Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

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Journal of Analytical and Applied Pyrolysis

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Parametric study of the catalytic fast pyrolysis of rice husk over hierarchical
micro-mesoporous composite catalyst in a microwave-heated fluidized bed
Zhaoying Li a, b, Zhaoping Zhong a, *, Bo Zhang a, Wei Wang a, Hao Zhao a, Haoxi Ben b
a
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, 210096, China
b
State Key Lab Biofibers & Ecotext, College of Mechanical and Electrical Engineering, Qingdao University, Qingdao, 266071, China

A R T I C L E I N F O A B S T R A C T

Keywords: To improve the efficiency of the catalyst fast pyrolysis (CFP) of rice husk and the quality of bio-oil, we integrate
Microwave-heated fluidized bed both microwave heating and fluidized bed reactor methods and build a microwave-heated fluidized bed system.
Hierarchical micro-mesoporous catalyst In this study, the liquid yield from the CFP of rice husk in a microwave-heated fluidized bed (55.3 wt.%) is
Upgrading bio-oil
significantly higher than that obtained from a fixed bed (47.6 wt.%). Meanwhile, the relative content of hy­
Ratio of biomass to catalyst
Catalyst regeneration test
drocarbons from microwave assisted catalytic fast pyrolysis (MACFP) of rice husk (RH) over a hierarchical micro-
mesoporous composite molecular sieve (HM-2.0 T) is 67.6 % higher than that (51.6 %) of the organic base
modified HZSM-5 (HT-2.0) and HZSM-5 (40.2 %) in the microwave-heated fluidized bed system. Furthermore,
we focused on the ratio of biomass to catalyst in CFP processing and discover that the increased amount of
catalyst promoted the decarbonylation and decarboxylation reactions, producing more hydrocarbon compounds,
however, the excessive amount of catalyst does not contribution to higher monocyclic aromatic hydrocarbon
selectivity. Besides, the hierarchical micro-mesoporous composite catalyst had strong regeneration ability and
reusability. The selectivity of monocyclic aromatics remained high when the regeneration times increase from 1
to 4, which provided possibilities for applications of hierarchical micro-mesoporous composite catalyst in in­
dustrial production in the future.

1. Introduction heat-absorbing material, for example, silicon carbon (SiC), which ab­
sorbs heat and then transfers it to the biomass [7]. Undri et al. [8]
Fast pyrolysis is a typical chemical recycling method that has been studied the effects of different operating conditions on the products of
widely used in the conversion of biomass [1,2]. However, conventional microwave heating pyrolysis of waste tires, and found that compared
pyrolysis methods such as electric heating are characterized by low with traditional heating, microwave heating promotes the rapid reaction
heating efficiency, long pyrolysis time, slow heating rates, and low of the reactants. Wang et al. [9] compared microwave asssited catalytic
product quality [3]. The new method of catalytic fast pyrolysis by mi­ fast pyrolysis and catalytic fast pyrolysis of agricultural waste, and
crowave heating quickly heats the biomass to the required temperature demonstrated that MACFP reduced the coke contents in the products
for the reaction and overcomes the shortcomings of the conventional and improved the quality of the bio-oil. Various studies of
catalytic fast pyrolysis (CFP) method. Moreover, heat absorbents microwave-assisted catalytic fast pyrolysis are performed in a fixed bed
improve the heating and reaction characteristics for microwave-assisted [5,10,11], however, the microwave fixed-bed reactor also has the dis­
catalytic fast pyrolysis (MACFP) [4,5]. The MACFP method involves two advantages of feed discontinuity, simple structure, slow heating and
mechanisms that take place simultaneously: the first one involves heat poor heat transfer effect, which is unfavorable for the catalytic fast py­
penetrating the sample and causing the interior molecules of the rolysis of biomass for high-quality bio-oil production, large-scale pro­
biomass to vibrate, generating heat. However, lignocellulosic biomass is duction and industrial applications.
characterized by a low dielectric loss factor, meaning that these mate­ The fluidized bed reactor technology is well-developed and widely
rials are not effective in converting incident microwave energy into heat used in chemical, energy, biological and other fields. Martniez et al. [12]
[6]. To promote more efficient heat transfer, exogenous microwave compared the difference in catalytic fast pyrolysis of biomass in the fixed
absorbents can be used. The second method involves the use of a bed of bed and fluidized bed reactors, they found that the use of fluidized bed

* Corresponding author.
E-mail address: zzhong@seu.edu.cn (Z. Zhong).

https://doi.org/10.1016/j.jaap.2021.105210
Received 22 December 2020; Received in revised form 16 May 2021; Accepted 17 May 2021
Available online 12 June 2021
0165-2370/© 2021 Elsevier B.V. All rights reserved.
Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

reactors had a higher liquid phase yield. Wang et al. [13] conducted a mass fractions of cetyltrimethylammonium bromide (CTAB) solution
catalytic fast pyrolysis of bamboo and wood over MgO and HZSM-5 (125 mL) (the template for producing MCM-41) were added into the
catalysts in a bubbling fluidized bed and fixed-bed series reactor. The above solution (one at a time) and stirred for 60 min. The obtained so­
relative content of acids (2.44 %), furans (10.87 %) and ketones (4.51 lution was placed in an autoclave with poly tetra fluoroethylene (PTFE)
%) was kept at minimum level, and the relative content of aromatic lining and digested at a set temperature (110 ◦ C) for 24 h to complete the
hydrocarbons reached the maximum value (24.67 %) in the bubbling first step of the catalyst synthesis. After autoclaving, the samples were
fluidized bed. The advantages of fluidized beds are as follows: (1) full cooled down and the pH was adjusted to a value of 8.5. Then, the
contact of fluidizing gas, raw materials and bed materials leads to high samples were placed in autoclave with PTFE lining at 110 ◦ C crystalli­
heat transfer efficiency; (2) the uniformly mixed gas-solid fluidized bed zation temperature for 24 h. After crystallization, the solution was
has large thermal inertia, which easily controls the temperature pa­ filtered, washed, and dried to obtain a white powder which was calcined
rameters; (3) the residence time of pyrolysis products in the bed can be in air at 550 ◦ C for 6 h. The name of the hierarchical micro-mesoporous
controlled and effectively reduce the secondary pyrolysis oil within a composite catalyst is HM-2.0T.
certain range; (4) particles with fluid-like characteristics are continu­ The alkali-treated HZSM-5 has also been reported in our previous
ously fed through the feeding system, and the reactor has a large pro­ work [17]. Samples containing 10.0 g of HZSM-5 catalyst (Si/Al = 27)
cessing capacity [14,15]. However, in the process of biomass CFP in a were alkali-treated with 2.0 mol/L of TPAOH solution (100 mL) under
fluidized bed, there are obvious shortcomings such as the easy coking of agitation at 40 ◦ C for 60 min. Then, the solution was filtrated, washed
materials, incomplete pyrolysis of biomass and the agglomeration and and dried. The obtained solid sample was calcined in open air at 550 ◦ C
sintering of particles causing hot spots in the reactor. for 5 h. The catalyst was named HT-2.0. In addition, the catalyst char­
In previous studies, we prepared a hierarchical micro-mesoporous acterization of HM-2.0 T and HT-2.0 were published in our previous
composite catalyst, which was a combination of organic alkali treat­ works [16,17].
ment and the generation of an external layer of MCM-41-type meso­
porous channels [16]. The hierarchical micro-mesoporous composite 2.3. Experimental apparatus and procedure
catalyst has a “core-shell” structure, in which HZSM-5 is modified by
tetrapropylammonium hydroxide (TPAOH) as the core, and MCM-41 is Fig. 1 shows the MACFP fluidized bed system. For each experiment,
the shell. We assessed the effect of several catalyst synthesis parameters 20 g of RH was placed in the double-stage screw feeder, and the material
during the microwave-assisted catalytic fast pyrolysis of rice husk (RH). in the silo is fed at a fixed rate of the first-stage screw feeder. Addi­
The results showed that the best treatment conditions caused the highest tionally, the speed of the second-stage feeding rod is greater than the
hydrocarbon yields (60.5 %) from MACFP [17]. The hierarchical first-stage rod to prevent coking and blockage and realize fast feeding.
micro-mesoporous composite catalyst demonstrated excellent hydro­ Then, 100 g of SiC particles were placed in the quartz fluidized bed
carbon selectivity, however, the reusability of this catalyst is not reactor with an diameter of 32 mm and a height of 400 mm and used as
explored. microwave absorbent fluidized bed. The carrier gas of nitrogen (99.999
By combining the microwave-assisted heating and fluidized bed %) was the carrier gas, and pre-heated to 275 ◦ C prior to the microwave
methods, we designed and built a microwave-heated fluidized bed sys­ oven. Moreover, the water cooling device of the feed inlet and water
tem, and this paper offers an in-depth understanding of the difference circulation pump of the water condensation system was turned on. Then,
between in CFP of RH in a micro-heated fluidized bed as well as in a opening the nitrogen valve and adjusting the float flowmeter to control
micro-heated fixed bed and finally to improve the efficiency of the CFP the gas speed and ensure the normal fluidization of the material for 30
of biomass and bio-oil quality. Subsequently, the pyrolysis characteris­ min. The microwave oven has a maximum power of 1500 W and fre­
tics of different catalysts and different biomass and catalyst ratios are quency 2.45 GHz. When the temperature reached the desired value (550
analyzed, and then the yields of gas, liquid and solid phase products ◦
C), the biomass and catalysts were fed into the quartz reactor. The ratio
obtained under a series of experimental conditions are explored. of biomass to catalyst mass is 3:1, 2:1, 1:1, 1:2, and 1:3 respectively. The
Furthermore, based on various preparation conditions on the hierar­ condensing system adopted two-stage condensing, which was composed
chical micro-mesoporous composite catalyst in the previous work, we of condensing tube and liquid collecting bottle. The primary pyrolysis
performed a regeneration test on the hierarchical micro-mesoporous vapors flowed through the condensers, which were immersed in ice
composite catalyst to investigate its anti-coking properties, suggesting water (0− 5 ◦ C). The liquid products were then collected from the col­
possibilities for applications in industrial production. lector bottles connected to the bottom of the condensers. In this setup, a
pulse width modulation (PWM) was used to control the microwave oven
2. Materials and methods heater, and the temperature was maintained at the set point by turning
on and off every 10 s. A microwave detector (JHF-3S-RL) was used to
2.1. Materials monitor microwave leakage for safety reasons.

A sample of RH was collected from Suzhou, Jiangsu province, China. 2.4. Analysis of pyrolysis products
Before the experiments, we dried the sample at 105 ◦ C for 24 h, and then
ground it mechanically to pass a 60 mesh screen (250 μm). The ultimate Liquid products were collected in the collectors, and analyzed by gas
analysis results for RH (dry basis) indicate 40.5 wt.% carbon, 0.9 wt.% chromatography-mass spectrometry (GC–MS), in which the high-purity
nitrogen, 5.7 wt.% hydrogen, and 36.5 wt.% oxygen. The proximate helium was used as carrier gas (1 mL/min). We used a DB-5MS (0.25 mm
analysis and higher heating value (HHV) of RH (dry basis) results show × 0.25 um ×30 m) capillary column in the GC separation. The chro­
16.4 wt.% ash, 16.5 wt.% fixed carbon, 67.1 wt.% volatile matter and matographic peaks were identified with reference to the National
16.2 MJ/kg HHV. We purchased the silicon carbide (SiC) with the par­ Institute of Standards and Technology (NIST) MS library database and
ticle size of 1.18 mm from Zhejiang Doudou Limited Company. other literature data [18–20]. Proceeding this way, the material
composition of the vapors was obtained. In this study, we focused on the
2.2. Catalyst preparation analysis of aromatic hydrocarbons in the liquid product.

The hierarchical micro-mesoporous composite catalyst preparation 2.5. Data processing

has been reported in our previous work [16]. Samples containing 10.0 g
of HZSM-5 catalyst (Si/Al = 27) were alkali-treated with 2.0 mol/L of After each experiment, we accounted for liquids from the collectors
TPAOH solution (100 mL) under agitation at 40 ◦ C for 60 min. 20 wt.% and the liquids that adhered to the interior walls of the tubing of the

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Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

Fig. 1. Diagram of microwave-assisted catalytic fast pyrolysis fluidized bed system: (1)Nitrogen cylinder; (2) double-stage screw feeder; (3) pre-heater; (4) mi­
crowave oven (Makewave Co. Ltd, Qingdao); (5) quartz fluidized bed reactor; (6) catalyst inlet; (7) dust removal screen; (8) condensation system; (9) thermocouple.

Liquid yield = (wt. of liquid/wt. total feed) × 100 % (2)

condenser system by weighing all components before and after the re­
action. In addition, the solid residue was carefully collected from the Gas yield = 100 % - Solid yield - Liquid yield (3)
reactor after completion of the reaction. The gas yield was determined
by the difference according to the mass balance. The solid, liquid and gas The SiC, catalyst and the char and coke generated during the ex­
yields were calculated using following equations: periments have different particle sizes and densities. Screens with
different diameters were used to separate SiC from the other solids. The
Solid yield = (wt. of solid/wt. total feed) × 100 % (1) solid samples were dried at 120 ◦ C for 2 h in air, and then the dried
catalysts were placed in the muffle oven and combusted for 2 h at 650 ◦ C

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Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

to burn the coke which was quantified by subtracting the catalyst mass
before and after the procedure describe. The formula was as follows:
mu − mb
Ycoke = × 100% (4)
mb

Where mu is the mass of the coked catalysts after drying at 120 ◦ C, mb is

the mass of the coked catalysts after combustion.
The relative content of each aromatic hydrocarbon in the liquid
product was determined by calculating the area percentages of the
chromatograph peaks, following the equation:
Pi
Rcontent = (5)
Ptotal

Where Pi is the peak area of certain identified products, and Ptotal is the
total peak area under a certain condition.
In some cases, the catalysts used in MACFP were employed in reus­
ability experiments. To test the novel catalyst reusability, the used cat­
alysts were dried at 120 ◦ C for 2 h in air after every runs. Then, the dried
catalysts were placed in the muffle oven and combusted for 4 h at 550 ◦ C
to burn the coke prior to reuse. The name of catalysts were HM-2.0T-1,
HM-2.0T-2, HM-2.0T-3 and HM-2.0T-4 with regeneration times. Addi­
tionally, in this study, each experiment is repeated at least three times
under the same conditions in order to generate average values and
standard deviations (±0.5).

3. Results and discussion

3.1. Comparative study on the CFP of RH in a microwave-heated

fluidized bed and a fixed bed

Fig. 2a shows the three-phase yield of MACFP of RH using a

microwave-heated fixed bed and a fluidized bed at 550 ◦ C. The liquid
phase yield using the microwave-heated fluidized bed has significantly
increased from 47.6 wt.% to 55.3 wt.%. Cai et al. [21] studied that a
lab-scale catalytic pyrolysis unit was designed and manufactured with a
fluidized bed reactor, and the highest bio-oil yield was 46.9 wt% at 500
◦
C in catalytic pyrolysis process, which is lower than this study. More­
over, the solid phase yield and gas phase yield show a downward trend,
and their values decrease from 28.3 wt.% and 24.1 wt.% to 23.5 wt.%
and 21.2 wt.%, respectively. The reason for this phenomenon is that the
fluidized gas, RH and SiC are fully contacted in the microwave-heated
fluidized bed, which increases the heat transfer efficiency and makes
the temperature increase more quickly than those in the
microwave-heated fixed bed. In addition, the pyrolysis products remain
in the bed for a short time, which effectively reduces the secondary
cracking of the pyrolysis oil, and significantly increases the liquid phase
yield of the bio-oil. The individual compound of each chemical group are
listed in the Table 1. As depicted in Fig. 2b, the relative content of hy­
drocarbons (67.6 %) from MACFP of RH using a microwave-heated
fluidized bed is significantly higher than that from a (60.5 %)
microwave-heated fixed bed. Additionally, the relative contents of
oxygenated compounds, including acids, ketones, alcohols, phenols,
lipids and aldehydes, decrease to varying degrees. Compared to the
microwave-heated fixed bed, the SiC in the fluidized state with micro­
wave heating has better contact biomass and catalyst to achieve a higher
heat transfer effect. Therefore, the biomass undergoes a more fully Fig. 2. Comparison of the catalytic fast pyrolysis of rice husk in microwave-
heated fluidized bed and a fixed bed: (a) product yields; (b) product distribu­
hydrodeoxygenation reaction, which improves the bio-oil quality. The
tions; (c) selectivity of aromatic hydrocarbons (MAHs: monocyclic aromatic
decreasing trend of the relative content of oxygenated compounds il­
hydrocarbons).
lustrates the progress of the secondary cracking reactions such as
deoxygenation, aromatization, reforming and condensation, which
microwave-heated fluidized bed are mainly monocyclic aromatic hy­
remove oxygen atoms by breaking the C–O bond in oxygenated com­
pounds. Accordingly, the gas yield from CFP of biomass in the drocarbons and higher than those from the fixed bed, including benzene
(9.4 % vs. 8.3 %), toluene (14.6 % vs. 12.7 %), C8 hydrocarbon com­
microwave-heated fluidized bed is lower than that from the fixed bed
because of the second cracking of bio-oil. pounds (mainly ethylbenzene and xylene, 15.3 % vs. 12.8 %) and C9
hydrocarbon compounds (7.1 % vs. 6%). However, PAHs show the
In Fig. 2c, the relative contents of hydrocarbon products from the
opposite trend. The relative content of PAHs from the microwave-heated

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Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

Table 1 fluidized bed demonstrates little difference in the three-phase yield at a

Compounds identified by GC–MS: Bio-oil from catalytic fast pyrolysis of rice pyrolysis temperature of 550 ◦ C. As pictured in Fig. 3a, the liquid yields
husk in microwave-heated fluidized bed and a fixed bed. from MACFP of RH over different catalysts are approximately 55 wt.%,
Fixed bed Fluidized bed however, the solid yields have an opposite trend, owning the values of
Name Molecular Relative Relative 23.7 wt.% (HZSM-5), 22.2 wt.% (HT-2.0) and 21.2 wt.% (HM-2.0 T).
formula content (%) content (%) This result may be attributed to the high acidity and the pore size of
Acids 2.8 1.9 micropores of the HZSM-5, which promote polymerization of smaller
acetic acid C2H4O2 1.5 0.9 hydrocarbon molecules to form coke. Conversely, the MCM-41 cracks
propanoic acid C3H6O2 0.9 0.7
the macromolecular compounds to small molecules. The lower total
6-nonenoic acid C9H16O2 0.4 0.3
Ketones 2.8 2.1 acidity of the hierarchical catalytic system inhibited coke formation
2-butanone C4H8O 0.8 0.5 [23]. Liu et al. [24] found that the major production of steam reforming
1-hydroxy-2-propanone C3H6O2 1.3 1.1 of in-situ tar is phenol and phenol, 3-methyl on CFP of rice husk with and
2-hydroxy-2-cyclopenten-1- C5H6O2 0.7 0.5 without MCM-41 supported LaNiO3 catalyst in a double fixed-bed sys­
one, 2-hyd
tem. In addition, the reforming and cracking of pyrolysis volatiles are
Alcohols 4.2 3.8
4-methyl-, trans- C7H14O 3.1 2.9 promoted by the synergy between the MCM-41 and the HZSM-5 in the
cyclohexanol hierarchical catalyst, leading to a higher gas yield (23.5 wt. %)
2,4-dimethyl-cyclohexanol C8H16O 0.7 0.6 compared to HZSM-5 (21.4 wt. %) and HT-2.0 (22.6 wt. %).
2,4-hexadien-1-ol C6H10O 0.4 0.3
Furthermore, the product distribution in bio-oil greatly varies, and
Phenols 4.4 3.5
phenol C6H6O 0.7 0.6 the mesoporous composite molecular sieve shows excellent catalytic
4-methyl-phenol C7H8O 1.1 1.0 activity. HZSM-5 in the mesoporous composite catalyst promotes the
2-methoxy-phenol C7H8O2 0.8 0.6 separation of certain active groups in the biomass lignin component,
2-methoxy-4-methyl- C8H10O2 0.7 0.5 such as phenolic hydroxyl and methoxy groups, which reduces the
phenol
repolymerization reaction caused by these active groups, and further
4-ethyl-2-methoxy-phenol C9H12O2 0.6 0.4
2-methoxy-4-(1-propenyl)- C10H12O2 0.5 0.4 improves the pyrolysis conversion rate. Therefore, the relative content
phenol
Ester 4.8 3.6
ethyl Acetate C4H8O2 4.8 3.6
Aldehydes 12.6 10.2
formaldehyde CH2O 3.7 3.2
butanedial C4H6O2 4.9 3.8
heptanal C7H14O 4.0 3.2
Hydrocarbons 60.5 67.6
benzene C6H6 8.3 9.4
toluene C7H8 12.7 14.6
ethylbenzene C8H10 3.4 3.6
xylene C8H10 9.3 11.7
benzene, 1-ethyl-3-methyl- C9H12 4.1 4.8
benzene, 1,2,3-trimethyl- C9H12 2.9 2.3
Indane C9H10 7.4 6.9
benzene,(1-methyl-2- C10H10 3.5 4.7
cyclopropen-1-yl)-
benzene, 1,3-diethyl- C10H14 1.1 2.6
benzene,(1,1-dimethyl-2- C11H14 0.9 2.1
propenyl)-
Naphthalene C10H8 5.4 3.5
Anthracene C14H10 2.5 1.8
Other Oxygenates 4.3 3.9
Other Substances 3.6 3.4

fluidized bed pyrolysis system is 4.9 % and is lower than that of the fixed
bed, which is 7.9 %. It is probably that it is easier to crack large mole­
cules into small molecules in the fluidized state [15]. The coking resis­
tance of the catalyst in the microwave-heated fluidized bed pyrolysis
system, catalytic activity and service life are improved, which will be
described in detail in Section 3.4. The relative content of furfurals from
MACFP of RH in microwave-heated fluidized bed decreases from 12.6%
to 10.2% because hemicellulose is catalyzed and cracked into xylose,
which is subsequently converted into furfural through dehydration.
Moreover, the furfual catalytic pyrolysis cracks to produce furan and
dimethylfuran through Diels-Alder cyclization [22]. In the
microwave-heated fluidized bed pyrolysis system, the biomass is more
prone to Diels-Alder reaction, dehydration, dehydroxylation, decar­
boxylation and other reactions, which improves the quality of bio-oil
from MACFP of RH.

3.2. Effect of different catalysts on the CFP of RH in a microwave-heated

fluidized bed Fig. 3. MACFP of rice husk over different catalysts in a microwave-heated
fluidized bed systeam: (a) products distribution; (b) selectivity of aromatic
The different catalysts used on the CFP of RH in a microwave-heated hydrocarbon.

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Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

of hydrocarbons from MACFP of RH over mesoporous composite mo­ effects on the selectivity of phenol. Therefore, the relative content of
lecular sieve (HM-2.0 T) is 67.6 % higher than that (51.6 %) of the phenols from MACFP of RH over HZSM-5(14.6 %) is higher than those
organic base modified HZSM-5 (HT-2.0) and HZSM-5 (40.2 %) in over HT-2.0 (12.7 %) and HM-2.0 T (3.5 %). Otherwise, the relative
Fig. 3a. In addition, the values of CFP of RH over HM-2.0 T in fluidized contents of other oxygenated compounds decrease to varying degrees.
bed are higher than those in the pyrolysis product using a microwave
fixed bed [16]. Compared with the results reported by Ding et al., cat­ 3.3. Effects of different ratios of RH to the catalyst on the catalytic fast
alytic fast pyrolysis process of rice husk over HZSM-5 modified with CaO pyrolysis in a microwave-heated fluidized bed
was carried out, the relative content of hydrocarbons was 45 % lower
than that of the hydrocarbons (67.6 %) mesoporous composite molec­ Fig. 4a exhibits the effect of the ratio of RH to catalyst on the three-
ular sieve catalyst products prepared in this study [25]. In the researches phase yield (the ratio is 3:1, 2:1, 1:1, 1:2 and 1:3), where the catalytic
of Wang et al. [26], the highest bio-oil yield obtained CFP of rice husk pyrolysis temperature is 550 ◦ C. When the ratio of the catalyst increases,
over MCM-41 at microwave-assisted pyrolysis system was about 27 wt. the liquid phase yield first increases to 55.3 wt.% (the ratio from 3:1 to
%, additionally, the contents of carboxylic acids (10.75 %) and furans 1:1), and subsequently remains stable (the ratio from 1:1 to 1:3). The gas
(18.38 %) were more higher, and the content of phenolic compounds yield has an identical trend to the liquid yield, and the value increases
(36.84 %) was the highest. The mesoporous composite molecular sieve from 21.3 wt.% to 25.8 wt.% (the ratio from 3:1 to 1:2) and subsequently
exhibits excellent catalytic activity in the microwave-heated fluidized remains stable (the ratio from 1:2 to 1:3). The solid yield first decreases
bed, especially for the formation of hydrocarbons. and subsequently remains basically unchanged. When the ratio of
Compared with the other two catalysts, HM-2.0 T has two ways to biomass to catalyst changes from 3:1 to 1:2, the value decreases from
produce monocyclic aromatic hydrocarbons. On one hand, the C–O and 30.4 wt.% to 19.9 wt.% because of that the increased catalysts have a
CC– bonds of large intermediates (e.g., guaiacol) are broken at the greater chance of contacting with biomass and then more condensable
acidic sites of zeolite with a series of reactions (for example, dehydra­ volatiles convert into uncondensable gas products. In addition, larger
tion, decarboxylation, dealkylation, cleavage, isomerization and oligo­ number of catalysts increase the secondary pyrolysis in catalytic fast
merization) [27]. On the other hand, the small olefin fragments pyrolysis processing and produce more gas phase products [32]. While
decomposed from the aliphatic linker of lignin are converted into when the ratio of biomass is too high, more coke will be produced and
monocyclic aromatic hydrocarbons by aromatization on the catalyti­ attached to the catalyst, which causes the catalyst to deactivate.
cally active sites of HZSM-5, which is the mesoporous composite mo­
lecular sieve core [28]. Fig. 3b shows the selectivity of hydrocarbon
aromatics from CFP of RH over different catalysts in a microwave-heated
fluidized bed. The selectivity of the mesoporous composite molecular
sieve catalyst (HM-2.0 T) to monocyclic aromatics is significantly higher
than that of organic alkali-modified catalysts (HT-2.0) and HZSM-5. The
selectivity of benzene is 9.4 % (HM-2.0 T), 6.6 % (HT-2.0) and 5.5 %
(HZSM-5); the selectivity of ethylbenzene is 14.6 % (HM-2.0 T), 10.7 %
(HT-2.0) and 6.3 % (HZSM-5); the selectivity of C8 hydrocarbon com­
pounds are 15.3 % (HM-2.0 T), 11.1 % (HT-2.0) and 8.4 % (HZSM-5);
the selectivity of C9 hydrocarbon compounds are 7.1 % (HM-2.0 T), 6.4
% (HT-2.0) and 5.1 % (HZSM-5); the selectivity of other monocyclic
aromatic hydrocarbons are 16.3 % (HM-2.0 T), 11.4 % (HT-2.0) and 8.3
% (HZSM-5), respectively.
However, because of the mesoporous structure on the catalyst, the
selectivity for polycyclic aromatic hydrocarbons using HT-2.0 (5.4 %)
and HM-2.0 T (4.9 %) is lower than that using HZSM-5 (6.9 %). The
moderate pore size of the MCM-41 facilitates the diffusion of macro­
molecular substances generated by biomass pyrolysis. Furthermore,
macromolecular substances are cracked into small molecular substances
in the mesoporous pores of MCM-41, however, the weak acidity of
MCM-41 leads to poor deoxidation of the volatiles [29]. In contrast, the
microporous structure of HZSM-5 is conducive to deoxygenation re­
actions, such as dehydration, decarbonylation, and decarboxylation, of
the pyrolysis vapors. Macromolecular substances do not easily enter
HZSM-5 micropores, causing generation of coke on the surface. The
formation of coke restricts the diffusion of reactants and products,
leading to pore blockage and subsequent deactivation of the catalyst.
The hierarchical HZSM-5/MCM-41 catalyst used in the present work has
a regular and orderly MCM-41 shell on the surface of HZSM-5 modified
by an organic alkali solution (TAPOH). Qiu et al. [30] researched the
effects of different biochar catalysts on the quality of bio-oil derived
from co-pyrolysis of sewage sludge and rice husk. The relative content of
monocyclic aromatic hydrocarbons increased due to the addition of the
bio-char catalyst, and reached the 30.87 % and 33.39 % used sewage
sludge biochar and rice husk biochar, which is lower than those from
HM-2.0 T (62.7 %). In addition, phenols, such as phenol and cresol,
which are the main components of oxygenated compounds, are mainly
produced by the deoxygenation of lignin aromatic units. The production
of phenols is probably related to the acidic sites of the catalyst [31]. Fig. 4. Effects of different ratios of rice husk to the catalyst on the CFP in
Compared with the parent zeolite HZSM-5, the alkali treatment has microwave-heated fluidized bed: (a) product yields; (b) product distributions.

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Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

However, when the ratio of biomass is low, the macromolecular volatiles microwave-heated fluidized bed system significantly increases from 4.2
will be decomposed into smaller molecules, which would not deposited % (R:C = 3:1) to 9.4 % (R:C = 1:1) and 6.7 % (B:C = 3:1) to 15.3 % (B:C
on the catalyst. = 1:1), respectively. When the amount of catalyst increases, toluene
The distribution of pyrolysis products under different ratios of RH to increases from 6.2 % (B:C = 3:1) to 15.2 % (B:C = 1:2), and the increased
catalyst (R:C) is shown in Fig. 4b. The relative content of oxygenates is catalyst played an important role in promoting the decarbonylation and
59.6 % at an RH-to-catalyst ratio of 3:1. Moreover, when the ratio of decarboxylation reactions and producing more hydrocarbon com­
biomass decreases, the relative content of oxygenated compounds in the pounds. Compared to monocyclic aromatic hydrocarbons, the relative
pyrolysis products decreases: when the ratio is 2:1, 1:1, 1:2 and 1:3, content of polycyclic aromatic hydrocarbons shows the opposite trend,
respectively, the relative content of oxygenated compounds is 45.2 %, and the value decreases from 11.2 % (B:C = 3:1) to 4.9 % (B:C = 1:1).
32.4 %, 29.8 % and 29.6 %, respectively. This is principally because the The increasing ratio of biomass to catalyst lead to the relative content of
hierarchical micro-mesoporous composite catalyst (HM-2.0 T) has a HZSM-5 increase, which promotes the separation of phenolic hydroxyl
sufficient amount of pores for catalysis and excellent shape selectivity and methoxy active groups in lignin, thereby reducing the repolymeri­
effect. The proportion of aromatic hydrocarbons in the products is much zation caused by these active groups and further improving the pyrolysis
higher than that of oxygenated compounds. Even if part of the catalysts conversion rate [34]. Basically, the increase of MCM-41 in the hierar­
is deactivated after the catalysis process, there are still a sufficient chical micro-mesoporous composite catalyst is also conducive to the
amount of normal catalyst to catalyze the remaining reactants. How­ depolymerization of macromolecular substances. Above all, the addition
ever, the relative content of hydrocarbons increases from 40.4 % to 70.2 of too much catalyst does not lead to higher monocyclic aromatic hy­
% with increasing of the catalyst ratio from 3:1 to 1:1. When the pro­ drocarbon selectivity.
portion of biomass increases, the coking intermediate o-methylene
quinone produced during the catalysis process increases, and further 3.4. Regeneration test of the hierarchical micro-mesoporous composite
polymerize to form macromolecules leading to deactivate the catalyst catalyst in a microwave-heated fluidized bed system
[33]. Additionally, the relative content of hydrocarbons slightly changes
when the ratio of RH to catalyst decreases from 1:1 to 1:3 in Fig. 4b. In The three-phase yield of the regeneration test of MACFP of RH over
this process, the pyrolysis gas first enters the MCM-41 layer of the hi­ the hierarchical micro-mesoporous composite catalyst in a microwave
erarchical micro-mesoporous composite catalyst to form carbonyl fluidized bed system is shown in Fig. 6a. The liquid yield slightly in­
compounds and other small molecules through decarboxylation and creases from 55.3 wt.% to 60.4 wt.% with the increase in the number of
dehydroxylation; then, small molecular compounds enter the HZSM-5 regenerations. Specifically, the first three cycles have a similar liquid
core of the hierarchical composite catalyst for further deoxygenation yield to the parent HM-2.0 T (approximately 55.9 wt.%), but the fourth
and aromatization to form hydrocarbons. In addition, increasing the cycle has slightly higher yield (60.4 wt.%) than the previous three cycles
catalyst did not achieve a better deoxidation effect when the catalyst and parent catalyst. It is generally believed that the increase in pyrolysis
ratio reached 1:2. oil yield is an important reaction indicator for the decrease of the overall
As Fig. 5 shows, the selectivity of benzene and C8 hydrocarbon activity of the catalyst when other conditions are unchanged, indicating
compounds (ethylbenzene and xylene) from MACFP of RH in the that the activity of the catalyst has decreased after regeneration [35]. In

Fig. 5. Selectivity of aromatic hydrocarbons from MACFP of different ratios of rice husk to catalyst: (a) benzene; (b) toluene; (c) C8 compounds and (d) PAHs.

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Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

the gas yield gradually decreases from 23.5 wt.% to 10.2 wt.% when the
regeneration times increase from 0 to 4.
The distribution of pyrolysis products of RH using different regen­
eration catalysts in a microwave fluidized bed is shown in Fig. 6b. The
relative content of hydrocarbons shows a downward trend when the
number of regenerations increases (from 0 to 4), and the values change
from 67.6% to 65.1%, 62.7 %, 60.4 % and 58.3 %. However, acids,
ketones, alcohols, phenols, esters and aldehydes show an upward trend:
they increase from 1.9 %, 2.1 %, 3.8 %, 3.5 %, 3.6 % and 10.2% to 3.3%,
3.3 %, 5.4 %, 4.8 %, 5.1 % and 10.9 %, respectively. In the first (65.1 %)
and second (62.7 %) regeneration tests, the selectivity for hydrocarbons
was higher than that of the precoked HZSM-5 catalyst and regenerated
HZSM-5 catalyst (40.1 % and 33.2 %, respectively) in Zhang et al. [36].
Moreover, Bonnin et al. [37] performed that the balance between Lewis
(Zn) and Bronsted (H+) acid sites is a good descriptor for predicting the
catalyst stability on Zn/HZSM-5. Additionally, both poisoning and
dealumination of macromolecular chelates destroy the structure of
HZSM-5 and weaken the aromatization ability.
In this study, the catalytic activity slightly decreases with regener­
ation, i.e., a small amount of coke covered the external surface acidic
sites of the catalyst. However, when the number of regeneration tests
increases, the internal structure of the catalyst will be slightly damaged,
which increases the deposits of permanent carbon and slightly decreases
the catalytic activity of the catalyst. It can also be expressed in the
selectivity to aromatic compounds (see Fig. 7). On one hand, the
selectivity of PAHs increases when the number of regenerations in­
creases from 4.9 % to 8.6 %. On the other hand, the selectivity of
monocyclic aromatics gradually decreases with an increase of re­
generations. The selectivity of monocyclic aromatics reaches a high level
once and twice, but when there are 3 regenerations, the selectivity of
monocyclic aromatics is slightly reduced. Specifically, the relative
contents of benzene, toluene, ethylbenzene and xylene (C8 hydrocarbon
compounds) decrease from 9.4 %, 14.6 % and 15.3% to 9.1%, 13.8 %
and 14.9 % (1 time), 8.6 %, 12.3 % and 14.1 % (2 times), 7.3 %, 11.8 %
and 13.7 % (3 times) and 6.8 %, 11.3 % and 13.2 % (4 times), respec­
tively. Above all, the hierarchical micro-mesoporous composite catalyst
has strong regeneration ability and reusability, which provides the
possibilities for the large-scale applications.
Fig. 6. Effects of the hierarchical catalyst regeneration times on CFP in a
microwave-heated fluidized bed: (a) product yields; (b) product distributions. 4. Conclusion

addition, the solid phase yield of the catalyst remains basically un­ In this study, we firstly performed a microwave-heated fluidized bed
changed in the first three regeneration tests, and the fourth regeneration system for the CFP of RH over a hierarchical micro-mesoporous com­
has higher yield (4.5 wt. %) than the third regeneration. This phenom­ posite catalyst. Based on this system,
enon is related to an increase in coke content. With an increase in the
number of regenerations, the content of the hierarchical (1) We compared the difference between CFP of RH in the
micro-mesoporous composite catalyst coke increases from 4 wt.% to 5.7 microwave-heated fluidized bed and fixed bed. The pyrolysis
wt.% (see Table 2). We conclude that there are two for the coke for­ products remained in the microwave-heated fluidized reactor for
mation mechanisms. First, macromolecular oxygenated compounds a short time, which effectively reduces the secondary cracking of
from the primary pyrolysis gas experience condensation reactions at the the pyrolysis oil and significantly increases the yield of the bio-
acidic sites on the surface of the hierarchical micro-mesoporous com­ oil.
posite catalyst core HZSM-5. Second, further polymerization of small (2) The mesoporous composite molecular sieve exhibited excellent
molecule furan compounds, the generated olefins and aromatic com­ catalytic activity in the microwave-heated fluidized bed. Macro­
pounds are performed on the acidic sites of the HZSM-5 catalyst surface. molecular oxygenates underwent cracking and produced small
Nevertheless, after 4 regeneration cycles, the hierarchical molecules on MCM-41 channels, and then the cracked molecules
micro-mesoporous composite catalyst maintains relatively good coking diffuse through HZSM-5 structure, where they further reacted to
resistance, which promotes maintenance of the catalytic activity, and produce aromatic and aliphatic hydrocarbons by decarbon­
ylation, decarboxylation and aromatization.
(3) The increased amount of catalysts had a greater chance of con­
Table 2
tacting biomass, so more condensable volatiles converted into
Coke formation on regeneration test of hierarchical micro-mesoporous com­
uncondensable gas products. Additionally, more catalysts could
posite catalyst.
increase the secondary pyrolysis in catalytic fast pyrolysis pro­
HM- HM-2.0T- HM-2.0T- HM-2.0T- HM-2.0T- cessing and produce more gas phase products, meanwhile, the
2.0T 1 2 3 4
increase in catalyst promoted the decarbonylation and decar­
Coke yield (wt. 4 4.4 4.8 5.2 5.7 boxylation reactions, producing more hydrocarbon compounds.
%)

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Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

Fig. 7. Selectivity of aromatic hydrocarbons from CFP of different regeneration times hierarchical catalyst in microwave-heated fluidized bed: (a) benzene; (b)
toluene; (c) C8 compounds and (d) PAHs.

(4) The hierarchical micro-mesoporous composite catalyst had References

strong regeneration ability and reusability. The relative content
of hydrocarbons showed a slow downward trend when the [1] M.M. Rahman, R.H. Liu, J.M. Cai, Catalytic fast pyrolysis of biomass over zeolites
for high quality bio-oil - A review, Fuel Process. Technol. 180 (2018) 32–46.
number of regenerations increased. [2] X. Chen, Q.F. Che, S.J. Li, Z.H. Liu, H.P. Yang, Y.Q. Chen, X.H. Wang, J.G. Shao, H.
P. Chen, Recent developments in lignocellulosic biomass catalytic fast pyrolysis:
Overall, the microwave-heated fluidized bed system combined the strategies for the optimization of bio-oil quality and yield, Fuel Process. Technol.
196 (2019) 106180.
advantages of microwave heating and fluidized bed reactor and further [3] M.F. Yang, J.A. Shao, Z.X. Yang, H.P. Yang, X.H. Wang, Z.S. Wu, H.P. Chen,
improved the quality of bio-oil. The hierarchical catalyst adopted in this Conversion of lignin into light olefins and aromatics over Fe/ZSM-5 catalytic fast
work contained a moderate amount of mesopores structures, which pyrolysis: significance of Fe contents and temperature, J. Anal. Appl. Pyrolysis 137
(2019) 259–265.
allowed for effective upgrading of pyrolysis vapors and therefore, [4] K. Qiao, X. Shi, F. Zhou, H. Chen, J. Fu, H.X. Ma, H. Huang, Catalytic fast pyrolysis
addressed a significant problem in the development of the catalytic fast of cellulose in a microreactor system using hierarchical zsm-5 zeolites treated with
pyrolysis processes. various alkalis, Appl. Catal. A-Gen. 547 (2017) 274–282.
[5] S. Aravind, P.S. Kumar, N.S. Kumar, N. Siddarth, Conversion of green algal biomass
into bioenergy by pyrolysis. A review, Environ. Chem. Lett. 18 (2020) 829–849.
CRediT authorship contribution statement [6] H.W. Huang, S. Zhou, C. Yu, H. Huang, J. Zhao, L. Dai, J. Qiu, Rapid and energy-
efficient microwave pyrolysis for high-yield production of highly-active
bifunctional electrocatalysts for water splitting, Energy Environ. Sci. 13 (2020)
Zhaoying Li: Conceptualization, Methodology, Validation, Formal
545–553.
analysis, Writing - original draft, Writing - review & editing. Zhaoping [7] Q. Dong, H.J. Li, M.M. Niu, C.P. Luo, J.F. Zhang, B. Qi, X.Q. Li, W. Zhong,
Zhong: Conceptualization, Writing - review & editing, Supervision, Microwave pyrolysis of moso bamboo for syngas production and bio-oil upgrading
Project administration, Funding acquisition. Bo Zhang: Writing - review over bamboo-based biochar catalyst, Bioresour. Technol. 266 (2018) 284–290.
[8] A. Undri, S. Meini, L. Rosi, M. Frediani, P. Frediani, Microwave pyrolysis of
& editing, Project administration, Funding acquisition. Wei Wang: polymeric materials: waste tires treatment and characterization of the value-added
Validation, Formal analysis. Hao Zhao: Validation, Formal analysis. products, J. Anal. Appl. Pyrolysis 103 (2013) 149–158.
Haoxi Ben: Writing - review & editing. [9] Y.P. Wang, Z.H. Zeng, X.J. Tian, L.L. Dai, J. Ling, S.M. Zhang, Q.H. Wu, P.W. Wen,
G.M. Fu, Y.H. Liu, R. Ruan, Production of bio-oil from agricultural waste by using a
continuous fast microwave pyrolysis system, Bioresour. Technol. 269 (2018)
Declaration of Competing Interest 162–168.
[10] S.P. Zhang, Q. Dong, L. Zhang, Y.Q. Xiong, High quality syngas production from
microwave pyrolysis of rice husk with char-supported metallic catalysts, Bioresour.
The authors report no declarations of interest. Technol. 191 (2015) 17–23.
[11] S.S. Lam, W.A.W. Mahari, Y.S. Ok, W.X. Peng, C.T. Chong, N.L. Ma, H.A. Chase,
Z. Liew, S. Yusup, E.E. Kwon, D.C.W. Tsang, Microwave vacuum pyrolysis of waste
Acknowledgements plastic and used cooking oil for simultaneous waste reduction and sustainable
energy conversion: recovery of cleaner liquid fuel and techno-economic analysis,
This paper was sponsored by the National Natural Science Fund Renew. Sustain. Energy Rev. 115 (2019) 109359.
[12] J.D. Martínez, A. Veses, A.M. Mastral, R. Murillo, M.V. Navarro, N. Puy,
Program of China (51776042), the National Key R&D Program of China
A. Artigues, J. Bartroli, T. Garcia, Co-pyrolysis of biomass with waste tyres:
(2018YFB1501405) and the Scientific Research Foundation of Graduate upgrading of liquid bio-fuel, Fuel Process. Technol. 119 (2014) 263–271.
School of Southeast University (YBPY1904).

9
Z. Li et al. Journal of Analytical and Applied Pyrolysis 157 (2021) 105210

[13] J. Wang, Z.P. Zhong, K. Ding, A.D. Deng, N.J. Hao, X.Z. Meng, H.X. Ben, R. Ruan, [25] K. Ding, Z.P. Zhong, J. Wang, et al., Improving hydrocarbon yield from catalytic
A.J. Ragauskas, Catalytic fast pyrolysis of bamboo sawdust: synergistic effect of fast co-pyrolysis of hemicellulose and plastic in the dual-catalyst bed of CaO and
alkali metal oxides and HZSM-5 via a two-step bench scale bubbling fluidized bed/ HZSM-5, Bioresour. Technol. 261 (2018) 86–92.
fixed bed reactor, Energy Convers. Manage. 176 (2018) 287–298. [26] X.Y. Wang, X. Wang, G.X. Qin, M.Q. Chen, J. Wang, Microwave-assisted pyrolysis
[14] H.Y. Zhang, T.R. Carlson, R. Xiao, G.W. Huber, Catalytic fast pyrolysis of wood and of rice husk for bio-oil production, J. Biobased Mater. Bioenergy 13 (2020)
alcohol mixtures in a fluidized bed reactor, Green Chem. 14 (2012) 98–100. 144–148.
[15] B. Peterson, C. Engtrakul, T.J. Evans, K. Iisa, M.J. Watson, M.W. Jarvis, D. [27] X.Y. Li, L. Su, Y.J. Wang, Y.Q. Yu, C.W. Wang, X.L. Li, Z.H. Wang, Catalytic fast
J. Robichaud, C. Mukarakate, M.R. Nimlos, Optimization of biomass pyrolysis pyrolysis of Kraft lignin with HZSM-5 zeolite for producing aromatic hydrocarbons,
vapor upgrading using a laminar entrained-flow reactor system, Energy Fuels 34 Front. Environ. Sci. Eng. 6 (2012) 295–303.
(2020) 6030–6040. [28] K. Li, G. Zhang, Z.X. Wang, B. Hu, Q. Lu, Calcium formate assisted catalytic
[16] Z.Y. Li, Z.P. Zhong, B. Zhang, W. Wang, H. Zhao, G.V.S. Seufitelli, F.L.P. Resende, pyrolysis of pine for enhanced production of monocyclic aromatic hydrocarbons
Microwave-assisted catalytic fast pyrolysis of rice husk over a hierarchical HZSM- over bimetal-modified HZSM-5, Bioresour. Technol. 315 (2020) 123805.
5/MCM-41 catalyst prepared by organic base alkaline solutions, Sci. Total Environ. [29] J. Adam, M. Blazsó, E. Mészáros, M. Stöcker, M.H. Nilsen, A. Bouzga, J.E. Hustad,
750 (2021) 141215. M. Grønli, G. Øye, Pyrolysis of biomass in the presence of Al-MCM-41 type
[17] Z.Y. Li, Z.P. Zhong, B. Zhang, W. Wang, H. Zhao, G.V.S. Seufitelli, F.L.P. Resende, catalysts, Fuel 84 (2015) 1494–1502.
Effect of alkali-treated HZSM-5 zeolite on the production of aromatic hydrocarbons [30] Z.Z. Qiu, Y.B. Zhai, S.H. Li, X.M. Liu, X.P. Liu, B. Wang, Y.L. Liu, C.T. Li, Y.J. Hu,
from microwave assisted catalytic fast pyrolysis (MACFP) of rice husk, Sci. Total Catalytic co-pyrolysis of sewage sludge and rice husk over biochar catalyst: bio-oil
Environ. 703 (2020) 134605. upgrading and catalytic mechanism, Waste Manag. 114 (2020) 225–233.
[18] F. Sotoudehniakarani, A. Alayat, A.G. Mcdonald, Characterization and comparison [31] C.A. Mullen, A.A. Boateng, Catalytic pyrolysis-GC/MS of lignin from several
of pyrolysis products from fast pyrolysis of commercial Chlorella vulgaris and sources, Fuel Process. Technol. 91 (2010) 1446–1458.
cultivated microalgae, J. Anal. Appl. Pyrolysis 139 (2019) 258–273. [32] Y. Yang, Z.Y. Luo, S.M. Li, K.Y. Lu, W.B. Wang, Catalytic pyrolysis of hemicellulose
[19] G.X. Dai, S.R. Wang, S.Q. Huang, Q. Zou, Enhancement of aromatics production to produce aromatic hydrocarbons, BioResources 14 (2019) 5816–5831.
from catalytic pyrolysis of biomass over HZSM-5 modified by chemical liquid [33] R.G. Zou, Y.P. Wang, L. Jiang, Z.T. Yu, Y.F. Zhao, Q.H. Wu, L.L. Dai, L.Y. Ke, Y.
deposition, J. Anal. Appl. Pyrolysis 134 (2018) 439–445. H. Liu, R. Ruan, Microwave-assisted co-pyrolysis of lignin and waste oil catalyzed
[20] H.H. Wu, L. Wang, G.B. Ji, H.W. Lei, H. Qu, J. Chen, F.B. Wang, J. Liu, Renewable by hierarchical ZSM-5/MCM-41 catalyst to produce aromatic hydrocarbons,
production of nitrogen-containing compounds and hydrocarbons from catalytic Bioresour. Technol. 289 (2019) 121609.
microwave-assisted pyrolysis of chlorella over metal-doped HZSM-5 catalysts, [34] X.C. Xian, C. Ran, P. Yang, Y.R. Chu, S. Zhao, L.C. Dong, Effect of the acidity of
J. Anal. Appl. Pyrolysis 151 (2020) 104902. HZSM-5/MCM-41 hierarchical zeolite on its catalytic performance in supercritical
[21] W.F. Cai, D. Li, R.H. Liu, Catalytic fast pyrolysis of rice husk for bio-oil production, catalytic cracking of n-dodecane: experiments and mechanism, Catal. Sci. Technol.
Energy 154 (2018) 477–487. 8 (2018) 4241–4256.
[22] J. Liang, G.C. Shan, Y.F. Sun, Catalytic fast pyrolysis of lignocellulosic biomass: [35] L.L. Dai, Z.H. Zeng, Q. Yang, S. Yang, Y.P. Wang, Y.H. Liu, R. Ruan, C. He, Z.T. Yu,
critical role of zeolite catalysts, Renew. Sustain. Energy Rev. 139 (2021) 110707. L. Jiang, Synthesis of iron nanoparticles-based hydrochar catalyst for ex-situ
[23] Q.H. Wu, Y.P. Wang, Y.J. Peng, L.Y.Ke Y. Qi, J. Lin, L.L. Dai, Y.H. Liu, R. Ruan, D. catalytic microwave-assisted pyrolysis of lignocellulosic biomass to renewable
H. Xia, J. Li, Microwave-assisted pyrolysis of waste cooking oil for hydrocarbon phenols, Fuel 279 (2020) 118532.
bio-oil over metal oxides and HZSM-5 catalysts, Energy Convers. Manage. 220 [36] B. Zhang, Z.P. Zhong, X.B. Wang, K. Ding, Z.W. Song, Catalytic upgrading of fast
(2020) 113124. pyrolysis biomass vapors over fresh, spent and regenerated ZSM-5 zeolites, Fuel
[24] C.L. Liu, D. Chen, Y.G. Cao, T.X. Zhang, Y.Y. Mao, W.J. Wang, Z.G. Wang, S. Kawi, Process. Technol. 138 (2015) 430–434.
Catalytic steam reforming of in-situ tar from rice husk over MCM-41 supported [37] A. Bonnin, Y. Pouilloux, V. Coupard, D. Uzio, L. Pinard, Deactivation mechanism
LaNiO3 to produce hydrogen rich syngas, Renew. Energy 161 (2020) 408–418. and regeneration study of Zn/HZSM-5 catalyst in ethylene transformation, Appl.
Catal. A Gen. 611 (2021) 117976.

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