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org/IECR Article

Microwave Fixed-Bed Reactor for Gas-Phase Glycerol Dehydration:

Experimental and Simulation Studies
Qinglong Xie, Tongbo Pan, Gaoji Zheng, Yuqiang Zhou, Shangzhi Yu, Ying Duan, and Yong Nie*
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ABSTRACT: Conventional fixed-bed reactors have the issue of uneven temperature distribution within the catalyst bed, which
influences product selectivity and catalyst stability. Microwave irradiation can realize uniform and bulk heating due to its unique
penetration capability. Here, a microwave fixed-bed reactor was developed and applied in a gas-phase glycerol dehydration reaction.
Nine microwave-absorbing binary metal oxide catalysts were used to verify the versatility of microwave reactors in gas−solid
reactions. Compared with an electric-heating reactor, much better catalyst stability was obtained in a microwave reactor for all of the
catalysts. Moreover, no obvious change in catalyst stability was observed with increasing reactor size. Numerical simulation was
adopted to explore the intensification mechanism of microwave heating. The largest temperature difference in the microwave reactor
was around 10 °C, much smaller than that in the electric-heating reactor which reached 57 °C. The electric field distribution within
the penetration depth of microwave irradiation was homogeneous, resulting in uniform temperature distribution in the microwave
reactor and hence good catalyst stability.

1. INTRODUCTION frequency electromagnetic field to generate heat.7 Different

Fixed-bed reactors are widely used in gas−solid and liquid−
solid catalytic reactions due to their simple construction and
high surface-area-to-volume ratio.1 However, the issue of
uneven temperature distribution within the catalyst bed usually
exists in fixed-bed reactors because of the conventional
conduction heating method and poor thermal conductivity of
most catalysts.2 To improve the heat transfer, a multistage
fixed-bed reactor system was developed that uses interstage
heat exchange and reduces the overall temperature variation of
the catalyst bed, and yet the radial temperature gradient within
the bed still exists.3 The temperature distribution is enhanced
in a multitubular reactor through the reduction of tube
diameter.4 However, a very small tube size causes the wall
effect resulting in uneven airflow in the catalyst bed and hence
restricted heat and mass transfer between the fluid and catalyst
particles.5 In addition, the reduction of tube and catalyst size
leads to an increase in the pressure drop and thus energy
consumption for the fixed-bed reactor.6
Microwave irradiation can induce the rapid movement and
friction of polar molecules (dipoles) in the presence of a high-
from conventional heating modes, microwave heating can
realize the bulk heating of feedstock through the dissipation of
microwave energy inside the dielectric.8 Consequently,
compared with conventional heating, the temperature gradient
within the feedstock can be effectively reduced under
microwave heating to achieve a more uniform temperature
distribution.
Microwave heating has been widely used in various organic
reactions and proved to have an obvious intensification effect
by significantly reducing the reaction time.9 Recently, micro-
wave-assisted biomass pyrolysis for biofuel production has
attracted much attention.10,11 Rapid and efficient conversion of
Received: April 4, 2022
Revised: July 2, 2022
Accepted: July 11, 2022
Published: July 20, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acs.iecr.2c01176

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Industrial & Engineering Chemistry Research
biomass can be achieved using a premixed method in which
feedstock is mixed with a microwave absorbent or a non-
premixed method, i.e., feedstock is poured onto the heated
microwave absorbent bed.11 Our group previously reported
methyl ricinoleate pyrolysis by microwave heating coupled
with atomization feeding and obtained high product yields.12,13
However, the above microwave-assisted processes mainly
involved liquid−liquid, liquid−solid, and solid−solid reactions
in tank reactors, and few studies on gas−solid catalytic
reactions in fixed-bed reactors under microwave heating have
been reported.
Gas-phase glycerol dehydration is usually adopted for the
production of acrolein, which is an important chemical
intermediate to produce value-added chemicals such as acrylic,
1,3-propanediol, and methionine.14 The dehydration reaction
is usually performed in a fixed-bed reactor packed with solid
acid catalysts such as heteropoly acids, phosphates, molecular
sieves, and metal oxides.15 However, the glycerol dehydration
process belongs to complex reactions that are highly sensitive
to temperature.16 Parallel side reaction of glycerol polymer-
ization and series side reaction of acrolein polymerization are
favored at lower and higher temperatures, respectively, to form
coke on the surface of the catalyst.17 Thus, rapid catalyst
deactivation ascribed to coke deposition is often observed in
conventional fixed-bed reactors due to the existence of a
temperature gradient. The acrolein yield obtained in the gas-
phase glycerol dehydration was reported to reach around 60%,
yet the deactivation of most catalysts occurred within 10 h.18
In our previous work, microwave-assisted glycerol dehy-
dration to acrolein was conducted over a coated microwave-
absorbing catalyst WO3−ZrO2@SiC.19 Higher acrolein yield
and better catalyst stability were achieved under microwave
heating compared with the electric-heating process. However,
the physicochemical properties of the catalytic materials may
influence the distributions of electromagnetic and temperature
fields in the microwave reactor. Therefore, the versatility of a
microwave fixed-bed reactor in gas−solid catalytic reactions
over different catalysts should be explored. Moreover, the
mechanism of microwave heating in the improvement of
product yield and catalyst stability has not been investigated.
In this work, a microwave fixed-bed reactor was developed
for the gas-phase glycerol dehydration reaction. The versatility
of the microwave reactor was verified by being packed with
nine typical catalysts for glycerol dehydration. The catalyst
stability in microwave-assisted glycerol dehydration was
experimentally studied and compared with the conventional
heating method. To explore the intensification mechanism of
microwave heating, the temperature distribution of the catalyst
bed and the electric field distribution within the reactor were
determined by numerical simulation.
2. EXPERIMENTAL SECTION
2.1. Experimental Setup of the Microwave Fixed-Bed
Reactor. The experimental setup of the microwave fixed-bed
reactor is shown in Figure 1. The microwave irradiation was
provided in a self-manufactured microwave cavity equipped
with a water-cooled magnetron (LG 2M246) at a power of
1000 W and a frequency of 2450 MHz. The microwave power
can be controlled by adjusting the anode current of the
magnetron using a potentiometer. The microwaves generated
by the magnetron were transmitted into the cavity through a
standard BJ26 waveguide (L × W = 86 mm × 43 mm). A
vertical quartz tubular reactor packed with catalysts was
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Figure 1. Experimental setup of a microwave fixed-bed reactor. (1)
Infrared radiation thermometer, (2) microwave cavity, (3) fixed-bed
reactor, (4) catalyst bed, (5) microwave constraint chamber, (6)
magnetron, and (7) waveguide.
located in the middle of the microwave cavity. The
temperature of the catalyst bed was measured by an infrared
radiation thermometer, with the signal feedback controlling the
magnetron to be on or off. A microwave constraint chamber
with the height same as the catalyst bed was connected with
the waveguide, with the purpose of increasing the power
density of microwave energy. In addition, a microwave
detector (DT-2G, CEM Corporation) was used to monitor
microwave leakage for safety purposes.
2.2. Catalyst Preparation and Characterization. Nine
typical binary metal oxide catalysts for glycerol dehydration
were prepared with SiC of 500 nm particle size as the
microwave absorbent. Among these, four catalysts, i.e.,
Nb2O5−ZrO2@SiC, Nb2O5−Al2O3@SiC, WO3−ZrO2@SiC,
and WO3−Al2O3@SiC, were obtained using an excessive
impregnation method, which were labeled as Nb−Zr, Nb−Al,
W−Zr, and W−Al, respectively. A certain amount of SiC was
first dispersed in deionized water, followed by the addition of
ZrOCl2 or Al(NO3)3 solution. Afterward, diluted aqueous
ammonia was added dropwise to the solution with a pH of
9.0−10.0, which was then aged for 1 h. The precipitate was
filtered, exhaustively washed, dried at 110 °C for 12 h, and
finally calcined at 550 °C for 4 h. Subsequently, the obtained
powder was impregnated with ammonium metatungstate or
niobium ammonium oxalate solution. The mixture was stirred
and exposed to infrared radiation at 50 °C for 24 h, followed
by being calcined at 600 °C for 6 h yielding the microwave-
absorbing binary metal oxide catalysts.
The co-precipitation method was used to prepare the other
five catalysts, i.e., 10%SnO2−ZrO2@SiC (SnO2:(SnO2 +
ZrO2) = 10 wt%, similarly hereinafter), 30%SnO2−ZrO2@
SiC, 50%SnO2−ZrO2@SiC, TiO2−ZrO2@SiC, and TiO2−
SnO2@SiC, which were labeled as 10%Sn−Zr, 30%Sn−Zr,
50%Sn−Zr, Ti−Zr, and Ti−Sn, respectively. A certain amount
of SiC was first dispersed in deionized water, followed by the
addition of SnCl4, TiCl4, and ZrOCl2 in ethanol solution.
Afterward, diluted aqueous ammonia was added dropwise to
the solution with a pH of 9.0−10.0, which was then aged for 1
h. The precipitate was filtered, exhaustively washed, dried at
110 °C for 12 h, and finally calcined at 600 °C for 6 h.
The catalysts were characterized to determine their
physicochemical properties. The specific surface area and
pore size, morphology, crystalline structures, and acid proper-
ties of catalysts were analyzed by Brunauer−Emmett−Teller
(BET) method, transmission electron microscopy (TEM)
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Figure 2. TEM and HAADF-STEM images and the corresponding elemental mapping of (a) W−Zr and (b) 50%Sn−Zr (the red rectangle is the
area for elemental mapping).
coupled with elemental mapping, X-ray diffraction (XRD),
Fourier-transform infrared spectroscopy of pyridine (pyridine-
FTIR), and thermogravimetry-differential scanning calorimetry
(TG-DSC), respectively. The details of these characterization
techniques can be found in our previous work.19 In addition,
thermogravimetric analysis/infrared (TG-IR) spectrometry
analysis of the used catalyst was performed using a NETZSCH
TG55 thermal analyzer and a Thermo Scientific NicoletiS50
spectrometer. The sample was placed on an alumina crucible
and heated from room temperature to 800 °C at a rate of 10
°C/min under the air atmosphere. Solid-state C13 nuclear
magnetic resonance (NMR) spectra of used catalysts were
obtained on a Bruker 400 M spectrometer equipped with a 4
mm probe at a spinning rate of 40 kHz. The complex
permittivity of catalysts was measured in the frequency range
from 1 to 18 GHz at 150 °C by means of the coaxial method
using an Agilent PNA-N5234A vector network analyzer. The
thermal diffusivity and specific heat capacity of catalysts were
determined on a NETZSCH LFA 457 MicroFlash laser-flash
apparatus, which were then used for the calculation of the
thermal conductivity of catalysts.
2.3. Catalytic Tests. The gas-phase glycerol dehydration
reactions were performed in the microwave fixed-bed reactor at
various diameters (10, 15, and 20 mm). Prior to microwave
heating, N2 at a flow rate of 30 mL/min was introduced to
remove the air in the reactor. The catalysts absorbed the
microwaves and were heated under microwave irradiation.
Once the reaction temperature was reached, an aqueous
solution of glycerol (20 wt%), after being preheated and
vaporized, was fed into the reactor by a peristaltic pump.
During the reaction, the temperature of the catalyst bed
monitored by the infrared thermometer was maintained stable
by controlling the magnetron on or off by the signal feedback.
The reaction products were condensed and collected for
subsequent analysis. The yield of the liquid product was
calculated using eq 1.
liquid product yield (wt%)
the weight of liquid product
= × 100%
the weight of feedstock (1)
In addition, glycerol dehydration under conventional electric
heating was conducted and compared with the microwave-
heating method. The experimental procedures and reaction
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conditions were consistent with those of the microwave-
heating process.
2.4. Product Analysis. For the methods for product
analysis, we can refer to our previous report.19 Briefly, glycerol
in the liquid was analyzed using a Shimadzu LC-20AT high-
performance liquid chromatograph (HPLC) equipped with a
XAmide column and a refractive index detector (RID), with
the glycerol conversion calculated by eq 2. Acrolein and
byproducts (mainly acetaldehyde and hydroxyacetone) were
analyzed using an Agilent 7890A gas chromatograph (GC)
with a DB-WAX capillary column and a flame ionization
detector (FID). The selectivity and yield of products were
determined using eqs 3 and 4.
glycerol conversion (%)
ij the amount of glycerol in liquid product yzz
= jjj1 z
j
k the amount of glycerol in feedstock zz{
× 100% (2)
product selectivity (%)
the amount of glycerol converted to a product
= × 100%
the amount of reacted glycerol
(3)
product yield (%)
the amount of glycerol converted to a product
= × 100%
the amount of glycerol in feedstock
(4)
3. RESULTS AND DISCUSSION
3.1. Characterization of the Catalysts. The specific
surface area and pore structure of nine microwave-absorbing
catalysts are listed in Table S1. Compared with the SiC alone,
the specific surface area and pore volume were obviously
increased for the binary metal oxide catalysts. This indicated
that certain pore structures were formed during the catalyst
preparation, which could favor the dispersion of active
components and hence improve the activity of catalysts.
Figure 2 shows the TEM images of W−Zr and 50%Sn−Zr
that were obtained using the excessive impregnation and co-
precipitation methods, respectively (TEM images of other
catalysts are displayed in Figure S1). The platelet-shaped
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Figure 3. XRD patterns of binary metal oxide catalysts prepared by (a) excessive impregnation method and (b) co-precipitation method.

microstructures can be observed for all of the catalysts. In

addition, the distributions of Si, O, and metal elements on the
catalysts were quite uniform, as seen from the elemental
mapping acquired using high-angle annular dark-field STEM
(HAADF-STEM) with an energy-dispersive X-ray (EDX)
spectrometer.
The powder XRD patterns of the nine microwave-absorbing
binary metal oxide catalysts are displayed in Figure 3. The
characteristic peaks of SiC and most metal oxides can be
obviously found for catalysts prepared by both excessive
impregnation and co-precipitation methods, indicating the
existence of corresponding crystalline phases in the catalysts.
However, since TiO2 after being calcined at 600 °C basically
existed in the amorphous phase,20 no characteristic peaks of
TiO2 were observed in the XRD spectrum of the Ti−Zn or
Ti−Zr catalyst.
The Brønsted and Lewis acid sites on the catalysts were Figure 4. Pyridine-FTIR profiles at a desorption temperature of 200
analyzed according to the pyridine-FTIR spectra obtained at °C for nine binary metal oxide catalysts.
200 and 350 °C. As shown in Figures 4 and S2, similar FTIR
profiles and desorption peaks were observed for the nine
binary metal oxide catalysts at both desorption temperatures. centered at around 1490 cm −1 were ascribed to the
The bands resulting from Brønsted acid sites existed at around combination of Brønsted and Lewis acid sites.22 The density
1546 and 1640 cm−1, with those attributed to Lewis acid sites of Brønsted and Lewis acid sites on the catalysts was
appearing at ca. 1445, 1546, and 1610 cm−1.21 The peaks determined from the integrated areas of corresponding peaks
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using the extinction coefficients,23 as listed in Table 1. The obtained over various catalysts were significantly different at
amounts of Brønsted and Lewis acid sites and the ratio of both dehydration temperatures, which was primarily attributed
to the catalyst acidity.24 It is accepted that the existence of
Table 1. Acidity of Nine Binary Metal Oxide Catalysts as Brønsted acid sites enhances the glycerol dehydration to
Determined by the Pyridine-FTIR Technique acrolein by protonating the secondary hydroxyl group of
glycerol.25 More Lewis acid sites on the catalyst would cause
density of acid sites by pyridine-FTIR (μmol/gcat.)
an increase in the formation of byproducts such as
catalysts B200a L200a B200/L200 B350a L350a B350/L350 hydroxyacetone (Table S2) and hence the reduction in
W−Zr 119.4 20.6 5.8 103.2 10.0 10.3 acrolein selectivity.26 However, according to Tables 1 and 2,
Nb−Zr 121.3 29.9 4.1 51.4 8.9 5.8 the acrolein selectivity exhibited no obvious correlation with
W−Al 101.4 20.8 4.9 69.8 6.0 11.6 the density of Brønsted or Lewis acid sites on the catalysts.
Nb−Al 87.2 21.0 4.2 16.4 4.6 3.5 Figure 5 displays the relationship between acrolein selectivity
10Sn−Zr 171.1 90.0 1.9 97.5 39.7 2.5 and the Brønsted-to-Lewis-acid density ratio, with a certain
30Sn−Zr 84.6 52.7 1.6 48.7 15.6 3.1 positive correlation observed. It indicated that the acrolein
50Sn−Zr 69.0 45.4 1.5 47.9 8.9 5.4 selectivity in the glycerol dehydration process largely depended
Sn−Ti 145.6 95.4 1.5 42.5 22.1 1.9 on the ratio of Brønsted to Lewis acid density on the catalyst
Zr−Ti 101.4 51.9 1.9 36.2 7.7 4.7 rather than their respective amounts. In addition, as shown in
a
B: Brønsted acid sites and L: Lewis acid sites. The number after B Tables 2 and S3, higher glycerol conversion was obtained at
and L refers to the pyridine desorption temperature (in °C). the higher temperature for all of the catalysts mainly because of
the higher reaction rate of glycerol dehydration. On the other
Brønsted acid density to Lewis acid density were very different hand, side reactions such as glycerol polymerization were
for various binary metal oxide catalysts, which would lead to promoted at the lower temperature,27 which resulted in lower
their difference in catalytic performance in glycerol dehy- acrolein selectivity.
dration. 3.3. Catalyst Stability. The stability of the nine binary
3.2. Glycerol Dehydration Tests in the Microwave metal oxide microwave-absorbing catalysts in gas-phase
Fixed-Bed Reactor. The tests of glycerol dehydration in a glycerol dehydration using the microwave fixed-bed reactor
microwave fixed-bed reactor packed with nine binary metal was examined and compared with that in a conventional
oxide catalysts were conducted at 250 and 300 °C. As shown in electric-heating reactor. The stability of the catalysts prepared
Table 2, the glycerol conversion and acrolein selectivity by excessive impregnation and co-precipitation methods is
shown in Figures 6 and 7, respectively. The stability
Table 2. Glycerol Dehydration in the Microwave Fixed-Bed performance varied for different catalysts. Overall, the catalysts
Reactor Packed with Various Binary Metal Oxide Catalysts with a higher Brønsted-to-Lewis-acid density ratio exhibited
at 250 and 300 °C better stability than those with a lower ratio. This was mainly
liquid product glycerol conversion acrolein selectivity because more byproducts such as hydroxyacetone and
yield (wt%) (%) (%) acetaldehyde were generated when the Lewis acid density
catalysts 250 °C 300 °C 250 °C 300 °C 250 °C 300 °C was relatively high, which enhanced the formation of coke
W−Zr 97.0 97.5 98.5 99.7 68.1 73.2
deposits on the catalyst and hence reduced the catalyst
Nb−Zr 99.8 99.1 51.0 86.2 36.7 58.4
stability.
W−Al 98.4 96.9 90.9 99.5 52.9 59.0
For all of the catalysts and both dehydration temperatures,
Nb−Al 99.1 99.7 27.1 94.0 45.7 62.3
better catalyst stability was observed in the microwave fixed-
10Sn−Zr 94.1 96.6 42.3 87.6 15.6 20.7
bed reactor compared with the conventional electric-heating
30Sn−Zr 92.2 98.2 35.7 78.1 9.7 17.3
reactor. The main possible reason for this lies in the unique
50Sn−Zr 99.4 97.9 22.6 75.2 18.9 22.7 penetration capability and bulk heating of microwave
Sn−Ti 92.4 96.6 43.0 78.8 20.2 20.0 irradiation, which resulted in more uniform temperature
Zr−Ti 98.4 99.4 68.7 97.4 30.0 39.1 distribution of the catalyst bed. By contrast, since the
temperature was monitored and controlled at the outer wall

Figure 5. Correlation between acrolein selectivity and Brønsted-to-Lewis-acid density ratio for various binary metal oxide catalysts at (a) 250 °C
and (b) 300 °C.

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Figure 6. Glycerol conversion with time on stream in the microwave fixed-bed reactor (filled symbols with solid lines) and an electric-heating
reactor (open symbols with dashed lines) packed with catalysts prepared by the excessive impregnation method including (a) W−Zr, (b) Nb−Zr,
(c) W−Al, and (d) Nb−Al at temperatures of (●) 250 °C and (■) 300 °C.
of the electric-heating reactor, the temperature gradient caused
by the thermal resistance of catalyst particles and heat
consumption of the glycerol dehydration reaction led to
lower temperatures within the catalyst bed. Thus, side
reactions, especially glycerol polymerization, were promoted,
which increased the coke formation for catalyst deactivation.28
This can be confirmed by the better catalyst stability obtained
at the temperature of 300 °C than that at 250 °C for all of the
catalysts. Since various binary metal oxide catalysts with
different physicochemical properties were used, the results
proved the universal superiority of microwave fixed-bed
reactors over electric-heating reactors in gas−solid catalytic
reactions.
The advantage of a microwave fixed-bed reactor over a
conventional electric-heating reactor became more obvious
with increasing reactor size. As shown in Figure 8, the catalyst
stability in the electric-heating reactor was continuously
reduced when the reactor diameter was increased from 10 to
20 mm. The glycerol conversion obtained in the 20 mm
reactor was lower than 80% after a 16 h run over the W−Zr
catalyst at 250 °C. By contrast, no significant difference in
catalyst stability was observed for microwave fixed-bed reactors
of various sizes. The glycerol conversion was still higher than
95% after the 16 h reaction. For common fixed-bed reactors
with the heat transfer mainly through conduction, the
temperature difference within the catalyst bed would be
greater at a larger reactor size. Consequently, the even lower
temperature enhanced the side reactions for the coking of
catalysts. Because of the special heating mechanism of
microwave irradiation, the bulk and uniform heating of the
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catalyst bed can be achieved as long as the reactor size was
within the penetration depth of microwaves. From this
perspective, the microwave fixed-bed reactor has more
potential for reactor scale-up.
3.4. Coking of Catalysts. According to our previous study
and other reports, coking of catalyst was considered the main
reason for the reduction of catalyst stability during glycerol
dehydration.17,19 Characterization techniques including TG-
DSC, TG-IR, and NMR were used to explore the mechanism
of coke formation. Figure 9a displays TG-DSC curves of a
typical catalyst after a 16 h reaction at 250 °C in the electric-
heating reactor. DTG and DSC peaks of the used catalyst at
around 460 °C can be clearly observed. According to the
corresponding TG-IR curves, as shown in Figure 9b, the
weight loss at 460 °C resulted in the formation of CO2. Thus,
the TG-DSC-IR results verified the existence of carbonaceous
deposits on the used catalyst. In addition, the weight loss
increased from 6.8 to 11.5% for the used catalysts in electric-
heating reactors with diameters increasing from 10 to 20 mm.
This indicated the generation of more coke deposits at a larger
reactor size, which caused more rapid catalyst deactivation as
presented in Figure 8.
The typical 13C NMR spectrum of the used catalyst at 250
°C as shown in Figure S3 exhibited two main peaks at σ = 71
and 73 ppm as well as two minor peaks at σ = 20 and 132 ppm.
The main peaks corresponding to branched oxygen-containing
groups were attributed to polyglycol compounds.29 This
confirmed that the primary reason for the coking of catalysts
was glycerol polymerization, which usually occurs at lower
temperatures. The peak at σ = 20 ppm was associated with
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Figure 7. Glycerol conversion with time on stream in the microwave fixed-bed reactor (filled symbols with solid lines) and an electric-heating
reactor (open symbols with dashed lines) packed with catalysts prepared by the co-precipitation method including (a) 10Sn−Zr, (b) 30Sn−Zr, (c)
50Sn−Zr, (d) Sn−Ti, and (e) Zr−Ti at temperatures of (●) 250 °C and (■) 300 °C.

saturated carbon atoms of terminal chains bound to the
oligomeric compounds that had not yet cyclized, with that
centered at σ = 132 ppm ascribed to polyaromatic
compounds.29 These minor carbonaceous deposits may be
produced from aldol condensation of acrolein, hydroxyacetone,
and acetaldehyde.30
3.5. Numerical Simulation. According to the experimen-
tal results, the temperature distribution of the catalyst bed is a
key factor influencing the catalyst stability in the fixed-bed
reactor. Thus, it is essential to determine and compare the
temperature distributions within the electric-heating and
microwave-heating reactors. However, it is difficult to monitor
all of the temperature points within the catalyst bed, especially
under microwave irradiation.31 In this work, a numerical
simulation based on the finite element method (FEM) was
10729
adopted to determine the temperature distributions using the
COMSOL Multiphysics software.
3.5.1. Model Simplification. The simulation involving an
electromagnetic field coupled with heat transfer is a highly
coupling and nonlinear process. To reduce the difficulty of
simulation and save simulation time, some reasonable
assumptions are proposed to simplify the model. (1) The
microwave absorption capacity of air and glass is zero, (2) the
catalyst bed is the only heat source and the reaction heat of the
endothermic glycerol dehydration reaction is considered as
equivalent heat loss from the whole catalyst bed, (3) the
catalyst particles within the reactor are spatially homogeneous
with the whole catalyst bed simplified as a porous medium for
simulation, and (4) the dielectric and thermal properties of the
catalysts are constants with temperature.
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Table 3. Dimensions of the Main Components of the

Microwave Fixed-Bed Reactor
length width height
(mm) (mm) (mm)
microwave cavity 300 320 320
waveguide 86 86 43
microwave constraint chamber 180 160 60
catalyst bed 50

device. The microwave cavity, waveguide, and microwave

Figure 8. Glycerol conversion with time on stream using reactors with
various diameters. The reaction temperature was 250 °C, and the
catalyst was WO3−ZrO2@SiC.
Figure 9. (a) Typical TG-DSC curves of the used (solid lines) and
fresh (dashed lines) catalyst and (b) the corresponding TG-IR curves
of the used catalyst.
3.5.2. Geometry. The geometric model of the microwave
fixed-bed reactor in the COMSOL graphic interface was
developed based on the experimental apparatus, as shown in
Figure S4. The dimensions of the main components including
microwave cavity, waveguide, microwave constraint chamber,
and catalyst bed are listed in Table 3. In addition, the
percentage of voids in the catalyst bed was measured to be
65.2%.
3.5.3. Material Properties. The material properties of the
geometric model were defined according to the experimental
10730
constraint chamber were polished 304 steel, with the reactor
being made of quartz. The properties of catalysts were used
according to their measurements. The dielectric and thermal
properties of steel, quartz, and typical catalysts used for
simulation work are displayed in Table 4.
3.5.4. Governing Equations. The electromagnetic field
distribution in the microwave cavity is solved using Maxwell’s
equations. The governing equation of the electric field is
expressed as follows
ij j yzz
× 1
( ×E) k 02jjj zzE = 0
r j r z
k 0{ (5)
where μr is the relative permeability of materials, E represents
the electric field, k0 is the wave number in vacuum, εr is the
relative permittivity of materials, σ is the electrical conductivity
in S/m, ω is the angular frequency in Hz, and ε0 denotes the
vacuum dielectric constant (8.85 × 10−12 F/m).
Fourier’s equation describing the heat transfer is used to
solve the temperature distribution in the microwave cavity.
The governing equation of the temperature field is shown as
follows
T
CP = · (k T ) + Q
t (6)
3
where ρ is the density of materials in kg/m , Cp represents the
specific heat capacity in J/(kg·K), T is the temperature in K, k
denotes the thermal conductivity in W/(m·K), and Q refers to
the dissipated microwave energy in the microwave-absorbing
catalyst bed in W, which is expressed by the following equation
1
Q= ( + 0 )E 2
2 (7)
where ε″ represents the imaginary part of the complex relative
permittivity, which is also known as the loss factor.
3.5.5. Boundary Conditions. The impedance boundary
condition refers to the surface of the microwave cavity and
waveguide (Figure S4b), which is expressed using the following
equation
0 r
n×H+E (n·E)n = (n·Es)n Es
0 r j (8)
where μ0 is the relative permeability in vacuum, H is the
magnetic field, and Es is the electric field on the surface of the
microwave cavity and waveguide.
Microwaves at a frequency of 2450 MHz are excited through
a rectangular port in the TE10 mode. The boundary of the port
describes the area of microwave irradiation entering the
microwave cavity, as shown in Figure S4c. The propagation
constant (β) of microwave is defined as follows
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Table 4. Dielectric and Thermal Properties of Materials Used for Simulation Work
properties steela quartza W−Zr Nb−Al Sn−Zr Sn−Ti
relative permeability 1.0135 1 7.72 1.92 2.50 2.07
relative permittivityb 1 3.8 1.9332−0.2142*j 0.6233−0.9075*j 1.1333−0.0523*j 0.6067−0.8733*j
electrical conductivity (S/m) 4.032 × 106 1 × 10−14 0 0 0 0
specific heat capacity (J/(kg·K)) 741 699 925 724 980
density (kg/m3) 2485 3059 2052 2467 2667
thermal conductivity (W/(m·K)) 1.4 0.399 0.911 0.682 0.373
a
The properties are taken from the COMSOL built-in material library. bFor relative permittivity, j is the imaginary number i.

Figure 10. Temperature distributions in electric-heating fixed-bed reactors packed with various binary metal oxide catalysts including (a) W−Zr,
(b) Nb−Al, (c) Sn−Zr, and (d) Sn−Ti.

2 2 2 as shown in Figure S4d. The number of region, edge, and

= c
c0
where c0 is the velocity of light and ν and νc refer to the
frequency and cutoff frequency of microwave in Hz,
respectively.
In the microwave fixed-bed reactor, the temperature of the
catalyst bed was monitored by an infrared radiation
thermometer that was located on the left side of the microwave
cavity. To keep the simulation consistent with the experimental
setup, the temperature measurement point in the simulation
was set on the left side of the catalyst bed, as displayed in
Figure S4a. The temperature of this point was defined as the
integral of temperature at the point that was labeled as
intop(T). In the simulation work, the heating process of the
microwave fixed-bed reactor is controlled by the following
command:
if (in top(T ) 300 [deg C], emw. Q , 0)
which means that the excited microwave power is Q if the
temperature of the measurement point is equal to or lower
than the set value (taking 300 °C as an example), otherwise
zero.
3.5.6. Mesh. To guarantee the simulation accuracy, the
largest size of the mesh elements for the whole geometry was
restricted to be one-tenth of the microwave wavelength. The
part of the catalyst bed was even performed a finer subdivision,
(9) vertex elements were 341 435, 23 434, and 1053, respectively.
3.5.7. Solver. The solver based on the generalized minimum
residual method (GMRES) was used to solve the wave
equations in the electromagnetic field, which belongs to
frequency domain analysis. The parallel direct solver
(PARDISO) was selected to analyze the heat transfer, which
is a transient solution process.
3.5.8. Model Validation. To verify the reliability and
accuracy of the model, the temperature of the catalyst bed
under microwave heating monitored by the infrared radiation
thermometer was recorded and compared with that acquired in
the simulation work. As shown in Figure S5, the simulated
temperature profile agreed well with the experimental data.
This indicated that the simulation process was close to the
actual experimental conditions. The slight difference between
experimental and simulated results was probably due to the
(10)
assumption that the dielectric and thermal properties of the
catalysts are constant with temperature. In fact, these
parameters such as thermal conductivity and specific heat
capacity of the catalysts slightly change with temperature,32
which would cause a small deviation of the simulation results.
In addition, the temperature of the catalyst bed in the
electric-heating reactors with various diameters was also
detected by a thermocouple and compared with the simulated
values. The results showed that the deviation of simulated
temperatures from the actual measurements at different
10731 https://doi.org/10.1021/acs.iecr.2c01176
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Figure 11. Temperature distributions of the catalyst bed in electric-heating fixed-bed reactors with various diameters of (a) 10 mm, (b) 15 mm,
and (c, d) 20 mm. The temperature of the measurement point for (a−c) is 250 °C and that for (d) is 300 °C.

Figure 12. Temperature distributions in microwave fixed-bed reactors packed with various binary metal oxide catalysts including (a) W−Zr, (b)
Nb−Al, (c) Sn−Zr, and (d) Sn−Ti.

locations in the catalyst bed was within ±5 °C. This
demonstrated that the parameter settings in the simulation
work and the assumptions to simplify the simulation are
reasonable. Overall, the established model can be used to
describe the temperature distributions in both microwave-
heating and electric-heating fixed-bed reactors.
3.5.9. Temperature Distributions in Fixed-Bed Reactors.
Figure 10 shows the radial temperature distributions of the
catalyst bed in the electric-heating fixed-bed reactor with a
diameter of 20 mm. The temperature difference between the
center and the wall of the reactor was up to around 50 °C for
various catalysts. This was mainly due to the low thermal
conductivity of the binary metal oxide catalysts, which resulted
10732
in large thermal resistance and hence a large temperature
gradient within the catalyst bed under the heat transfer mode
of conduction. The temperature distributions of the catalyst
bed in electric-heating fixed-bed reactors with various
diameters are displayed in Figure 11. The temperature
difference between the center and the wall of the reactor
increased from 19 °C at the diameter of 10 mm to 44 °C at 20
mm. This meant that the lowest temperature at the center of
the 20 mm reactor was only 206 °C. Side reactions during the
glycerol dehydration process, especially glycerol polymer-
ization, would occur at such low temperatures, resulting in
the formation of coke deposits on the catalyst. In addition, as
shown in Figure 11d, the largest temperature difference for a
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Figure 13. Temperature distributions of the catalyst bed in microwave fixed-bed reactors with various diameters of (a) 10 mm, (b) 15 mm, and (c,
d) 20 mm. The temperature of the measurement point for (a−c) is 250 °C and that for (d) is 300 °C.

Figure 14. Electric field distributions within the catalyst bed in microwave fixed-bed reactors with various diameters of (a) 10 mm, (b) 15 mm, and
(c, d) 20 mm. The temperature of the measurement point for (a−c) is 250 °C and that for (d) is 300 °C.

20 mm reactor with the temperature of a measurement point at
300 °C reached up to 57 °C. Overall, the simulation results
confirmed the existence of a large temperature gradient in a
conventional electric-heating fixed-bed reactor, which was the
main reason for rapid catalyst deactivation.
By comparison, a more uniform temperature distribution
was achieved in the microwave fixed-bed reactor. As presented
in Figure 12, a small temperature gradient within the whole
catalyst bed can be observed for various catalysts, with the
largest temperature difference being only 7−16 °C. The slight
difference in temperature gradient for various catalysts was
attributed to their different dielectric properties including
relative permittivity and relative permeability. Moreover, as
10733
shown in Figure 13, no obvious change in the temperature
distribution of the catalyst bed was observed for reactors with
increasing diameters from 10 to 20 mm. The largest
temperature difference for the 20 mm reactor at the control
temperature of 300 °C was only 15 °C. Thus, uniform and
bulk heating of the catalyst bed achieved in the microwave
fixed-bed reactor owing to the unique penetration capability of
microwave irradiation was verified by the simulation results.
According to Figure 13c, the central temperature of the 20 mm
reactor with the temperature of a measurement point at 250
was 263 °C. The slightly higher temperature within the catalyst
bed could reduce the occurrence of side reactions and hence
improve the catalyst stability.
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Industrial & Engineering Chemistry Research
To further understand the intensification mechanism of
microwave heating, the electric field distributions within the
reactors were examined in the simulation work. As displayed in
Figure 14, for microwave fixed-bed reactors with different sizes,
the electric field distributions within the reactors were basically
uniform. This can be explained by the homogeneity of the
electromagnetic field within the penetration depth (Dp) of
microwave irradiation. According to eq 11, the Dp of 2450
MHz microwave into the microwave-absorbing binary metal
oxide catalysts prepared in this work was calculated to be 2−40
cm. The larger Dp than the reactor diameters led to the
uniform electric field distributions within the reactors and
hence the uniform temperature distributions of the catalyst
bed. It can be noted that for W−Zr, which is the most effective
catalyst in glycerol dehydration to acrolein in this study, the Dp
is 12.7 cm, which even reaches 34 cm if the industrial
magnetron at the microwave frequency of 915 MHz is used.
Therefore, the microwave fixed-bed reactor is a promising
alternative to the conventional reactors for glycerol dehy-
dration and other gas−solid catalytic reactions, especially as a
multitubular reactor for industrial scale-up.
c0
Dp = ÄÅ ÉÑ
ÅÅ 2 ÑÑ
Å Ñ
2 2 ÅÅÅ 1 + () 1ÑÑÑ
ÅÅ ÑÑ
ÅÇ ÑÖ (11)
where ε′ refers to the real part of the complex relative
permittivity.
4. CONCLUSIONS
In this study, we developed a microwave fixed-bed reactor
packed with nine microwave-absorbing binary metal oxide
catalysts with different physicochemical properties for gas-
phase glycerol dehydration to acrolein. The acrolein selectivity
exhibited a positive correlation with the Brønsted-to-Lewis-
acid density ratio on the catalyst. More importantly, for all of
the catalysts at dehydration temperatures of 250 and 300 °C,
better catalyst stability was observed in the microwave fixed-
bed reactor compared with the conventional electric-heating
reactor. In addition, the catalyst stability in the electric-heating
reactor was continuously reduced with increasing reactor size;
yet this showed almost no difference in the microwave reactor.
The characterization of used catalysts confirmed that the rapid
catalyst deactivation in the electric-heating reactor was mainly
attributed to coke formation caused by glycerol polymerization
at lower temperatures. The simulation of temperature
distribution indicated the largest temperature difference of
57 °C within the 20 mm electric-heating reactor, which was
only around 10 °C for microwave reactors with various
diameters. The more uniform temperature distribution in the
microwave reactor resulted from the homogeneous electric
field distribution within the penetration depth of microwave
irradiation, which contributed to better catalyst stability.
Overall, the microwave fixed-bed reactor demonstrates its
effectiveness and versatility in gas−solid catalytic reactions,
with great potential in reactor scale-up.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.2c01176.
10734
pubs.acs.org/IECR Article
TEM and HAADF-STEM images and the corresponding
elemental mapping of various binary metal oxide
catalysts including Nb−Zr, W−Al, Nb-Al, 10Sn−Zr,
30Sn−Zr, Sn−Ti, and Zr−Ti; pyridine-FTIR profiles at
a desorption temperature of 350 °C for nine binary
metal oxide catalysts; typical 13C NMR spectrum of used
catalyst; geometric model of the microwave fixed-bed
reactor in the COMSOL graphic interface; comparison
between experimental and simulated temperature
profiles of the catalyst bed under microwave heating;
specific surface area and pore size of SiC and nine binary
metal oxide catalysts; hydroxyacetone and acetaldehyde
selectivities in microwave and electric-heating fixed-bed
reactors packed with various binary metal oxide catalysts
at 250 and 300 °C; and glycerol dehydration in the
electric-heating fixed-bed reactor packed with various
binary metal oxide catalysts at 250 and 300 °C (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Yong Nie − Biodiesel Laboratory of China Petroleum and
Chemical Industry Federation, Zhejiang Provincial Key
Laboratory of Biofuel, and College of Chemical Engineering,
Zhejiang University of Technology, Hangzhou 310014,
China; orcid.org/0000-0002-1671-7669;
Email: ny_zjut@zjut.edu.cn/nieyongnieyyucheng@
gmail.com
Authors
Qinglong Xie − Biodiesel Laboratory of China Petroleum and
Chemical Industry Federation, Zhejiang Provincial Key
Laboratory of Biofuel, and College of Chemical Engineering,
Zhejiang University of Technology, Hangzhou 310014,
China
Tongbo Pan − Biodiesel Laboratory of China Petroleum and
Chemical Industry Federation, Zhejiang Provincial Key
Laboratory of Biofuel, and College of Chemical Engineering,
Zhejiang University of Technology, Hangzhou 310014,
China
Gaoji Zheng − Biodiesel Laboratory of China Petroleum and
Chemical Industry Federation, Zhejiang Provincial Key
Laboratory of Biofuel, and College of Chemical Engineering,
Zhejiang University of Technology, Hangzhou 310014,
China
Yuqiang Zhou − Biodiesel Laboratory of China Petroleum and
Chemical Industry Federation, Zhejiang Provincial Key
Laboratory of Biofuel, and College of Chemical Engineering,
Zhejiang University of Technology, Hangzhou 310014,
China
Shangzhi Yu − Biodiesel Laboratory of China Petroleum and
Chemical Industry Federation, Zhejiang Provincial Key
Laboratory of Biofuel, and College of Chemical Engineering,
Zhejiang University of Technology, Hangzhou 310014,
China
Ying Duan − Biodiesel Laboratory of China Petroleum and
Chemical Industry Federation, Zhejiang Provincial Key
Laboratory of Biofuel, and College of Chemical Engineering,
Zhejiang University of Technology, Hangzhou 310014,
China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.2c01176
https://doi.org/10.1021/acs.iecr.2c01176
Ind. Eng. Chem. Res. 2022, 61, 10723−10735
Industrial & Engineering Chemistry Research
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors express their great appreciation to the National
Natural Science Foundation of China (22178313, 21808203,
and 21776261), the Zhejiang Provincial “Jianbing” “Lingyan”
Research and Development Program of China (2022C01191),
and the Natural Science Foundation of Zhejiang Province
(LQ17B060003) for their financial support for this work.
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