Journal of CO₂ Utilization 32 (2019) 163–169

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Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Development of LaFeO3 modified with potassium as catalyst for coal char T

CO2 gasification
⁎
Qiyao Wang1, Cong Luo1, Xiaoshan Li , Haoran Ding, Cheng Shen, Dingshan Cao, Liqi Zhang
State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China

A R T I C LE I N FO A B S T R A C T

Keywords: Coal catalytic gasification is an effective way to realize clean coal utilization. The core of this technology is the
Coal char preparation of highly efficient and stable catalysts. At present, perovskite-type oxides have attracted increasing
CO2 gasification attention as a promising catalyst because of its good thermal stability and redox activity. In this study, per-
Perovskite ovskite-type oxides were proposed to act as catalyst for coal char CO2 gasification, and K was further used for
Potassium
LaFeO3 catalyst modification to improve its catalytic activity. The catalytic performances of La1-xKxFeO3 (x=0-
0.9) were tested by thermogravimetric analysis and fixed-bed tube reactor. The crystal structure was determined
by X-ray diffraction (XRD), the percentage content and valence state of surface elements were examined by X-ray
photoelectron spectroscopy (XPS), the surface morphology of perovskite samples was observed by scanning
electron microscopy (SEM). Besides, the specific surface area and average particle diameter were analyzed by N2
absorption/desorption technology (BET) and laser particle size analyzer, respectively. Results suggested that the
perovskite-type catalyst can effectively lowered the initial reaction temperature and exhibited improved cata-
lytic activity after a part of La3+ at A-site was replaced by K+. The time required to achieve 50% carbon
conversion in the initial reaction was reduced by 87.3% when the molar ratio of K+ increased from 0 to 0.7. The
La0.3K0.7FeO3 perovskite also exhibited relatively stable catalytic activity during cyclic process, and its optimal
temperature in coal char CO2 gasification was approximately 850 °C. The XRD patterns indicated that the
perovskite structure of catalyst can remain unchanged when K+ doping ratio was lower than 0.8. Therefore, 0.7
is a suitable doping ratio. The perovskite La0.3K0.7FeO3 still exhibited perovskite crystal structure after 10 cycles
of experiment. The XPS results indicated that additional oxygen vacancies and Fe4+ formed after K+ doping,
which contributed to gas adsorption and electron transfer and improved oxidation performance. SEM and BET
showed that the pore structure of catalyst was destroyed during cyclic gasification, resulted in the enlargement
of particle size detected by laser particle size analyzer. Leading to the decrease in effective contact area and
catalytic performance. Thus, K+-modified perovskite La1-xKxFeO3 is a kind of equipment-friendly, efficient and
recyclable catalyst and can be used as a promising catalyst for coal char CO2 gasification.

1. Introduction
Coal is the main fossil resource and energy in China, but pollutants
originating from coal combustion have considerably harmed the eco-
logical environment and human health. Developing clean coal tech-
nology becomes an inevitable choice. Considering the influences of CO2
on global climate change, how to utilize CO2 after it was captured from
flue gas is a hot research topic. Coal gasification with CO2 can realize
the utilization of CO2 and then the CO product can be further used for
chemical industry [1–4]. Therefore, Carbon dioxide gasification of coal
char that could achieve the clean utilization of coal and CO2 utilization
at the same time has received increasing attention. Conventional
gasification techniques do not use catalysts and the operating tem-
perature is generally higher than 1000 °C. The gas composition is
complicated and difficult to purify, thereby restricting its development
and utilization. However, the use of catalyst in coal gasification can
effectively reduce the reaction temperature, shorten the gasification
time, and regulate the components of gaseous production, thereby
lowering the energy consumption and equipment requirements of the
gasification reaction [5–7]. Many studies have been carried out to date
and found that alkali and alkaline earth metals (K, Na, Ca, etc.) are the
most commonly used as catalysts for coal char CO2 gasification due to
their relatively low cost and acceptable catalytic performance. How-
ever, these types of catalysts are easy to vaporize, corrode equipment

⁎
Corresponding author.
E-mail address: lxs0721@hust.edu.cn (X. Li).
1
Authors Q.W. and C.L. contributed equally.

https://doi.org/10.1016/j.jcou.2019.04.010
Received 11 January 2019; Received in revised form 2 March 2019; Accepted 16 April 2019
2212-9820/ © 2019 Elsevier Ltd. All rights reserved.
Q. Wang, et al.
during high temperature reactions, and are difficult recycle [8–10].
Transition metals (Fe, Ni, etc.) are also considered as good catalysts
because of their advantages of noncorrosive to equipment, low con-
sumption, good catalytic activity, and the ability to regulate the com-
position of product gas. However, the vulnerability of transition metals
to poisoning and inactivation in gasification limits their wide used in
coal gasification process [6,11]. The exploration of new catalysts for
coal gasification with high efficiency and good cyclic performance is
still a topic receiving considerable attention.
Perovskite-type oxides have been widely studied and used as a
catalyst previously because of their high thermal stability, good redox
property, and strong lattice O transportation ability. The structural
formula of perovskite oxides is ABO3, where A-cations are located on
the edge of the crystal structure and play a major role in stabilization,
and B-cations are located in the center of structure and mainly affect the
catalytic activity because of their variable valence states. The elements
at A- and B-sites can be completely or partially replaced by other me-
tallic elements without destroying the perovskite-type crystal structure,
which indicated that catalytic performances of the materials can easily
be controlled by adjusting the constituent elements [12–15]. Among all
these studies, La-Fe perovskite has received considerable attention due
to its low price, easy molding, and good thermal stability, and many
efforts have been devoted to improve the catalytic properties of LaFeO3
by doping at the A/B site. Runduo et al. [16,17]investigated the effects
of Cu2+ and Pb2+ ion doping on LaFeO3 for catalytic reduction of NO
by propene and found that N2 yields were improved significantly after
partial Fe3+ was substituted. Sun et al. [18] reported that the high Ce
content is unconducive to the formation of perovskite structure, but
moderate doping can provide active O and considerably improve cat-
alytic performance without destroying the crystal structure. Khine et al.
[19] studied the capabilities of (La0.7A0.3)BO3 (A = Ba, Ca, Mg, Sr, and
B = Cr or Fe) for the partial oxidation of CH4 and found that Sr doping
improves the mobility of lattice O, and (La0.75Sr0.25)FeO3 can achieve
65% CH4 conversion and obtain the highest H yield.
We have previously investigated the properties of perovskite-type
oxides as O carrier for chemical looping reforming of CH4 and studied
the characteristics, especially the catalytic performance and O deso-
rption [20,21], in detail. Perovskite-type oxides exhibit excellent cata-
lytic performance for high-temperature gas–solid reactions. Thus,
whether perovskite can be further used in catalytic gasification of coal
char with CO2 is an attractive research topic. This work aimed to use La-
Fe-based perovskite oxides as a new catalyst for coal char CO2 gasifi-
cation. K+ ions, which demonstrate low valence, high activity, and
mobility and contribute to the formation of O vacancies and the in-
crease in valence state of B-site ions [22–24],were selected for A-site
doping to improve the catalytic properties of La-Fe-based perovskite
oxides. New La1-xKxFeO3 (x = 0-0.9) catalysts were prepared via sol-gel
method. The catalytic activity and cycle performance were tested using
a thermogravimetric analyzer and fixed-bed reactor, and the proper
doping ratio of K+ and reaction temperature for coal char CO2 gasifi-
cation were investigated. The crystal structure, surface states of O and
Fe, and surface topography after K+ doping and gasification reaction
were characterized by X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS), and scanning electron microscopy (SEM), respec-
tively.
2. Experimental
2.1. Material preparation and characterization
Zhundong(ZD) coal from Xinjiang region in China was selected for
this study. The coal was ground below 48 μm. To avoid the potential
confusion from minerals in coal, de-mineral coal was prepared by HCL-
HF method. Detailed steps are as follows: 100 g zhundong raw coal was
added to a solution of 1 L hydrochloric acid (6 mol/L) and 3 L deionized
water, the mixture was stirred for 24 h and placed for 12 h under
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Journal of CO₂ Utilization 32 (2019) 163–169
Table 1
Zhundong demineral coal properties.
proximate analysis (wt.%,air-dry) Ultimate analysis (wt.%,dry and ash
free)
M A V FC C H Oa N
2.78 0.52 2.7 94 69.86 0.81 28.89 0.44
a
Calculated by difference method.
ambient condition, and then deionized water was used to wash the coal
until the solution was neutral. After filtration, the coal was added to a
solution of 2 L hydrofluoric acid (3 mol/L) and 2 L deionized water and
repeat the stirring and washing process as described above. The samples
after filtration were dried at 105℃ for 24 h to obtain the de-mineral
coal. In the end the de-mineral coal were heated from room tempera-
ture to 950℃ at the rate of 10℃/min and stay at 950℃ for 30 min to
obtain the de-mineral char. The analyses data of ultimate de-mineral
char were shown in Table 1
The perovskite-type oxides La1-xKxFeO3 were prepared by em-
ploying citric acid-aided sol-gel method. The starting materials were
analytical purity, metal nitrate La(NO3)3·6H2O, KNO3 and Fe
(NO3)3·9H2O were prepared according to stoichiometric ratio and dis-
solved in citric acid aqueous solvent and stirred at 70℃ for 4 h until
sticky gel was formed, then the gel was placed in an air-circulating oven
at 105℃ for 12 h. The dried gel was heated from ambient temperature
to 400℃ at a rate of 10℃/min and kept at 400℃ for 1 h to burn out the
organic compounds. The final remains were calcined at 750℃ for 5 h
for nitrate decomposition and the perovskite-type catalysts were ob-
tained after grinding, the particle size of grinded samples was less than
1 μm.
2.2. Gasification tests
The experiment samples were prepared by mixing perovskite and
de-mineral coal char (50:50wt.%) mechanically for 10 min in agate
mortar, then put it in an oven for drying. The catalytic activity of cat-
alyst for de-mineral coal CO2 gasification was investigated in the
thermogravimetric analysis (TGA). About 18 mg of experiment samples
were heated from 200℃ to 950℃ at 10℃/min heating rate in a flow of
CO2 (100 ml/min). The initial reaction temperature (Ti) and the tem-
perature at maximum weight loss rate (Tm) were used as an evaluation
index of catalytic performance.
The cyclic performance of catalysts was investigated in a fixed-bed
tubular quartz reactor system (Φ = 20 mm, L = 600 mm).
Approximately 0.5 ± 0.005 g reaction samples were added into quartz
boat and placed into a quartz tube that was in the mixed flow of CO2/N2
(100:400 ml/min flow rate). The quartz tube was placed into the tube
furnace at a predetermined temperature, and the composition of gas
productions was monitored continuously by an online gas analyzer
(Cubic Inc., Gasboard-3100). The feeding gas was switched to air
(200 ml/min) until the CO concentration dropped to 0. Then, the quartz
tube was removed from the furnace to cool the reactor to room tem-
perature. The reaction catalyst sample remaining in the quartz boat was
recovered and weighed for the next cycle. The number of cycles (3–10)
varied with the catalyst. t50%, which was defined as the time for carbon
conversions to reach 50%, was used to evaluate the catalytic activities
of the catalyst; the lower the t50% value was, the better the catalytic
performance was.
2.3. Characterization
The perovskite-type phase of as-prepared catalysts was measured by
X-ray diffusion (XRD) on X’Pert PRO (PANalytical B.V.) with Cu Kα
radiation (λ = 0.1542 nm). X-ray tube voltage and current were 40 kV
and 30 mA respectively. The diffractogram in the 2θ range of 20°–80°
Q. Wang, et al.
Fig. 1. DTG profiles of CO2 catalytic gasification over La1-xKxFeO3.
was recorded with a scanning step of 0.02°.The surface content and
valence of oxygen and iron were carried out via X-ray photoelectron
spectroscopy (XPS), performed with AXIS-ULTRA DLD X-ray
Photoelectron Spectrometer and an Al-Kα anode. Binding energies were
calibrated by using C1s at 284.8 eV as internal standard. The micro-
structures of particles were obtained by scanning electron microscopy
(SEM) on FEI Inspect F50 operated at 10 kV. The Brunauer, Emmett and
Teller (BET) specific surface area analysis were tested by N2 at 77 K on a
3H-2000PS instrument (Beishide Instrument Technology Co., Ltd.). The
average size of the samples were determined by Laser particle size
analyzer (ZS90, Malvern Instruments Ltd., UK).
3. Results and discussions
3.1. Catalytic performance of different perovskites
The CO2 catalytic activity of ZD dem-char with different perovskites
evaluated by TGA is shown in Fig. 1. The figure indicates that LaFeO3
catalyst exhibited the lowest activities and has insignificant effect on
the increase in the coal char CO2 gasification rate. The catalytic per-
formance of La-Fe-based perovskite was enhanced when 10% (molar
fraction) of La3+ at A-site was replaced by K+, but it still can only react
at high temperatures. When the doping ratio x increased from 0.1 to
0.3, a significant improvement in the catalytic performance was ob-
served. The carbon conversion rate did not only increased significantly,
but the Ti value also decreased from 821 °C to 713 °C. Afterward, the Ti
and Tm values showed a decreasing trend with the increase of K+ ions
at the A-site, which indicated that the catalytic performance was further
improved, and the requirement of temperature was reduced. One pos-
sible reason for the increased catalytic activity of K+-doped perovskite
is the change in Fe valence state and oxygen vacancy formation to
maintain electron neutrality when some parts of trivalent La3+ are
substituted by monovalent K+ [23,24,24]. Another reason may due to
the high catalytic activity of K+ for coal gasification processes [25,26].
Therefore, the K+ doped at the A-site positively affects catalytic per-
formance improvement.
When the molar ratios of K+ at the A-site was > 0.7, the reaction
curves showed that further K+ doping at A-site only slightly con-
tributed to the improvement of the catalyzing performance of the
modified perovskite-type catalyst. This result was possibly observed
because the degree of substitution of the A-site ions was limited.
Excessive K+ ions can only attached to the surface of catalyst after
saturation. Although those K+ can complement the lattice K+ ions
during cyclic reactions. Surface K+ ions were also easy to melt in ga-
sification reaction because of its low melting point, leading to the in-
crease of agglomerate strength of catalyst particles [14,27]. According
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Journal of CO₂ Utilization 32 (2019) 163–169
Fig. 2. Carbon conversion of catalytic ZD-dem char CO2 gasification with
La0.7K0.3FeO3 under different temperatures.
to these results, the effect of reaction temperatures and cyclic perfor-
mance of catalyst on char CO2 gasification experiments were carried
out using La0.7K0.3FeO3 as catalyst.
To investigate the influence of reaction temperature on the catalytic
activity of La0.7K0.3FeO3 further, we carried out CO2 gasification ex-
periments at the temperature ranging from 700 to °C 900 °C. As shown
in Fig. 2, the reaction rates increased with temperature, especially
ranging from 700 °C 850 °C. Coal char CO2 gasification is an en-
dothermic reaction, and the increase in temperature is conducive to the
gasification process. Because the adsorption process is an exothermic
process, high reaction temperature contributed to the desorption of
adsorbed oxygen species. Our previous research [20,28] also suggested
that perovskite-type oxides exhibited better catalytic activity at higher
temperature, promoting the consumption of adsorbed oxygen. Thus,
more lattice oxygen would travel through oxygen vacancies to supply
the oxygen species on the surface and be released, which leads to im-
proved redox performance. When the temperature reaches 850 °C, the
catalytic activity is relatively high, and the carbon conversion rate of
gasification is mainly dependent upon the redox performance of the
catalyst. Excessively high temperature has a negative effect on the
surface morphology of catalyst. Thus, 850 °C is considered as the op-
timal temperature for the catalytic CO2 gasification of ZD-dem char
with perovskite.
3.2. Cyclic performance of recovered catalysts
To study the cyclic stability of K+-doped perovskite catalysts, we
reused La1-xKxFeO3 for coal-char gasification in fixed-bed reactor at
850 °C, and the results are presented in Fig. 3. The results showed that
LaFeO3 perovskite without K+ doping required the longest reaction
time to achieve 50% carbon conversion. After a small amount of K+
was doped at the A-site of perovskite, the catalytic activity of
La0.9K0.1FeO3 was enhanced significantly, which was in agreement with
the TGA results. However, the catalytic performance of perovskite
catalyst with low K+ amounts showed significant reduction in cycle
experiments.
With the introduction of additional K+, the catalysts exhibited in-
creased catalytic activity and cycling performance stability. Compared
with undoped sample perovskite, the t50% value of La0.3K0.7FeO3 in the
first cycle decreased by 87.3% and only increased by 2.6 min after re-
using 7 times. A significant decrease in the reaction time was observed
between the seventh and eighth cycle, which was still less than that of
La0.3K0.7FeO3 during the first cycle.
The detailed data of the catalytic coal char CO2 gasification by using
La0.3K0.7FeO3 catalyst at 850 °C on fixed bed are shown in Fig. 4. The
Q. Wang, et al. Journal of CO₂ Utilization 32 (2019) 163–169

Fig. 3. t50% value of CO2 catalytic gasification over La1-xKxFeO3 for different
cycle times.

Fig. 4. Reaction rates of La0.7K0.3FeO3 for cyclic ZD-dem char CO2 gasification.

undoped perovskite was included as a reference. The figure indicates

that the carbon conversion increased to 90% in a straight line over time
and exhibited stable catalytic performance in the first seven cycles.
Fig. 5. XRD patterns of La1-xKxFeO3(x = 0–0.9); (a) the whole range; (b) an
Then, the carbon conversion rate decreased gradually, which was
enlarged screenshot of La1-xKxFeO3(x = 0.7–0.9, 2θ = 29°–44°).
possibly due to the fact that sintering on the perovskite surface reduced
the contact efficiency between coal char and catalyst, and the sintering
phenomenon became increasingly serious with the progress of the
cyclic reaction. Thus, the carbon conversion rate began to decline when
the carbon conversion ratio reached 80%.

3.3. Catalyst characterization

Fig. 5 displays the XRD patterns of La1-xKxFeO3(x = 0-0.9). All the

characteristic peaks of perovskite weakened with the increase in K+ at
the A-site but still exhibited the perovskite crystal structure when the
molar ratio of K+ was < 0.8. The peaks of other impurities were un-
detected, which indicated that K+ ions entered into the lattice of
perovskite [29,30]. Fig. 5(b) shows the enlarged XRD patterns
(2θ = 29°–44°) of the modified perovskite (x = 0.7–0.9) after the excess
K + was incorporated into the perovskite oxides. Some byproduct peaks
were observed. A weak diffraction peak at 30.1° corresponded to the
cubic structure of Fe3O4 (JCPDS 87–2334), and the peak at 32.9° that
contributed to the distortion of the main characteristic peak of per-
ovskite was ascribed to K3FeO2 (JCPDS 48-0957).
Fig. 6. XRD patterns of La0.3K0.7FeO3 before and after different cycles at 850℃.
The changes in the crystal structure of La0.3K0.7FeO3 after different

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Q. Wang, et al. Journal of CO₂ Utilization 32 (2019) 163–169

Fig. 7. O1s and Fe2p XPS spectra of perovskite samples; (a, d) fresh LaFeO3, (b) (e) fresh La0.3K0.7FeO3, and (c) (f) La0.3K0.7FeO3 after the first gasification.

reaction times were investigated, as shown in Fig. 6. Although the peaks
of Fe3O4, which was produced by the reaction of perovskite with CO2,
were detected, the modified perovskite still exhibited the characteristic
peaks of the perovskite after the first cycle. After nine additional gasi-
fication cycles, the perovskite characteristic peaks were still detected,
which were only slightly weakened. These results suggested that the
modified perovskite La0.3K0.7FeO3 had high crystal structure stability.
XPS characterization was performed to investigate the surface state
of undoped perovskite and modified perovskite samples before and
after gasification. The fitting results of O1s and Fe2p XPS spectra are
shown in Fig. 7, and the relative percentages that were calculated from
the integrated area of these subpeaks are listed in Table 2. The O1s
spectrum for all the three samples showed two peaks in the range of
526–537 eV. After peak separation, three small peaks representing the
three different types of oxygen species were obtained. The first peak at
529.15–529.21 eV was ascribed to lattice oxygen and marked as Olat.
The second peak at 530.99–531.35 eV possibly originated from carbo-
nate species and C1s and was marked as Ocar. Finally, the third peak at
532.02–532.32 eV was ascribed to physical adsorbed oxygen and
marked as Oads [21,31]. The comparison results of Fig. 7(a) and (b)
suggested that the modified perovskite-type catalyst exhibited high Oads
peak and low Olat due to oxygen vacancy formation caused by the
partial substitution of monovalent K+ for trivalent La3+, which has
been proven to increase oxygen fluidity, facilitate electron transfer, and
enhance catalytic activity [32]. The binding energy of modified per-
ovskite was also lower than that of undoped perovskite, which in-
dicated that the lattice O activity was enhanced by K+ doping [33].
Thus, modified perovskite catalysts exhibit improved redox perfor-
mance. After catalytic gasification reaction, the Olat and Oads contents
decreased, and that of Ocar increased, as shown in Fig. 7(c). This result

Table 2
Binding energies (BEs) of the Fe2p3/2 and O1s and calculated perovskite sample percentages.
Samples O1s Fe2p3/2

Olat Ocar Oads Fe2+ Fe3+ Fe4+

BE % BE % BE % BE % BE % BE %
(eV) (eV) (eV) (eV) (eV) (eV)

LaFeO3 529.2 60 531.3 28 532.2 12 709.8 45 711.3 29 713.1 26

La0.3K0.7FeO3 528.9 47 531.5 27 532.1 26 709.6 32 711.0 32 713.3 36
La0.3K0.7FeO3 1 st 528.8 23 531.0 61 532.5 16 709.6 38 710.9 35 713.0 27

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Q. Wang, et al. Journal of CO₂ Utilization 32 (2019) 163–169

Fig. 8. SEM images of La0.3K0.7FeO3 sample; (a) fresh sample, (b) after 1 st gasification, and (c) after 10th gasification.

indicated that the lattice and surface oxygen were involved in catalytic Table 4
coal char gasification. The high Ocar peak may due to CO2 adsorption. Specific surface area of La1-xKxFeO3 (x = 0–0.9) cata-
As shown in Fig. 7, the Fe2p3/2 spectra deconvoluted into three lysts.
subpeaks. The peaks at 709.6–709.9, 710.9–711.9, and 712–714 eV Perovskite SBET(m2/g)
were assigned to Fe2+, Fe3+, and Fe4+, respectively [34,35].A com-
parison of Fig. 7(d) and (e) suggested that additional Fe3+ and Fe4+ LaFeO3 2.6
La0.9K0.1FeO3 1.5
existed in modified perovskite to maintain electrical neutrality. Fe4+
La0.7K0.3FeO3 8.7
showed strong redox activity and was beneficial to the gasification re- La0.5K0.5FeO3 4.3
action of coal char. After catalytic gasification, the perovskite sample La0.3K0.7FeO3 3.3
showed low Fe4+ peak in Fig. 7(f), which indicated that some Fe4+ in La0.2K0.8FeO3 2.0
the lattice were converted to Fe3+ and Fe2+ during the catalytic re- La0.3K0.7FeO3 1 st 1.7

action. This result agreed with the XRD analysis shown in Fig. 6. The
reduction reaction of Fe can also promote the charge transfer from
that the changes of specific surface area related to the expansion of unit
adsorbed oxygen to the adsorbed oxygen and O2.
cells due to the radius of K+ is slightly higher than La3+ [37]. However,
The morphological changes in La0.3K0.7FeO3 during cyclic reactions
the formation of oxygen vacancies resulted in the shrank of unit cell
obtained by SEM were shown in Fig. 8. The fresh sample had uniform
when partial of trivalent La3+ was replaced by K+. Thus, the specific
spherical crystalline grain distribution and porous structure, as shown
surface area decreased after more K+ ions were doped at A-site. It was
in Fig. 8(a). Such structure was beneficial for the improved contact of
also can be seen that the specific surface area of modified perovskite
the catalyst with coke particles. The crystalline grains structure was
La0.3K0.7FeO3 decreased from 3.3 to 1.7 m2/g after one times of gasi-
maintained and showed slight agglomeration after the first cycle, as
fication, which proved that the pore structure of the catalyst was da-
shown in Fig. 8(b). However, after 10 cycles of the experiment, the
maged, the results of BET analysis were consistent with the results of
crystalline grains melted and fused with other grains, which destroyed
SEM.
the pore structure of the catalyst, as presented in Fig. 8(c). The de-
creased contact efficiency between coal char and catalyst decreased the
4. Conclusions
carbon conversion rate, as shown in Fig. 4.
The average size of the samples was determined by Laser particle
A series of K+-modified perovskite catalysts La1-xKxFeO3 (x = 0-0.9)
size analyzer. It can be seen from Table 3 that the particle size of
was synthesized by the sol-gel method, and their catalytic and cycle
modified perovskite La0.3K0.7FeO3 changed a little after first cycle of
performances for coal char CO2 gasification were investigated by TGA
gasification. But the average size of La0.3K0.7FeO3 after 10 cycles in-
and fixed-bed reactor, respectively. The catalytic and cycle perfor-
creased significantly, which is due to the agglomeration of perovskite
mances of perovskite-type catalysts were significantly improved by the
particles according to the SEM characterization results. Therefore, the
partial substitution of La3+ by K+ until the molar ratio of
agglomeration of perovskite will resulted in the increase of particle size,
K + reached > 0.7. For La0.3K0.7FeO3, the Ti value of first reaction
which reduced the effective contact area between coal char and per-
dropped from 821 °C to 643 °C, and the t50% value only increased by
ovskite. And eventually lead to a decline in carbon conversion rate
2.6 min after seven cycles of reaction. The further increase in K+ ions at
during cyclic experiments.
the A-site did not decrease the reaction time and temperature. The in-
The specific surface areas of La1−xKxFeO3 catalysts tested by N2
crease in temperature was also beneficial to the improvement of cata-
absorption/desorption method were listed in Table 4. The BET specific
lytic performance. When the adverse effect of further heating on the
surface of K-modified perovskite were between 1 and 9 m2/g, which is
surface morphology was considered, 850 °C was the optimal gasifica-
in agreement with previous study [36]. As can be seen, K+-doping had
tion temperature. The XRD patterns showed that the pure perovskite
a significant effect on the specific surface area of the catalyst, but the
phase was obtained for all catalyst samples when the molar ratio
change was not linear with doping ratio at A-site. The undoped per-
was < 0.7. Thus, 0.7 is the best x value of La1-xKxFeO3. The XRD results
ovskite had a relatively low specific surface area, 2.6 m2/g, and
also suggested that La0.3K0.7FeO3 had good structural stability because
La0.7K0.3FeO3 had the largest specific area, 8.7 m2/g. It was reported
its characteristic perovskite-type crystal structure was maintained after
10 cycles of gasification. The XPS results showed that additional oxygen
Table 3 vacancies and Fe4+ formed after partial La3+ were replaced by K+ to
Average particle diameter of La0.3K0.7FeO3 during cylic ex- preserve electroneutrality. Thus, the modified perovskite exhibits in-
periments.
creased catalytic activity in coal char CO2 gasification. SEM analysis
Perovskite Particle size(nm) indicated that the spherical particles were uniformly distributed on the
surface of fresh catalyst samples, but the La0.3K0.7FeO3 particles melted
La0.3K0.7FeO3 fresh 680
and merged together in CO2 gasification reaction processing. Besides,
La0.3K0.7FeO3 1 st 743
La0.3K0.7FeO3 10th 1234 the results of BET analysis and laser particle size analyser showed that
the catalyst was sintered and the particle size increased during cyclic

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Q. Wang, et al.
reactions, which was not conducive to the effective contact between
perovskite and coal char and cycling performance of modified per-
ovskite.
Acknowledgements
This work was supported by National Key R&D Program of China
(2016YFB0600801), National Natural Science Foundation of China
(No.51606076) and Analytical and Testing Center of HUST for XRD
measurements.
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