Article

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Comparison of HTSM and TGA Experiments of Gasification

Characteristics of Different Coal Chars and Petcoke
Ming Liu, Zhihao Zhou, Zhongjie Shen, Qinfeng Liang, Jianliang Xu, and Haifeng Liu*
Key Laboratory of Coal Gasification and Energy Chemical Engineering of Ministry of Education, Shanghai Engineering Research
Center of Coal Gasification, East China University of Science and Technology, P.O. Box 272, Shanghai 200237, People’s Republic
of China

ABSTRACT: The thermogravimetric analyzer (TGA) is an ideal experimental method to estimate the gasification kinetics.
However, the diffusion resistance was significant in high-temperature gasification process. In this study, comparison of different
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coal chars and petcoke gasification characteristics between high-temperature stage microscope (HTSM) and TGA experiments
at high temperature were carried out. The gasification reactivity of different coal chars and petcoke in HTSM was higher than
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that in TGA experiments. The gasification reactivity of lignite and bituminous char in HTSM was much higher than that in
TGA experiments. Meanwhile, the reactivity index of anthracite and petcoke in HTSM was merely double of that in TGA
experiments. Interparticle diffusion process limited the gasification reactivity of different coal chars and petcoke in TGA
experiments. The diffusion resistance of lignite and bituminous char was severe in TGA experiments. Moreover, the complete
reaction time of bituminous coal char in HTSM experiments at high reaction temperature showed an agreement with industrial
operating data.

1. INTRODUCTION sample bed was extremely lower than that expected

Entrained flow gasifier was an efficient technology that
converted solid fuel (e.g., coal and petcoke) into syngas,
which was widely used for chemical production, power
generation (integrated gasification combined cycle), indirect
liquefaction, and so on.1,2 Coal gasification reactivity was an
important factor that affects the efficiency of gasifier.3−6 Thus,
it was imperative to apply an approximate experimental
method to study the gasification properties of coal. At present,
the thermal gravimetric analyzer (TGA) was widely accepted
as an applicable laboratory experimental method to estimate
the gasification reactivity of coal.7−12 But the diffusion
resistance was severe at high temperatures. The application
of reaction kinetics parameters obtained at low temperatures to
high-temperature reactions was not appropriate because of the
ash melting at high temperatures. The drop tube furnace
(DTF) reactor was an appropriate experimental method to
study the gasification of coal and petcoke at high temper-
atures.3,13−16 But the limited residence time of the samples in
DTF reactors restricted the reaction time of coal gasification.
The wire mesh reactor also was applied to investigate the
pyrolysis and gasification process of coal.17−19 However, the
carbon conversion of samples during the gasification process
was difficult to directly estimate. The high-temperature stage
microscope (HTSM) system also was applied to investigate the
gasification characteristics (morphological evolution and
shrinkage rate) of coal char at high temperatures.20−22 And
the experimental results showed novel characteristics.
Thermogravimetric analyzer was generally applied to
investigate the gasification kinetics of coal char, biomass
char, and petcoke.23−27 It is an effective experimental method
to study the gasification kinetics of coal char. The diffusion
resistance of gasifying agent in the crucible also is a problem
when studying the intrinsic reaction kinetics of coal char at
high temperatures.28−34 The CO2 partial pressure in the
(atmosphere pressure).28 Ollero et al.35 found that the internal
diffusion in the sample bed was significant during the
gasification of wood matter. Besides, the internal diffusion in
the sample bed should not be disregarded in kinetics
evaluations. Gomez et al.36 pointed out that the maximum
reaction rate during coal gasification process was caused by the
switching of inlet gas. And, the reaction rate obtained from an
improved gasification procedure was higher than from the
novel TGA experiments. New experimental method was
developed to reduce the interparticle diffusion.37 The sample
bed thickness was reduced to decrease the diffusion resistance
in this method. Even though, the diffusion limitation control
the reaction process when the reaction temperature was above
900 °C. Single-step kinetics models were thought inappro-
priate for estimating kinetics parameters because of the
diffusion hindrance.
The high-temperature stage microscope system was initially
used by Ding et al. to study the morphology evolution of coal
char during the gasification process.38 Shen et al.20 studied the
gasification characteristics of coal char particles on molten slag
by a HTSM system. The conversion of coal char particles on
molten slag was obtained by measuring the projecting area of
char particles. It was found that the gasification rate of char
particle on molten slag was higher than that of char particles.
Combustion characteristics of coal char on molten slag also
was investigated by a HTSM system.21 The reaction rate of
coal particles on molten was lower than of coal char particles.
Besides, the HTSM system was applied to investigate the
gasification of coal char and petcoke by Shen et al. and Liu et
Received: January 1, 2019
Revised: February 9, 2019
Published: March 7, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.9b00005

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Table 1. Proximate and Ultimate Analyses of Samplesa

proximate analysis (wt %) ultimate analysis (wt %, ad)
sample Mad Vad Aad FCad C H N S
XLT coal 1.49 29.60 15.60 53.31 60.01 4.10 0.90 1.27
XLT char 0.60 2.24 26.92 70.24 65.10 0.50 0.82 5.18
SM coal 3.08 32.95 9.53 54.44 72.86 4.83 1.05 1.04
SM char 2.60 1.93 19.93 75.54 82.28 0.84 1.26 1.31
GP coal 1.17 9.23 14.26 75.34 76.17 3.03 1.06 3.58
GP char 1.79 1.63 14.49 82.09 81.37 0.77 1.11 3.38
PC 0.71 7.99 2.03 89.27 91.63 3.46 1.68 2.78
a
M: moisture; V: volatile matter; A: ash; FC: fixed carbon.

al.22,39−42 Furthermore, Liu et al.43 studied the gasification

characteristics of petcoke particle swarms using a HTSM
system. It was found that the particle concentration
significantly affected the gasification of the samples. It was
inferred that the interparticle diffusion restricted the diffusion
process. The gasifying agent concentration in particle swarms
was lower than expected. It was suggested that gasification
kinetics characteristics of coal char obtained from fixed-bed
reactors should be re-evaluated.
The gasification kinetics of coal char, biomass char, and Figure 1. Schematic of high-temperature stage microscope. (1)
petcoke could be well estimated by a TGA experimental Digital camera, (2) objective lens, (3) cooling water inlet, (4) cooling
water outlet, (5) gas inlet, (6) cooling water inlet, (7) gas outlet, (8)
apparatus at lower temperatures (<900 °C). However, the cooling water outlet, (9) char particle, (10) sapphire slip, (11)
interparticle diffusion resistance of gasifying agent in the ceramic crucible, (12) thermal couple, and (13) heating strip.
sample bed restricted the reaction rate, especially at high
temperatures. A HTSM system could be used for investigating process, the carrier gas was Ar at the flow rate of 300 mL/min. The
the gasification characteristics (e.g., morphological evolution) sample was held for a minute at the temperature of 1300 °C to
of a single char particle and particle swarms. The interparticle stabilize the particle temperature. After that, the reaction began with
diffusion could be dramatically decreased and even excluded in switching Ar into CO2 at the flow rate of 300 mL/min. At the same
HTSM experiments. The gasification kinetics of char particles time, the microscope camera was turned on to record the whole
also could be measured using a HTSM system, which was not reaction process. The projecting area of char particles during the
referred in our previous studies. The flow dynamics of fluidized gasification process was measured by ImageJ software.
2.2.2. TGA Experimental Method. The gasification experiments of
bed reactors are different from those of fixed-bed reactors. The different coal chars were performed in NETZSCH thermogravimetric
TGA apparatus are typical fixed-bed reactors and comparison analyzer (STA 2500). Main composition of the experimental
of gasification kinetics between TGA and HTSM experimental apparatus is shown in Figure 2. The cylindrical crucible (7 mm
method also contributes to the understanding of the
applicability. Thus, the gasification characteristics of different
coal chars and petcoke were compared using TGA and HTSM
experimental system in this study.

2. EXPERIMENTAL METHOD
2.1. Char Preparation. Three different ranked coal chars and a
petcoke were used in this study: Xiaolongtan lignite (XLT), Shenmu
bituminous (SM), and Gaoping anthracite (GP). The three raw coals
were predried, ground, and dried, respectively. Furthermore, the char
samples were obtained after a pyrolysis process using a wire mesh
reactor in an argon atmosphere. The wire mesh basket was hung in a
corundum tube. The pyrolysis temperature in the corundum tube of
the reactor was 1000 °C. The particle size of the coal char and Figure 2. Schematic of thermogravimetric analyzer. (1) Gas outlet,
petcoke significantly affected the gasification process.22 Thus, the char (2) reaction cavity, (3) sample, (4) sample rod, (5) reference, (6) gas
samples and petcoke were sieved into the size ranging from 200 to inlet, (7) protecting crucible, (8) protecting shell, (9) samples, and
250 μm. The proximate and ultimate analyses of the three char (10) quartz sand.
samples are carried out according to the Chinese standards of GB/
T212-2008 and GB/T476-2008 and are summarized in Table 1.
2.2. Char Gasification. 2.2.1. HTSM Experimental Method. The
gasification reactivity of different coal chars was investigated using a inside diameter, 4 mm high) was filled with silica sand (SiO2, 99%
HTSM experimental setup. The HTSM system mainly consisted of a purity) at the bottom of the crucible, allowing a good exposure of the
TS 1500 heating stage (Linkam) and a DM 4500P microscope sample layer to the gasifying agent. The sample layer was laid on the
(Leica), as shown in Figure 1. Detailed introduction of the HTSM
surface of silica sand as shown in Figure 2. The weight of the char
system can be referred in our previous study.20 Few char samples were
spread on the sapphire slip, which was placed in the crucible in case samples in the crucible was 10 ± 0.5 mg. System control and data
the sample was blow away by the inlet gas. The sample was heated to acquisition were performed on a personal computer. The procedure
1300 °C at the heating rate of 100 °C/min. During the heating used for each experiment in TGA was as follows:

B DOI: 10.1021/acs.energyfuels.9b00005
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Figure 3. Gasification process of coal chars and petcoke in HTSM experiments: (a) XLT, (b) SM, (c) GP, and (d) PC.
(1) In an inert atmosphere of pure N2, the sample was heated from
ambient temperature to 1300 °C at the heating rate of 30 °C/
min.
(2) The char was gasified with switching of N2 to CO2 (at the flow
rate of 120 mL/min) until a constant weight was reached.
(3) The gasification process ended when a constant weight was
reached.
3. RESULTS AND DISCUSSION
3.1. In Situ Investigation of Coal Chars and Petcoke
Gasification. 3.1.1. Gasification Process. Gasification process
of different coal chars and petcoke particle in HTSM
experiments is shown in Figure 3. At the temperature of
1300 °C, the gasification of different coal chars and petcoke
particles all showed a shrinking particle mode. The forming
coal ash melted to slag and adhered on the surface of the
particle at high temperature. The density of slag was higher
than that of coal ash and the porosity was lower than that of
coal ash. Thus, the shrinkage of char particles was more
evident compared with the gasification process at lower
reaction temperatures.44,45 For SM and PC char particles,
the ash content was limited, which resulted in the shrinking
particle mode.
Figure 3a show the gasification process of XLT lignite char
particle. The initial particle diameter was about 210 μm and
the diameter of the residue was about 80 μm. It was found that
the shrinkage of char particle was limited at the initial reaction
stage (0−7 s). The shrinkage of the char particle was evident
and the reaction rate evidently increased as the gasification
proceeded. Molten slag on the surface of char particle appeared
at the later reaction stage. The coverage of melting slag
decreased the reaction rate and the shrinkage of the particle
was not obvious in the later reaction stage (13−16 s).
Gasification process of SM bituminous char particle is
shown in Figure 3b. Similar to the gasification of XLT char
particle, the reaction process also showed a shrinking particle
C DOI: 10.1021/acs.energyfuels.9b00005
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mode. Compared with XLT char particle, the shrinkage of SM
char particle at the initial reaction stage was evident. The
gasification residue was less, resulting from the low ash content
in SM coal char.
Char gasification process of GP char particle in HTSM
experiments is shown in Figure 3c. The diameter of the char
particle was about 250 μm and the char particle showed a
shrinking particle mode during the gasification process. The
complete reaction time of the GP char particle was about 160
s. And the particle had a rotary movement during the reaction
process. It also was found that ash melting occurred at the later
reaction stage (130−160 s).
Figure 3d shows the gasification process of petcoke in
HTSM experiments. The gasification reactivity of petcoke was
low and the complete reaction time was about 260 s. The
initial diameter of the petcoke particle was about 200 μm.
Besides, the ash content in the petcoke was extremely low and
the gasification residue was less. Moreover, the shrinkage rate
of the petcoke particle during the gasification process was
uniform, which indicated the reaction rate was not evidently
changed.
3.1.2. Definition of Carbon Conversion. In HTSM
experiments, the carbon material in coal char and petcoke
was gasified and the forming ash melted and adhered on the
surface of char particles. It was assumed that the coal char and
petcoke particles were spherical. The shrinkage rate of coal
char and petcoke particles was defined as
d p3
s=
d03 (1)
where dp is the diameter of coal char and petcoke particles in
the reaction process. The initial diameter of the particles was
d0. The carbon conversion of coal char and petcoke particles
was expressed as eq 2.
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Δm d3
x= = 1 − c3
mc d0 (2)
where Δm is the mass loss of coal char and petcoke and mc is
the total weight of carbon in coal char and petcoke. dc was the
diameter of the unreacted core. The relationship between
unreacted core, slag layer thickness δ, and particle diameter of
coal char is shown in eq 3
d p = dc + 2δ
(3)
Equation 4 was obtained according to the conservation of mass
π 3
d0 ρ xwa ≈ πd p2δρa (1 − εa)
6 c (4)
where ρc is the density of coal char, wa is the weight of coal ash
in char particles, ρa is the density of coal ash/slag, and εa is the
porosity of ash/slag layer. Equation 4 was rewritten as eq 5 by
combing eqs 2 and 3
(d03 − dc3)ρc wa ≈ 3d p2(d p − dc)ρa (1 − εa) (5)
The carbon conversion of coal char and petcoke particles was
calculated based on eqs 2 and 5. In this experiments, the
forming ash in XLT, SM, and GP coal char was melted. The
porosity of the slag layer on particle surface εa was zero. The
ash content of PC was limited and the forming ash on particle
surface was neglected.
The thickness of the ash/slag layer on particle surface was
mainly decided by the ash content of char particles. The
differences between the shrinkage rate and carbon conversion
should increase with increase in the ash content according to
eqs 1−3. The char particle with the highest ash content among
the different coal chars is XLT coal char. The shrinkage rate
and the carbon conversion of XLT coal char was calculated as
shown in Figure 4. The slag layer thickness was limited at the
Figure 4. Comparison between shrinkage rate and carbon conversion
of XLT coal char.
initial reaction stage. The values of carbon conversion was
approximate to the shrinkage rate at the same reaction time
when the carbon conversion was below about 0.5. The slag
layer thickness increased as the reaction proceeded. The value
of carbon conversion was 0.1 higher than that of the shrinkage
at the same reaction time when the carbon conversion was
above 0.8. The slag layer thickness was related to the ash
content and the ash content was high in XLT coal char.
Differences in the values between carbon conversion and
shrinkage rate was less for other samples. Therefore, the
particle shrinkage rate s was regarded as the carbon conversion,
as shown in eq 6
D DOI: 10.1021/acs.energyfuels.9b00005
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Δm d3
x= = 1 − c3 ≈ s
mc d0 (6)
3.2. Carbon Conversion. Figure 5 shows the carbon
conversion curve versus time of coal char and petcoke particles
in TGA and HTSM experiments. The carbon conversion curve
of XLT coal char particles is shown in Figure 5a, and the
particle diameters were in the range of 197−256 μm. The
complete reaction time of large particles is slightly more than
that of small particles, as shown in Figure 5a. The complete
reaction of XLT coal char was about 16 s. Besides, it was found
that the reaction rate was slow in the initial and later stages.
The gas replacement in the initial stage accounted for the slow
reaction rate.36,37 At the later reaction stage, the slag coverage
and decrease of reaction surface area decreased the reaction
rate.46,47 The carbon conversion curve of SM coal char
particles is shown in Figure 5b. The particle diameters were in
the range of 213−254 μm and the complete reaction time of
char particles was about 32 s. The complete reaction time of
bituminous coal char was double that of lignite coal char in this
experiments. The carbon conversion of GP char particles
during the gasification process is shown in Figure 5c. The
particle size was in the range of 223−262 μm, as shown in
Figure 5c. As a result of different ash content and carbon
structure in different char particles, the complete reaction time
of char particle was in the range of 130−160 s. The complete
reaction time of anthracite char was about 10 times more than
that of lignite char in this experiments. Figure 5d shows the
carbon conversion curve of petcoke particles. The carbon
conversion curve of the petcoke particles was almost linear,
which indicated that the reaction rate was constant. The
particle size was about 200 μm and the complete reaction time
was about 260 s, which is 16 times more than that of lignite
coal char particles. The above results showed that the HTSM
experimental method is proper to investigate the gasification
kinetics of single char particles.
The carbon conversion of char and petcoke particles in
HTSM experiments was regard as the particle shrinkage rate.
Thus, the average carbon conversion xa in HTSM experiments
was calculated by eq 7.
∑ d p3
xa = 1 −
∑ d03 (7)
Carbon conversion of coal chars and petcoke in TGA
experiments was defined as eq 8
m − ma
x=1− t
m0 − ma (8)
where mt is the mass of the samples at time t, ma is the mass of
the gasification residues, and m0 is the initial mass of the
samples.
A comparison of carbon conversion of XLT char between
HTSM and TGA experimental methods is shown in Figure 6.
The evolution of conversion curve versus time of different
experimental methods was similar. The complete reaction time
of XLT coal char in HTSM and TGA experiments was about
16 and 80 s, respectively. The reaction time in HTSM
experiments was about 5 times more than that in TGA
experiments. Moreover, the reaction rate was both slow in the
initial reaction stage in HTSM and TGA experiments. This
phenomenon was related to the gas replacement, which was
reported in literatures.36,37
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Figure 5. Carbon conversion of different coal chars and petcoke particles: (a) XLT, (b) SM, (c) GP, and (d) PC.

Figure 6. Comparison of carbon conversion of XLT char between (a) HTSM and (b) TGA experimental methods.

Figure 7. Comparison of carbon conversion of SM char between (a) HTSM and (b) TGA experimental methods.

Figure 7 shows the carbon conversion curve of SM coal char about 150 s, which was 5 times more than that in HTSM
in HTSM and TGA experiments. The complete reaction time experiments. Main factors that affected the gasification
of coal char in HTSM experiments was about 32 s. The reactivity of coal char were gasifying agent concentration and
complete reaction time of coal char in TGA experiments was reaction temperature. The amount of char particles in HTSM
E DOI: 10.1021/acs.energyfuels.9b00005
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Figure 8. Comparison of carbon conversion of GP char between (a) HTSM and (b) TGA experimental methods.

Figure 9. Comparison of carbon conversion of PC between (a) HTSM and (b) TGA experimental methods.

Figure 10. Comparison of gasification rate of XLT between (a) HTSM and (b) TGA experimental methods.

experiments was limited and the amount of CO produced was
less. Meanwhile, the amount of char particles in TGA
experiments was much more than that in HTSM experiments.
The amount of CO produced also was more than that in
HTSM experiments. The high concentration of CO decreased
the gasifying agent concentration in the sample bed, which
further decreased the reaction reactivity.
A comparison of carbon conversion of GP char between
HTSM and TGA experimental methods is shown in Figure 8.
The average carbon conversion of GP char was about 0.85 in
HTSM experiments. The complete reaction time of GP char in
HTSM experiments was about 160 s. The reaction time of GP
char in TGA experiments was about 560 s, which was about
3.5 times more that in HTSM experiments. Moreover, the
reaction time of GP char was about 7 times more that of XLT
char particles in TGA experiments. Meanwhile, the reaction
time of GP char was about 10 times more that of XLT char
particles in HTSM experiments. It was inferred that the
F DOI: 10.1021/acs.energyfuels.9b00005
gasifying agent concentration was different between the
gasification of XLT char and GP char. Compared with GP
char, the fast reaction of XLT char led to a higher CO
concentration in the sample bed. The amount of char particles
in HTSM was limited, resulting in the low CO concentration
in particle swarm. Thus, the gasifying agent concentration
between different coal chars was more approximate in HTSM
experiments. A detailed investigation of the effects of gasifying
agent concentration on the gasification process is be
introduced in Section 3.4.
Figure 9 shows the comparison of carbon conversion of
petcoke in different experiments. The carbon conversion of
petcoke particles showed a linear change in different
experiments, which reflected the reaction rate mainly was
constant during the gasification process. Figure 9a shows the
carbon conversion of the petcoke particles in HTSM
experiments. The complete reaction time was about 260 s.
The ash content in petcoke was low and the carbon conversion
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Figure 11. Comparison of gasification rate of SM between (a) HTSM and (b) TGA experimental methods.

Figure 12. Comparison of gasification rate of GP between (a) HTSM and (b) TGA experimental methods.

Figure 13. Comparison of gasification rate of PC between (a) HTSM and (b) TGA experimental methods.

reached up to 0.99. The reaction time of petcoke in TGA
experiments was about 900 s, which was about 3.6 times more
than that in HTSM experiments. The reaction reactivity of
petcoke was low and the CO production was limited. Thus, the
concentration of the gasifying agent in the petcoke sample bed
was higher compared with that in the XLT and SM char
sample bed. The reaction time of XLT and SM char in HTSM
experiments was about 5 times more than that in TGA
experiments. The reaction time differences of petcoke between
HTSM and TGA experiments was less.
3.3. Gasification Reaction Kinetics. The reaction rate
curves versus the carbon conversion of XLT char particles in
TGA and HTSM experiments are shown in Figure 10. The
gasification rate of char particles in different experiments both
first increased and then decreased. This phenomenon was due
to the gas replacement, as explained above. The reaction rate
curve showed fluctuation as shown in Figure 10a, which
resulted from the nonspherical shape of char particles and the
G DOI: 10.1021/acs.energyfuels.9b00005
irregular change of the projecting area. Figure 10b shows the
reaction rate of XLT char particle with different conversions. It
was found that the maximum reaction rate of char particle was
about 0.022 s−1, which was about 1/6 times lower than that in
HTSM experiments. The gasification rate of char particle in
HTSM experiments dramatically higher than that in TGA
experiments.
Figure 11 shows the gasification rate of SM char particles in
TGA and HTSM experiments. The maximum reaction rate of
char particles in HTSM experiments was about 0.05 s−1, which
was about 5 times higher than that in TGA experiments.
Similar to the gasification rate of XLT char particles, the
reaction rate of SM char particles also first increased and then
decreased during the reaction process. The reaction rate of the
SM coal char particle in HTSM experiments also was
approximate to that in drop tube furnace reactors.48
Comparison of gasification rate of GP char particles between
HTSM and TGA experiments is shown in Figure 12. The
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gasification rate of char particles both decreased with carbon
conversion in different experiments. The maximum reaction
rate of GP char particles in HTSM experiments was about
0.009 s−1, which was double of that in TGA experiments. In
HTSM experiments, the reaction rate generally was constant in
the initial and middle stages. The reaction rate decreased with
conversion in the later reaction stage. The reaction rate
constantly decreased with carbon conversion in TGA experi-
ments, as shown in Figure 12b.
The reaction rate curve of petcoke versus carbon conversion
in HTSM experiments is shown in Figure 13a. The reaction
rate slightly increased with carbon conversion when the
conversion was below 0.8. The reaction rate of petcoke
particles decreased at the later reaction stage. The maximum
reaction rate in HTSM experiments was about 0.005 s−1.
Figure 13b shows the evolution of the reaction rate with
conversion of petcoke in TGA experiments. The reaction rate
decreased with the carbon conversion during the whole
gasification process. The maximum reaction rate was about
0.0016 s−1, which was about 1/3 of that in HTSM experiments.
The carbon conversion of char particles was not complete
and the conversion curves showed fluctuation. Therefore, the
reactivity index R0.5 was adopted to estimate the gasification
reactivity of coal chars and petcoke. The reactivity index was
defined as in eq 9
0.5
R 0.5 =
t0.5 (9)
A comparison of the reactivity index of different coal chars and
petcoke between HTSM and TGA experimental methods is
shown in Figure 14. And, the ratios of reactivity index λ
Figure 14. Comparison of reactivity index of different coal chars and
petcoke between (a) HTSM and (b) TGA experimental methods.
between HTSM and TGA experiments are shown in Figure 15.
The reactivity index of XLT coal char was about 0.06 s−1 in
HTSM experiments and 0.015 s−1 in TGA experiments. The
reactivity index of XLT char in HTSM was 3.6 times higher
than that in TGA experiments. The reactivity index of SM char
in HTSM and TGA experiments was 0.035 and 0.0085 s−1,
respectively. The reactivity index of SM char in HTSM also
was 4.3 times higher than that in TGA experiments. The
reactivity index of GP anthracite char in HTSM experiments
was about 0.0078 s−1. The reactivity index in HTSM
experiments was about double of that in TGA experiments,
as shown in Figure 15. The reactivity index of petcoke in
HTSM experiments was merely 0.0033 s−1. The compact
carbon structure restricted the gasification of petcoke. The
reactivity index of petcoke particles in TGA experiments also
H DOI: 10.1021/acs.energyfuels.9b00005
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Figure 15. Ratios of R0.5 between HTSM and TGA experimental
methods.
was extremely low, as shown in Figure 14. The reactivity index
of petcoke in HTSM was about 2.5 times higher than that in
TGA experiments. It was concluded that the differences of the
reaction rate between different char and petcoke particles
decreased with the gasification reactivity of the samples.
3.4. Comparison of HTSM and TGA Experimental
Methods. The relationship between reaction rate and the
partial pressure of gasifying agent Pi is shown in eq 10.
dx
= kPin
dt (10)
It was assumed that the reaction rate constant k was constant
with the evolution of carbon conversion at a certain reaction
temperature. Thus, the integration form of eq 10 was obtained
as shown in eq 11
kPinτ = 1 (11)
The reaction order n was adopted as 0.53 according to relevant
studies.49 The average residence time τ of bituminous char
particles in opposed multiburner gasifier was about 8 s and the
carbon conversion was 99.3%.49 Therefore, the complete
reaction time of char particles was about 40 s under
atmosphere pressure according to eq 11. The gasification
reactivity of coal char also was related to the heating rate of the
pyrolysis process. The reactivity of slow-pyrolysis coal char was
different from that of fast-pyrolysis coal char.50 The coal
undergo fast-pyrolysis process in gasifier and slow-pyrolysis
process in this study. In this HTSM experiment, the reaction
time of bituminous char was approximate to the results
considering the pyrolysis process. The reaction time of
bituminous char in TGA experiments was much more than
the results. Besides, the reaction rate of bituminous char in
HTSM experiments was approximate to that in drop tube
furnace reactors.48 In this case, the experimental results in
HTSM experiments also could be used to verify the reliability
of numerical simulation results.
Figure 16 shows the particle distribution in HTSM and TGA
experiments. The particles in HTSM showed a sparse
distribution and the interparticle distance was about 500 μm.
The particles showed a compact accumulation in the crucible
of TGA experiments. In this study, the areal density was
adopted to compare the particle concentration in HTSM and
TGA experiments. The areal density of the samples in HTSM
experiments DH was defined as
nd03ρc
DH =
6S (12)
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
Figure 16. Particle distribution in (a) HTSM and (b) TGA experiments.
where n is the number of particles and S is the visual area. The
areal density of the samples in TGA experiments DT was
defined as eq 13.
DT = d0̅ ρs (13)
The average diameter of coal chars and petcoke particles d0̅
was about 200 μm. ρs was the stacking density of coal char and
petcoke in the crucible.
The number of char particles was about 3−10 in HTSM
experiments. The areal density of the particles in HTSM
experiments was in the range of 1.22−4.08 × 10−3 g/m2. The
areal density of the particles in TGA experiments was about
190 g/m2. The areal density of the sample in HTSM
experiments was extremely lower than that in TGA experi-
ments. Thus, the concentration of the gasification product in
TGA experiments should be higher than that in HTSM
experiments. The higher concentration of CO decreased the
concentration of the gasifying agent in particle swarms.
Therefore, the reaction rate also decreased according to eq
7. Relevant studies pointed out that the diffusion resistance
increased with reaction temperature in TGA experiments.33,37
With the increase of particle temperature, the pore diffusion
hindrance restricted the reaction rate of the single char particle.
The transformation was dependent on the coal properties, such
as porosity, reactivity, and particle size.19 Furthermore, the
controlling step transformed from pore diffusion control to
bulk diffusion control with further increase in particle
temperature. This transformation was decided by the gasifying
agent concentration around the boundary of the single char
particle.
The comparison of experimental results between HTSM and
TGA experiments shows that the reaction rate of coal char and
petcoke particles in HTSM experiments was about 2−4 times
higher than that in TGA experiments. In TGA experiments, the
accumulation of char particles in the crucible increased the
diffusion resistance at the temperature of 1300 °C. The bulk
diffusion hindrance for the single char particle occurred in
TGA experiments at high temperatures. During the gasification
of single char particles, the bulk diffusion resistance could be
eliminated in HTSM experiments. The operation temperature
range of the entrained flow gasifier was about 1200−1600 °C.
Relevant studies pointed out that the gasification reaction of
coal char in the entrained flow gasifier was limited by diffusion
process, in which pore diffusion was the main factor.15,51 Thus,
HTSM experimental method was more suitable for gasification
estimation at high temperatures.
It also was found that the reactivity differences of coal char
and petcoke between HTSM and TGA experiments was
I DOI: 10.1021/acs.energyfuels.9b00005
Article
different. The gasification reactivity index of lignite and
bituminous in HTSM experiments was about 4 times higher
than that in TGA experiments. However, the reactivity index of
anthracite and petcoke in HTSM experiments was about
double of that in TGA experiments. It was inferred that the
different producing rates of CO resulted in different
concentrations of gasifying agent at the external surface of
the single char particle. For coal char particles with high
reactivity, the gasifying agent concentration was lower than
that of char particles with low reactivity. It was demonstrated
that the bulk diffusion resistance for high reactivity coal char
was more evident compared with char particles with low
reactivity.
4. CONCLUSIONS
A comparison of different coal chars and petcoke gasification
characteristics between HTSM and TGA experiments was
made. As a result of the ash melting or limited ash content of
the samples, different coal chars and petcoke particles showed
a shrinking particle mode during the gasification process. The
gasification reactivity of coal chars and petcoke in HTSM
experiments was higher than that in TGA experiments.
Interparticle diffusion process limited the gasification reactivity
of different coal chars and petcoke in TGA experiments. The
gasification reactivity of lignite and bituminous char in HTSM
experiments was much higher than in TGA experiments.
However, the reactivity index of anthracite and petcoke in
HTSM experiments was merely double of that in TGA
experiments. It was demonstrated that the interparticle
diffusion hindrance was more significant for coal chars with
high reactivity. Moreover, the complete reaction time of
bituminous coal char in HTSM experiments showed a good
agreement with industrial operating data. The HTSM
experimental method was effective in investigating the
gasification kinetics at high temperatures.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: hfliu@ecust.edu.cn. Tel/Fax: +86 21 64251418.
ORCID
Haifeng Liu: 0000-0002-2572-8693
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors thank the financial support from the Shanghai
Engineering Research Center of Coal Gasification
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
(18DZ2283900) and National Nature Science Foundation of
China (21878082).
■
REFERENCES
(1) Xu, J.; Yang, Y.; Li, Y. Recent development in converting coal to
clean fuels in China. Fuel 2015, 152, 122−130.
(2) Higman, C.; Tam, S. Advances in coal gasification, hydro-
genation, and gas treating for the production of chemicals and fuels.
Chem. Rev. 2014, 114, 1673−708.
(3) Kajitani, S.; Suzuki, N.; Ashizawa, M.; Hara, S. CO2 gasification
rate analysis of coal char in entrained flow coal gasifier. Fuel 2006, 85,
163−169.
(4) Gonzalo-Tirado, C.; Jiménez, S.; Ballester, J. Gasification of a
pulverized sub-bituminous coal in CO2 at atmospheric pressure in an
entrained flow reactor. Combust. Flame 2012, 159, 385−395.
(5) Steibel, M.; Halama, S.; Geißler, A.; Spliethoff, H. Gasification
kinetics of a bituminous coal at elevated pressures: Entrained flow
experiments and numerical simulations. Fuel 2017, 196, 210−216.
(6) Troiano, M.; Santagata, T.; Montagnaro, F.; Salatino, P.;
Solimene, R. Impact experiments of char and ash particles relevant to
entrained-flow coal gasifiers. Fuel 2017, 202, 665−674.
(7) Gomez, A.; Mahinpey, N. A new model to estimate CO2 coal
gasification kinetics based only on parent coal characterization
properties. Appl. Energy 2015, 137, 126−133.
(8) Wang, G.; Zhang, J.; Hou, X.; Shao, J.; Geng, W. Study on
CO(2) gasification properties and kinetics of biomass chars and
anthracite char. Bioresour. Technol. 2015, 177, 66−73.
(9) Wang, Y.; Zhu, S.; Gao, M.; Yang, Z.; Yan, L.; Bai, Y.; Li, F. A
study of char gasification in H2O and CO2 mixtures: Role of inherent
minerals in the coal. Fuel Process. Technol. 2016, 141, 9−15.
(10) Dai, B.; Hoadley, A.; Zhang, L. Characteristics of high
temperature C-CO2 gasification reactivity of Victorian brown coal
char and its blends with high ash fusion temperature bituminous coal.
Fuel 2017, 202, 352−365.
(11) Jayaraman, K.; Kok, M. V.; Gokalp, I. Pyrolysis, combustion
and gasification studies of different sized coal particles using TGA-
MS. Appl. Therm. Eng. 2017, 125, 1446−1455.
(12) Tanner, J.; Bhattacharya, S. Kinetics of CO2 and steam
gasification of Victorian brown coal chars. Chem. Eng. J. 2016, 285,
331−340.
(13) Kelebopile, L.; Sun, R.; Wang, H.; Zhang, X.; Wu, S. Pore
development and combustion behavior of gasified semi-char in a drop
tube furnace. Fuel Process. Technol. 2013, 111, 42−54.
(14) Ren, L.; Yang, J.; Gao, F.; Yan, J. Laboratory study on
gasification reactivity of coals and petcokes in CO2/Steam at high
temperatures. Energy Fuels 2013, 27, 5054−5068.
(15) Kajitani, S.; Hara, S.; Matsuda, H. Gasification rate analysis of
coal char with a pressurized drop tube furnace. Fuel 2002, 81, 539−
546.
(16) De Micco, G.; Nasjleti, A.; Bohé, A. E. Kinetics of the
gasification of a Rio Turbio coal under different pyrolysis temper-
atures. Fuel 2012, 95, 537−543.
(17) Jamil, K.; Hayashi, J.-i.; Li, C.-Z. Pyrolysis of a Victorian brown
coal and gasification of nascent char in CO2 atmosphere in a wire-
mesh reactor. Fuel 2004, 83, 833−843.
(18) Peralta, D.; Paterson, N.; Dugwell, D.; Kandiyoti, R. Pyrolysis
and CO2 Gasification of Chinese Coals in a High-Pressure Wire-Mesh
Reactor under Conditions Relevant to Entrained-Flow Gasification.
Energy Fuels 2005, 19, 532−537.
(19) Tremel, A.; Haselsteiner, T.; Kunze, C.; Spliethoff, H.
Experimental investigation of high temperature and high pressure
coal gasification. Appl. Energy 2012, 92, 279−285.
(20) Shen, Z.; Liang, Q.; Xu, J.; Zhang, B.; Liu, H. In-situ
experimental study of CO2 gasification of char particles on molten
slag surface. Fuel 2015, 160, 560−567.
(21) Shen, Z.; Liang, Q.; Xu, J.; Zhang, B.; Han, D.; Liu, H. In situ
experimental study on the combustion characteristics of captured
chars on the molten slag surface. Combust. Flame 2016, 166, 333−
342.
J DOI: 10.1021/acs.energyfuels.9b00005
Article
(22) Shen, Z.; Xu, J.; Liu, H.; Liang, Q. Modeling study for the effect
of particle size on char gasification with CO2. AIChE J. 2017, 63,
716−724.
(23) Puig-Gamero, M.; Lara-Díaz, J.; Valverde, J. L.; Sanchez-Silva,
L.; Sánchez, P. Dolomite effect on steam co-gasification of olive
pomace, coal and petcoke: TGA-MS analysis, reactivity and
synergistic effect. Fuel 2018, 234, 142−150.
(24) Xiao, R.; Yang, W. Kinetics characteristics of straw semi-char
gasification with carbon dioxide. Bioresour. Technol. 2016, 207, 180−
187.
(25) Liu, L.; Cao, Y.; Liu, Q. Kinetics studies and structure
characteristics of coal char under pressurized CO2 gasification
conditions. Fuel 2015, 146, 103−110.
(26) Liu, X.; Zhou, Z.; Zhang, B.; Chen, L.; Wang, F. Effect of
Microwave Treatment on Structural Changes and Gasification
Reactivity of Petroleum Coke. Ind. Eng. Chem. Res. 2011, 50,
9063−9068.
(27) Zhang, L.; Huang, J.; Fang, Y.; Yang, W. Gasification Reactivity
and Kinetics of Typical Chinese Anthracite Chars with Steam and
CO2. Energy Fuels 2006, 20, 1201−1210.
(28) Gomezbarea, A.; Ollero, P.; Arjona, R. Reaction-diffusion
model of TGA gasification experiments for estimating diffusional
effects. Fuel 2005, 84, 1695−1704.
(29) Gómez-Barea, A.; Ollero, P.; Fernndez-Baco, C. Diffusional
Effects in CO2 Gasification Experiments with Single Biomass Char
Particles. 1. Experimental Investigation. Energy Fuels 2006, 20, 2202−
2210.
(30) Gómez-Barea, A.; Ollero, P.; Villanueva, A. Diffusional Effects
in CO2 Gasification Experiments with Single Biomass Char Particles.
2. Theoretical Predictions. Energy Fuels 2006, 20, 2211−2222.
(31) Jess, A.; Andresen, A.-K. Influence of mass transfer on
thermogravimetric analysis of combustion and gasification reactivity
of coke. Fuel 2010, 89, 1541−1548.
(32) Mani, T.; Mahinpey, N.; Murugan, P. Reaction kinetics and
mass transfer studies of biomass char gasification with CO2. Chem.
Eng. Sci. 2011, 66, 36−41.
(33) Kim, R. G.; Hwang, C. W.; Jeon, C. H. Kinetics of coal char
gasification with CO2: Impact of internal/external diffusion at high
temperature and elevated pressure. Appl. Energy 2014, 129, 299−307.
(34) Vincent, S. S.; Mahinpey, N.; Aqsha, A. Mass transfer studies
during CO2 gasification of torrefied and pyrolyzed chars. Energy 2014,
67, 319−327.
(35) Ollero, P.; Serrera, A.; Arjona, R.; Alcantarilla, S. Diffusional
effects in TGA gasification experiments for kinetic determination. Fuel
2002, 81, 1989−2000.
(36) Gomez, A.; Silbermann, R.; Mahinpey, N. A comprehensive
experimental procedure for CO2 coal gasification: Is there really a
maximum reaction rate ? Appl. Energy 2014, 124, 73−81.
(37) Gomez, A.; Mahinpey, N. Kinetic study of coal steam and CO2
gasification: A new method to reduce interparticle diffusion. Fuel
2015, 148, 160−167.
(38) Ding, L.; Zhou, Z.; Huo, W.; Wang, Y.; Yu, G. In Situ Heating
Stage Analysis of Fusion and Catalytic Effects of a Na2CO3 Additive
on Coal Char Particle Gasification. Ind. Eng. Chem. Res. 2014, 53,
19159−19167.
(39) Shen, Z.; Liang, Q.; Xu, J.; Liu, H. In situ study on the
formation mechanism of bubbles during the reaction of captured
chars on molten slag surface. Int. J. Heat Mass Transfer 2016, 95,
517−524.
(40) Shen, Z. J.; Liang, Q. F.; Xu, J. L.; Liu, H. F.; Lin, K. F. Study
on the Fragmentation Behaviors of Deposited Particles on the Molten
Slag Surface and Their Effects on Gasification for Different Coal
Ranks and Petroleum Coke. Energy Fuels 2018, 32, 9243−9254.
(41) Liu, M.; Shen, Z.; Liang, Q.; Xu, J.; Liu, H. Morphological
evolution of a single char particle with a low ash fusion temperature
during the whole gasification process. Energy Fuels 2018, 32, 1550−
1557.
(42) Shen, Z.; Zhang, L.; Liang, Q.; Xu, J.; Lin, K.; Liu, H. In situ
experimental and modeling study on coal char combustion for coarse
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels Article

particle with effect of gasification in air (O2/N2) and O2/CO2

atmospheres. Fuel 2018, 233, 177−187.
(43) Liu, M.; Shen, Z.; Xu, J.; Liang, Q.; Liu, H. Experimental
studies on CO2 gasification of petcoke particle swarm at high
temperatures. AIChE J. 2018, 64, 4009−4018.
(44) Ding, L.; Zhou, Z.; Guo, Q.; Huo, W.; Yu, G. Catalytic effects
of Na2CO3 additive on coal pyrolysis and gasification. Fuel 2015, 142,
134−144.
(45) Aranda, G.; Grootjes, A. J.; van der Meijden, C. M.; van der
Drift, A.; Gupta, D. F.; Sonde, R. R.; Poojari, S.; Mitra, C. B.
Conversion of high-ash coal under steam and CO2 gasification
conditions. Fuel Process. Technol. 2016, 141, 16−30.
(46) Ma, Z.; Bai, J.; Bai, Z.; Kong, L.; Guo, Z.; Yan, J.; Li, W.
Mineral transformation in char and its effect on coal char gasification
reactivity at high temperatures, Part 2: char gasification. Energy Fuels
2014, 28, 1846−1853.
(47) Zou, X.; Ding, L.; Liu, X.; Guo, Q.; Lu, H.; Gong, X. Study on
effects of ash on the evolution of physical and chemical structures of
char during CO2 gasification. Fuel 2018, 217, 587−596.
(48) Zeng, C.; Chen, L.; Liu, G.; Li, W.; et al. Advances in the
development of wire mesh reactor for coal gasification studies. Rev.
Sci. Instrum. 2008, 79, No. 084102.
(49) Sun, Z.; Dai, Z.; Zhou, Z.; Guo, Q.; Yu, G. Numerical
Simulation of Industrial Opposed Multiburner Coal−Water Slurry
Entrained Flow Gasifier. Ind. Eng. Chem. Res. 2012, 51, 2560−2569.
(50) Feng, J.; Li, W.; Xie, K. Relation between coal pyrolysis and
corresponding coal char gasification in CO2. Energy Sources 2004, 26,
841−848.
(51) Ahn, D. H.; Gibbs, B. M.; Ko, K. H.; Kim, J. J. Gasification
kinetics of an Indonesian sub-bituminous coal-char with CO2 at
elevated pressure. Fuel 2001, 80, 1651−1658.

K DOI: 10.1021/acs.energyfuels.9b00005
Energy Fuels XXXX, XXX, XXX−XXX