molecules

Article
A Microwave-Assisted Boudouard Reaction: A Highly Effective
Reduction of the Greenhouse Gas CO2 to Useful CO Feedstock
with Semi-Coke
Huan Dai 1,2 , Hong Zhao 1, * , Siyuan Chen 3 and Biao Jiang 3, *

1 Green Chemical Engineering Research Center, Shanghai Advanced Research Institute,

Chinese Academy of Sciences, Shanghai 201210, China; [email protected]
2 University of Chinese Academy of Sciences, Beijing 100049, China
3 Shanghai Green Chemical Engineering Research Center, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China; [email protected]
* Correspondence: [email protected] (H.Z.); [email protected] (B.J.)

Abstract: The conversion of CO2 into more synthetically flexible CO is an effective and potential
method for CO2 remediation, utilization and carbon emission reduction. In this paper, the reaction of
carbon-carbon dioxide (the Boudouard reaction) was performed in a microwave fixed bed reactor
using semi-coke (SC) as both the microwave absorber and reactant and was systematically compared
with that heated in a conventional thermal field. The effects of the heating source, SC particle size,
CO2 flow rate and additives on CO2 conversion and CO output were investigated. By microwave
heating (MWH), CO2 conversion reached more than 99% while by conventional heating (CH), the
maximum conversion of CO2 was approximately 29% at 900 ◦ C. Meanwhile, for the reaction with





 5 wt% barium carbonate added as a promoter, the reaction temperature was significantly reduced to
Citation: Dai, H.; Zhao, H.; Chen, S.; 750 ◦ C with an almost quantitative conversion of CO2 . Further kinetic calculations showed that the
Jiang, B. A Microwave-Assisted apparent activation energy of the reaction under microwave heating was 46.3 kJ/mol, which was
Boudouard Reaction: A Highly only one-third of that observed under conventional heating. The microwave-assisted Boudouard
Effective Reduction of the Greenhouse reaction with catalytic barium carbonate is a promising method for carbon dioxide utilization.
Gas CO2 to Useful CO Feedstock with
Semi-Coke. Molecules 2021, 26, 1507. Keywords: microwave heating; CO2 conversion; semi-coke; Boudouard reaction
https://doi.org/10.3390/
molecules26061507

Academic Editor: Ionel Mangalagiu 1. Introduction

In the face of climate change due to global warming, converting carbon dioxide into
Received: 31 January 2021
Accepted: 3 March 2021
synthetic, flexible and useful molecules rather than capturing CO2 for storage is the most
Published: 10 March 2021
attractive approach to climate change mitigation solutions (Scheme 1) [1]. Nevertheless, the
dynamics and thermodynamic stability of CO2 severely limit conversion. Efficient reducing
Publisher’s Note: MDPI stays neutral
agents and precious metal catalysts are required to facilitate its conversion into useful chem-
with regard to jurisdictional claims in
icals [2]. A simple and well-known response is the Boudouard reaction (C + CO2 = 2CO) in
published maps and institutional affil- which CO2 reacts with carbon to produce carbon monoxide [3]. CO is not only the feedstock
iations. for Fischer–Tropsch’s synthetic oils and waxes but also a raw material of carbonylation
reactions to synthesize a number of fine chemicals [4] and it provides important hydrogen
energy through water-gas shift reactions [5].
However, the Boudouard reaction is a highly endothermic gas-solid reaction with a
Copyright: © 2021 by the authors.
large positive enthalpy (172 kJ/mol at 298 K) in which very high temperatures, typically
Licensee MDPI, Basel, Switzerland.
above 700 ◦ C, are required to shift the equilibrium towards CO production [3]. Over
This article is an open access article
the past decade, interest in using microwaves to activate chemical reactions has become
distributed under the terms and widespread, creating significant advantages in the field of heterogeneous catalysis [6]. In
conditions of the Creative Commons particular, high-temperature microwaves have a special advantage in inducing chemical
Attribution (CC BY) license (https:// reactions derived from heterogeneous catalysts with unique opportunities to control the
creativecommons.org/licenses/by/ energy input [7]. Therefore, the ideal microwave catalyst has a dual role both as a catalyst
4.0/). for chemical reactions and as an efficient converter of the thermal energy required for

Molecules 2021, 26, 1507. https://doi.org/10.3390/molecules26061507 https://www.mdpi.com/journal/molecules

Molecules 2021, 26, 1507 2 of 11

the event and reaction activation from microwave energy [8]. Carbonaceous materials
are known as excellent microwave receptors [9] and the high temperatures required for
the Boudouard reaction could be provided by microwave irradiation [10]. Microwave-
enhanced CO2 gasification of oil palm shell char [11,12], coconut shell char [13] and sewage
sludge waste has been studied [14]. The results showed that microwave radiation was
more effective than conventional heating and the reaction temperature was reduced by
approximately 200 ◦ C in a short time. The reactivity of biochar was found to be dependent
on the pore structure of the char and its morphology, the catalytic activity of the associated
ash, the availability of carbon active sites as well as catalytic active sites on the char,
Molecules 2021, 26, x FOR PEER REVIEW the
2 of 11
thermal history of the char during pyrolysis and the type of carbon source.

Biomass-Derived

MW Waste Utilization
Semi-Coal C + CO2 2CO Organic Compounds
5% BaCO3 Polymers and Materials
End of Life Cycle
(Carbonization)
Scheme1.
Scheme 1. The
The Boudouard
Boudouard reaction
reactionin
insustainable
sustainabletotal
totalcarbon
carbonrecycling.
recycling.

However,
China is a the Boudouard
coal-rich country reaction is a highly endothermic
and implementing gas-solidisreaction
carbon neutrality the country’s with a
large positive
strategy enthalpy climate
for mitigating (172 kJ/mol at 298
change. K) in which
Semi-coke, very blue
named high coal,
temperatures,
is prepared typically
from
above 700
Jurassic °C, are required
low-quality coal with to shift the equilibrium
reserves of 100 billion towards
tons inCO production
China [15]. As[3]. a newOver the
type
of carbon
past decade,material
interestwith its high
in using fixed carbon
microwaves content,
to activate high chemical
chemical reactions has activity
become andwide-low
ash content,
spread, semi-coke
creating can advantages
significant replace charin(metallurgical coke) and is widely
the field of heterogeneous catalysisused in par-
[6]. In the
chemical, smelting, gasification and other industries. In this paper,
ticular, high-temperature microwaves have a special advantage in inducing chemical re- we report the results
of an investigation
actions derived from specifically focused
heterogeneous on the with
catalysts conversion
uniqueof CO2 into COtowith
opportunities controlsemi-coke
the en-
under microwave
ergy input irradiation
[7]. Therefore, the and
idealcatalysis.
microwave To catalyst
the besthas of our
a dualknowledge,
role bothsimilar data
as a catalyst
are
for not foundreactions
chemical in the literature
and as an and the Boudouard
efficient converter of reaction was carried
the thermal energy out with afor
required CO the
2
conversion
event and rate of 99%
reaction at 900 ◦ Cfrom
activation withmicrowave
an excellentenergy
microwave absorption performance
[8]. Carbonaceous materials are of
the semi-coke.
known Whenmicrowave
as excellent barium carbonate
receptors was[9]added as a high
and the promoter, the reaction
temperatures temperature
required for the
was significantly reduced to 750 ◦ C with an almost quantitative conversion of CO .
Boudouard reaction could be provided by microwave irradiation [10]. Microwave-en- 2
hanced CO2 gasification of oil palm shell char [11,12], coconut shell char [13] and sewage
2. Results and Discussions
sludge waste has been studied [14]. The results showed that microwave radiation was
2.1. Temperature Correction of the Microwave Fixed Bed Reactor
more effective than conventional heating and the reaction temperature was reduced by
The application
approximately 200 °Cofinmicrowave
a short time. irradiation to a gas-solid
The reactivity of biochar reaction
was foundhas been
to bestudied
dependent for
more than 20 years. However, due to the practical difficulties of the
on the pore structure of the char and its morphology, the catalytic activity of the associated temperature mea-
surement and uniform
ash, the availability of temperature
carbon activedistribution
sites as well in as
thecatalytic
microwave active(MW)sitesfield,
on the comparing
char, the
reaction
thermal performances under
history of the char conventional
during pyrolysis heating
and the (CH)
typeand microwave
of carbon source.heating (MWH)
always would
China is abecoal-rich
explained as the formation
country of hot spots
and implementing in theneutrality
carbon reaction system as a con-
is the country's
sequence of MWH. In this paper, we obtained a relatively even
strategy for mitigating climate change. Semi-coke, named blue coal, is prepared from temperature field in theJu-
microwave fixed bed by using three silicon carbide (SiC) rings
rassic low-quality coal with reserves of 100 billion tons in China [15]. As a new typewith a width of 0.5 cm as of
thermal loads thatwith
carbon material wereitssheathed
high fixedoutside the quartz
carbon content, tube.
highMoreover,
chemicalthree optical
activity andradiation
low ash
pyrometers were used
content, semi-coke cantoreplace
monitorchar the (metallurgical
surface temperature coke) ofand theisbed.
widelyBefore
used theinBoudouard
the chemi-
reaction experiments, we corrected the heating temperature and
cal, smelting, gasification and other industries. In this paper, we report the results confirmed the constant
of an
temperature area in the microwave fixed bed reactor. We used a
investigation specifically focused on the conversion of CO2 into CO with semi-coke undersilicon carbide rod with
a length of 13 cm and a diameter of 3.5 cm as a heat carrier for the temperature range
microwave irradiation and catalysis. To the best of our knowledge, similar data are not
correction (SiC is an excellent microwave absorber material [16,17]). Figure 1 shows the
found in the literature and the Boudouard reaction was carried out with a CO2 conversion
temperature distribution of the bed with an error of ±10 ◦ C, identifying the uniformity of
rate of 99% at 900 °C with an excellent microwave absorption performance of the semi-
the temperature distribution. After that, we measured the temperature distribution using
coke. When barium carbonate was added as a promoter, the reaction temperature was
semi-coke (SC) as the heat carrier. The SC bed exhibited a relatively even temperature zone
significantly reduced to 750 °C with an almost quantitative conversion of CO2.
ranging from about ±3 cm from the center of the temperature zone, which met the needs
2. Results and Discussions
2.1. Temperature Correction of the Microwave Fixed Bed Reactor
The application of microwave irradiation to a gas-solid reaction has been studied for
more than 20 years. However, due to the practical difficulties of the temperature meas-
 range correction (SiC is an excellent microwave absorber materia
the temperature distribution of the bed with an error of ± 10 °C, id
of the temperature distribution. After that, we measured the tem
Molecules 2021, 26, 1507 ing semi-coke (SC) as the heat carrier. The SC bed exhibited 3 of 11 a rela

zone ranging from about ± 3 cm from the center of the temperat

needs of our experiments. The temperature distribution of the fi
of our experiments. The temperature distribution of the fixed bed is shown in Figure 1 and
ure
its 1was
error and its ±
within error was also
25 ◦ C, which within
met the±needs
25 °C, which
of our also met the needs
experiments.

Figure 1. Temperature correction diagram of silicon carbide (SiC) and semi-coke (SC).
Figure 1. Temperature correction diagram of silicon carbide (SiC) and s
2.2. The Boudouard Reaction in Both Microwave and Conventional Thermal Fields

2.2.ToTheinvestigate the characteristics of the CO2 gasification of SC in both microwave and

Boudouard Reaction in Both Microwave and Conventional Th
conventional thermal fields, typical experiments were conducted with an SC particle size
of 0.200–0.450 mm and a CO2 space velocity of 3.20 m3 /(mof 3 (SC)·h) at 750 ◦ C. The effect of
To investigate the characteristics the CO2 gasification of SC
the temperature on the Boudouard reaction in both fields is shown in Figure 2a,b. As we
conventional
can see from Figure 2a, thermal fields, typical
the CO2 conversion experiments
and SC conversion wereheating
by conventional conducted
increased slowly with an increase in temperature but were at a low level. CO2 conversion
of 0.200–0.450 mm and a CO2 space velocity of 3.20 m3/(m3(SC)·h
increased from 5.0% at 800 ◦ C to 10.3%, 14.4% and 29.1% at 850 ◦ C, 900 ◦ C and 950 ◦ C,
the temperature
respectively. The results on werethe Boudouard
consistent reaction
with the strong endotherm in both fields is show
of the Boudouard
reaction. The high temperature pushed the balance to CO production when heated by con-
can see from Figure 2a, the CO2 conversion and SC conversion
ventional methods. Figure 2b shows the experimental results when heated by microwave
increased
irradiation. slowly
Clearly, when thewith an increase
reaction temperature in wastemperature but were
750 ◦ C, the CO2 conversion rate at a lo
was 77.2%, which was much higher than that carried out at 950 ◦ C by conventional heating.
increased from 5.0% at 800 °C to 10.3%, 14.4% and 29.1% at 850
When the reaction temperature increased to 900 ◦ C, the CO2 conversion increased to 99.7%.
respectively.
In addition, Figure 2cThe results
compares the CO were
output ofconsistent
the two heatingwith sources.the
Fromstrong
Figure 2c, endot
it can be clearly seen that by conventional heating, the CO output ranged from 8.1 mmol
atreaction. The
800 ◦ C to 59.1 mmol high
at 950 temperature
◦ C while by microwave pushedheatingthe balance
the CO to CO prod
output increased
◦ ◦
conventional
from 1163 mmol at 750methods.
C to 2000 mmol Figure
at 900 2b shows
C, which thethan
was more
◦
experimental
60 times than thatresults
obtained by conventional heating. The clear CO output at 950 C was only approximately
wave irradiation.
one-twentieth of that carriedClearly, when the
out in the microwave reaction
reactor at 750 ◦ C. temperature
We know that SC iswasa 75
rateheating
good wasconductor
77.2%,and which wastemperature
the possible much higher than from
gradient derived thatthecarried
character- out a
istics of microwave heating would not be great enough to cause such a distinct Boudouard
heating.
reaction Whenbetween
performance the reaction
the two thermaltemperature increased
fields. Therefore, the obviously tohigher
900CO°C,2
the C
to 99.7%.
conversion andIn
COaddition,
output obtained Figure 2c compares
in the microwave reactor werethe notCO output
caused of the tw
by incorrect
temperature measurements or uneven temperature distributions in the microwave reactor.
Figure
The 2c,
fact that theitBoudouard
can be reaction
clearlyunder seen that byheating
microwave conventional
proceeded more heating,
easily the
suggested
8.1 mmol a great
atenhancement
800 °C to of the
59.1Boudouard
mmolreaction
at 950 with°C microwave
whileheating.
by microwave
increased from 1163 mmol at 750 °C to 2000 mmol at 900 °C, w
times than that obtained by conventional heating. The clear CO o
approximately one-twentieth of that carried out in the microwa
Molecules 2021, 26, x FOR PEER REVIEW 4 of 11

Molecules 2021, 26, 1507 4 of 11

proceeded more easily suggested a great enhancement of the Boudouard reaction with
microwave heating.

Figure 2. (a) 2.
Figure Effect of gasification
(a) Effect temperature
of gasification under under
temperature conventional heating;
conventional (b) Effect
heating; (b)of gasification
Effect temperature
of gasification under microwave
temperature under
heating; (c) Production of CO under microwave heating and conventional heating with the reaction times of 144 min.
microwave heating; (c) Production of CO under microwave heating and conventional heating with the reaction times of
144 min.
This superior performance of microwaves is believed to be related to the mechanism
of microwave heating
This superior [18]. SC isof
performance anmicrowaves
excellent material for absorbing
is believed microwaves
to be related that can
to the mechanism
be firmly coupled
of microwave with[18].
heating microwaves
SC is an to carry out
excellent chemical
material for reactions.
absorbingWhen the microwave
microwaves that can
acted
be firmlyon the SC, the
coupled microwave
with microwaves energy could
to carry outdirectly
chemical couple with When
reactions. carbonthe molecules
microwave so
that
acted theondielectric heating
the SC, the effect ofenergy
microwave the microwave couldcouple
could directly effectively
withheat the raw
carbon material.
molecules so
This is different
that the dielectricfrom conventional
heating heating
effect of the in that the
microwave couldmain mechanism
effectively heatof microwave
the raw material.ab-
sorption in dielectric
This is different frommaterials is to heating
conventional excite electronic
in that the oscillations at the frequency
main mechanism of the
of microwave
absorption in
microwave dielectric materials is to excite electronic oscillations at the frequency of the
source.
microwave source.
2.3. Influence of the SC Particle Size
2.3. Influence of the SC Particle Size
The effect of the SC particle size on CO2 conversion and CO output in the microwave
reactorThewas
effect of the SC particle
investigated size on COof
at a temperature 2 conversion
800 °C andand a COCO output in the microwave
2 flow rate of 125 mL/min.
reactor was investigated at a temperature of 800 ◦ C and a CO flow rate of 125 mL/min.
As shown in Figure 3a, the CO2 conversion improved from 83.0% 2 for particles in the range
As0.850–1.400
of shown in Figure
mm to3a, the CO
98.0% conversion
for2 particles improved
in the range of from 83.0% formm;
0.200–0.450 particles
at theinsame
the range
time,
of 0.850–1.400 mm to 98.0% for particles in the range of 0.200–0.450 mm;
the CO2 conversion was maintained above 90%. As the particle size of the SC decreased, at the same time,
the gasification
the CO2 conversion was maintained
reactivity improved. Thisabove 90%. Asinthe
is because theparticle size of
gasification the SCthe
process, decreased,
smaller
the gasification reactivity improved. This is because in the gasification
particles of SC have better heat and mass transfer processes. Within a certain particleprocess, the smaller
size
particles of SC have better heat and mass transfer processes. Within a
range, the decreased SC particle size would give a larger contact area between CO2 and certain particle size
range, the decreased SC particle size would give a larger contact area between CO2 and SC,
SC, causing a more complete reaction. In addition, the reduced SC particle size was help-
causing a more complete reaction. In addition, the reduced SC particle size was helpful
ful in reducing the effects of internal diffusion, which could also increase the gasification
in reducing the effects of internal diffusion, which could also increase the gasification
reaction rate. It can be seen that the CO2 conversion of the SC particle size < 0.200 mm was
reaction rate. It can be seen that the CO2 conversion of the SC particle size < 0.200 mm
generally lower than that of the SC particle size 0.200–0.450 mm as the reaction time in-
was generally lower than that of the SC particle size 0.200–0.450 mm as the reaction time
creased and this may be because too small a particle size would give a larger external
increased and this may be because too small a particle size would give a larger external
diffusion resistance and the CO2 reactant would be more difficult to evenly diffuse into
diffusion resistance and the CO2 reactant would be more difficult to evenly diffuse into
the SC bed. Figure 3b shows the effect of different particle sizes on the CO output. We can
the SC bed. Figure 3b shows the effect of different particle sizes on the CO output. We can
see that the CO output also shows the same trend as the CO2 conversion. When the SC
see that the CO output also shows the same trend as the CO2 conversion. When the SC
particle size was 0.200–0.450 mm, the maximum CO output was 1371 mmol.
particle size was 0.200–0.450 mm, the maximum CO output was 1371 mmol.
2.4.
2.4. Influence
Influence of
of the
the CO
CO22 Gas
GasFlow
FlowRate
Rate
Figure
Figure 3c shows the influence of
3c shows the influence of the
the CO
CO22 gas
gas flow
flow rate
rate on
on the
the CO
CO22 conversion
conversion of of SC.
SC.
The CO conversion decreased from 97.3% to 67.2% when the CO
The CO2 conversion decreased from 97.3% to 67.2% when the CO2 flow increased from
2 2 flow increased from
125
125 mL/min
mL/minto to 200
200 mL/min.
mL/min.This Thiswas
wasbecause
becausethetheincrease
increase in
in the
the CO
CO22 flow
flow shortened
shortened thethe
residence time of
residence time ofCO
CO22 gas
gasininthe
thecarbon
carbonbedbedand
and then
then reduced
reduced thethe chance
chance of CO
of CO 2 2 conver-
conversion
sion therefore
therefore causing
causing a significant
a significant dropdrop in2CO
in CO 2 conversion.
conversion. Figure
Figure 3d 3d shows
shows thethe
COCO out-
output
put
underunder
the the different
different gasgas flows.
flows. The
The results
results indicatedthat
indicated thatthe
theCOCOoutput
output increased
increased from
1462 mmol to 1581 mmol when when the
the CO
CO22 flow increased
increased from
from 125
125mL/min
mL/min to 200 mL/min.
mL/min.
However, with the increase in CO2 flow, the output of CO was not obviously changed. This
might be due to the increase in CO2 flow, resulting in the reduction in the CO2 external
 Molecules 2021, 26, x FOR PEER REVIEW 5 of 11

Molecules 2021, 26, 1507 5 of 11

However, with the increase in CO2 flow, the output of CO was not obviously changed.
This might be due to the increase in CO2 flow, resulting in the reduction in the CO2 exter-
diffusion resistance
nal diffusion and the
resistance andincrease in COin2 CO
the increase diffusion into SC
2 diffusion intoparticles, which
SC particles, intensified
which intensi-
the CO conversion reaction.
fied the CO2 conversion reaction.
2

Figure3.3.(a)
Figure (a)Effect
EffectofofSC
SCparticle
particlesize
sizeononCOCO conversion;(b)
2 2conversion; (b)CO
COoutput
outputatatdifferent
differentparticle
particlesizes.
sizes.
Reaction conditions: the CO2 flow was 125 mL/min, the reaction temperature was 800 C, reac-
Reaction conditions: the CO2 flow was 125 mL/min, the reaction temperature was 800 °C, ◦the the
tion time
reaction was
time 144144
was min; (c)(c)
min; Effect of of
Effect gasgas
flow rate
flow onon
rate 2 conversion; (d) CO output at different gas
COCO conversion; (d) CO output at different
2
flow rates. Reaction conditions: the SC particle size was 0.200–0.450 mm, the reaction temperature
gas flow rates. Reaction conditions: the SC particle size was 0.200–0.450 mm, the reaction temperature
was 800 °C, the reaction time was 144 min.
was 800 ◦ C, the reaction time was 144 min.

2.5.Influence
2.5. InfluenceofofthetheCatalyst
Catalyst
ItIthas
hasbeen
been reported
reported that
that thethe salts
salts of alkali
of alkali metalsmetals
andand alkaline
alkaline earthearth metals
metals such such
as Na,as
Na, K and Ca have a good catalytic performance for char gasification
K and Ca have a good catalytic performance for char gasification reactions [19–21] but the reactions [19–21] but
the effect of barium salt on the Boudouard reaction has been scarcely
effect of barium salt on the Boudouard reaction has been scarcely investigated. Here, BaCO3 investigated. Here,
BaCO
was used 3 was
as aused as aand
catalyst catalyst and compared
compared with CaOwith in theCaO in the gasification
gasification reaction ofreaction
SC and CO of SC
2
and CO
under 2 under microwave
microwave radiation.
radiation. Figure Figurethe
4a exhibits 4aCOexhibits
2 the
conversion CO of2 conversion
the SC of the
with/without SC
5 with/without
wt% CaO and5awt% BaCO CaO and a BaCO 3 addition at a reaction ◦ C and a of
temperature CO750 °C and
rate a
3 addition at a reaction temperature of 750 2 flow
ofCO1752 flow
mL/minrate of 175 mL/min
under microwave under microwave
heating. Without heating. Without
a catalyst, a catalyst,
the initial the initial CO
CO2 conversion at 2
750 ◦
conversion
C was 86.2%at 750and°C then
was decreased
86.2% andquickly
then decreased quickly to
to approximately 40%approximately
after 144 min.40% after
Under
144catalysis
the min. Underof BaCOthe 3catalysis
and CaO, ofthe
BaCO 3 and
initial COCaO, the initial
2 conversion CO99.9%
was 2 conversion
but BaCO was 99.9% but
3 exhibited
a BaCO
better3 catalytic
exhibitedlife. Figurecatalytic
a better 4b shows that
life. the CO
Figure output that
4b shows also the
increased
CO outputsignificantly from
also increased
1689 mmol to 2392
significantly frommmol1689 and
mmol 2520
to mmol when and
2392 mmol CaO2520 and BaCO were used
mmol3 when CaOas catalysts.
and BaCO3 The were
experimental results
used as catalysts. Theindicated that BaCO
experimental results
3 and CaO
indicated had an
that excellent
BaCO 3 and catalytic
CaO performance
had an excellent
for the Boudouard
catalytic performance reaction
for theand reduced the
Boudouard reaction
reaction and temperature.
reduced the reactionThe reason for the
temperature.
higher reactivity of SC catalyzed
The reason for the higher reactivity of SC by BaCO would be that BaCO improved
3 catalyzed by BaCO33 would be that BaCO3 im-the adsorption
capacity
proved of theSC for CO2 , thereby
adsorption capacityobtaining
of SC foraCO higher reactivity.
2, thereby obtaining a higher reactivity.
PEER REVIEW
Molecules 2021, 26, 1507 6 of6 of
1111

Figure 4. (a) Comparison of SC, SC/BaCO3 and SC/CaO gasification reactivity under a microwave (MW) at 750 ◦ C; (b) CO
Figure 4.different
output at (a) Comparison of SC, SC/BaCO
experiment reactions 3 andtimes
with the reaction SC/CaO
of 144 gasification
min. reactivity under a microwave
(MW) at 750 °C; (b) CO output at different experiment reactions with the reaction times of 144
min. Figure 5 shows the surface morphologies of gasified SC before and after a reaction
under different reaction conditions. It can be seen from Figure 5a that the un-gasified SC
Figure 5 shows had
theasurface
relativelymorphologies
smooth surface and ofthe carbon layer
gasified SC structure
before andwas complete
after a and without
reaction
obvious pores inside the bulk SC particles. By conventional heating, the SC particles shown
under different reaction conditions. It can be seen from Figure 5a that the un-gasified SC
in Figure 5b exhibited an inconspicuous lamellar structure with a few large pores and the
had a relatively smooth
carbonsurface and thewas
layer structure carbon layer
relatively structure
complete. The was complete
possible reason isand
that without
gasified SC
obvious pores insidehardly
the occurs
bulk atSC lowparticles.
temperaturesBy conventional
in conventional heating,
heating. the SCofparticles
The morphology gasified SC
under microwave radiation is shown in Figure 5c. The surface of the SC was obviously
shown in Figure 5b exhibited an inconspicuous lamellar structure with a few large pores
damaged and a few large pores were formed. As shown in Figure 5d, BaCO3 particles on
and the carbon layer structure was relatively
gasified SC obtained complete.
at 750 ◦ C showed The
that the possible
carbon reasonwas
layer structure is further
that gasified
destroyed
SC hardly occurs at low
and thetemperatures in conventional
surface carbon structure heating.
was more uniformly The morphology
distributed. of gasi-
The results indicated that
the reaction rate of CO on the surface of SC was more
fied SC under microwave radiation is shown in Figure 5c. The surface of the SC was ob-
2 intense in the presence of barium
salt. Table 1 shows the specific surface areas and volume pores for SCs heated by different
viously damaged andtechniques.
a few large The pores
specificwere
surface formed.
area andAs poreshown
volumein of Figure 5d, BaCO
raw SC were par-
2.16 m32 /g and
ticles on gasified SC obtained
1.30 × 10 at− 3 cm750
3 /g,°C showedAfter
respectively. that conventional
the carbonand layer structure
microwave wasthe
heating, further
specific
surface area
destroyed and the surface carbon was increased
structure from was m2 /g touniformly
2.16more 3.60 m2 /g for CH-SC, 18.2 mThe
distributed.
2 /g for MW-SC
results
and 14.3 m2 /g for MW-SC/BaCO3 while the pore volume also showed the same trend. The
indicated that the reaction rate of CO2 on the surface of SC was more intense in the pres-
results indicated that microwaves enhanced the reactivity of SC, resulting in a higher CO2
ence of barium salt. conversion
Table 1 shows and CO the specific surface areas and volume pores for SCs
output.
heated by different techniques. The specific surface area and pore volume of raw SC were
2.6. Analysis of Gasification Kinetics
2.16 m2/g and 1.30 × 10–3 cm3/g, respectively. After conventional and microwave heating,
In order to compare the reaction performances in both thermal fields, the gasification
the specific surface area was
kinetics increased
in the two thermalfrom
fields2.16
werem
2/g to 3.60 m2/g for CH-SC, 18.2 m2/g
studied based on the experimental data exhibited in
for MW-SC and 14.3 m 2 /g for
Section 2.2.MW-SC/BaCO 3 while
Both diffusional and massthe poreinfluences
transfer volumewere alsoruled
showed
out. Wethe same
know that
the volume reaction model is a commonly used kinetic model in the Boudouard reaction.
trend. The results indicated that microwaves enhanced the reactivity of SC, resulting in a
The volume reaction model (VRM) assumes that the gasification reaction occurs at the
higher CO2 conversion and
active siteCO
andoutput.
is evenly distributed throughout the carbon particles [22–25]. By the kinetic
analysis of the isothermal gasification experiment and then the conversion of the first-order
kinetics into the Arrhenius relationship, the kinetics of several coal conversion processes
could be represented. Therefore, we performed kinetic calculations on the experimental
results under conventional and microwave (non-catalysis) thermal fields. The reaction rate
equation was expressed as follows:

dX
r= = kVRM (1 − X ). (1)
dt
 Molecules 2021, 26, 1507 7 of 11

Molecules 2021, 26, x FOR PEER REVIEW

ln(1 − X ) = −kVRM t. (2)

Figure 5. SEM micrographs of (a) raw SC; (b) SC after CO2 gasification in conventional heating (CH);
Figure 5. SEM micrographs of (a) raw SC; (b) SC after CO2 gasification in conventi
(c) SC after CO2 gasification in a microwave (MW); (d) SC/BaCO3 after CO2 gasification in a MW.
(CH); (c) SC after CO2 gasification in a microwave (MW); (d) SC/BaCO3 after CO2 g
Reaction conditions: the SC particle size was 0.200–0.450 mm and the reaction temperature was
MW.
750 ◦ C. Reaction conditions: the SC particle size was 0.200–0.450 mm and the reactio

was 750 °C.

Table 1. The calculations of specific surface area (BET), and total pore volume.
Table 1．The calculations
Sample Raw SC
of specific surface areaMW-SC
CH-SC
(BET), and MW-SC/BaCO
total pore volume.
3

Sbet(m2 /g) 2.2 3.6 18.2 14.3

Sample
Vtotal (cm3 /g)
Raw
1.3 × 10−3
SC 1.7 × 10−3
CH-SC 2.8 × 10−3
MW-SC 2.5 × 10−3
MW-
Sbet (m2/g) 2.2 3.6 18.2
Vtotalthe
From (cm 3/g)
graph of ln(1 −1.3 × t,10the
x) − –3 1.7
value of the× first-order
10–3 2.8 × rate
reaction 10–3constant 2.
kVAM at each temperature could be obtained. The temperature dependence of kVAM was
expressed by the Arrhenius equation as follows:
2.6. Analysis of Gasification Kinetics
 
Ea
In order to comparekVRM the reaction
= Aexp − performances
. in both thermal (3)fields,
RT
kinetics in the two thermal fields were studied based on the experimental
Ea
in Section 2.2. Both diffusional lnkVRM = and
− mass transfer influences were ruled
+ lnA. (4) out
RT
the volume reaction model is a commonly −used kinetic model in the Boud
In the formula, the kVRM is the rate constant, min 1 ; the A is the pre-exponential
The min
factor, volume
−1 ; the reaction model
Ea is the reaction (VRM)energy,
activation assumes
kJ/mol;that
the the gasification
R is the gas constantreactio
active
(8.314 site and
J/mol/K) andis
theevenly
X is the distributed
SC conversion.throughout the carbon particles [22–25
Figure 6a,b shows the relationship
analysis of the isothermal gasification between the microwave
experiment and conventional
and then reaction
the conversi
times and carbon conversions. The slope of the fitted straight line was the reaction rate
order kinetics
constant into the ItArrhenius
at this temperature. was suggestedrelationship, therate
that the reaction kinetics
constantofincreased
several coal c
cesses
with couldinbe
an increase represented.
temperature Therefore,
in the two we performed
heating methods, which indicatedkinetic calculations
that when the
temperature increased, the reaction rate increased. Figure 6c shows
mental results under conventional and microwave (non-catalysis) thermathe Arrhenius diagram

action rate equation was expressed as follows:

= = 1− .
 min−1; the is the reaction activation energy, kJ/mol; the R is the gas constant (8.314
J/mol/K) and the X is the SC conversion.
Figure 6a,b shows the relationship between the microwave and conventional reaction
times and carbon conversions. The slope of the fitted straight line was the reaction rate
Molecules 2021, 26, 1507 constant at this temperature. It was suggested that the reaction rate constant increased 8 of 11
with an increase in temperature in the two heating methods, which indicated that when
the temperature increased, the reaction rate increased. Figure 6c shows the Arrhenius di-
agram of microwave and conventional reactions. For microwave and conventional reac-
of microwave
tion experiments, andhigher
conventional
regressionreactions.
coefficients For microwave
were obtained. and conventional
The activation reaction
energy and
experiments, higher regression coefficients were obtained. The activation
pre-exponential factor were obtained from the slope of the fitted straight line. Table energy and pre-2
exponential factor were
shows the activation obtained
energy from the slope of
and pre-exponential the fitted
energy understraight line. Table
microwave 2 shows
and conven-
the activation
tional heating. energy and pre-exponential
The activation energies were 47.1 energy under
kJ·mol –1 andmicrowave
148.9 kJ·mol and conventional
–1, respectively.
heating. The activation energies were 47.1 kJ · mol −1 and 148.9 kJ·mol−1 , respectively. The
The activation energy was much smaller than that under conventional heating. The large
activation energy was
difference between much smaller than reaction
the microwave-induced that under rateconventional
and the thermal heating.
reactionThe ratelarge
in-
difference
dicated that the rate constant must have had a fundamentally different dependence rate
between the microwave-induced reaction rate and the thermal reaction on
indicated
temperature,thatwhich
the rate
wasconstant must have
demonstrated had
in the a fundamentally
Arrhenius parameter. different dependence
In addition, as shown on
temperature,
in Table 2, the exponential factor of the microwave heating reaction was significantlyin
which was demonstrated in the Arrhenius parameter. In addition, as shown
Table
smaller2, the
thanexponential factor of the microwave
that of the conventional heating
thermal reaction byreaction was1,000
more than significantly
orders ofsmaller
mag-
than
nitude. Hunt et al. [26] suggested that a lower reaction temperature in theofmicrowave
that of the conventional thermal reaction by more than 1000 orders magnitude.
Hunt et al. [26]
experiment suggested
caused a lowerthat a lower
collision reaction of
frequency temperature
reactants toinreduce
the microwave experiment
the pre-exponential
caused a lower
term. That is to collision frequency
say, microwave of reactants
heating to reduce
should lead the pre-exponential
to a more efficient collisionterm. That is
frequency
to say, microwave
of reactants. heating should lead to a more efficient collision frequency of reactants.

Figure 6. (a) Conversion versus time under MW; (b) Conversion versus time under CH; (c) Dynamic parameters obtained through
Figure 6. (a) Conversion versus time under MW; (b) Conversion versus time under CH; (c) Dynamic parameters obtained
the Arrhenius
through thediagram.
Arrhenius diagram.

Table2.2. Kinetic
Table Kinetic parameters
parameters under
under microwave
microwave heating
heating and
and conventional
conventionalheating.
heating.
Parameters
Parameters
Raw SC
Raw SC
CH-SC
CH-SC
Ea/kJ·mol−–11 47.1 148.9
Ea/kJ·mol 47.1 148.9
A/min−–11 0.3 1088.6
A/min 0.3 1088.6

3. Materials and Methods

3. Materials and Methods
3.1. Materials
3.1. Materials
The semi-coke was provided by the Shanxi Lu'an Coal Industry (Changzhi, China).
The semi-coke was provided by the Shanxi Lu’an Coal Industry (Changzhi, China).
The ultimate analysis and proximate analysis are shown in Table 3. The semi-coke was
The ultimate
dried, crushedanalysis andinto
and sieved proximate analysis
four particle sizesare
of <shown in Table
0.200 mm, 3. The
0.200–0.450 semi-coke
mm, 0.450–
was dried, crushed and sieved into four particle sizes of <0.200 mm, 0.200–0.450 mm,
0.450–0.850 mm and 0.850–1.40 mm. Before the experiment, the semi-coke was contin-
uously dried at 105 ◦ C for 12 hrs and then stored in a well-sealed dryer for use in the
experiment. This article named semi-coke as SC. Ar and CO2 (purity of 99.9%), calcium
oxide (CaO, 99% from Aldrich) and barium carbonate (BaCO3 , 99% from Aldrich) were
used in the experiment.

Table 3. The ultimate and proximate analysis of SC.

Ultimate Analysis (%) Proximate Analysis (%)

C H N O S FC M V Ash
82.3 0.7 1.15 14.8 0.9 81.7 1.5 2.9 14.8
FC: Fixed carbon; M: Moisture; V: Volatile.
Molecules 2021, 26, 1507 9 of 11

3.2. Methods
The reactions heated by microwaves were carried out in a microwave fixed bed reactor
(Synotherm Corporation, Changsha, China) and the experimental schematic diagram is
shown in Figure S1. The microwave fixed bed reactor was heated by a monomodal cavity
with a magnetron generator operating at 2.45 GHz (the maximum output power was
1500 W). The reactor was equipped with a temperature automatic control system and a
quartz glass tube with an inner diameter of 38 mm and a length of 90 cm. For conventional
heating, the reactions were carried out in a fixed bed reactor under the same conditions. In
the experiment, approximately 40.0 ± 0.01 g of SC was first put into a quartz glass tube.
Before the reaction, Ar was introduced into the reactor at a flow rate of 100 mL/min for
30 min. When the temperature reached the desired value, CO2 gas was precisely introduced
into the reactor and the reaction started. The composition of the gas products was analyzed
online by a gas chromatograph (GC) (SHIMADZU, 2014C, Japan) equipped with a thermal
conductivity detector (TCD) and a packed column (Porapak Q 80–100 mesh, 2 m × 4 mm)
and the reacted SC was analyzed after the reaction. In our experiments, the heating rate
in the conventional fixed bed reactor was 10 ◦ C/min while in the microwave reactor the
heating rate was 60 ◦ C/min although the input power of the conventional fixed bed reactor
and the microwave oven were 1200 kw and 800 kw, respectively.

3.3. Carbon Characterization and Data Analysis

The pore structures of SC were measured using a Micromeritics ASAP 2460 N2 ad-
sorption analyzer (ASAP 2460, Micromeritics, the United States). SC (0.1 g) was weighed
and placed in a quartz tube for high-temperature vacuum degassing and then placed in a
bottle containing liquid nitrogen at −196 ◦ C for the N2 adsorption/desorption experiments.
The specific surface area was calculated using the BET equation and the average pore size
data were calculated from the H-K equation (Horvath-Kawazoe equation). The surface
structure of SC was observed by scanning electron microscopy (SEM) (FEI Nova Nono 450,
Netherlands) with an accelerating voltage of 5.0 kV.
The real-time composition of the outlet gas was measured by a GC and the CO2
conversion, CO output and SC conversion were calculated according to the changes before
and after the CO2 reaction as follows:
m − mt
ConSC = (5)
m − m ash

where m, mt and m ash represented the initial mass of SC, the mass of SC after the reaction
and the mass of ash in SC, respectively.

nb − n a
ConCO2 = (6)
nb

where nb and n a represented the moles of CO2 before the reaction and the moles of CO2
after the reaction, respectively.

4. Conclusions
The CO2 gasification of semi-coke was studied through microwave radiation. We
found that microwaves do have an excellent enhancement effect on the reaction. The
experimental results showed that the maximum CO2 conversion was 99.9% in the presence
of barium carbonate. Based on the kinetic study, the activation energy for microwave
heating was 47.1 kJ/mol while this value was 148.9 kJ/mol for conventional heating,
indicating that microwaves could increase the Boudouard reaction and reduce the reaction
activation energy. Thus, BaCO3 for an enhanced microwave chemical Boudouard reaction
makes the zero emission of CO2 and the clean utilization of coal resources possible.

Supplementary Materials: The following are available online, Figure S1: Schematic diagram of the
microwave experiment device; Table S1: Experiment data.
Molecules 2021, 26, 1507 10 of 11

Author Contributions: Conceptualization, B.J. and H.Z.; research ideas: B.J., H.Z. and S.C.; inves-
tigation, H.D.; methodology, H.D. and S.C.; software, H.D.; validation, B.J., H.Z. and H.D.; formal
analysis, H.D. and S.C.; data management: H.D.; writing—original draft preparation, H.D.; writing—
review and editing, B.J. and H.Z.; supervision, B.J. and H.Z.; project administration, H.Z.; funding
acquisition, B.J. All authors have read and agreed to the published version of the manuscript.
Funding: This work was supported by the Shanghai Science and Technology Committee(15DZ1206800).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Not available.

References
1. Song, C. Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving
energy, catalysis, adsorption and chemical processing. Catal. Today 2006, 115, 2–32. [CrossRef]
2. Das Neves Gomes, C.; Blondiaux, E.; Thuery, P.; Cantat, T. Metal-free reduction of CO2 with hydroboranes: Two effi-cient
pathways at play for the reduction of CO2 to methanol. Chemistry 2014, 20, 7098–7106. [CrossRef] [PubMed]
3. Lahijani, P.; Zainal, Z.A.; Mohammadi, M.; Mohamed, A.R. Conversion of the greenhouse gas CO2 to the fuel gas CO via the
Boudouard reaction: A review. Renew. Sustain. Energy Rev. 2015, 41, 615–632. [CrossRef]
4. Beller, M. Catalytic Carbonylation Reaction. Organomet. Chem. 2006, 18, 1–283.
5. Ratnasamy, C.; Wagner, J.P. Water Gas Shift Catalysis. Catal. Rev. 2009, 51, 325–440. [CrossRef]
6. Leadbeater, N.E. Microwave Heating as a Tool for Sustainable Chemistry; CRC Press: Boca Raton, FL, USA, 2017.
7. Bykov, Y.V.; Rybakov, K.I.; Semenov, V.E. High temperature microwave processing. Appl. Phys. 2001, 34, 55–75.
8. Gabriel, C.; Gabriel, S.; Grant, E.H.; Halstead, B.S.J.; Mingos, D.M.P. Dielectric parameters relevant to microwave dielectric
heating. Chem. Soc. Rev. 1998, 27, 213–224. [CrossRef]
9. Jia, Z.; Lin, K.; Wu, G.; Xing, H.; Wu, H. Recent Progresses of High-Temperature Micro-wave-Absorbing Materials. NANO 2018,
13, 1830005. [CrossRef]
10. Bermúdez, J.M.; Ruisánchez, E.; Arenillas, A.; Moreno, A.H.; Menéndez, J.A. New concept for energy storage: Mi-crowave-
induced carbon gasification with CO2 . Energy Convers. Manag. 2014, 78, 559–564. [CrossRef]
11. Lahijani, P.; Mohammadi, M.; Zainal, Z.A.; Mohamed, A.R. Improvement of biomass char-CO2 gasification reactivity using
microwave irradiation and natural catalyst. Thermochim. Acta 2015, 604, 61–66. [CrossRef]
12. Lahijani, P.; Zainal, Z.A.; Mohamed, A.R.; Mohammadi, M. Microwave-enhanced CO2 gasification of oil palm shell char. Bioresour.
Technol. 2014, 158, 193–200. [CrossRef]
13. Chun, Y.N.; Song, H.G. Microwave-induced carbon-CO2 gasification for energy conversion. Energy 2020, 190, 116386. [CrossRef]
14. Chun, Y.N.; Song, H.G. Microwave-enhanced gasification of sewage sludge waste. Environ. Eng. Res. 2018, 24, 591–599. [CrossRef]
15. Lartey-Young, G.; Ma, L. Remediation with Semicoke-Preparation, Characterization, and Adsorption Application. Materials 2020,
13, 4334. [CrossRef]
16. Ramirez, A.; Hueso, J.L.; Abian, M.; Alzueta, M.U.; Mallada, R.; Santamaria, J. Escaping undesired gas-phase chemistry:
Microwave-driven selectivity enhancement in heterogeneous catalytic reactors. Sci. Adv. 2019, 5, eaau9000. [CrossRef]
17. Sugawara, H.; Kashimura, K.; Hayashi, M.; Ishihara, S.; Mitani, T.; Shinohara, N. Behavior of microwave-heated silicon carbide
particles at frequencies of 2.0–13.5 GHz. Appl. Phys. Lett. 2014, 105, 034103. [CrossRef]
18. Thostenson, E.T.; Chou, T.W. Microwave processing fundamentals and applications. Compos. Part A Appl. Sci. 1999, 30, 1055–1071.
[CrossRef]
19. Liu, Y.; Guan, Y.; Zhang, K. CO2 gasification performance and alkali/alkaline earth metals catalytic mechanism of Zhundong coal
char. Korean J. Chem. Eng. 2018, 35, 859–866. [CrossRef]
20. Uwaoma, R.C.; Strydom, C.A.; Bunt, J.R.; Okolo, G.N.; Matjie, R.H. The catalytic effect of Benfield waste salt on CO2 gasification
of a typical South African Highveld coal. J. Therm. Anal. Calorim. 2018, 135, 2723–2732. [CrossRef]
21. Lahijani, P.; Mohammadi, M.; Mohamed, A.R. Catalytic CO2 gasification of rubber seed shell-derived hydrochar: Reactivity and
kinetic studies. Environ. Sci. Pollut. Res. 2019, 26, 11767–11780. [CrossRef]
22. Irfan, M.F.; Usman, M.R.; Kusakabe, K. Coal gasification in CO2 atmosphere and its kinetics since 1948: A brief review. Energy
2011, 36, 12–40. [CrossRef]
23. Wen, X.D.; Man, S.F.; Long, Y.J.; Xin, J.; Yan, Z.h.; Jian, G.Q.; Xin, L.J. Combustion characteristics of unburned pulverized coal and
its reaction kinetics with CO2 . Int. J. Miner. Metall. Mater. 2019, 26, 811–821.
24. Zhang, Y.; Geng, P.; Zheng, Y. Exploration and practice to improve the kinetic analysis of char-CO2 gasification via thermogravi-
metric analysis. Chem. Eng. J. 2019, 359, 298–304. [CrossRef]
Molecules 2021, 26, 1507 11 of 11

25. Bhui, B.; Vairakannu, P. Experimental and kinetic studies on in-situ CO2 gasification based chemical looping combus-tion of low
ash coal using Fe2 O3 as the oxygen carrier. J. CO2 Util. 2019, 29, 103–116. [CrossRef]
26. Hunt, J.; Ferrari, A.; Lita, A.; Crosswhite, M.; Ashley, B.; Stiegman, A.E. Microwave-Specific Enhancement of the Carbon–Carbon
Dioxide (Boudouard) Reaction. J. Phys. Chem. C 2013, 117, 26871–26880. [CrossRef]