Energy 261 (2022) 125307

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Energy
journal homepage: www.elsevier.com/locate/energy

Enhancement of the production of aromatics and bio-syngas from

microwave ex-situ pyrolysis based on Zn/Zr modified biochar and
multi-catalysts
Xiaopeng Shi a, b, Pan Li a, b, d, *, Xianhua Wang c, Jiande Song b, Shuqi Fang a, b, Chun Chang a, b, d,
Shusheng Pang a, e
a
School of Mechanical and Power Engineering, Zhengzhou University, Zhengzhou, China
b
Henan Key Laboratory of Green Manufacturing of Biobased Chemicals, Puyang, China
c
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, China
d
State Key Laboratory of Motor Vehicle Biofuel Technology, Nanyang, China
e
Department of Chemical and Process Engineering, University of Canterbury, Christchurch, New Zealand

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

Keywords: The main purpose of this work was to explore the effect of metal modified biochar and multi-catalysts on
Microwave pyrolysis improving the quality of products by microwave pyrolysis (MVP) of biomass. Single-component catalysts and
Modified biochar multi-catalysts were prepared by Zn/Zr impregnation methods. The prepared catalysts were evaluated by XRD,
Multi-catalysts
BET, FT-IR and SEM. The properties, composition and product distribution of bio-oil and bio-syngas were
Aromatics
Bio-syngas
analyzed. The results showed that ZSM-5 obtained more bio-oil (42.16 wt%) at the expense of gas product yield,
and BC obtained the highest gas yield (43.10 wt%). Zn promoted the selectivity of aromatic hydrocarbons in bio-
oil, Zr could effectively improve the yield of syngas and upgrading bio-oil, respectively. Zr-modified multi-
catalyst was prepared, and the highest syngas yield (91.54 vol%) and aromatic hydrocarbon products were
obtained. Among them, the selectivity of monocyclic aromatic hydrocarbons (MAHs) reached 21.82%. The
mechanism of MVP of biomass under the effect of Zn/Zr modified different catalysts was proposed. The study has
successfully demonstrated an approach for producing high-value bio-oil and bio-syngas from microwave multi-
catalyst pyrolytic system.

1. Introduction energy into heat energy through the agitation of molecules in an elec­
tromagnetic field, and the generated heat diffuses from the inside of the
As the fourth largest energy source after coal, oil and natural gas in feedstock to the outside [6,7]. The internal temperature of the raw
the world, Biomass had attracted extensive attention due to its renew­ material was higher than the external temperature, forming a “hot spot”,
able and environment-friendly properties [1]. Through various thermal which was conducive to the escape of volatiles in the raw material and
conversion processes such as gasification and pyrolysis, biomass could improves the reaction efficiency [8]. Microwave heating was mainly
be converted into gaseous products for combustion/power generation or used for fast pyrolysis (heating rate>10–200 ◦ C/s, residence time
transportation fuels [2]. Conventional pyrolysis equipment mainly 0.5–10s, usually <2s), which could efficiently heat biomass, shorten the
applied external thermal energy to all substances in the equipment initial time of pyrolysis reaction, and has higher liquid yield [9,10].
cavity, including the gas around the pyrolysis volatiles and the reactor Huang et al. [11] pointed out that microwave heating is superior to
chamber itself [3,4]. The energy did not completely act on the raw conventional heating methods in terms of heating rate and efficiency.
materials that need to be heated, which leads to low effective utilization Compared with conventional pyrolysis methods, MVP did not signifi­
rate and large energy loss of the whole process [5]. Unlike electric cantly increase the yield of liquid products [12]. Limited by the raw
heating or combustion heating methods, microwave heating didn’t use material characteristics of the original biomass itself, liquid products
an external temperature field to heat biomass, but converts microwave had high oxygen content, low calorific value, complex and unstable

* Corresponding author. School of Mechanical and Power Engineering, Zhengzhou University, Zhengzhou, China.
E-mail addresses: lipan@zzu.edu.cn, lipanhust@163.com (P. Li).

https://doi.org/10.1016/j.energy.2022.125307
Received 15 May 2022; Received in revised form 24 August 2022; Accepted 25 August 2022
Available online 30 August 2022
0360-5442/© 2022 Elsevier Ltd. All rights reserved.
X. Shi et al. Energy 261 (2022) 125307

components, and requires catalytic upgrading of products [13,14]. Ac­ preparation of biochar, the pore structures of biochar of the same type
cording to the way the raw materials react with the catalyst, microwave and batch are also different to some extent. Whether biochar can be used
catalytic pyrolysis can be divided into in-situ and ex-situ catalytic py­ as a single catalyst carrier to have a continuous and stable catalytic ef­
rolysis. Compared with in-situ catalytic pyrolysis, ex-situ catalytic py­ fect still needs to be studied.
rolysis produces lower yields of bio-oil and higher aromatics selectivity, According to past research findings, there is still a lack of compara­
and ex-situ catalytic pyrolysis can obtain more syngas and less CO2 [15]. tive research on single-component catalysts and multi-catalysts under
And the catalyst was not easy to coke, which was conducive to recycling MVP. In this study, multi-catalysts were prepared for catalytic pyrolysis
and reuse [16]. effect mechanism and product properties. Considering the advantages of
Microwave had great advantages in accelerating the reaction rate different catalysts under microwave heating conditions, ZSM-5 zeolites
and increasing the product yield, but it was not capable of directional and char-based catalysts under different metal modifying conditions
enrichment of specific products, so adding suitable catalysts could were prepared, and bamboo was used as the raw material for pyrolysis.
greatly affect the efficiency and product selectivity of MVP [17]. The Firstly, the catalytic properties of two types of catalysts under different
main function of the catalyst is to deoxygenate the bio-oil during the metal modifying conditions were studied. And compared the catalytic
pyrolysis process and promote its further reactions such as decarboxyl­ performance difference between the single-component catalysts and the
ation, decarboxylation and dehydration [18]. ZSM-5 molecular sieve is a multi-catalysts. The possibility of co-production of high-value bio-oil
kind of microporous molecular sieve, which is widely used in the field of and bio-syngas with multi-component catalysts was explored. The
microwave catalytic pyrolysis due to its high selectivity to aromatic possible reaction mechanism of bamboo under the synergistic effect of
compounds [19]. Hong et al. [20] studied the effect of various MVP and multi-catalysts was speculated. The multi-catalyst could
metal-modified HZSM-5 on bio-oil components during pyrolysis, the realize the composite function of comprehensive microwave absorption
results showed that they can effectively reduce N content in bio-oil, and and high-activity catalytic conversion, realize the organic combination
Zn promotes the increase of hydrocarbons in bio-oil. Carbon deposition of microwave effect and catalyst, and promote the directional conver­
formed by aromatic carbon/graphite carbon, pyrrole and pyridine sion and enrichment of high-value products. The findings are envisaged
compounds leads to deactivation of the catalyst. Zheng et al. [21] to be useful for build up the microwave multi-catalytic pyrolysis system
summarized the reaction pathway of metal-modified HZSM-5 for of biomass for energy applications.
biomass pyrolysis upgrading to produce aromatic hydrocarbons.
Co-based catalysts had the highest selectivity to indene. Ni-based cata­ 2. Materials and methods
lysts could significantly improve the selectivity of benzene and C10+
polycyclic aromatic hydrocarbons (PAHs). Zn-ZSM-5 was the most 2.1. Experimental materials
efficient catalyst available for the production of aromatics. But there still
had several problems to solve such as the catalysts were prone to coking Bamboo was collected from local furniture factory (Zhengzhou,
and deactivation, low recycling rate, poor directional selectivity, and Henan Province, China) which used as raw materials for pyrolysis and
high cost. prepared for pyrolytic char. After received, the bamboo was dried at
In the biomass thermochemical conversion process, in addition to the 105 ◦ C for 24 h and ground to particles with particle size in the range of
gas produced by biomass gasification and the liquid fuel (ie bio-oil) 0.18–0.25 mm, and the silicon carbide (SiC) particles were sieved to a
produced by biomass pyrolysis, biochar was an important by-product particle size between 0.55 mm and 0.83 mm. Proximate analysis and
and it was also a potential catalyst, respectively. It could be used to ultimate analysis were then performed and the results were given in
upgrade bio-oil produced by pyrolysis and tar produced by catalytic Table 1. Proximate analysis was done according to the national standard
conversion of biomass gasification [22]. At present, biochar is widely GB/T 28731-2012 of the People’s Republic of China. Ultimate analysis
used in catalytic pyrolysis [23], microbial capture [24], enzyme of samples was analyzed by an Organic element analyzer (Elementar
immobilization carrier material [25], soil conditioner [26], organic Vario El cube).
pollutant degradation [27] and other fields. Various elements such as C,
Ca, Mg, Si, O, S, and Na contained in biochar had certain value-added 2.2. Preparation and modification of catalysts
potential, and as an ideal material, provided a sustainable and envi­
ronmentally friendly way for the production of catalysts or catalyst Bamboo pyrolytic char (BC) is used as the precursor of char-based
supports [28]. On the other hand, char-based catalyst can be used as catalyst. The preparation method of pyrolysis char was as follows: put
both catalysts and microwave absorbers in the process of microwave the screened bamboo raw material in the quartz tube reactor (GSL-
catalytic pyrolysis due to its strong wave-absorbing ability and catalytic 1200X Three-Temperature Zone Vertical Tube Furnace) for pyrolysis.
performance [29,30]. Char-based catalyst had the advantage of syner­ Previous work had shown that to reduce the impact of biochar decom­
gistic catalysis under microwave heating conditions. The quality and position on the pyrolysis products of biomass, the preparation temper­
yield of the two phases is beneficial for bio-oil upgrading and syngas ature of biochar should be higher than the temperature of the biomass
production. Dai et al. [31] studied Fe-modified biochar catalyst to pyrolysis process [32]. Before pyrolysis, placed the quartz tube filled
catalyze pyrolysis of baked corn cob under microwave-assisted pyrolysis with raw materials on the shelf in the tube furnace, the nitrogen flow
conditions. It was found that Fe-modified biochar catalyst mainly pre­ rate is 200 mL/min, and the temperature rises after 0.5 h, the heating
sents strong acid sites, and the use of biochar catalyst can reduce the rate was 5 ◦ C/min, and the final temperature was 600 ◦ C for 2 h. Wait for
bio-oil yield and increase gas yield, catalytic pyrolysis using Fe-modified the reactor to cool down to room temperature, take out the solid
biochar catalyst helps to improve the yield and selectivity of phenol and remaining in the quartz tube, which is the BC. ZSM-5 catalyst was
cresol, and the catalytic performance of biochar catalyst was better than purchased from the Catalyst Factory of Nankai University with a
that of commercial activated carbon. Char-based catalysts shown high SiO2/Al2O3 molar ratio of 46, and was calcined in a muffle furnace at
catalytic efficiency in the thermal conversion process, and their complex 600 ◦ C for 4 h before modifying metal.
pore structure and surface functional groups have high catalytic activity. Eight different catalysts (BC, 10 wt%Zn/BC, 10 wt%Zr/BC, ZSM-5,
The introduction of heteroatoms and nano-metal particles can further 10 wt%Zn/ZSM-5, 10 wt%Zr/ZSM-5, BC-ZSM-5 1:1, 10 wt%Zr/BC-
enrich the application scenarios of char-based catalysts. However, the ZSM-5 1:1) were prepared by impregnation method, which were named
discussion of its in-depth catalytic mechanism is still being explored, and as BC, ZnB, ZrB, ZSM, ZnZ, ZrZ, BZ, ZrBZ, respectively. The metal active
there is a lack of a complete theoretical system of catalytic pyrolysis phase was loaded to modify catalyst precursor through incipient wetness
mechanism, which limits its further industrial expansion. On the other impregnation method. Zinc nitrate (Zn (NO3)2⋅6H2O, 99.999% metal
hand, due to the complex chemical reactions that occur during the basis) and zirconium nitrate (Zr (NO3)4⋅4H2O, 99.999% metal basis)

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X. Shi et al. Energy 261 (2022) 125307

Table-1
Proximate analysis and ultimate analysis of bamboo.
Feedstock Proximate analysis/(wt.%) Ultimate analysis/(wt.%)
a
(Dry basis) M A V FC N C H S Oa

Bamboo 1.71 1.88 78.65 17.76 1.47 49.15 4.51 2.75 42.12
a
Estimated by difference.

were purchased from Aladdin Biochemical Technology Co., Ltd. in nitrogen flow rate was adjusted to 50 mL/min then the catalytic pyrol­
Shanghai. Zn (NO3)2⋅6H2O, Zr (NO3)4⋅4H2O were used as precursors of ysis experiment was started. The effect of temperature on the yield of
the catalyst active phase. The percentage of the metal loading refers to MVP products was preliminarily tested, and the optimum pyrolysis
the mass ratio of the cation in the active pphase precursor to the catalyst temperature was determined to be 550 ◦ C. The microwave power was
precursor. Calculate the mass of the active phase precursor according to set to 1200 W, and after reaching the reaction temperature (550 ◦ C), the
the preset percentage of the metal loading, dissolve the active phase inside of the reactor was kept at 550 ◦ C for 30 min by means of a tem­
precursor into 150 mL of water, add 6 g (BZ and ZrBZ added 3 g BC and perature control device, and the experiment was terminated. After the
3 g ZSM-5 to the beaker) of BC or ZSM-5, and stir on a magnetic stirrer at device was cooled to room temperature, the products were collected for
600 r/min for 6 h. It was then dried at 105 ◦ C and stirred for 2 min every analysis, respectively. Each catalytic pyrolysis experiment was repeated
half an hour until the water was completely evaporated. Then it was 3 times. The yields of pyrolytic products were calculated by equations
dried 24 h at 105 ◦ C, and the dried sample was placed in the quartz tube [33]:
reactor and calcined at 600 ◦ C for 4 h. Catalysts without modifying metal
Yl = ml /M × 100% (1)
were subjected to the same operation with the same amount of deionized
water before use.
Ys = ms /M × 100% (2)

2.3. Catalytic pyrolysis experiment Yg = 100% − Ys − Yl (3)

The microwave catalytic pyrolysis device was shown in Fig. 1. The l = liquid product, s = solid product, g = gas products, Y is the yield of
experimental device was a vertical microwave catalytic reactor (CY- pyrolytic products, m and M represent the weight of pyrolytic products
CR1000C–S, CHANGEMV). The microwave frequency was 2.45 GHz. In and feedstock, respectively.
order to increase the heating rate of biomass raw materials, it was 1- Nitrogen cylinder, 2- Microwave pyrolysis experiment bench, 3-
necessary to add microwave absorbers. Before the experiment, 4 g Rotameter, 4- Control system, 5- Thermocouple, 6- Quartz outer tube, 7-
sample mixed with 28 g SiC was put in the quartz inner tube. 4 g catalyst Quartz inner tube, 8- Raw material layer, 9- Catalyst layer, 10- Quartz
and the quartz inner tube containing the mixture of sample and SiC was wool, 11- Condensation tube, 12- Condenser, 13- Liquid collecting
put into the quartz outer tube, respectively. The catalyst was under the bottle, 14- Scrubber (containing silica gel and absorbent cotton), 15- Air
quartz inner tube to ensure the conduct of ex-situ experiment. The flow bag.
rate of nitrogen was 150 mL/min which introduced for 20 min to ensure
that the pyrolysis was carried out under an inert atmosphere after the
2.4. Catalysts and products characterization
device was connected. When the air in the reactor was emptied, the
Several characterization methods and instruments were adopted to
measure the catalysts prepared in this study, including specific surface
area and pore size analysis (Brunauer-Emmett-Teller formula, BET), X-
ray diffraction (XRD), scanning electron microscopy (SEM), Fourier
Transform Infrared Spectrometer (FT-IR). Two analysis methods, Gas
chromatograph (GC-14C) and Gas Chromatography/Mass Spectrometer
(GC/MS), were mainly used to analyze the composition of gas and liquid
for pyrolysis products. A detailed description of the methods and
apparatus is in previous researches [32,33]:
BK100-01 automatic surface area and pore analyzer based on N2
adsorption and desorption isotherm, manufactured by Beijing Jingwei
Gaobo Science and Technology Co., Ltd., was used to determine the pore
structure parameters of catalysts. Before the analysis, the catalyst sam­
ple was degassed in vacuum at 300 ◦ C for 5 h, using N2 as the adsorption
gas, and its specific surface area was calculated according to the
Brunauer-Emmett-Teller (BET) formula. The result is the average of
three measurements. X-ray diffraction (XRD) of model X’ Pert PRO X-ray
diffractometer of PANalytical, Netherlands, was used to analyze the
crystalline phase characteristics of the catalysts. Parameter settings for
the analysis were 40 kV voltage, 40 mA current, Cu as anode target with
scan step of 0.0167◦ and scan speed of 5◦ /min in the scan range of
10◦ ~80◦ . A desktop scanning electron microscope (JCM-6000PLUS,
JEOL) was used to analyze the surface characterization and morphology
of catalysts. Because of the weak electrical conductivity of dried sam­
ples, they were sprayed with metal before analysis. FT-IR using KBr
compressed tablets to prepare samples, was used to analyze the catalysts
in spectral analysis range of 400 cm− 1 - 4000 cm− 1 with resolution of 1
Fig. 1. Schematic diagram of microwave-assisted catalytic pyrolysis device. cm− 1. Structural groups in catalysts can be identified by FT-IR [34].

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X. Shi et al. Energy 261 (2022) 125307

Obtaining the FTIR spectrum of the catalyst allowed the identification of catalysts were shown in Fig. 2. It can be seen from Fig. 2(a) that,
the structural groups in it [35]. compared with the diffraction peaks of BC, ZrB had four distinct
Gas chromatograph (GC-14C, Shimadzu Corporation) was used to diffraction peaks at 2ɵ = ~30.1◦ , ~35.1◦ , ~50.2◦ and ~60.0◦ , respec­
analyze the gas products. Standard gas control procedure was firstly tively, corresponding to the surface of ZrO2 cube structure. ZnB had
used to identify the gas species and the external standards were used to eight distinct diffraction peaks at 2ɵ = ~31.8◦ , ~34.4◦ , ~36.3◦ , ~47.5◦ ,
quantitatively analyze the main components of gas products (CO, CO2, ~56.6◦ , ~62.9◦ , ~68.0◦ , ~69.1◦ , corresponding to the structure of ZnO,
H2, CH4). The instrument conditions for the measurement: Column is of which indicated that ZrO2 and ZnO were well load on BC. It can be seen
Shimadzu TDX-01 (2 m × 3 mm), carrier gas is Ar, carrier(M) pressure is from Fig. 2(b) that the characteristic peaks of the structure of ZSM were
0.1 MPa, injection volume is 100 μL, injection port temperature is 2ɵ = ~7.9◦ , ~8.8◦ , ~23.1◦ , ~23.9◦ , suggesting that the ZSM-5 zeolite
100 ◦ C, column box temperature is 80 ◦ C, detector temperature is framework remained intact after loading metal species. The modified
150 ◦ C. The result is the average of six measurements. Gas Chroma­ catalyst had no obvious change in the trend of ZSM characteristic peak,
tography/Mass Spectrometer (GC-8860/MS-5977 A, Agilent Technolo­ while the peak intensity was slightly weakened. Compared with the
gies Co., Ltd.) was used to analyze liquid product components. The diffraction peaks of ZSM, no diffraction peaks corresponding to Zr par­
instrument conditions for the measurement: 1) GC conditions: Column is ticles were found in the XRD pattern of ZrZ. Through analysis, it was
of HP-5MS (30 m × 0.25 mm × 0.25 mm), carrier gas is He, gas flow rate found that the Zr particles had a high degree of dispersion on the ZrZ and
is 1.0 mL/min, split ratio is 50:1, injection volume is 1.0 μL, the tem­ were highly overlapped with the diffraction peaks of ZSM-5, which
perature of the injector was 290 ◦ C, the column heating program was means that Zr is on the channels of ZSM-5 [39]. The other cases were
that the initial temperature was 40 ◦ C, lasted for 4min, then the tem­ also similar to ZrZ excepted that the tiny peak shape of ZnO could be
perature raised to 280 ◦ C at the rate of 5 ◦ C/min and lasted for 5min; 2) observed at 2ɵ = ~12.4◦ . Metals modified on ZSM exist in a highly
MS conditions: the MS interface temperature was 290 ◦ C, scanning range dispersed form inside the pores, which is beneficial for the catalyst to
is from 30 to 500 (m/Z), solvent delay time was 2 min. Shake the liquid
product before dilution and shake the solution before testing to ensure
the homogeneity of the solution [36]. Their mass spectral data with
those from the NIST17.L mass spectral databases.

3. Results and discussions

3.1. Characterization of catalysts

3.1.1. BET
Pore structure parameters of different catalysts has shown in Table 2.
The specific surface area, pore volume and pore diameter of the carrier
BC were 228.66 m2/g, 0.18 cm3/g, and 3.12 nm, respectively, which
belonged to the mesoporous catalyst. The effect of different metal
modifying on BC was relatively weak.
ZSM had the larger specific surface area and pore volume, which are
349.15 m2/g and 0.22 cm3/g, respectively, and the average pore size
was 2.54 nm, which was much better than the corresponding parameters
of BC. Compared with ZSM, the specific surface area and pore volume of
ZnZ and ZrZ were significantly reduced, but the average pore size was
increased. It can be understood that the supported metal has a related
relationship with the carrier, so that the pores are increased [37]. The
decreasing of parameters for ZSM after metal modification decreased
more obviously compared with metal-modified BC. This may be because
the metal components introduced by the modification were dispersed on
the catalyst surface or entered into the pores, covering part of the inner
and outer surfaces of the pore channels [38]. In the metal modified ZSM,
the blocked pores were mainly micropores and mesopores, and the
overall pore size increased after averaging. The increased of the average
pore size provides favorable conditions for the shape-selective catalysis
of oxygen-containing macromolecules in the later stage, and reduces the
coking and deactivation of the catalyst.

3.1.2. XRD
The X-ray diffraction patterns of metal modified biochar and ZSM-5

Table 2
Pore structure parameters of catalysts.
Catalyst SBET/(m2/ Average pore diameter/ Average pore volume/
g) nm (cm3/g)

BC 228.66 3.12 0.18

ZnB 227.64 2.62 0.15
ZrB 213.50 2.30 0.14
ZSM 349.15 2.54 0.22
ZnZ 220.14 3.00 0.17
Fig. 2. X-ray diffraction for different catalysts. (a) Char-based Catalysts (b)
ZrZ 224.99 3.26 0.18
ZSM-5 Catalysts.

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X. Shi et al. Energy 261 (2022) 125307

exert the catalytic effect of metal particles during the pyrolysis process particles had a certain “cluster” phenomenon, and the grains were ar­
[19]. Compared with the effect of different metal components, the effect ranged more densely and neatly. ZrZ maintains more excellent
of the change of Zr loading on the X-ray diffraction pattern of the morphological characteristics and had better structural stability. Over­
catalyst was less obvious. It could be considered that the modifying ef­ all, given the solid aluminosilicate framework structure of molecular
fect of ZrZ is better than ZnZ. sieves, the modification of metal components had limited influence on
catalyst grain morphology.
3.1.3. FT-IR
In order to further explored the functional group status of catalysts
after metal modification, Fig. 3 showed the Fourier transform infrared 3.2. Characteristic analysis of pyrolysis products with catalysts
(FT-IR) spectra of different catalysts, which characterized the chemical
bonds on the surface of the catalysts, so as to analyzed the types of 3.2.1. Catalytic effects on product yield
groups. Fig. 3. (a) showed the functional group types of char-based It can be seen from Fig. 5(a) that BC produced more pyrolysis gas
catalysts among which the stretching vibration of –OH at 3439 cm− 1 (43.10 wt%), while ZSM obtained more bio-oil (42.16 wt%) at the
and 549 cm− 1. The peak intensity of aliphatic CH2 (2928 cm− 1 and 2865 expense of pyrolysis gas yield, this is consistent with Zheng et al. [21]. It
cm− 1) increased with the mental modification, while the peak intensity may be because BC has good wave absorption properties, which can
of ZnB was higher. The three peaks at 1626 cm− 1, 1098 cm− 1, 549 cm− 1 better absorb microwaves under microwave conditions, and promote
are attributed to the ensile vibrations of C– – O, C–O and –OH out-of- the conversion of products to final products instead of intermediate
plane bending vibrations, respectively. After Zr modification, the in­ products, making the reaction more thorough. Blank used the same
tensity of C–O and –OH adsorption peaks increased and the vibration amount of SiC to replace the catalyst, resulting in a faster heating rate of
was enhanced. The ZnB and ZrB did not change the types of functional biomass during microwave heating. The absorbing effect of ZSM-5 was
groups on the BC surface, but the intensity of the absorption peak and weaker than that of SiC. On the other hand, due to its unique pore
the position of the spectrum shifted. structure, ZSM-5 promoted the remodeling of pyrolytic intermediates,
It can be seen from Fig. 4. (b) that the ZSM has very typical infrared thus obtaining more high-value components [41]. Compared with the
vibration peaks, and the spectrum in this experiment basically corre­ ZSM, the metal-modified ZSM-5 catalyst decreased the yield of liquid
sponds to the description in the relevant investigation [40]. No new product and increased the yield of gas product. This may be due to the
peaks were observed in the spectra of the ZnZ and ZrZ. Compared with change of the active sites on the catalyst surface after metal loading,
ZSM, it was found that the original typical ZSM-5 vibration peak has which promotes the secondary cracking reaction and generates more
several intensity changes. The original structure of metal and molecular bio-gas [41]. In fact, MVP produces higher gas yields and higher syngas
sieve undergoes ion exchange, and only the peak intensity is weakened content than conventional heating pyrolysis the corresponding energy
and no new peak appears. Comparing the analysis of XRD and SEM, it and exergy rates of gas under microwave heating were found to be
can be found that the metal load is relatively dispersed. higher than those of conventional one [42]. This was due to the gener­
ation of more hydrogen by microwave pyrolysis of biomass. The
3.1.4. SEM mechanism of microwave catalytic pyrolysis to promote bio-gas will be
Fig. 4 presented the SEM results of different catalysts. It could be discussed later in section 3.2.2.
seen from the figure that BC had a large number of pore structures. Zn/ Since the experiment adopted an ex-situ catalytic pyrolysis scheme,
Zr were mainly supported on the surface and internal pores of the carbon the catalyst was not in direct contact with the feedstock. The yield of
skeleton, and the active components were uniformly distributed on the chars did not vary much, because the yield of solid product was mainly
surface of BC in the form of metal nanoparticles. There was no large- affected by the interaction between microwave power and heating time
scale agglomeration, which was attributed to the good pore structure [43]. The yields of each group of chars did not very much, with ZrB
of BC. ZSM-5 catalyst particles were slightly smaller, and the shape was a having the lowest char yield (28.47 wt%), which promoted more con­
typical hexagonal prism structure, the arrangement was loose, rela­ version of the products to the gas and liquid phases under the same
tively. After the modification of Zn/Zr metal components, the catalyst pyrolysis conditions. Bamboo pyrolysis catalyzed by ZnB had the lowest
yield of liquid products (25.91 wt%), but higher gas yields (42.41 wt%)

Fig. 3. FT-IR spectra for catalysts. (a) Char-based Catalysts (b) ZSM-5 Catalysts.

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X. Shi et al. Energy 261 (2022) 125307

Fig. 4. SEM micrographs of catalysts: A(BC), B(ZnB), C(ZrB), D(ZSM), E(ZnZ), F(ZrZ).

were obtained. ZrB provided the production of 32.71 wt% of liquid cracking of reaction intermediates, which resulting more H2.
products and 38.82 wt% of gas products. It may be due to the fact that The volume fractions of CO after pyrolysis of ZSM, ZnZ and ZrZ were
the char-based catalyst itself had a strong wave-absorbing ability, 69.78 vol%, 53.32 vol%, and 59.86 vol%, respectively, which were
resulting in a local “hot spot " effect [44], leading to an increase in the higher than the volume of CO generated by the pyrolysis of char-based
temperature of the raw material near the catalyst part, which promotes catalysts (33.68–39.59 vol%). It can be seen that ZSM-5 molecular sieve
its decomposition and reduces the yield of solid products, while a higher has excellent deoxidation ability. The oxygen of oxygen-containing
yield of liquid products is obtained. The yield of biochar under micro­ substances in the pyrolysis will be removed under the deoxidation of
wave conditions is more sensitive to the change of reaction temperature, the catalyst and released in the form of CO and CO2 [48]. The increase in
and lower reaction temperature and microwave power tend to yield CO yield helped to improve the low calorific value of bio-gas [49]. On
more biochar [45]. the contrary, the CO volume fraction decreased correspondingly after
metal loading, and the CO reduction was more obvious after Zn loading,
3.2.2. Gas product characteristic which may be due to the change of the active sites and acidity of the
Fig. 5. (b) presented the gas product yield distributions of different catalyst surface.
catalysts for bamboo MVP at 550 ◦ C. The four main components of the
gaseous product were H2, CH4, CO and CO2. It can be seen from the 3.2.3. Liquid product characteristic
figure that with the application of biochar as a catalyst, the H2 content Bio-oil from bamboo pyrolysis consists of a complex mixture of
increased significantly, especially when BC was used as a catalyst, it oxygenated organic molecules from cellulose, hemicellulose and lignin.
reached a maximum value of 50.93 vol%, and the yield was increased by Due to the complexity of bio-oil components, the identified compounds
77.33% compared with no catalyst added. Char-based catalyst might were divided into aromatics, furans, aldehydes, ketones, phenols, and
promote cleavage of C–H bonds and aromatic C– – C bonds [46]. Mean­ acids to facilitate comparison of results. Notably, the sum of the total
while, compared with BC, ZnB and ZrB promoted the yields of CO and peak area % was less than 100%, which should be due to unidentified
CO2, indicating that the decarbonylation and decarboxylation of biochar compounds in the ion chromatogram. From Fig. 5. (c), it can be seen that
was enhanced after metal loading. Compared with the Blank, the CO the bio-oil obtained by MVP without catalyst is mainly oxygen com­
yield decreased (from 53.75 vol% to 33.68–39.59 vol%), which may be pounds, and hardly contains aromatics. The acids, ketones, aldehydes
related to the secondary reactions [20]. Ren et al. [47] proposed the and furans contained in the bio-oil reached 13.01%, 6.03%, 3.33% and
water-gas shift reaction of carbon-based catalysts in the production of 10.94%, respectively. The mainly components of bio-oil were phenols,
biosynthesis gas under microwave catalysis: reached 48.62%. More oxygenated compounds in bio-oil caused to
lower heating value [50]. The addition of catalyst will reduce the acidity
CO + H2 O ↔ CO2 + H2 (4)
of bio-oil, and the reduction of oxygen content can improve the stability
of bio-oil. BC exhibited inhibitory effects on ketones and aldehydes, and
C + CO2 ↔ 2CO (5)
reduced the content of phenols. The addition of char-based catalysts
CH4 ↔ C + 2H2 (6) could significantly increase the content of aromatic hydrocarbons in
bio-oil. ZSM exhibited inhibitory effects on furans, as well as the ability
CH4 + CO2 ↔ 2CO + 2H2 (7) to converted them into monocyclic aromatic hydrocarbons. The content
of aromatics increased after the catalyst was introduced, and the highest
Previous studies [32] have found that carbon-based catalysts can yield appeared in ZnB (55.89%).
promote the cleavage of methyl and methoxy groups to generate more The metal-modified catalyst significantly reduced the content of
CH4. However, under the synergistic effect of microwave catalytic py­ oxygenates and the content of aromatics increased to varying degrees.
rolysis and char-based catalysts, CH4 was further decomposed into The acid content of bio-oil obtained by microwave pyrolysis of bamboo
carbon and hydrogen through methane reforming (see formula (6)), without catalyst was 13.01%, and the acid content was reduced to
which may be the reason why carbon-based catalysts generate more 2.53%–10.80% after adding catalyst. The highest aromatics yield
hydrogen under MVP conditions. Microwave irradiation and the ab­ appeared in ZnB (55.89%), and the content of acids, phenols, ketones,
sorption properties of char-based catalysts promote the secondary aldehydes, furans in bio-oil decreased to 2.53%, 14.63%, 2.96%, 0.88%,

6
X. Shi et al. Energy 261 (2022) 125307

single-component catalysts have various performances in product

selectivity, there was still a problem of low directional selectivity. Based
on this, it is proposed to use char-based catalyst and ZSM-5 zeolite as
catalyst supports, and support Zr metal with good selectivity to gas
products as active sites to explore the best catalysts for co-production of
aromatic-rich bio-oil and bio-syngas.

3.3.1. Product yield and gas characteristic of multi-catalyst

In the previous pyrolysis results, the char-based catalysts mainly
showed higher yields of gas products, while ZSM-5 zeolite obtained
more liquid products at the expense of gas product yields. In Fig. 6(a),
compared with the single-component catalyst, the multi-catalyst was
mainly reflected in the upgrading of the product. In Fig. 6 (b), BZ ob­
tained a syngas yield of 83.98 vol%, and the H2/CO ratio reached 1.18.
ZrBZ had a higher gas yield than ZrB, reaching 39.95 wt%, while its
syngas yield reached 91.54 vol% and H2/CO ratio reached 1.08.
Compared with BC, although the gas product yield decreased, the con­
tent of syngas components in the gas product increased by 8.21%. The
syngas produced from biomass contains higher levels of CH4 and CO2,
which are greenhouse gases that are not friendly to the environment
[52]. the bio-syngas obtained from ZrBZ had lower CH4 (6.49 vol%) and
CO2 (1.98 vol%) contents. In order to obtain higher bio-syngas in

Fig. 5. Effects of application of different catalysts in microwave pyrolysis of

bamboo (a) The distribution of products by microwave pyrolysis with different
catalysts (b) The pyrolytic gas distribution of different catalysts (c) The liquid
product distribution of pyrolysis over different catalysts.

3.55%, respectively. The oil had the lowest content of oxygenates and a
significant deoxidation effect. Lower ketones, aldehydes and furans
yields were achieved with the BC, ZrB and ZSM catalysts at 2.45%,
0.21%, and 0.40%, respectively. The order of aromatics produced by
different metal-supported catalysts is: ZnB (55.89%) > ZrB (42.54%) >
ZnZ (17.11%)> ZrZ (14.52%). In the process of pyrolysis, the metal sites
of metal oxides and the acidic sites of ZSM-5 can effectively accelerate
the C–O bond and C–C cracking and shape-selective catalysis, thereby
promoting the formation of aromatics [51].

3.3. Comparative analysis of single-component catalysts & multi-catalysts

pyrolysis to produce aromatics Fig. 6. Product yield and gas characteristic of multi-catalyst (a) The distribu­
tion of products with multi-catalyst (b) The pyrolytic gas distribution with
Combined with the analysis of the experimental results, although the multi-catalyst.

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X. Shi et al. Energy 261 (2022) 125307

conventional pyrolysis gasification, more energy was often required to 3.4. Mechanism of bamboo with multi-catalysts through microwave
generate higher pyrolysis temperature (800–1200 ◦ C). ZrBZ in MVP pyrolysis
conditions can obtain similar pyrolysis gas composition at 550 ◦ C. This is
suitable for producing bio-syngas. In the process of MVP, the active sites of char-based catalysts and the
acidic sites of ZSM-5 could effectively accelerate the cracking of C–O
3.3.2. Liquid product characteristic of multi-catalyst bonds, C–C bonds and shape-selective catalysis, thereby promoted the
Fig. 7 compared the characteristics of different catalyst liquid formation of aromatics (especially MAHs) (Fig. 8). Firstly, the large
products. Although BC had a high yield of aromatics (51.98%), the molecular weight oxygenates were cracked into low molecular weight
content of MAHs was very low, only 2.33%, in which there are a large hydrocarbon precursors by microwave radiation, which was conducive
number of PAHs, including naphthalene, fluorene, phenanthrene, etc. to diffusion into the ZSM-5 for catalytic reaction, and improves the chain
From Fig. 7. (a) it can be seen that ZSM zeolite had higher MAHs mass transfer reaction and catalytic activity. Under the action of metal
selectivity but lower relativity content resulting in poor overall yield. active sites on the surface of metal-modified char-based catalysts, lignin-
Correspondingly, BZ increased the content of aromatics in bio-oil, derived phenolic compounds undergo dehydration, deoxygenation, and
reaching 52.81%. And compared with BC, the content of MAHs decarboxylation reactions, accompanied by the formation of CH4 and
increased by 60.57%. The introduction of Zr-modified multi-catalyst H2O [54]. Through hydrodeoxygenation, hydrocracking, demethox­
showed more excellent effect on liquid products. The contents of acids, ylation and demethylation reactions, phenolic products were converted
ketones, aldehydes and furans in the bio-oil were 3.62%, 3.87%, 0.46% into aromatic hydrocarbons under the action of catalysts. And
and 3.85%, respectively, which had a good deoxidation effect and the char-based catalysts promoted cyclization and polymerization, which
obtained bio-oil was more stable. Compared with BC, the yield of MAHs further converted them to PAHs. For cellulose and hemicellulose, they
of ZrBZ increased from 2.33% to 14.67%, and the selectivity of MAHs were firstly split into furans, acids and ketones under the microwave
increased from 3.50% to 21.82%. At the same time, the Aromatics/ irradiation. Those products underwent deoxygenation, dehydration,
Phenols reached 2.64, prompting the conversion of more phenols to decarbonylation, and decarboxylation reactions to form hydrocarbon
aromatics, especially MAHs. This was attributed to the synergistic effect pools under the effect of catalyst. Oxygenated compounds such as phe­
of the multi-component catalyst with MVP. The multi-catalyst had a nols, alkylphenols, and ketones further catalyzed the precursors through
certain deoxygenation effect, and inhibits the excessive conversion of decarbonylation, and aromatize to form aromatic hydrocarbons, which
MAHs to PAHs, obtained higher MAHs yield. This was conducive to the were accompanied by CO, CO2, and H2O [55]. Although metal-modified
high-value utilization of bio-oil. The hydrodeoxygenation of phenol into char-based catalysts promoted the formation of aromatic products, the
benzene occurred, with the formation of bicyclic products, such as selectivity of MAHs was poor. The introduction of ZSM-5 catalyst to
biphenyl and 2-phenylphenol, owing to the alkylation of the phenolic prepared multi-catalyst can not only optimize the pore structure of the
and aromatic rings [53]. Therefore, the generation of aromatic hydro­ catalyst, but also enhance the shape selection and deoxidation ability.
carbons could be attributed to the dehydrogenation and dealkylation of While ensuring the yield of aromatic hydrocarbons, it had high selec­
cyclic hydrocarbons (see Fig. 8). tivity of MAHs, which promoted the conversion of phenols to aromatic
hydrocarbons.

4. Conclusions

The addition of different catalysts had a great influence on the

biomass MVP process and product characteristics. In this manuscript,
bamboo was used as the raw material to explore the synergistic effect of
different catalysts in the process. Through the characterization of the
catalyst and the analysis of the product characteristics, the following
conclusions are drawn:

1) In the MVP process, the char-based catalysts mainly showed higher

yields of gas products (43.10 wt%), while ZSM-5 zeolite obtained
more liquid products (42.16 wt%) at the expense of gas product
yields. Zn promoted the selectivity of aromatic hydrocarbons in bio-
oil, Zr could effectively improve the yield of syngas and upgrading
bio-oil, respectively.
2) In the process of MVP, ZSM-5 catalyst mainly played a role in the
directional selection of MAHs products, but reduced the yield of total
aromatics and phenols. The content of CO in gas products was
increased to 69.78 vol%. Correspondingly, the char-based catalyst
obtained more aromatic products, which could effectively convert
the phenols in the bio-oil into aromatics, and obtained a higher H2
yield (50.93 vol%).
3) It was initially explored that the metal-supported multi-catalyst
prepared by the combination of the two could co-produce bio-oil and
bio-syngas with high selectivity of MAHs and the highest syngas
yield (91.54 vol%). The selectivity of MAHs reached 21.82%, which
promoted the conversion of more phenols to aromatics. Aromatics
production could be attributed to the synergistic effect of different
components in the catalyst and microwave irradiation. The catalyst
Fig. 7. Liquid product characteristic of multi-catalyst (a) The liquid product had good deoxidation effect, and bio-oil was more stable.
distribution of pyrolysis over multi-catalyst (b) Yield and selectivity of aromatic
compounds over multi-catalyst.

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X. Shi et al. Energy 261 (2022) 125307

Fig. 8. The possible reaction pathways of bamboo during microwave catalytic pyrolysis.

Credit author statement in pyrolysis conversion of waste into value-added liquid pyro-oil, with focus on
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