Article

Cite This: Energy Fuels 2020, 34, 294−303 pubs.acs.org/EF

Reactivity, Synergy, and Kinetics Analysis of CO2 Co-pyrolysis/Co-

gasification of Biomass after Hydrothermal Treatment and Coal
Blends
Juntao Wei,†,‡ Xudong Song,† Qinghua Guo,‡ Lu Ding,*,‡ Kunio Yoshikawa,§ and Guangsuo Yu*,†,‡
†
State Key Laboratory of High-Efficiency Coal Utilization and Green Chemical Engineering, Ningxia University, Yinchuan 750021,
PR China
‡
Institute of Clean Coal Technology, East China University of Science and Technology, Shanghai 200237, PR China
§
Department of Environmental Science and Technology, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama
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226-8503, Japan
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ABSTRACT: Co-gasification of biomass after hydrothermal treatment (HTT) and coal blends had great potential to realize
the clean and efficient co-conversion of biomass and coal. In this study, co-gasification reactivity and synergy of Shenfu
bituminous coal and rice straw (RS) hydrochar (prepared at HTT temperatures of 200, 220, and 240 °C) blends (denoted as
SF-RS200, SF-RS220, and SF-RS240) were investigated using a nonisothermal thermogravimetric analysis, and gasification
kinetic analysis was conducted based on the Coats−Redfern method. The results show that different blends showed little
difference in the initial temperature for weight loss, the final temperature for weight loss, and the temperature corresponding to
the maximum weight loss rate during both co-pyrolysis (stage 1) and blended char co-gasification (stage 2), and only the
maximum weight loss rate of different blends showed a relatively large difference. Reactivity of blends at both stage 1 and stage
2 decreased at a higher HTT temperature. There was no synergy behavior at stage 1. However, the synergistic effect at stage 2
was observed and was more significant for SF-RS200 and SF-RS220 compared with SF-RS240, which was mainly attributed to
the potassium concentration difference among RS hydrochar samples led to various catalytic effects on coal char gasification at
stage 2. Kinetics analysis demonstrates that both volumetric reaction model (O1) and shrinking core model (R2, R3) all showed
high correlation coefficients (>0.95) for different samples and reaction stages. There were obvious kinetic compensation effects
in the gasification process, and activation energy (E) and pre-exponential factor (A) of different samples followed a positive
correlation relationship as ln A = 0.2340 × E − 4.3186 for stage 1 and ln A = 0.1217 × E − 6.2181 for stage 2.

1. INTRODUCTION conversion and utilization of the biomass resource.6,7 In

Biomass was an important carbon friendly source and played an
important role in the world’s energy production and
consumption systems. Gasification technology demonstrated
the huge advantages of achieving efficient and clean conversion
of biomass,1,2 but currently there were few applications of
industrial gasifiers using pure biomass as raw materials because
of the significant disadvantages of biomass such as low energy
density, high moisture content, irregular particle morphology,
and poor grindability and slurryability.3,4 Hydrothermal treat-
ment (HTT) has gained increasing attention as a promising
biomass pretreatment technology3−5 because it could effectively
solve the above-mentioned drawbacks of raw biomass through
dehydration and decarboxylation reactions, and the solid
product derived from biomass HTT (known as biomass
hydrochar) could be directly used as a solid fuel.4,5
Although HTT would significantly improve the fuel proper-
ties of raw biomass, biomass hydrochar still had some
application limitations compared to coal, which was the leading
raw material for industrial gasifiers. Co-gasification of biomass
hydrochar and coal could effectively integrate the advantages of
biomass gasification and coal gasification, which was not only
conducive to reducing coal resource consumption, increasing
coal gasification reaction rate, and reducing NOx/SOx emissions
during coal utilization, but also favorable to promote the
addition, byproduct pressurized steam from an industrial coal
gasifier could be conveyed into the HTT reactor and involved in
dehydration and decarboxylation reactions, which was favorable
for the reduction of total operation cost of biomass hydrochar
preparation.8 Thus, it was concluded that biomass hydrochar
and coal co-gasification has great prospects of commercial
application compared with raw biomass and coal co-gasification
and biomass gasification.
Recently, there have been extensive researches on reactivity
characteristics, synergy behaviors, and kinetics of biomass and
coal co-gasification. Most of the previous studies reported that
gasification reactivity of biomass and coal blends was higher than
that of single coal, and pointed out that there was a synergistic
effect in the co-gasification process, which was mainly owing to
the catalytic effect of alkali and alkaline earth metal (AAEM)
species contained in biomass ash.7,9−11 Ding et al.12 and Habibi
et al.13 also found that the inactivation of potassium in biomass
ash during co-gasification resulted in the inhibition effect on co-
gasification reactivity. Our previous research also explored the
form and intensity transformation of synergy behavior at
Received: October 25, 2019
Revised: December 5, 2019
Published: December 17, 2019

© 2019 American Chemical Society 294 DOI: 10.1021/acs.energyfuels.9b03721

Energy Fuels 2020, 34, 294−303
Energy & Fuels Article

different co-gasification conversions.14 In addition, some Table 1. Experimental Conditions for Biomass HTT
researchers also carried out the co-gasification kinetic Experiments
analysis.15−17 Xu et al.15 stated that activation energy involved
reaction conditions
in the co-gasification process decreased as the biomass
proportion in the mixture increased. Gil et al.16 studied the samples temperature/°C pressure/bar holding time/min
applicability of different kinetic models for blended char co- RS200 200 15.0 30
gasification using nonisothermal thermogravimetric (TG) RS220 220 22.5 30
analysis. RS240 240 35.0 30
Accordingly, it could be found that the relevant previous
studies mainly focused on the co-gasification of raw biomass and Table 1 lists the experimental conditions for biomass HTT
coal blends. However, there were scarce researches on the co- experiments. Table 2 shows the results of proximate analysis, ultimate
gasification of biomass hydrochar and coal, especially the co- analysis, and metal element contents of SF and RS hydrochar samples.
gasification reactivity, synergy, and kinetics.8,18 On the other
hand, biomass HTT conditions had significant effects on the Table 2. Proximate Analysis, Ultimate Analysis, and Metal
physicochemical structure and thermal conversion character- Element Contents of Tested Samples
istics of biomass hydrochar,19−21 but the research on the samples SF RS200 RS220 RS240
influence of biomass HTT conditions on the reactivity
Proximate Analysis/Dry Basis, wt %
characteristics and synergy behaviors of biomass hydrochar
volatile matter 35.42 67.82 63.94 55.76
and coal co-gasification was almost a blank. Therefore, in this
fixed carbon 58.29 19.72 24.76 32.98
study the TG analysis method was used to investigate the co-
ash 6.29 12.46 11.30 11.26
gasification behavior and reactivity of biomass hydrochar
Ultimate Analysis/Dry Basis, wt %
(prepared under different HTT conditions) and coal blends,
C 79.14 44.50 47.59 51.34
and the gasification kinetics analysis was carried out based on the
H 2.32 4.01 3.95 3.69
Coats−Redfern method. This work would help to make a clear
N 1.12 0.77 0.76 0.80
understanding of the co-gasification mechanism of biomass
O 10.36 38.12 36.26 32.66
hydrochar and coal blends, and provide reference data for the
S 0.77 0.14 0.14 0.25
industrial application of co-gasification technology.
Metal Element Concentrations/wt %
2. EXPERIMENTAL SECTION Si 1.12 2.33 2.58 3.10
Al 0.54 <0.10 <0.10 <0.10
2.1. Raw Materials and Biomass Hydrochar Preparation.
K <0.10 1.16 1.05 0.81
Shenfu bituminous coal (SF), a typical gasification coal in China, was
selected as the raw coal sample. Rice straw (RS), a major agricultural Ca 1.16 0.32 0.31 0.27
waste in China, was selected as the raw biomass sample for HTT Na <0.10 <0.10 <0.10 <0.10
experiments, which were carried out by means of an autoclave reactor Mg <0.10 <0.10 <0.10 <0.10
(its schematic diagram is shown in Figure 1). The specific experimental Fe 0.24 <0.10 <0.10 <0.10

Figure 1. Schematic diagram of the HTT reactor and biomass
hydrochar.
procedures were as follows: raw biomass with a length of about 10 mm
and ultrapure water mixture (biomass (dry basis)-to-water ratio of
1:10) was added into the HTT reactor. Purge gas (argon) was
continuously injected for 20 min before heating, to ensure an inert
environment inside reactor. With continuous stirring of the built-in
stirrer, the reactor was heated up to the target HTT temperature (200,
220, and 240 °C), and then held for 30 min. After the reactor cooled
down to room temperature, the gas product was slowly discharged and
the solid−liquid mixture inside the reactor was collected. Afterward, the
solid product was obtained by vacuum filtration of the solid−liquid
mixture, and then dried at 105 °C for 24 h using a vacuum oven to
obtain biomass hydrochar. RS hydrochar samples prepared at different
temperatures were recorded as RS200, RS220, and RS240, respectively.
The raw coal and biomass hydrochar samples were sieved to 80−120
μm as the experimental samples for subsequent analysis. The blends of
coal and biomass hydrochar were obtained by thoroughly mixing RS
hydrochar and SF (blended ratio of 1:1) using a vortex mixer. The
corresponding blends were denoted as SF-RS200, SF-RS220, and SF-
RS240, respectively.
2.2. Gasification Behavior and Reactivity Tests. TG analysis
could simply and accurately record the weight variations of the tested
sample under a specified reaction program, and thus was often used for
reactivity and kinetics analysis of thermochemical conversion (gas-
ification, combustion, pyrolysis, etc.) of carbonaceous materials.22
Thus, in this study a NETZSCH STA 449F3 thermogravimetric
analyzer was adopted to perform gasification experiments at
atmospheric pressure. The sample (∼15 mg) was loaded in a crucible,
and the temperature was raised up to 1300 °C at the heating rate pf 10
K/min under a carbon dioxide atmosphere (120 mL/min). The
experiment was stopped for cooling down after the weight loss curve
was leveled. To ensure the reliability and repeatability of the test data,
each experiment was repeated at least three times.
The variations of sample weight and weight loss rate as a function of
the reaction temperature/time [i.e., TG curve and derivative TG
(DTG) curve] could be obtained by TG analysis. The carbon
conversion of the gasification reaction was determined by the following
equation.
w − wt
x= 0
w0 − wa (1)
where w0, wa, and wt refer to the initial sample weight during gasification
(wt %), the residue weight during gasification (wt %), and the sample
weight at the reaction time of t min(wt %), respectively.

295 DOI: 10.1021/acs.energyfuels.9b03721

Energy Fuels 2020, 34, 294−303
Energy & Fuels Article

R0.5 was commonly used to quantitatively characterize the gas- 3. RESULTS AND DISCUSSION
ification reactivity, and its expression is shown in eq 2.23 The larger R0.5
value represents the higher gasification reactivity. 3.1. Gasification Behavior and Reactivity Analysis of
Tested Samples. 3.1.1. Single Coal and Single Biomass
0.5 Hydrochar. Figure 2 shows the TG/DTG curves for single coal/
R 0.5 =
tx = 0.5 (2) biomass hydrochar gasification. DTG curves obviously indicates
where 0.5 represents the conversion fraction of 0.5, and tx=0.5 represents that the gasification process of RS hydrochar and SF could be
the gasification time when the conversion fraction reaches 0.5.” mainly divided into two reaction stages: the pyrolysis stage at
Assuming that there was no interaction between biomass hydrochar low temperature (stage 1) and the char gasification stage at high
and coal during co-gasification, the TG/DTG theoretical curves of temperature (stage 2). The gasification characteristic parame-
blends could be obtained based on the TG/DTG curve of individual ters, such as the initial temperature for weight loss (Ti), the final
coal and individual biomass hydrochar. The corresponding calculation temperature for weight loss (Tf), the maximum weight loss rate
formulas are shown in eqs 3 and 4, respectively.15 (DTGm), and the reaction temperature corresponding to
wblend = Fcwc + Fbwb (3) DTGm (Tm) can be obtained from the DTG curves. The
corresponding results are summarized in Table 4.
dw dw dw
= Fc + Fb Stage 1, A (solid) → B (char) + C1 (gas)
dtblend dtc dt b (4) (6)
where Fc and Fb represent the proportion of coal and biomass hydrochar Stage 2, B(char) → C 2 (gas) + D (ash) (7)
in blends, respectively.
2.3. Kinetics Analysis. The Coats−Redfern method was often used At stage 1, the Ti and Tf values of SF were 288.3 and 659.0 °C,
for kinetics analysis of nonisothermal thermal-chemical conversion respectively, which were higher than those of RS hydrochar
such as gasification,16,24 combustion,18,25 and pyrolysis,4,26 and the samples (Ti: ∼166 °C, Tf: ∼604 °C). The DTGm1 value of the

ÅÄÅ g (x) ÑÉÑ ÅÄÅ ÑÉ

equation is shown as below.27 SF sample (−1.38%·min−1) was significantly lower than that of
Å Ñ Å AR i 2RT zyÑÑÑ
lnÅÅÅÅ 2 ÑÑÑÑ = lnÅÅÅÅ jjj1 − zzÑÑÑ −
the RS hydrochar samples (−3.40 to −6.56%·min−1), and the
ÅÅÇ T ÑÑÖ ÅÅÇ βE k E {ÑÑÖ RT
E
Tm1 value of the SF sample (443.7 °C) was significantly higher
(5) than that of RS hydrochar samples (∼336 °C). These results
where R is the universal gas constant (8.3145 J·mol−1·K−1), E is the indicate that the pyrolysis reactivities of RS hydrochar samples
activation energy (J mol−1), A is the pre-exponential factor (min−1), β is were higher than that of SF. The differences in the above
the heating rate of the gasification reaction (K/min), T is the reaction gasification characteristic parameters were mainly attributed to

ÄÅ É
temperature (K), and g(x) is the integral form of the reaction

2RT Ñ
the differences in composition and structure of coal and biomass
Å AR Ñ
lnÅÅÅ βE 1 − E ÑÑÑ in eq 5 was almost a constant f or most of the
mechanism model.

ÅÇ ÑÖ
( )
activation energy and the gasification temperature range.24 Hence, a
straight line could be obtained when ln[g(x)/T2] was plotted versus 1/
T, which would show a higher correlation coefficient (R2) of linear
regression analysis when the correct mechanism model was adopted.
Accordingly, the activation energy and the pre-exponential factor could
be determined from the slope and intercept, respectively.
g(x) depended on the reaction mechanism and the particle structure
of the tested samples. Table 3 shows the formulas of three basic models
Table 3. Expressions of f(x) or g(x) for Kinetic Model
Functionsa,4,24,25
mechanism model for solid−state reaction f(x) g(x)
Chemical Reaction (VRM)
first-order O1 1−x −ln(1 − x)
Phase Boundary Controlled Reaction (SCM)
two dimensions (contracting cylinder) R2 2(1 − x)1/2 1 − (1 − x)1/2
three dimensions (contracting sphere) R3 3(1 − x)2/3 1 − (1 − x)1/3
a difference of volatile matter content among different RS
Where f(x) is the mechanism model involved in dx/dt = kf(x) and
g(x) is the integrate form of dx/f(x).
commonly used for the kinetic analysis of the solid state reaction,
including the volumetric reaction model (VRM) or first-order chemical
reaction model, and shrinking core model (SCM) or phase boundary
control reaction model. The former model represents that the chemical
reaction was a controlled step and the reaction happened simulta-
neously through the whole particle, and the latter model assumed that
the reaction initially occurred on the particle external surface and
progressively moved toward the surface of the internal nonreacted
core.4,24,25
296
hydrochar. Hemicellulose, cellulose, and lignin, which con-
stituted the macromolecular structure of biomass, were linked
together by a weak ether bond (R−O−R with a bond energy of
380−420 kJ/mol). In contrast, the coal structure was mainly
composed of dense polycyclic aromatic hydrocarbons, which
were linked together by CC with relatively high bond energy
(1000 kJ/mol). Thus, it was easy for the breakage of R−O−R in
biomass hydrochar at a lower temperature,28 which led to the
lower pyrolysis temperature of RS hydrochar compared with SF.
Comparing the gasification characteristic parameters of different
RS hydrochar samples, it can be seen in Table 4 that the
differences of Ti, Tf, and Tm1 of RS200, RS220, and RS240 were
very small (∼165, ∼604, and ∼336 °C, respectively). However,
DTGm1 values of different RS hydrochar samples showed a
relatively large difference and the basic order was RS200 >
RS220 > RS240. The above results indicate that the effects of
HTT conditions on Ti, Tf, and Tm1 of RS hydrochar pyrolysis
(stage 1) were negligible, but that on DTGm1 of RS hydrochar
pyrolysis was relatively large, which was mainly caused by the
hydrochar samples (as shown in Table 2).
At stage 2, the Ti value of the SF sample was close to that of RS
hydrochar samples, but the Tf (1037.8 °C) and Tm3 (966.4 °C)
values of the SF sample were significantly higher than those of
RS hydrochar samples (Tf, 972.2−986.5 °C; DTGm3, 918.4−
927.4 °C), respectively. These results imply that RS hydrochar
samples showed higher char gasification reactivity than SF. The
DTG m3 value of the SF sample (−4.33%·min −1 ) was
significantly higher than that of RS hydrochar samples (−2.21
to −2.63%·min−1). Comparing the gasification characteristic
parameters of different RS hydrochar samples at stage 2, it can be
seen in Table 4 that the Ti difference among RS200, RS220, and
RS240 was little, but Tf and Tm3 showed a certain difference
among these three RS hydrochar samples with the basic order of
DOI: 10.1021/acs.energyfuels.9b03721
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Energy & Fuels Article

Figure 2. TG and DTG curves of gasification of SF and RS hydrochar samples.

Table 4. Gasification Characteristic Parameters of SF, RS Hydrochar, and Their Blendsa

stage 1 stage 2
samples Ti Tf Tm1 DTGm1 Tm2 DTGm2 R0.5 Ti Tf Tm3 DTGm3 R0.5
SF 288.3 659.0 443.7 −1.38 2.45 717.1 1037.8 966.4 −4.33 2.25
RS200 162.9 604.6 335.5 −6.56 3.01 720.3 972.6 918.4 −2.21 2.84
RS220 166.8 602.7 336.9 −5.46 2.94 718.7 972.2 920.7 −2.24 2.81
RS240 167.0 604.1 335.9 −3.40 2.75 719.8 986.5 927.4 −2.63 2.67
SF-RS200 172.8 631.6 340.3 −3.42 442.1 −1.02 2.92 716.0 993.0 930.7 −3.56 2.49
SF-RS220 171.0 632.7 341.3 −2.88 439.2 −1.09 2.85 715.2 993.2 933.1 −3.60 2.48
SF-RS240 169.7 632.8 339.8 −1.81 437.8 −1.19 2.64 714.8 996.8 934.2 −3.71 2.43
a
Ti-the initial temperature for weight loss (°C), Tf-the final temperature for weight loss (°C), DTGm-the maximum weight loss rate (%·min−1), Tm-
the reaction temperature corresponding to DTGm (°C), and R0.5-reactivity index (min−1).

Figure 3. TG and DTG curves of co-gasification of coal and RS hydrochar blends.

RS240 > RS220 > RS200, which indicates that RS200 had higher
char gasification reactivity than RS220 and RS240. In addition, it
can be found that the DTGm3 of the RS hydrochar samples had a
relatively large difference with the basic order of RS240 > RS220
> RS200, which was mainly attributed to the difference in the
carbon content of RS hydrochars.
The reactivity index (R0.5) values of different single samples at
different reaction stages are also given in Table 4. It can be seen
that the basic sequence of reactivity of single samples was RS200
> RS220 > RS240 > SF for both stage 1 and stage 2.
297
3.1.2. Biomass Hydrochar and Coal Blends. Figure 3 shows
the TG/DTG curves of RS hydrochar and SF blends. At stage 1
(co-pyrolysis), there were two DTG peaks. Ti, Tf, Tm1, and Tm2
values of different blends at stage 1 were basically consistent
(∼170, ∼632, ∼340,and ∼440 °C, respectively). The basic
order of DTGm1 and DTGm2 of blends were SF-RS200 > SF-
RS220 > SF-RS240 and SF-RS240 > SF-RS220 > SF-RS200,
respectively. However, the difference in DTGm2 of different
blends was significantly smaller than that in DTGm1. These
results indicate that the biomass HTT conditions employed in
DOI: 10.1021/acs.energyfuels.9b03721
Energy Fuels 2020, 34, 294−303
Energy & Fuels Article

Figure 4. Comparison between experimental and calculated TG/DTG curves of co-gasification of SF and RS hydrochar blends.

Table 5. Gasification Characteristic Parameters of SF and RS Hydrochar Blends (Theoretical Value)

stage 1
samples Ti Tf Tm1 DTGm1 Tm2 DTGm2 R0.5 D(R0.5)
SF-RS200-Cal 172.1 633.3 337.7 −3.43 441.3 −1.03 2.90 0.69
SF-RS220-Cal 174.5 634.1 339.3 −2.89 439.6 −1.10 2.83 0.71
SF-RS240-Cal 170.8 632.6 338.1 −1.82 440.9 −1.19 2.64 0.38
stage 2
samples Ti Tf Tm3 DTGm3 R0.5 D(R0.5)
SF-RS200-Cal 713.3 1028.5 932.1 −3.07 2.31 7.78
SF-RS220-Cal 713.8 1027.3 934.8 −3.11 2.31 7.36
SF-RS240-Cal 714.5 1027.8 940.6 −3.38 2.30 5.65

this work had negligible effects on Ti, Tf and Tm1 and Tm2 of
blends co-pyrolysis (stage 1), and only affected the DTG peak
value of the co-pyrolysis process (stage 1). By comparing the
gasification characteristic parameters of SF, RS hydrochar, and
their blends at stage 1, it can be found in Table 4 that the Ti and
Tm1 values of blends were close to those of the corresponding
single RS hydrochar, and the Tm2 of blends was close to that of
SF, which demonstrated the first and the second DTG peaks at
stage 1 were mainly attributed to RS hydrochar pyrolysis and SF
pyrolysis, respectively. In addition, the Tf, DTGm1, and DTGm2
values of blends at stage 1 were between single SF and the
corresponding single RS hydrochar.
298
At stage 2 (blended char co-gasification), different blends
showed little difference in gasification characteristic parameters,
such as Ti, Tf, and Tm3 (∼715, ∼995, and ∼930 °C, respectively).
The basic order of DTGm3 of blends was SF-RS240 > SF-RS220
> SF-RS200, but the DTGm3 difference among different blends
was significantly small. These results indicate that for blended
char co-gasification, the biomass HTT condition had negligible
effects on Ti, Tf, and Tm3, and showed slight effects on DTGm3.
The Ti value of blends was close to that of both single SF and
single RS hydrochar, and the Tf, Tm3, and DTGm3 values of
blends were between SF and the corresponding RS hydrochar.
It could be seen from the R0.5 results in Table 4, the basic
sequence of the reactivity of blends at both stage 1 and stage 2
DOI: 10.1021/acs.energyfuels.9b03721
Energy Fuels 2020, 34, 294−303
Energy & Fuels
was SF-RS200 > SF-RS220 > SF-RS240, but the difference in
reactivity of blends at stage 2 was obviously smaller than that at
stage 1. Moreover, it was found that at both stage 1 and stage 2,
the reactivity of blends was between SF and the corresponding
RS hydrochar.
3.2. Synergy Behavior during Blends Co-Gasification.
The theoretical TG/DTG curves of blends co-gasification were
obtained according to eqs 3 and 4. The comparison between the
theoretical and experimental TG/DTG curves could evaluate
the synergy behavior during co-pyrolysis (stage 1) and blended
char co-gasification (stage 2). In addition, the relative deviation
of R0.5 [D(R0.5), defined as below] was used as the quantitative
index for evaluating co-gasification synergy.
R 0.5,exp − R 0.5,cal
D(R 0.5) = × 100%
R 0.5,cal (8)
Figure 4 shows the comparison between experimental and
theoretical TG/DTG curves of blend co-gasification. The
theoretical gasification characteristic parameters of blends
could be directly obtained from the theoretical TG/DTG
curves, and the corresponding results are summarized in Table 5.
It can be clearly seen in Figure 4 that at stage 1, the experimental
TG/DTG curves of different blends were substantially
coincident with the corresponding theoretical curves. Tables 4
and 5 also show that the experimental values of Ti, Tf, Tm1, Tm2,
DTGm1, and DTGm2 values of blends were also substantially the
same as the corresponding theoretical values. In addition, the
D(R0.5) values of different blends was less than 1%. The above
results show that there was no synergy behavior during the co-
pyrolysis of SF and RS hydrochar blends (stage 1). Some
researchers7,29,30 also observed no interaction during the co-
pyrolysis of biomass (wood, soybean straw, and RS) and coal
blends.
In contrast, Figure 4 indicates that at stage 2, the TG/DTG
experimental curves of different blends showed a relatively large
difference compared with the corresponding theoretical curves.
The theoretical Ti, Tf, and Tm3 values of different blends were
basically the same (∼714, ∼1029, and ∼935 °C, respectively).
The basic trend of the theoretical DTGm3 was SF-RS240 > SF-
RS220 > SF-RS200. The theoretical Ti and Tm3 values of blends
were close to the corresponding experimental values. However,
the theoretical Tf values of blends were ∼35 °C larger than the
corresponding experimental values, and the theoretical DTGm3
values of blends were smaller than the corresponding
experimental values. Moreover, the D(R0.5) values of different
blends were within the range of 5.65−7.78%. These results
indicate that there was a relatively obvious synergistic effect
existing in the blended char co-gasification process (stage 2).
Many researchers have also observed the synergistic effect on
co-gasification of biomass char and coal char, and pointed out
that AAEM species rich in biomass ash was the main reason for it
because AAEM would exhibit catalytic effects on char
gasification of carbonaceous materials.9−11 Among different
AAEM species, potassium showed superior catalysis.31,32 It can
be seen in Table 2 that K content in SF was extremely low
(<0.1%), while that in RS hydrochar samples was significantly
high (0.81−1.16%). Thus, K contained in RS hydrochar might
be the main reason for the synergistic effect of stage 2. In order to
provide more detailed data and explore which chemical forms of
K were responsible for the catalysis. Char samples of RS
hydrochar were prepared using TGA (the final temperature was
800 °C), and the total K concentration and water-soluble K
299
Article
concentration in these chars were measured based on the
chemical fraction analysis coupled with an inductively coupled
plasma optical emission spectrometer (ICP−OES), details of
which were shown in our previous studies8,14). The related
results are summarized in Table 6. It could be seen that the total
Table 6. Total and Water-Soluble K Concentrations in Char
Samples of RS200, RS220, and RS240
K concentration/mg·g−1
samples total K water-soluble K
RS200 char 25.7 20.6
RS220 char 22.2 17.8
RS240 char 14.8 12.1
K concentration and water-soluble K concentration in char
samples of RS hydrochar was 1.48−2.57 and 1.21−2.06%,
respectively, which obviously demonstrates that water-soluble K
was the dominant chemical form of K with a percentage of ∼80−
82%. Other researchers also pointed out a similar phenomenon
for pyrolysis char of RS.33,34 Water-soluble K was verified as
active potassium because of its catalytic effect on char
gasification,31,32,35 Therefore, it could be inferred that water-
soluble potassium contained in RS hydrochar was the main
reason for the synergistic effect during blended char co-
gasification (stage 2), and its possible catalytic mechanism was
shown as eqs 9 and 10.36
2K + CO2 → K 2O + CO (9)
K 2O + C → 2K + CO (10)
In addition, it could be found in Table 5 that the D(R0.5)
values of SF-RS200 and the SF-RS220 at stage 2 were close and
higher than that of SF-RS240, which demonstrates that the
synergistic effect on blended char co-gasification processes of
SF-RS200 and SF-RS220 was relatively significant and showed a
similar intensity, while that of SF-RS240 was relatively weak.
This phenomenon was mainly because of the difference in
AAEM species concentrations of different blends. Previous
studies have shown that the higher the AAEM species
concentration, the more obvious the catalytic effect on char
gasification.17,31 It can be seen in Table 6 that water-soluble K
concentration in char samples of RS hydrochar decreased with
the increase of the HTT temperature, and that in RS240 char
was obviously lower than that of RS200 char and RS220 char,
which could well explain the difference in catalytic effects on coal
char gasification during co-gasification of different blended
chars.
3.3. Kinetics analysis of gasification. Figure 5 show the
ln[g(x)/T2] − 1/T curves of single and blend samples obtained
based on VRM (O1) and SCM (R2 and R3). E, A, and R2 were
obtained by regression analysis, and the corresponding results
are listed in Table 7.
In general, the high correlation coefficients of regression
analysis reflected that the selected reaction mechanism model
agreed well with the experimental data.4,24,25 As can be seen in
Table 7, the selected three models all showed high correlation
coefficients (>0.95) for different tested samples and reaction
stages. Therefore, it seemed to be impossible to judge which
mechanism model was the most suitable for predicting the
gasification reaction based on correlation coefficients.24
E and A showed a close relationship with reactivity and the
sample structure, respectively.37,38 It can be seen in Table 7 that
DOI: 10.1021/acs.energyfuels.9b03721
Energy Fuels 2020, 34, 294−303
Energy & Fuels
Figure 5. Plots of ln[g(x)/T2] against 1/T of SF, RS hydrochar, and their blends. (a) SF, (b) RS200, (c) RS220, (d) RS240, (e) SF-RS200, (f) SF-
RS220, and (g) SF-RS240.
for different mechanism models, the E values of SF, RS
hydrochar, and their blends at stage 1 were 61.07−67.82,
33.39−63.80, and 35.81−67.69 kJ·mol−1, respectively, which
were close to those reported in previous studies.4,19,39,40 E values
of SF, RS hydrochar, and their blends at stage 2 were 157.48−
300
Article
185.02, 178.11−229.89, and 174.01−214.65 kJ·mol−1, respec-
tively, which were obviously larger than the corresponding E
values at stage 1. This phenomenon was owing to the obviously
faster reaction rate of pyrolysis than char gasification.24
Furthermore, it can be found in Table 7 that when the same
DOI: 10.1021/acs.energyfuels.9b03721
Energy Fuels 2020, 34, 294−303
Energy & Fuels Article

Table 7. Kinetic Parameters of SF, RS Hydrochar, and Their Blendsa

O1 R2 R3
samples stage E ln A R2 E ln A R2 E ln A R2
SF 1 67.82 8.79 0.9980 61.07 6.73 0.9971 63.26 6.77 0.9976
2 185.02 16.22 0.9929 157.48 12.40 0.9987 166.19 12.99 0.9976
RS200 1 63.80 10.38 0.9945 57.59 8.22 0.9953 56.601 8.30 0.9952
2 229.89 21.67 0.9949 195.80 17.10 0.9997 206.57 17.92 0.9990
RS220 1 51.71 7.75 0.9941 46.78 5.85 0.9964 48.38 5.84 0.9957
2 213.57 20.02 0.9967 181.19 15.60 0.9998 191.42 16.38 0.9998
RS240 1 36.59 4.07 0.9935 33.39 2.54 0.9958 34.43 2.41 0.9951
2 209.70 19.34 0.9953 178.11 15.04 0.9999 188.08 15.78 0.9993
SF-RS200 1 67.69 11.57 0.9851 59.25 8.88 0.9911 61.96 9.12 0.9894
2 214.65 19.82 0.9954 182.62 15.48 0.9995 192.74 16.23 0.9990
SF-RS220 1 55.38 8.89 0.9872 48.72 6.56 0.9936 50.83 6.68 0.9918
2 213.93 19.76 0.9950 182.20 15.46 0.9994 192.23 16.20 0.9988
SF-RS240 1 40.19 5.22 0.9901 35.81 3.39 0.9949 37.23 3.36 0.9935
2 204.79 18.78 0.9945 174.01 14.57 0.9995 183.73 15.28 0.9987
a
E-activation energy (kJ·mol−1), A-pre-exponential factor (min−1), R2-correlation coefficient.

Figure 6. ln A vs E of different samples. (a) stage 1, (b) stage 2.

mechanism model was employed, the basic sequence of E at meantime, which hindered the C(O) movement and led to a
stage 1 was SF > RS200 > RS220 > RS240 (single samples) and lower A value.
SF-RS200 > SF-RS220 > SF-RS240 (blends samples). The basic
Stage 1: ln A = 0.2340 × E − 4.3186
sequence of E at stage 2 was RS200 > RS220 > RS240 > SF
2
(single samples) and RS200 > SF-RS220 > SF-RS240 (blends (R = 0.9951) (11)
samples).
The E orders of different samples at stage 1 and stage 2 were Stage 2: ln A = 0.1217 × E − 6.2181
different from the reactivity sequence mentioned above. The 2
(R = 0.9932) (12)
main reason was that the gasification reaction rate was
controlled by both activation energy and pre-exponential factor.
4. CONCLUSIONS
It was generally believed that the lower E and the higher A, the
faster the reaction rate.41 As can be seen in Table 7, the A values (1) Different SF and RS hydrochar blends showed little
of different samples increased with the increase of E, which difference in Ti, Tf, and Tm values during both co-pyrolysis
indicates that the gasification reaction of different samples had a (stage 1) and blended char co-gasification (stage 2), and
relatively obvious kinetic compensation effect.41 Figure 6 shows only DTGm values of different blends showed a relatively
large difference. Reactivity of blends decreased with
the ln A versus E curves of different samples at stage 1 and stage
increasing HTT temperature during stage 1 and stage 2.
2, and it could be observed that there were obvious linear (2) There was no synergy behavior at stage 1. However, the
relationships between ln A and E, by following eqs 11 and 12. synergistic effect existed at stage 2 and was more obvious
Xie42 pointed out that for the reaction with lower E, it was easier for SF-RS200 and SF-RS220 compared with SF-RS240,
to make the free activated carbon connect with CO2 to generate which was mainly attributed to that of the AAEM
C(O), but the bond energy of C(O) was enhanced in the concentration difference of different RS hydrochars which
301 DOI: 10.1021/acs.energyfuels.9b03721
Energy Fuels 2020, 34, 294−303
Energy & Fuels Article

led to the different catalytic effects on coal char
gasification during co-gasification.
(3) For all samples and different reaction stages, the
mechanism models, such as VRM (O1) and SCM (R2
and R3), all high correlation coefficients (>0.95). There
were obvious kinetic compensation effects in the
gasification process of different samples.
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K.; Yang, W.; Blasiak, W. Gasification characteristics of hydrothermal
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■
(6) Krerkkaiwan, S.; Fushimi, C.; Tsutsumi, A.; Kuchonthara, P.
AUTHOR INFORMATION Synergetic effect during co-pyrolysis/gasification of biomass and sub-
bituminous coal. Fuel Process. Technol. 2013, 115, 11−18.
Corresponding Authors (7) Zhang, Y.; Zheng, Y.; Yang, M.; Song, Y. Effect of fuel origin on
*E-mail: dinglu@ecust.edu.cn. Phone: 86-21-64252974. Fax: synergy during co-gasification of biomass and coal in CO2. Bioresour.
86-21-64251312 (L.D.). Technol. 2016, 200, 789−794.
*E-mail: gsyu@nxu.edu.cn. Tel/Fax: +86-951-2062061 (G.Y.). (8) Wei, J.; Guo, Q.; He, Q.; Ding, L.; Yoshikawa, K.; Yu, G. Co-
ORCID gasification of bituminous coal and hydrochar derived from municipal
solid waste: Reactivity and synergy. Bioresour. Technol. 2017, 239, 482−
Juntao Wei: 0000-0001-5744-6749 489.
Guangsuo Yu: 0000-0003-4085-9736 (9) Oladejo, J. M.; Adegbite, S.; Pang, C. H.; Liu, H.; Parvez, A. M.;
Notes Wu, T. A novel index for the study of synergistic effects during the co-
The authors declare no competing financial interest. processing of coal and biomass. Appl. Energy 2017, 188, 215−225.

■
ACKNOWLEDGMENTS
The present work was supported by Project of Key Research
Plan of Ningxia (2019BCH01001), National Science Founda-
tion of China (21878093), and Key Program for Outstanding
PhD Candidate of East China University of Science and
Technology.
(10) Hu, J.; Shao, J.; Yang, H.; Lin, G.; Chen, Y.; Wang, X.; Zhang, W.;
Chen, H. Co-gasification of coal and biomass: synergy, characterization
and reactivity of the residual char. Bioresour. Technol. 2017, 244, 1−7.
(11) Mafu, L. D.; Neomagus, H. W. J. P.; Everson, R. C.; Okolo, G. N.;
Strydom, C. A.; Bunt, J. R. The carbon dioxide gasification
characteristics of biomass char samples and their effect on coal
gasification reactivity during co-gasification. Bioresour. Technol. 2018,
258, 70−78.

■
(12) Ding, L.; Zhang, Y.; Wang, Z.; Huang, J.; Fang, Y. Interaction and
NOMENCLATURE its induced inhibiting or synergistic effects during co-gasification of coal
char and biomass char. Bioresour. Technol. 2014, 173, 11−20.
A = pre-exponential factor (min−1) (13) Habibi, R.; Kopyscinski, J.; Masnadi, M. S.; Lam, J.; Grace, J. R.;
D(R0.5) = relative deviation of R0.5 (%) Mims, C. A.; Hill, J. M. Co-gasification of biomass and non-biomass
DTGm = maximum weight loss rate (%·min−1) feedstocks: synergistic and inhibition effects of switchgrass mixed with
E = activation energy (kJ·mol−1) sub-bituminous coal and fluid coke during CO2 gasification. Energy
Fb = biomass hydrochar proportion in blends (%) Fuels 2012, 27, 494−500.
Fc = coal proportion in blends (%) (14) Wei, J.; Gong, Y.; Guo, Q.; Chen, X.; Ding, L.; Yu, G. A
g(x) = reaction mechanism model mechanism investigation of synergy behaviour variations during
HTT = hydrothermal treatment blended char co-gasification of biomass and different rank coals.
O1 = first-order chemical reaction Renewable Energy 2019, 131, 597−605.
(15) Xu, C.; Hu, S.; Xiang, J.; Zhang, L.; Sun, L.; Shuai, C.; Chen, Q.;
R0.5 = reactivity index (min−1)
He, L.; Edreis, E. M. A. Interaction and kinetic analysis for coal and
R2 = correlation coefficient biomass co-gasification by TG-FTIR. Bioresour. Technol. 2014, 154,
R2 = phase boundary controlled reaction (two dimensions) 313−321.
R3 = phase boundary controlled reaction (three dimensions) (16) Fermoso, J.; Gil, M. V.; Pevida, C.; Pis, J. J.; Rubiera, F. Kinetic
T = reaction temperature (K) models comparison for non-isothermal steam gasification of coal-
Ti = initial temperature for weight loss (°C) biomass blend chars. Chem. Eng. J. 2010, 161, 276−284.
Tf = final temperature for weight loss (°C) (17) Jeong, H. J.; Park, S. S.; Hwang, J. Co-gasification of coal-biomass
Tm = temperature corresponding to the maximum weight loss blended char with CO2 at temperatures of 900-1100°C. Fuel 2014, 116,
rate (°C) 465−470.
w0 = initial sample weight of gasification (%) (18) Liu, Z.; Quek, A.; Kent Hoekman, S.; Srinivasan, M. P.;
wt = sample weight at the gasification time of t (%) Balasubramanian, R. Thermogravimetric investigation of hydrochar-
lignite co-combustion. Bioresour. Technol. 2012, 123, 646−652.
wa = residue weight of gasification (%)
(19) Bach, Q.-V.; Chen, W.-H.; Sheen, H.-K.; Chang, J.-S. Gasification
x = gasification conversion kinetics of raw and wet-torrefied microalgae Chlorella vulgaris ESP-31
β = heating rate of gasification reaction (K·min−1)

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