differences between the hydrochar and pychar in blast
furnace mixed coal injection. The theoretical guidance is provided for
the development of biomass hydrochar ironmaking and promoting the
development of green metallurgy. In order to achieve the above goals,
this study will be carried out through the following aspects: 1) The basic
characteristics of YAC, BR and BRC were studied by detecting the
physical and chemical characteristics of the samples, and the combus­
tion performance of the samples was predicted based on the basic
characteristics. 2) By analyzing the combustion characteristics of BR,
BRC, YAC and mixed coal in different mixing ratios, the influence of BRC
on the combustion characteristics of YAC in the process of blast furnace
mixed coal injection was explored. 3) The kinetic parameters of the
combustion reaction of samples and mixded coal were calculated by
kinetic model, and the best scheme of mixed coal was found out. 4) The
similarities and differences between pychar and hydrochar and the ad­
vantages of biomass hydrochar in blast furnace injection are found by
comparison.
2. Materials and methods
2.1. Experimental materials and preparation
Yangjing pingding anthracite (YAC), which is commonly used in
blast furnace coal injection, was selected as the experimental anthracite
sample. The biomass residues (BR) produced in a walnut milk factory in
South China was used as the biomass sample. The BR and deionized
water were placed in a high pressure reactor for HTC at a ratio of 1:5,
J. Li et al.
and heated to 260 ◦ C for 1 h to prepare the biomass residues hydrochar
(BRC) in this paper. The specific operation and equipment used were
referred to the previous paper [40]. The BR, BRC and YAC were dried in
a 105 ◦ C oven for 12 h, and then the samples were ground and screened
to powder with particle size less than 74 μm. Then the samples were
bailed and stored for future use. In order to identify the residual sub­
stances in the ash of the samples after combustion, some samples were
placed in muffle furnace and heated to a specific temperature in this
paper. After the samples were completely burned, the ash of BR, BRC,
YAC were obtained. It should be emphasized that the problem of alkali
metal volatilization during ash preparation of BR and BRC is taken into
account, the furnace temperature of BR and BRC ash burning in this
paper is 550℃, while that of YAC is 850 ◦ C. BRC and YAC were mixed
according to four schemes: 20%BRC + 80% YAC, 40% BRC + 60% YAC,
60% BRC + 40% YAC, 80% BRC + 20% YAC. They are called Plan1,
Plan2, Plan3 and Plan4.
2.2. Physical and chemical properties detection and analysis methods
This experiment used an elemental analyzer (Vario EL cube) to
analyze the elements (C/H/N/S) of samples, the O content was calcu­
lated by the difference. The proximate analysis of YAC was carried out in
accordance with the Chinese national standard GB/T212-2008, and the
proximate analysis of BR and BRC was carried out in accordance with
GB/T 28731-2012. The ultimate analysis and proximate analysis results
of YAC, BR and BRC are shown in Table 1. The ash content of samples
was measured by XRF-1800 ray fluorescence spectrometer.
As we all know, the combustion performance of fuel is closely related
to the surface microstructure of the fuel and the arrangement of internal
atoms and molecules. In order to ascertain the basic physical and
chemical properties of the three samples, the apparent morphology and
microstructure of the samples were analyzed by scanning electron mi­
croscope (SEM), X-ray diffractometer (XRD) and Raman spectrum
analyzer in this paper. The version of SEM used in this paper is ZEISS
EVO-18, the accelerating voltage is 20 KV, and the working distance is
11.5 mm. The surface microstructure of samples can be understood more
intuitively by SEM figures. However, SEM can only make preliminary
predictions about the possible performance of the fuel. In order to
further accurately grasp the factors that affecting the combustion per­
formance, the microstructure of the sample was analyzed by XRD that is
one of the most effective and widely used methods to analyze the
microstructure of matter. The structural parameters of carbon micro­
crystals of BRC and YAC were determined by X-ray diffractometer (XRD,
Smart Lab, Japan) with copper target (λ = 0.1541 nm) [16].The inter­
layer spacing (D), stacking height (LC) and the crystalline stacking layer
number (N) of YAC and BRC are calculated by referring to the work done
by Wang et al. [16] and Li et al. [41]. The calculation formula is shown
in Eqs. (1) - (3):
λ process of the samples, some special parameters representing the fuel
D= (1)
2sinθ(002)
0.89λ
Lc = (2)
β(002)cosθ(002)
Lc
N= +1 (3)
D
Table 1
Ultimate analysis and proximate analysis of samples.
Sample Proximate analysis (wt.%) Ultimate analysis (wt.%)
Ad Vd FCd C H
BR 4.55 82.26 13.20 50.26
BRC 1.21 51.11 47.68 69.72
YAC 11.44 8.25 80.31 81.37
Note: a stands for calculated value, A for ash, FC for fixed carbon, V for volatile, d for dry base.
3
Fuel 304 (2021) 121465
where θ(0 0 2) is the peak position of peak (0 0 2), and β(0 0 2) is the full
width at half-maximum (FWHM)of peak (0 0 2).
In the fitting peak of XRD, the aromaticity of fuel can be described
according to the area A of peak (0 0 2) and peak (γ). Eq. (4) is its
calculation formula. The higher the value off, the greater the proportion
of peak (0 0 2), that is, the higher the degree of orientation of the aro­
matic laminates of the sample [42,43].
f =
A002
(4)
A002 + Aγ
The specific surface area and pore structure of the sample are closely
related to the combustion performance. A large specific surface area
means that the fuel has a large contact area with the surrounding air,
and the pores on the fuel surface facilitate the release of volatiles during
combustion [16,44,45]. In this paper, the surface area and pore volume
were measured by QuantaGrome Automatic Independent Multi-Station
Specific Surface and Porosity Analyzer (Qudrasorb SI). The specific
surface area was obtained by BET method [46,47].
Raman spectroscopy is a nondestructive analysis technique that is
based on the interaction of light and chemical bonds within a material.
Raman spectroscopy can provide detailed information on the chemical
structure, phase and morphology, crystallinity, and molecular in­
teractions of the sample [48]. In this study, the carbon crystal structure
of YAC and BRC was analyzed by high resolution Raman spectrometer
(LabRAMHREvolution). The selected excitation wavelength was 532
nm, and the detection spectral range was 100–4000 cm− 1. The spectral
range of 800 ~ 2000 cm− 1 is intercepted for analysis in this paper,.
2.3. Combustion characteristic detection and analysis method
Thermogravimetric analysis is one of the most effective methods to
describe the thermal conversion performance of biomass and coal, and is
recognized by the Kinetics Committee of the International Confedera­
tion for Thermal Analysis and Calorimetry (ICTAC) [33,34]. In this
paper, the samples with particle size less than 74 μm were taken 5 mg
and placed in an alumina crucible of 3 mm × 1.5 mm, and the heating
rates were increased from room temperature to 900 ◦ C at 5 ◦ C/min, 10
◦
C/min, 15 ◦ C/min and 20 ◦ C/min, respectively. The experimental data
obtained by thermogravimetric balance (WCT-2C) can obtain X and dX/
dt data by Eq. (4) and (5). The Origin software can be used to draw the
weight loss curve and weight loss rate curve of the samples at different
heating rates [49–53].
mt − m0
X= (5)
m∞ − m0
dX
dX/dt = (6)
dt
In order to facilitate the quantitative analysis of the combustion
combustion were used in this paper. Eq. (7) can describe the mixed
combustion intensity of fuel (I0.5). In general, the larger the I0.5, the
more severe the reaction [54]. The comprehensive combustion charac­
teristic index (S) calculated by Eq. (8) is used to describe the compre­
hensive combustion characteristic of the fuel [55].
Atomic ratio
a
O N S H/C O/C
5.97 42.61 0.85 0.31 0.12 0.85
4.93 24.98 0.19 0.17 0.07 0.36
3.15 13.87 1.01 0.60 0.04 0.17
J. Li et al. Fuel 304 (2021) 121465

0.5 The combustion under the conditions of this study is a gas–solid

I0.5 = (7)
t0.5 heterogeneous reaction process [16,55]. At present, there are three ki­
netic models in the field of combustion and gasification, which are
S=
(dX/dt)max ∙(dX/dtmean
(8) recognized by the majority of researchers, namely the volume model
Ti2 ∙Tf (VM), the random pore model (RPM) and the unreacted pore model
(URCM) [38,53,60–63]. Many scholars have shown that the VM can
In Eqs. (5) to (8): mt is the mass of the sample at time t in the com­
better characterize the reaction process of fuel combustion and gasifi­
bustion experiment, m0 is the initial mass of the sample, and m∞ is the
cation [59,64]. However, the research results of Wang et al. [16] show
ash mass of the sample after the completion of the combustion reaction,
that compared to VM, the RPM model can better describe the combus­
mg; t0.5 is the duration when the weight loss rate is 0.5, min; (dX/dt)max
tion of anthracite and biomass pychar. Based on this, the combustion
is the maximum weight loss rate, mg/min; (dX/dt)mean is the average
kinetics of BRC and YAC were studied by using RPM and URCM, and the
rate of mass loss, the data of dX/dt from Ti to Tf was selected to calculate
accuracy of RPM and URCM were compared in this paper. Generally, the
its value in this paper, mg/min; Ti is the initial combustion temperature
burning rate of RPM and URCM can be described as Eqs. (12) and (13)
of fuel, K; Tf is the burnout temperature of the fuel, K.
[65–68]:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
2.4. Study on synergistic effect of co-combustion reaction dX
= kRPM (1 − X) 1 − ψ ln(1 − X) (12)
dt
In general, the combustion of each component in the mixed fuel
dX
combustion is not isolated but mutually influenced. Many researchers = kURCM (1 − X)2/3 (13)
dt
have found synergistic or antagonistic effects in the process of fuel
mixed combustion [16,56]. In order to study whether there is synergistic 4πL0 (1− ε0 )
where ψ = S20
,ψ is the structure and size parameter of the parti­
effect in the co-combustion of BRC and YAC, the value of combustion
conversion rate was calculated through Eq. (9), By comparing the cle.L0 , ε0 and S0 represent the pore length per unit volume, the porosity
calculated value with the experimental value, the synergistic effect of and the specific surface area of the particles at the initial reaction time,
BRC and YAC in the co-combustion reaction was studied. respectively.
In this study, the heating rate β of the sample is a constant, then:
XCalc = γXBRC + δXYAC (9)
T = T0 + βt (14)
where XCalc , XBRC andXYAC are the combustion conversion rate of mixed Eqs. (12) and (13) are combined with Eq. (14) to obtain Eqs. (15) and
coal composed of YAC and BRC, BRC and YAC, respectively. γ and δ are (16), respectively
the mass fraction of BRC and YAC in the mixed coal, where γ + δ = 1. Eq. ( ( ( )) ( ))
(9) was used to calculate the conversion rate of the mixed coal at each (T − T0 ) − E k0 (T − T0 ) − E
X = 1 − exp − k0 ⋅ ⋅exp ⋅(1+ ⋅ ⋅exp
temperature, and Origin was used to draw the conversion rate calcula­ β RT 4ψ β RT
tion curve of the mixed coal. By comparing the experimental curve and (15)
the calculated curve of each mixed coal, the interaction between the two
( ( ) )3
samples can be learned. If the calculated curve is at the upper right of the k0 (T − T0 ) − E
X = 1− 1− ⋅exp (16)
experimental curve, it indicates that the combustion of the experimental 3β RT
curve is better than that of the calculated curve, that is, there is a syn­
In order to solve kinetic parameters E, k0 and ψ in Eqs. (15) and (16),
ergistic effect between them; if the calculated curve is at the lower left of
MATLAB was used to complete the solution of the kinetic parameters of
the experimental curve, there is antagonistic effect between the two
RPM and URCM in this paper. The accuracy of the two kinetic calcula­
fuels [49,57].
tion models can be compared by the deviation between the calculated
value and the experimental value. The calculation formula is as follows
2.5. Kinetic model [60]:
(∑ ( )2 )1/2
The kinetic study of fuel combustion can provide optimized infor­ N
Xexp,i − Xcalc,i /N
mation for the fuel combustion process [16,38,39] however, there are
i=1
DEV(X)(%) = 100 × (17)
max(X)exp
few kinetic studies on the mixed combustion of hydrochar and pulver­
ized coal. In order to fully understand the effect of the amount of BRC
where: DEV(X)(%)represents the deviation value,Xexp,i and Xcalc,i are the
added on the combustion activation energy of the mixed coal during the
experimental conversion rate and calculated conversion rate corre­
co-combustion of the BRC and YAC, this study conducted a kinetic study
sponding to the selected i-th temperature point, respectively. N is the
on the mixed coal of YAC and BRC at various ratios. At present, many
total number of selected data points,max(X)exp is the maximum con­
scholars use Eq. (10) to describe the combustion reaction rate of solid
fuel [58,59]. version rate value obtained in the experiment.

dX
= k(T,P) f (X) (10) 3. Results and discussion
dt
3.1. Physical and chemical properties
where: f(X)is the reaction kinetic mechanism equation;k(T,P) is the re­
action rate constant.The value of k(T,P) is related to temperature and
The ultimate analysis and proximate analysis results of BR, BRC and
pressure. In the combustion experiment of this study, it can be assumed
YAC are shown in Table 1. By comparison, the ash and volatile content
that the pressure is constant. Combining the Arrhenius formula[51], the
of the obtained BRC are significantly lower than that of the BR after HTC
Eq. (10) can be changed to Eq. (11):
process, but the fixed carbon content is significantly higher. At the same
( )
dX E time, the ultimate analysis results of BRC, except for the increase in
= k0 exp − f (X) (11)
dt RT carbon content, the content of other elements has decreased. Therefore,
the H/C and O/C atomic ratios have decreased, this is consistent with
where: k0 is the former factor, E is the activation energy of the reaction, the research results of many scholars [40,69]. The main reason is that
R is the ideal gas constant, R = 8.314 Mol-1 K-1 the transformation of biomass organic matter from large molecules to

4
J. Li et al.
small molecules is realized through the decomposition, poly­
condensation and aromatization of HTC [18,70]. In addition, H and O
are released from the biomass into the gas or liquid phase, resulting in
the reduction of H, O and other substances in the solid phase, and ulti­
mately increasing the carbon content. This can be proved from the
evolution law of the stretching vibration intensity of the functional
group in the Fourier transform infrared spectroscopy of the biomass
hydrochar involved in the previous literature [40]. By comparing the
composition of samples, it can be found that the BRC composition is
closer to YAC than the BR.
The ash composition analysis of BR, BRC and YAC is shown in
Table 2. The ash composition of YAC is acidic oxide dominated by SiO2
and Al2O3, while BRC and BR are alkaline oxides dominated by CaO and
K2O. Comparing with the BR, the content of CaO and K2O in the BRC ash
is lower, and the remaining ash composition has little change. However,
under the premise that the total ash content decreases, this shows that
the HTC of biomass can not only greatly reduce its ash content, but also
effectively remove alkali metal elements like potassium and calcium.
which is consistent with the research results obtained by other scholars
[71].
Fig. 1 is SEM images of BR, BRC and YAC. As can be seen from Fig. 1,
the surface of YAC is smooth and its structure is compact and dense, and
almost no pore. There are a few large pores on the surface of BR and the
structure is also compact. The difference is BRC, the structure of it is
relatively loose. Due to the chemical bonds of BR are broken in the HTC
process, then small molecules of organic matter are separated from the
BR, therefore, there are many small pores formed on the surface of BRC
as seen in the 4000 times image. The biomass hydrochar prepared by
Liang et al. [40] has a similar structure.
The test results of the specific surface area and pore structure char­
acteristics of the sample are shown in Table 3. The specific surface area,
total pore volume and average pore diameter of BRC are the largest seen
from Table 3, the specific surface area of BRC is about 33 times and 14
times that of the BR and YAC, respectively. Certainly, the maximum pore
diameter of the BR is the largest, which is consistent with the observa­
tion results of SEM.
The research on the co-combustion behavior of BRC and YAC is the
focus of this paper. In order to predict the combustion performance of
BRC and YAC from the microstructure, XRD was used to analyze the
carbon microcrystalline structure of the BRC and YAC. The XRD patterns
of the two samples are shown in Fig. 2(a). The (0 0 2) peak near 26◦ in
Fig. 2(a) represents the degree of orientation of the aromatic carbon
sheet layer in the microcrystalline structure. The steeper the (0 0 2) peak
band indicates the better the degree of carbon orientation inside the
sample, the more perfect the crystal structure, and the higher the crys­
talline carbon content. The asymmetry of the (0 0 2) band indicates that
there is a contraction vibration of saturated amorphous carbon in the
side chain of crystalline carbon, the corresponding peak is located in the
(γ) peak band near 20◦ , (γ) band represents saturated amorphous carbon
[41,60,72]. It can be seen from Fig. 2 that the XRD curve of YAC has
many small peaks, this is because YAC is formed or mixed with other
minerals during the long-term geological process and mining process.
Some scholars have used the XRD curve of YAC to identify the kaolinite
and mullite other minerals contained in the coal [41]. The raw material
of BRC is crop residues, during the growth process, organisms selectively
extract required substances from nature, and combined with the results
of ash composition analysis, HTC can also effectively remove internal
minerals. Therefore, the XRD curve of BRC is smoother than that of YAC.
Table 2
Ash composition analysis of samples (wt.%).
Sample SiO2 Al2O3 Fe2O3 CaO
BR 3.51 1.38 1.80 61.82
BRC 6.20 1.50 4.64 56.25
YAC 50.12 37.44 3.02 2.58
5
Fuel 304 (2021) 121465
Due to the large number of peaks in the entire XRD pattern, this
paper selected the XRD pattern of 16◦ ~30◦ for peak-fitting, and the
peak-fitting result is shown in Fig. 2(b). the results of D, Lc, N, FWHM
and f of BRC and YAC are obtained after peak-fitting processing, it was
shown in Table 4. It can be seen from the data in Table 4 that the
diffraction angle of BRC is smaller compared with YAC. At the same
time, Lc, N and f are also smaller than that of YAC, but the spacing
between carbon layers (D) is larger than YAC, which means that the
amount of disordered carbon structure of BRC exceeds that of YAC, and
YAC has a larger microcrystalline structure. Based on the above con­
clusions, it can be inferred that the BRC should have better combustion
reactivity.
The Raman spectrum of YAC and BRC is shown in Fig. 3. From the
figure, YAC and BRC have two more obvious peaks, which are the D
band near 1350 cm− 1 and the G band near 1590 cm− 1. It is similar to
what other scholars have observed [73,74]. By observing the Raman
spectra of the two samples, it can be found that the D peak of BRC is
more obvious than that of YAC, while the G peak of YAC is wider than
that of BRC. In other words, the spectrum of YAC is mainly G peak, while
the BRC is mainly D peak. This is mainly because the D peak is related to
the in-plane defect between the disordered carbon atom and the basic
structural unit in the sample, while the G band is related to the aromatic
ring in the carbon material [75]. In order to obtain more accurate
structural parameters of the sample, the Raman spectrum of YAC and
BRC were divided into a Gaussian peak (D3) and four Lorentz peaks (D1,
D2, D4 and G) by Five peak-fitting method [38]. The corresponding peak
of D3 was located near 1500 cm− 1, and the peak of D1, D2, D4 and G were
1360 cm− 1,1620 cm− 1,1580 cm− 1,and 1180 cm− 1, respectively [59,73].
The main parameter concerned in this paper is AG/Aall, which is often
used to measure the graphitization degree of carbon materials [38]. The
bigger the value is, the stronger the G peak is, and the more perfect the
graphite lamella in the microcrystalline structure of the sample is, so the
graphitization degree is higher [76–79]. The results of Raman spectra of
the two samples are shown in Table 5. According to the data in Table 5,
the AG/Aall value of YAC is 0.027, while that of BRC is 0.015, which is
only about 1/2 that of YAC, indicating that the crystal structure
sequence and graphitization degree of YAC are higher than that of BRC.
Some scholars have shown that the fuel with smaller AG/Aall value has
better combustion performance [16]. It shows that the combustion
performance of YAC is weaker than that of BRC. This is consistent with
the results obtained by XRD.
The above research predicted the combustion performance based on
the microscopic morphology of the sample. However, the real combus­
tion performance of the fuel needs to be verified by experiments.
Therefore, the following work will study the actual situation of the
samples combustion.
3.2. Analysis of samples combustion characteristics
The purpose of the research on the co-combustion of BRC and YAC is
to analyze the combustion performance of BRC and YAC mixed injection
in blast furnace, so as to promote the development of biomass energy
ironmaking production. Before the study of co-combustion, it is neces­
sary to analyze the combustion performance of BR, BRC and YAC. Fig. 4
shows the combustion weight loss curves and combustion weight loss
rate curves of samples at the heating rate of 20 ◦ C/min.
As can be seen from Fig. 4(a), the weight loss curve of BR is on the
left, YAC is on the right, and BRC is between the BR and YAC. This
MgO K2 O Na2O MnO ZnO
5.72 21.01 0.19 0.12 0.02
5.49 13.37 2.01 0.20 0.03
0.30 0.61 1.60 0.06 0.03
J. Li et al. Fuel 304 (2021) 121465

BR BRC YAC

10 m 10 m 10 m

Fig. 1. 4000 times scanning electron micrograph of the sample.

of BR is still increasing slowly after 390℃, and the combustion is basi­

Table 3
cally completed at about 660℃. This is mainly due to the continued
Results of specific surface area and pore structure parameters of the samples.
combustion of alkali metals in the ash produced after the combustion of
BET Specific Total pore Maximum pore Average pore volatile matter and fixed carbon in this temperature range [80]. This
surface area volume(cc/g) Diameter(nm) Diameter(nm)
shows that the ash component of BR is high in alkali metal content from
(m2/g)
the perspective of the combustion weight loss curve, and direct injection
BR 0.281 5.9120E− 04 8.4256
≤565.1
of the blast furnace will increase the alkali load of the blast furnace [18].
BRC 9.423 3.0450E− 02 ≤139.3 12.9256
YAC 0.661 8.8160E− 04 ≤42.2 5.3337
Although it can be seen from Fig. 4(b) that the weight loss rate of the
BRC increases at about 500℃. There is also the combustion of alkali
metals in the ash of BRC, but its rate value and temperature range
indicates that BR is the easiest to burn, while YAC has the worst com­ (duration) are very small, which is similar to YAC and can be ignored.
bustion performance, and the combustion weight loss curves of the BRC Combining Fig. 4(a) and (b), the mass loss of BR is divided into three
with the largest specific surface area are between the two. The high stages. The first stage is the precipitation of crystal water and a small
volatile matter of BR is the main reason for this result. When the tem­ amount of volatile matter in the BR, the second stage is the combustion
perature rises to about 200 ◦ C, a large amount of volatile in the BR are of volatile matter and fixed carbon, and the last stage is the combustion
precipitated and burned, and the released heat ignites the fixed carbon, of alkali metals in the ash, of which the second stage is the main reac­
which makes the combustion reaction of BR finish faster. However, the tion. BRC combustion is divided into three stages: volatile matter pre­
low Ti of the BR and very high combustion reactivity increases the risk cipitation, volatile matter combustion, and fixed carbon combustion. Of
during the injection process, which is also a reason why biomass cannot course, ash combustion has also occurred, but it can be ignored due to
be directly used for blast furnace injection. As can be seen from the the low burning rate and short burning time. Due to the low volatile
combustion weight loss curve of BR in Fig. 4(a), the conversion ratio (X) content of YAC, the corresponding peak in the weight loss rate curve is

Fig. 2. XRD patterns of YAC and BRC.

Table 4
Structural parameters of YAC and BRC from XRD profiles.
sample 2θ002(deg) FWHM(deg) D(Å) Lc(Å) N A002 Aγ f

YAC 25.48 3.85 3.41 20.50 7.02 8707.30 856.30 0.91

BRC 23.72 4.96 3.66 15.86 5.34 4155.90 4002.60 0.51

6
J. Li et al. Fuel 304 (2021) 121465

Fig. 3. Raman spectra of YAC and BRC.

Table 5
Raman spectral carbon structure parameters and results of the sample.
sample AD1 AD2 AD3 AD4 AG AG/Aall

BRC 22413.80 14545.60 38799.63 2288.59 1198.99 0.015

YAC 51884.16 137760.00 4611.55 16550.92 5907.72 0.027

Fig. 4. Weight loss curve (a) and weight loss rate curve (b) of three samples.

combustion of fixed carbon.
The thermogravimetric analysis curve shows that the content of al­
kali metals in the BRC is low, which is consistent with the results of
proximate analysis and ash composition. YAC is different from the other
two samples. The Ti YAC is about 480 ◦ C, which is higher than the Tf of
BRC. According to the analysis results of the physicochemical charac­
teristics of YAC, the mainly reason for the weak combustion perfor­
mance of YAC is that YAC has less volatile matter, small specific surface
area, the largest carbon microcrystalline structure, high degree of
graphitization. The results of the combustion weight loss curve distri­
bution of the samples proved the accuracy and consistency of SEM, XRD,
specific surface area and pore structure analysis, and Raman spectros­
copy detection results for fuel performance prediction from the experi­
mental point of view.
3.3. Experimental results and analysis of mixed coal combustion
characteristics
In order to study the effect of adding different amounts of BRC to
YAC on its co-combustion performance, this paper also carried out
thermogravimetric analysis experiments on mixed coal at a heating rate
of 20 ◦ C/min. The weight loss and weight loss rate curves are shown in
Fig. 5.
It can be seen from Fig. 5(a) that the mixed coal combustion curves of
the four schemes are between YAC and BRC, and as the content of BRC
increases, the combustion curve and combustion rate curve gradually
shift to the low temperature zone. It shows that adding BRC to YAC can
significantly improve YAC combustion performance, which is consistent
with the results of Zhang et al. [81]. Combining the combustion rate
peaks of different coal blending schemes in Fig. 5(b), the combustion
curves of the four schemes can be roughly divided into three stages:

7
J. Li et al.
Fig. 5. Combustion weight loss curve (a) and weight loss rate curve (b) of the mixed coal.
volatile combustion, mixed combustion of volatile and fixed carbon, and
fixed carbon combustion. With the increase of BRC content, the fixed
carbon combustion peak in Fig. 5(b) gradually decreases and the peak
position gradually shifts to the low temperature region. While the mixed
combustion peak of volatile and fixed carbon increased and shifted to
the low temperature zone. The main reason is that the addition of BRC
increases the volatile content of mixed coal and the fixed carbon content
is reduced, the effect of volatiles on the ignition of YAC was enhanced.
Table 6 shows the calculated values of fixed carbon, volatile matter and
ash content of mixed coal.
In order to study the influence of different heating rates on the mixed
coal combustion performance, this paper conducts thermogravimetric
experiments on YAC, BRC and four kinds of mixed coal at four heating
rates of 5 ◦ C/min, 10 ◦ C/min, 15 ◦ C/min and 20 ◦ C/min, respectively.
The experimental curve results are shown in the Fig. 6.
From the weight loss curve and weight loss rate curve of mixed coal
combustion in Fig. 6, although the heating rate changes, the line shapes
of the weight loss curve and the weight loss rate curve are roughly
similar to each other. With the increase of heating rate, the thermog­
ravimetric curve of mixed coal combustion shifts to the high tempera­
ture zone, and the maximum weight loss rate increases with the increase
of heating rate. This is consistent with the research results of many
scholars [57,82].
Some characteristic parameters that characterize the combustion
performance, such as the Ti and Tf of the fuel, are found from Figs. 5 and
6. The corresponding parameters and numerical results are shown in
Table 7.
According to Table 7 as the heating rate increases, the S of the fuel
increases for the same scheme. By analyzing Eq. (7), it can be found that
this is mainly because the heating rate affects the maximum and average
value of the pulverized coal combustion rate under the same conditions.
The greater the heating rate, the combustion weight loss rate curve
moves to the upper right. Although the degree of shift to the right is
small, it also causes the maximum and average values of the pulverized
coal combustion rate to increase, which increases the S. Under the
conditions of the same heating rate and different mixed coal schemes,
Table 6
Calculated values of volatiles, ash and fixed carbon of the mixed coal (wt.%).
Scheme Vd Ad FCd
Plan 1 16.82 9.39 73.79
Plan 2 25.40 7.35 67.26
Plan 3 33.97 5.30 60.73
Plan 4 42.54 3.25 54.21
8
Fuel 304 (2021) 121465
the order of S value is plan 1 > plan2 > plan4 > plan3. The burning rate
curves of plan 1 and plan 2 have one peak, while plan 4 and plan 3 have
two peaks, which is the reason for this result. Twin peaks mean that the
combustion is divided into two major stages. In the mixed coal, the BRC
is burned first. As the heat released by the BRC combustion is constantly
absorbed by YAC, the maximum combustion rate of the BRC in the
mixed coal is reduced and the S value becomes smaller. From the
perspective of S, when the proportion of BRC in the mixed coal is 20%,
the mixed coal has the best combustion performance. This is inconsistent
with the analysis results of the combustion weight loss curve. Therefore,
it is not appropriate to use the S to measure the combustion of mixed
coal in this paper. The combustion intensity I0.5 was also used to char­
acterize the combustion performance of mixed coal in this paper.
Fig. 7 is the intuitive diagram of fuel combustion intensity. Different
from the calculation result of the S value, the I0.5 value of the mixed coal
increases with the increase of the heating rate and the BRC ratio from
Fig. 7, which is similar to the distribution of the weight loss curve of the
fuel. It shows that under the conditions of this paper, from the
perspective of quantitatively studying fuel combustion characteristics,
I0.5 can make a more accurate evaluation of fuel combustion perfor­
mance with different heating rates or different mixed ratios. According
to the value of I0.5, the combustion of different mixed coals under
different combustion conditions can be divided into 6 categories, each
color represents a category, among which red is the strongest and purple
is the weakest. The brown color is the burning of the residue, and its
value is the largest, which is reasonable because the residue is mainly
composed of volatile matter.
4. Research results and analysis of synergistic effects during co-
combustion
The research results of Wang et al. [16] showed that the co-
combustion of biomass pychar and anthracite has a synergistic effect
due to the presence of alkali metals in the pychar. In order to study
whether there is a synergistic effect between the co-combustion of YAC
and BRC, the combustion ratio of the two fuels is calculated at various
temperatures according to Eq. (9). The calculation curve and the
experimental curve are shown in Fig. 8, and there is a significant dif­
ference between the experimental curve and the calculated curve during
co-combustion of YAC and BRC. The four calculation curves are above
the experimental curve at the beginning of weightlessness but are not
particularly obvious, while the position of the early stage is lower than
the experimental curve, and the position in the late stages is higher than
the experimental curve. Due to the calculation curve of co-combustion
expresses the situation that YAC begins to burn after the BRC is
J. Li et al.
Fig. 6. The thermogravimetric curve of fuel at different heating rates.
completely burned, and the two combustions do not interfere with each
other, the non-overlapping of the calculated curve and the experimental
curve shows that the combustion of YAC and BRC in the mixed coal
affects each other, rather than independent of each other.
According to the results in Table.7, Tf of BRC is 469 ◦ C (742 K), Ti of
YAC is 498 ◦ C (771 K), Ti of YAC is higher than the Tf of BRC at 20 ◦ C/
min. Comparing the calculation curve and the experimental curve,
except for the red line above the black line at the beginning of the
combustion, the initial stage of the reaction is mainly but not entirely the
9
Fuel 304 (2021) 121465
combustion of BRC. During the combustion process, the surface tem­
perature of unburned YAC powder has not reached the Ti and it
continuously absorb heat from combustion of BRC, which adversely
affects the combustion of BRC, resulting in an antagonistic effect be­
tween the YAC and BRC. The later stage is mainly the combustion of
YAC. Due to the preheating effect of the early BRC combustion and
catalytic effect of alkali metals and the oxides in the ash from BRC
combustion [83–85], the experimental curve in the later period is lower
than the calculated curve, indicating that there is synergistic effect of the
J. Li et al. Fuel 304 (2021) 121465

Table 7
Combustion characteristic parameters of samples and mixed coal.
sample β (℃/min) Ti(K) Tf(K) Tp1(K) (dx/dt)max1 Tp2(K) (dx/dt)max2 (dx/dt)mean S (×10-13) I0.5

YAC 5 724 840 797 0.07 – – 0.006 9.123 0.006

10 743 868 813 0.12 – – 0.012 30.120 0.011
15 757 902 854 0.14 – – 0.018 48.361 0.016
20 771 933 882 0.16 – – 0.025 72.593 0.020

Plan 1 5 647 832 793 0.07 – – 0.006 11.999 0.006

10 646 861 813 0.11 – – 0.012 37.962 0.012
15 659 885 838 0.14 – – 0.016 58.282 0.017
20 658 919 856 0.15 – – 0.023 85.153 0.021

Plan 2 5 590 821 784 0.05 – – 0.006 10.795 0.006

10 603 850 806 0.08 – – 0.012 30.543 0.012
15 609 872 831 0.11 – – 0.016 55.441 0.018
20 609 894 848 0.12 – – 0.022 80.708 0.023

Plan 3 5 566 810 722 0.03 789 0.03 0.006 6.671 0.007
10 576 840 743 0.05 813 0.05 0.012 20.632 0.014
15 588 856 746 0.08 828 0.07 0.017 45.550 0.020
20 588 877 747 0.09 841 0.08 0.021 61.441 0.026

Plan 4 5 571 795 722 0.04 786 0.02 0.005 7.207 0.008
10 583 822 730 0.07 810 0.03 0.010 24.604 0.015
15 588 840 742 0.10 821 0.04 0.016 56.125 0.022
20 595 852 746 0.12 836 0.04 0.018 70.020 0.029

BRC 5 534 703 602 0.02 700 0.14 0.004 30.100 0.008
10 550 711 603 0.04 704 0.15 0.010 72.532 0.016
15 556 728 605 0.05 715 0.17 0.011 83.848 0.024
20 556 742 640 0.09 724 0.19 0.019 154.068 0.032
Residue 20 496 663 599 0.19 – – 0.018 211.587 0.044

Fig. 8. Calculation curve and experimental curve of combustion of

mixed samples.

4.1. Fuel combustion kinetics and parameter analysis

Fig. 7. Intuitive diagram of fuel combustion intensity.

The characteristic kinetic parameters of YAC, BRC and their mixed

co-combustion of the two samples in the later period. This result is very
coal are solved by MATLAB. The values are shown in Table 8. The
different from the combustion curve of the mixture of biomass pychar
squares of the correlation coefficients (R2) of the fitting results of the
and anthracite by Wang et al. [16] for two reasons: First, because the
solved kinetic characteristic parameters are all greater than 0.99. The
anthracite used in Wang’s paper has a lower Ti, the ignition effect of
calculation results of RPM and URCM show that YAC has the highest
biochar on anthracite is more obvious than this paper. Second, the ash
activation energy, which are 73.83 kJ/mol and 128.91 kJ/mol,
component of biomass pychar or BRC is mainly alkaline oxide, but the
respectively. This is consistent with the position of the YAC thermog­
ash content of the pychar studied by Wang is about 10 times that of BRC.
ravimetric curve in Fig. 9. In addition, except for Plan 1, the activation
Therefore, the combustion of mixed coals studied by Wang showed
energy of mixed coal is less than that of YAC and BRC. It shows that
obvious synergistic effects from beginning to end, but the combustion of
when the ratio of BRC exceeds 20%, the mixing of BRC and YAC can not
mixed coals in this paper had a significant synergistic effect in the later
only reduce the activation energy of the BRC combustion reaction in the
period.
mixed coal, but also reduce the activation energy of the YAC combustion
reaction, which means that there is a synergistic effect when the fuel

10
J. Li et al.
Table 8
Kinetic characteristic parameters.
Sample RPM
− 1
E (kJ/mol) kRPM (s ) ψ R
YAC 73.83 0.023 2.058E + 05
Plan 1 68.05 5.005 8.637
Plan 2 46.01 0.214 5.482
Plan 3 38.58 0.130 1.953
Plan 4 40.42 0.872 0.045
BRC 50.04 2.029 5.053
starts to burn. This can explain why the red calculation curve is above
the black experimental curve when the fuel just starts to burn in Fig. 8.
The activation energy results calculated by the two kinetic models have
some difference. The activation energy values required for the four
mixed coal combustion reactions are between 38.58 and 83.34 kJ/mol,
and the lowest activation energy in the RPM model is Plan 3, while the
URCM is Plan 4, with 38.58 kJ/mol and 39.61 kJ/mol, respectively.
The activation energy generally shows a decreasing trend on the
whole with the increase of the content of hydrochar in the mixed coal.
Combined with the combustion thermogravimetric curve of mixed coal
in Fig. 9, it can be seen that the catalytic effect of ash containing alkali
metals generated after biomass hydrochar combustion on the combus­
tion reaction is a major reason for this result [85]. In addition, the
structure and size parameters ψ of fuel particles are mainly related to the
porosity and specific surface area of fuel particles [38]. Yang et al. [53]
showed that the larger the ψ value of the particle, the smaller the
porosity of the particle and the larger the diffusion resistance of the gas
in the particle, and the reaction mainly occurred on the surface of the
particle; if the smaller the ψ value, the larger the porosity of the particle,
the smaller the diffusion resistance of the gas in the particle, and the
reaction was carried out on the whole particle. According to the calcu­
lated ψ value of the samples in Table 8, the ψ value of the mixed coal
decreases with the increase of the BRC proportion, and the ψ value of
YAC is much larger than that of the mixed coal and BRC. Therefore,
combined with SEM observation results, it can be inferred that the
combustion reaction of YAC mainly occurs on the surface of pulverized
coal, while BRC and blended coal are more comprehensive than YAC.
The addition of BRC in YAC can significantly improve the porosity of the
mixed coal, making the stacking state of mixed coal relatively loose, and
the combustion reaction is transformed from the surface of the pulver­
ized coal to the whole micelle composed of YAC and BRC, the reaction is
more intense, which is another factor affecting the change of activation
energy [38].
It should to be emphasized that when using MATLAB programming
for calculation, it is found that the RPM model can directly use the
experimental raw data, but the URCM model is relatively complicated.
When calculating with URCM, in order to obtain a higher R2 value, the
experimental data with obvious weight loss must be selected for calcu­
lation. Although the RPM involves more parameters than the URCM, the
workload is much less than that of the URCM model.
In order to analysis the reliability of RPM and URCM for calculating
mixed coal combustion, the parameter results calculated by MATLAB
could be substituted into Eqs. (15) and (16), and using the temperature T
of the experimental value as the independent variable value of Eqs. (15)
and (16) to obtain the corresponding conversion rate calculation value
(Xcalc), then draw the weight loss curve calculated by the two kinetic
models of RPM and URCM through Origin, the drawing result is shown
in Fig. 9. The black geometric scatter plot is the experimental weight loss
curve, the red dotted line is the weight loss curve calculated by the RPM.
The blue solid line is the weight loss curve calculated by the URCM.
Comparing the calculated weight loss curve and the experimental
weight loss curve in Fig. 9, it can be seen that the weight loss curves of
the two models can better coincide with the experimental curves. It
shows that both RPM and URCM can describe the weight loss process of
11
Fuel 304 (2021) 121465
URCM
2
E (kJ/mol) kURCM (s− 1) R2
0.99990 128.91 7.936E + 04 0.99669
0.99942 83.34 83.018 0.99700
0.99885 55.63 1.385 0.99474
0.99946 40.72 0.201 0.99862
0.99951 39.61 0.244 0.99757
0.99739 59.88 17.163 0.99015
the sample combustion process well.
According to the above analysis, it is difficult to judge the accuracy of
the two models by observing images. For this reason, this paper will use
Eq. (17) to calculate the deviation between the predicted value (calcu­
lated value) of the kinetic model and the experimental value. The larger
the deviation, the worse the accuracy. Table 9 shows the calculation
results of the deviation between the experimental weight loss rate and
the predicted value of each sample under the two models. From the
results, the deviation value of the RPM is always smaller than that of the
URCM at each ratio. It shows that the prediction of the combustion re­
action in this study is more accurate using the RPM. Many scholars have
also found that RPM is more superior in describing biochar combustion
and gasification [16,38,53,60–63].
The time of pulverized coal injected into the raceway of the blast
furnace is very short [86,87]. If the energy required for the reaction
(activation energy) cannot be obtained for combustion in a short time,
the amount of unburned powder in blast furnace gas will increase. This
will worsen the permeability of the blast furnace, resulting in insuffi­
cient hearth heat, increase the consumption of coke, and is not condu­
cive to the stable running of the blast furnace [88]. Therefore, the
activation energy required by the combustion reaction of the fuel is a
primary parameter of whether the fuel can be used for blast furnace
injection. Due to the higher prediction accuracy of RPM, it is considered
that Plan 3 has the lowest activation energy value of combustion reac­
tion among all the schemes in this paper. Although the I0.5 of Plan 4 is
better than that of Plan 3, the high volatile content of Plan 4 makes it
difficult to guarantee the safety and calorific value of blast furnace in­
jection of Plan 4 [18,89]. Based on the above, when the proportion of
BRC in mixed coal is 60 wt%, BRC has the most significant effect on the
combustion optimization of YAC, Plan 3 is most suitable for blast
furnace injection among the four schemes.
5. Conclusions
The co-combustion mechanism analysis and feasibility study of the
mixed injection of biomass hydrochar and anthracite, starting from the
basic physical and chemical properties of the fuel, after thermogravi­
metric analysis and kinetic calculation, the research results are as
follows:
1) Because the BR is rich in alkali metals, the direct blast furnace in­
jection of BR is restricted. However, HTC can effectively remove the
alkali metal of BR the ash content of BRC is only 1.12%, which is
lower than 4.55% of BR. The contents of CaO and K2O in ash
decreased from 61.82% and 21.01% to 56.25% and 13.37%
respectively after HTC.
2) The synergistic effect of mixed coal is not obvious until late com­
bustion period because of the low ash content of BRC.
3) The combustion reaction of YAC mainly occurs on its surface. The
combustion reactivity of BRC is better than that of YAC. The addition
of BRC in YAC can improve the porosity of mixed coal and enhance
the combustion performance of YAC in mixed coal, and with the
increase of the ratio of BRC, the improvement effect becomes more
obvious.
J. Li et al.
Fig. 9. Experimental weight loss curve and kinetic calculation weight loss curve of samples.
4) The combustion reaction activation energy is between 38.58 ~
83.34 kJ/mol, the accuracy of RPM is higher than that of URCM.
When the proportion of BRC in the mixed coal is 60 wt%, the acti­
vation energy of the mixed coal is the lowest, only 38.58 kJ/mol.
Under the research conditions, when the ratio of BRC is 60 wt%, the
mixed coal has the lowest activation energy and better combustion
characteristics. It shows that when the proportion of BRC in mixed coal
12
Fuel 304 (2021) 121465
is 60%, the combustion of BRC optimized YAC is the most obvious,
which has superior combustion characteristics in raceway of blast
furnace. HTC is a good way to achieve a high proportion of using
biomass energy to make iron. Although combustion characteristics
analysis cannot fully reflect industrial production, the results of this
study can provide theoretical guidance for energy-consuming enter­
prises such as ironmaking plant and thermal power plants to use biomass
energy for production.
J. Li et al.
Table 9
Accuracy evaluation results of the two models.
Sample Deviation(%)
RPM URCM
YAC 0.584 2.097
Plan 1 1.203 2.196
Plan2 1.632 2.539
Plan3 1.191 1.216
Plan4 1.053 1.758
BRC 2.311 3.759
CRediT authorship contribution statement
Jinhua Li: Investigation, Writing - original draft, Writing - review &
editing. Runsheng Xu: Conceptualization, Formal analysis. Guangwei
Wang: Project administration, Resources, Writing - review & editing.
Jianliang Zhang: Funding acquisition, Software, Supervision. Bo Song:
Methodology, Validation. Wang Liang: Data curation, Investigation,
Writing - review & editing. Chuan Wang: Formal analysis,
Visualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This work was supported by the National Natural Science Foundation
of China (No. 52074029, 51804026), VINNOVA (dnr:2017-01327 and
dnr: 2020-04140).
References
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