微波輔助炭基催化劑催化熱解生物質的研究進展

李攀; 胡秋輝; 胡俊豪; 陳志勇; 張永勝; 方書起; 常春

doi:10.13374/j.issn2095-9389.2022.11.16.002

微波輔助炭基催化劑催化熱解生物質的研究進展

doi: 10.13374/j.issn2095-9389.2022.11.16.002

李攀^{1, 2, 3},
胡秋輝^{1, 2,},
胡俊豪^{1, 2, 3},
陳志勇²,
張永勝^{1, 2, ,},
方書起^{1, 2, 3},
常春^{1, 2, 3}

1.
鄭州大學機械與動力工程學院，鄭州 450001
2.
河南省生物基化學品綠色制造重點實驗室，濮陽 457000
3.
生物質煉制技術與裝備河南省工程實驗室，鄭州 450001

基金項目: 國家自然科學基金資助項目（52006200）；河南省杰出外籍科學家工作室資助項目（GZS2022007）；南陽市協同創新重大專項（鄭州大學南陽研究院）資助項目（22XTCX12007）

詳細信息

通訊作者:
E-mail: yzhang@zzu.edu.cn

中圖分類號: TK6
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- 文章訪問數: 302
- HTML全文瀏覽量: 144
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- 被引次數: 0
出版歷程
- 收稿日期: 2022-11-16
- 網絡出版日期: 2023-01-12
- 刊出日期: 2023-09-25

Research progress on biomass catalytic pyrolysis via microwave effects combined with carbon-based catalysts

LI Pan^{1, 2, 3},
HU Qiuhui^{1, 2
,},
HU Junhao^{1, 2, 3},
CHEN Zhiyong²,
ZHANG Yongsheng^{1, 2
, ,},
FANG Shuqi^{1, 2, 3},
CHANG Chun^{1, 2, 3}

1.
School of Mechanical and Power Engineering, Zhengzhou University, Zhengzhou 450001, China
2.
Henan Key Laboratory of Green Manufacturing of Biobased Chemicals, Puyang 457000, China
3.
Henan Engineering Laboratory for Biorefinery Technology and Equipment, Zhengzhou 450001, China

More Information

Corresponding author: E-mail: yzhang@zzu.edu.cn

摘要

摘要: 炭基催化劑具有制備成本低、催化后處理簡單等優點，但存在易積碳失活、產物選擇性低等缺點，結合微波效應，可明顯提高炭基催化劑的競爭力。本文對微波輔助炭基催化劑熱解生物質的研究進展進行了現狀綜述。主要介紹了微波加熱原理，吸波劑和催化劑對于微波熱解的影響機制。分析了不同改性方法（金屬負載法、化學法、磺化等）對炭基催化劑的孔隙結構、含氧官能團和酸性基團及催化反應產物特性的影響。總結了微波輔助改性炭基催化劑在焦油重整和改善生物質熱解產物特性等方面的應用進展。本文對該研究方向存在的問題提出建議并進行展望，為基于微波催化熱解作用下炭基催化劑的選擇、改性和生物質高值化利用提供一定的參考。
- 炭基催化劑 /
- 生物質 /
- 微波催化熱解 /
- 改性 /
- 高值化利用
Abstract: It is critical to discover a clean energy source to replace fossil fuels such as coal to meet the targets of “emission peak” and “carbon neutrality” in 2030 and 2060, respectively. Biomass is a kind of renewable energy that is rich in reserves and can be directly converted into fuel. Pyrolysis is a common way to maximize the value of biomass, and the composition and distribution of products can be adjusted by the addition of catalysts. Carbon-based catalysts have the advantages of low preparation costs and easy treatment after catalysis. However, they have the disadvantages of easy carbon deposition inactivation and low product selectivity. The competitiveness of carbon-based catalysts can be improved when combined with the microwave effect. Herein, the research status of microwave-assisted carbon-based catalysts for the pyrolysis of biomass is reviewed. This study primarily introduces the microwave heating theory principle as well as the microwave absorber and catalyst effect mechanisms on the microwave for pyrolysis. The limitations of metal catalysts and molecular sieve catalysts are analyzed, and the unique advantages of modified carbon-based catalysts in the field of microwave pyrolysis are proposed. Microwave heating uses microwave radiation to create heat in the internal particles of biomass; therefore, microwave pyrolysis has the advantages of a high heating rate, uniform heating, low energy loss, a high energy conversion rate, and instantaneous adjustment. The effects of different modification methods (metal loading method, chemical method, sulfonation, etc.) on the pore structure, oxygen-containing functional groups, and acidic groups of carbon-based catalysts and the characteristics of catalytic products are analyzed. Among them, the preparation method’s precipitation method is difficult to manage, and the repeatability is low. The impregnation method has the advantages of being an easy preparation process, being inexpensive, and having a large production capacity. The chemical process will remarkably alter the oxygen-containing groups and acidity of the biochar. Too much acidity causes carbon deposition and catalyst deactivation, whereas too few acidic oxygen-containing groups induce pyrolysis rate decreasing. Therefore, the raw materials used in sulfonation are not environmentally friendly. The application progress of microwave-assisted modified carbon-based catalysts in tar reforming and improving the properties of biomass pyrolysis products is summarized. Carbon-based catalysts combined with microwave heating can increase the yield of phenols and syngas and improve the quality of pyrolysis products. Herein, some suggestions on the problems existing in this research direction are put forward and prospected, which provides some reference for the selection and modification of carbon-based catalysts and the high-value utilization of biomass based on microwave catalytic pyrolysis.
- carbon-based catalyst /
- biomass /
- microwave catalytic pyrolysis /
- modification /
- high-value utilization

HTML全文

圖 1 常規加熱和微波加熱方式對比^[13]. (a)常規加熱；(b) 微波加熱

Figure 1. Comparison of conventional and microwave heating^[13]: (a) conventional heating；(b) microwave heating

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圖 2 活性炭基催化劑催化熱解葡萄糖和纖維素制備酚類機理圖^[33]

Figure 2. Diagram of the mechanism of the activated carbon-based catalyst to catalyze the pyrolysis of glucose and cellulose to produce phenols^[33]

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圖 3 催化劑制備流程圖^[42]

Figure 3. Flow chart of catalyst preparation^[42]

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圖 4 不同溫度下木質素的熱解途徑^[51]

Figure 4. Pyrolysis pathway of lignin at different temperatures^[51]

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圖 5 棕櫚仁殼熱解蒸氣催化重整實驗裝置圖^[56]

Figure 5. Experimental setup of the palm kernel shell (PKS) pyrolysis steam catalytic reforming^[56]

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表 1 不同改性方法對炭基催化劑特性及熱解產物的影響

Table 1. Effects of different modification methods on the characteristics and pyrolysis products of carbon-based catalysts

Materials	Catalyst	Result	Reference
Corncob	Gp?SO₃H?H₂O₂	After H₂O₂ modification, the total amount of acidic groups increased from 1.80 mmol·g^?1 to 2.55 mmol·g^?1, and the xylose and glucose produced by corncob increased from 54.7% and 9.3% to 79.7% and 11.5% respectively.	[43]
Pine sawdust, plastics	Ni?CaO?C	Ni?CaO?C was synthesized by the rising pH method. The hydrogen production performance of Ni?CaO?C was better than that of Ni?Al₂O₃, and the co-pyrolysis effect of Ni?CaO?C on H₂ production was HDPE(high density polyethylene) > PP(polypropylene) > PS(polystyrene).	[44]
Douglas fir	MgO/phosphoric acid activated carbon catalyst	The main components of bio-oil produced by catalytic pyrolysis of Douglas Fir were phenols, ketones, aldehydes and furans, accounting for 75.9%–90.5%.	[45]
Peanut shells	HCl and MnCl₂-modified carbon-based catalysts	Carbon-based catalysts inhibited the formation of pyrolytic acids; HCl increased the selectivity of phenols and inhibited the formation of H₂; MnCl₂ improved the selectivity of phenol and alkylated phenols and promoted the formation of H₂ and CH₄.	[46]
Tar	Porous silicon film overcoating biomass char-supported catalyst	SiO₂ film combined with microporous biochar enhanced the adsorption of tar molecules and gas. The formed FeNi₃ nano-alloy particles can prevent the aggregation of nano-metal particles and reduce carbon deposition. After repeated use, the tar conversion rate was stable.	[47]
Tar	Activation of carbon-based catalysts by KOH, H₃PO₄ and ZnCl₂	The tar conversion rates of catalyst-free, RHC(rice husk char), ZnCl₂?RHC, H₃PO₄?RHC and KOH?RHC were 66.9%, 76.7%, 83.4%, 91.6% and 94.2%, respectively. RHC?KOH obtained the maximum yield of the four gas components.	[48]
Xylitol	Metal-modified carbon-based catalyst	The activity of Pt?Ni/C, Pt?Co/C and Pt?Ru/C catalysts and the selectivity of H₂ were close to those of Pt/C	[49]

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表 2 不同微波催化熱解條件下的主要產物

Table 2. Primary products under different microwave catalytic pyrolysis conditions

Materials	Catalyst	Product	Reference
Toluene	Ni/rice husk char	The cracking rate of toluene was 95.12%, and the concentration of hydrogen in the gaseous product was 92.04%.	[63]
Moso bamboo sawdust	Moso bamboo biochar	With the increase of biochar load, CO+H₂ also increased, with the highest yield of 65.31%.	[64]
Rice straw	Rice straw biochar	The tar removal efficiency was 94.03%, and the H₂ and syngas contents were 50.5% and 94.5%, respectively.	[65]
Douglas fir	Acid washed granular activated carbon	After the addition of activated carbon, the contents of total phenol and phenol increased to 66.9% and 39.0%, respectively.	[66]
Palm kernel shell	Activated carbon and lignite char	At 500 ℃, the mass fraction of phenol and total phenol in bio-oil reached 64.58% and 71.24%, respectively.	[67]
Corn cob	Fe/phosphoric acid acidified biochar	The main components of bio-oil obtained by microwave catalytic pyrolysis were phenols, and the yields of bio-oil and phenols were not closely related to the times of use.	[68]
Tar	Ni/ rice husk char	When the load increased to 16.86% (mass fraction), the tar conversion increased from 78.6% to 98.6%. Microwave promoted the removal of tar and the formation of syngas and improved the stability of catalytic cracking of Ni/ rice husk char.	[69]
Douglas fir	Ferrum-modified activated carbon	Under certain conditions, the ketone content accounted for about 38% of the bio-oil, and the organic acid content decreased significantly.	[70]
Lignin, polyethylene	Zn modified lignin-based char	At 450 °C, when the LDPE (low density polyethylene) dosage was 12.5%, the hydrocarbon yield was the highest. At 550 °C, when the LDPE dosage was 20%, the phenolic yield was the highest.	[71]
Dunaliella salina	Na₂CO₃/AC，CaCO₃/AC	The dehydration effect of activated carbon catalyst on microalgae was better than that of Na₂CO₃ and CaCO₃; In the process of microwave pyrolysis, AC/Na₂CO₃ was better than AC/CaCO₃.	[72]

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參考文獻(72)

[1]	Zhu J H, Mu L W, Jiang G C, et al. Biomass integrated industrial processes for system energy conservation, pollution reduction and carbon dioxide mitigation. Chem Ind Eng Prog, 2022, 41(3): 1111 doi: 10.16085/j.issn.1000-6613.2021-2229 朱家華, 穆立文, 蔣管聰, 等. 生物質協同流程工業節能、降污、減碳路徑思考. 化工進展, 2022, 41(3):1111 doi: 10.16085/j.issn.1000-6613.2021-2229
[2]	Wang K Y, Li X, Lu J D, et al. Low-carbon development strategies of livestock industry to achieve goal of carbon neutrality in China. Trans Chin Soc Agric Eng, 2022, 38(1): 230 doi: 10.11975/j.issn.1002-6819.2022.01.026 汪開英, 李鑫, 陸建定, 等. 碳中和目標下畜牧業低碳發展路徑. 農業工程學報, 2022, 38(1):230 doi: 10.11975/j.issn.1002-6819.2022.01.026
[3]	National Coal Chemical Information Center. Energy production, consumption, import and export in China in 2021. Coal Chem Ind, 2022, 50(1): 4 doi: 10.3969/j.issn.1005-9598.2022.01.003 全國煤化工信息總站. 2021年中國能源生產、消費、進出口. 煤化工, 2022, 50(1):4 doi: 10.3969/j.issn.1005-9598.2022.01.003
[4]	Wang F, Liu X F, Chen L G, et al. Research status and development prospect of energy and high value utilization of biomass resources. Trans Chin Soc Agric Eng, 2021, 37(18): 219 王芳, 劉曉風, 陳倫剛, 等. 生物質資源能源化與高值利用研究現狀及發展前景. 農業工程學報, 2021, 37(18):219
[5]	Pan T, Xue N T, Sun C H, et al. Distribution characteristics of ammonia emission from livestock farming industry in Beijing. Environ Sci Technol, 2015, 38(3): 159 潘濤, 薛念濤, 孫長虹, 等. 北京市畜禽養殖業氨排放的分布特征. 環境科學與技術, 2015, 38(3):159
[6]	Lu X B, Yu Y Y, Fu Y, et al. Characterization and identification method of ambient air quality influenced by straw burning. Adm Tech Environ Monit, 2014, 26(4): 17 doi: 10.3969/j.issn.1006-2009.2014.04.005 陸曉波, 喻義勇, 傅寅, 等. 秸稈焚燒對空氣質量影響特征及判別方法的研究. 環境監測管理與技術, 2014, 26(4):17 doi: 10.3969/j.issn.1006-2009.2014.04.005
[7]	Xin X, Dell K, Udugama I A, et al. Transforming biomass pyrolysis technologies to produce liquid smoke food flavouring. J Clean Prod, 2021, 294: 125368 doi: 10.1016/j.jclepro.2020.125368
[8]	Tawalbeh M, Al-Othman A, Salamah T, et al. A critical review on metal-based catalysts used in the pyrolysis of lignocellulosic biomass materials. J Environ Manag, 2021, 299: 113597 doi: 10.1016/j.jenvman.2021.113597
[9]	Ethaib S, Omar R, Kamal S M M, et al. Microwave-assisted pyrolysis of biomass waste: A mini review. Processes, 2020, 8(9): 1190 doi: 10.3390/pr8091190
[10]	Zeng Y, Wang Y P, Zhang S M, et al. Research progress in preparation of liquid fuels and chemicals by microwave pyrolysis of biomass. Chem Ind Eng Prog, 2021, 40(6): 3151 曾媛, 王允圃, 張淑梅, 等. 生物質微波熱解制備液體燃料和化學品的研究進展. 化工進展, 2021, 40(6):3151
[11]	Zhang Y N, Cui Y L, Liu S Y, et al. Fast microwave-assisted pyrolysis of wastes for biofuels production — A review. Bioresour Technol, 2020, 297: 122480 doi: 10.1016/j.biortech.2019.122480
[12]	Motasemi F, Afzal M T. A review on the microwave-assisted pyrolysis technique. Renew Sustain Energy Rev, 2013, 28: 317 doi: 10.1016/j.rser.2013.08.008
[13]	Li P, Shi X P, Song J D, et al. Research progress of biomass microwave catalytic pyrolysis for preparation of high value-added products. Chem Ind Eng Prog, 2022, 41(1): 133 doi: 10.16085/j.issn.1000-6613.2021-0303 李攀, 師曉鵬, 宋建德, 等. 生物質微波催化熱解制備高值產品的研究進展. 化工進展, 2022, 41(1):133 doi: 10.16085/j.issn.1000-6613.2021-0303
[14]	Wang G Y, Dai Y J, Yang H P, et al. A review of recent advances in biomass pyrolysis. Energy Fuels. 2020, 34(12): 15557
[15]	Wang Y P, Dai L L, Wang R P, et al. Hydrocarbon fuel production from soapstock through fast microwave-assisted pyrolysis using microwave absorbent. J Anal Appl Pyrolysis, 2016, 119: 251 doi: 10.1016/j.jaap.2016.01.008
[16]	Fodah A E M, Ghosal M K, Behera D. Quality assessment of bio-oil and biochar from microwave-assisted pyrolysis of corn stover using different adsorbents. J Energy Inst, 2021, 98: 63 doi: 10.1016/j.joei.2021.06.008
[17]	Fang S Q, Wang Y Q, Li P, et al. Research progress of main catalyst in biomass pyrolysis and utilization. Chem Ind Eng Prog, 2021, 40(9): 5195 doi: 10.16085/j.issn.1000-6613.2021-0245 方書起, 王毓謙, 李攀, 等. 生物質熱解利用中主要催化劑的研究進展. 化工進展, 2021, 40(9):5195 doi: 10.16085/j.issn.1000-6613.2021-0245
[18]	Zhang B, Zhong Z P, Li T, et al. Bio-oil production from sequential two-step microwave-assisted catalytic fast pyrolysis of water hyacinth using Ce-doped γ-Al₂O₃/ZrO₂ composite mesoporous catalyst. J Anal Appl Pyrolysis, 2018, 132: 143 doi: 10.1016/j.jaap.2018.03.006
[19]	Nishu, Liu R H, Rahman M M, et al. A review on the catalytic pyrolysis of biomass for the bio-oil production with ZSM-5: Focus on structure. Fuel Process Technol, 2020, 199: 106301 doi: 10.1016/j.fuproc.2019.106301
[20]	Wang L, Lei H W, Ren S J, et al. Aromatics and phenols from catalytic pyrolysis of Douglas fir pellets in microwave with ZSM-5 as a catalyst. J Anal Appl Pyrolysis, 2012, 98: 194 doi: 10.1016/j.jaap.2012.08.002
[21]	Yang Z X, Kumar A, Apblett A. Integration of biomass catalytic pyrolysis and methane aromatization over Mo/HZSM-5 catalysts. J Anal Appl Pyrolysis, 2016, 120: 484 doi: 10.1016/j.jaap.2016.06.021
[22]	Wang J X, Zhang S P, Su Y H, et al. Construction of Fe embedded graphene nanoshell/carbon nanofibers catalyst for catalytic cracking of biomass tar: Effect of CO₂ etching. Fuel, 2021, 305: 121552 doi: 10.1016/j.fuel.2021.121552
[23]	Shen Y F. Chars as carbonaceous adsorbents/catalysts for tar elimination during biomass pyrolysis or gasification. Renew Sustain Energy Rev, 2015, 43: 281 doi: 10.1016/j.rser.2014.11.061
[24]	Dong Q, Niu M M, Bi D M, et al. Microwave-assisted catalytic pyrolysis of moso bamboo for high syngas production. Bioresour Technol, 2018, 256: 145 doi: 10.1016/j.biortech.2018.02.018
[25]	Wang J J. Experimental Study on Catalytic Pyrolysis of HZSM-5 Modified by Fe, Co and Cu to Prepare Bio-oil. [Dissertation]. Zhenjiang: Jiangsu University, 2017 王嘉駿. Fe, Co, Cu改性HZSM-5催化熱解制備生物油的試驗研究[學位論文]. 鎮江: 江蘇大學, 2017
[26]	Liang S, Guo F Q, Du S L, et al. Synthesis of Sargassum char-supported Ni-Fe nanoparticles and its application in tar cracking during biomass pyrolysis. Fuel, 2020, 275: 117923 doi: 10.1016/j.fuel.2020.117923
[27]	Liu S S, Wu G, Syed-Hassan S S A, et al. Catalytic pyrolysis of pine wood over char-supported Fe: Bio-oil upgrading and catalyst regeneration by CO₂/H₂O. Fuel, 2022, 307: 121778 doi: 10.1016/j.fuel.2021.121778
[28]	Tang W, Cao J P, Wang Z H, et al. Comparative evaluation of tar steam reforming over graphitic carbon supported Ni and Co catalysts at low temperature. Energy Convers Manag, 2021, 244: 114454 doi: 10.1016/j.enconman.2021.114454
[29]	Wang Y, Jiang L, Hu S, et al. Evolution of structure and activity of char-supported iron catalysts prepared for steam reforming of bio-oil. Fuel Process Technol, 2017, 158: 180 doi: 10.1016/j.fuproc.2017.01.002
[30]	Shang S, Guo C Q, Lan K, et al. Hydrogen-rich syngas production via catalytic gasification of sewage sludge and wheat straw using corn stalk char-supported catalysts. BioResources, 2020, 15(2): 4294 doi: 10.15376/biores.15.2.4294-4313
[31]	Lan K, Qin Z H, Li Z S, et al. Syngas production by catalytic pyrolysis of rice straw over modified Ni-based catalyst. BioResources, 2020, 15(2): 2293 doi: 10.15376/biores.15.2.2293-2309
[32]	Cao L C, Yu I K M, Tsang D C W, et al. Phosphoric acid-activated wood biochar for catalytic conversion of starch-rich food waste into glucose and 5-hydroxymethylfurfural. Bioresour Technol, 2018, 267: 242 doi: 10.1016/j.biortech.2018.07.048
[33]	Zhang Y Y, Lei H W, Yang Z X, et al. From glucose-based carbohydrates to phenol-rich bio-oils integrated with syngas production via catalytic pyrolysis over an activated carbon catalyst. Green Chem, 2018, 20(14): 3346 doi: 10.1039/C8GC00593A
[34]	Yang H P, Chen Z Q, Chen W, et al. Role of porous structure and active O-containing groups of activated biochar catalyst during biomass catalytic pyrolysis. Energy, 2020, 210: 118646 doi: 10.1016/j.energy.2020.118646
[35]	Xiong X N, Yu I K M, Cao L C, et al. A review of biochar-based catalysts for chemical synthesis, biofuel production, and pollution control. Bioresour Technol, 2017, 246: 254 doi: 10.1016/j.biortech.2017.06.163
[36]	Xie Q Q, Yang X, Xu K N, et al. Conversion of biochar to sulfonated solid acid catalysts for spiramycin hydrolysis: Insights into the sulfonation process. Environ Res, 2020, 188: 109887 doi: 10.1016/j.envres.2020.109887
[37]	Wang Y T, Delbecq F, Kwapinski W, et al. Application of sulfonated carbon-based catalyst for the furfural production from d-xylose and xylan in a microwave-assisted biphasic reaction. Mol Catal, 2017, 438: 167 doi: 10.1016/j.mcat.2017.05.031
[38]	Zhang T W, Li W Z, Jin Y C, et al. Synthesis of sulfonated chitosan-derived carbon-based catalysts and their applications in the production of 5-hydroxymethylfurfural. Int J Biol Macromol, 2020, 157: 368 doi: 10.1016/j.ijbiomac.2020.04.148
[39]	Lin Q Q, Zhang S P, Wang J X, et al. Synthesis of modified char-supported Ni–Fe catalyst with hierarchical structure for catalytic cracking of biomass tar. Renew Energy, 2021, 174: 188 doi: 10.1016/j.renene.2021.04.084
[40]	Hao J Y, Qi B J, Li D, et al. Catalytic co-pyrolysis of rice straw and ulva prolifera macroalgae: Effects of process parameter on bio-oil up-gradation. Renew Energy, 2021, 164: 460 doi: 10.1016/j.renene.2020.09.056
[41]	Lu Q X, Yuan S F, Wang X Y, et al. Coking behavior and syngas composition of the char supported Fe catalyst of biomass pyrolysis volatiles reforming. Fuel, 2021, 298: 120830 doi: 10.1016/j.fuel.2021.120830
[42]	Fan X D, Wu Y J, Tu R, et al. Hydrodeoxygenation of guaiacol via rice husk char supported Ni based catalysts: The influence of char supports. Renew Energy, 2020, 157: 1035 doi: 10.1016/j.renene.2020.05.045
[43]	Xu Y, Li X, Zhang X C, et al. Hydrolysis of corncob using a modified carbon-based solid acid catalyst. BioResources, 2016, 11(4): 10469
[44]	Chai Y, Wang M H, Gao N B, et al. Experimental study on pyrolysis/gasification of biomass and plastics for H₂ production under new dual-support catalyst. Chem Eng J, 2020, 396: 125260 doi: 10.1016/j.cej.2020.125260
[45]	Huo E G, Duan D L, Lei H W, et al. Phenols production form Douglas fir catalytic pyrolysis with MgO and biomass-derived activated carbon catalysts. Energy, 2020, 199: 117459 doi: 10.1016/j.energy.2020.117459
[46]	Chang C, Liu Z H, Li P, et al. Study on products characteristics from catalytic fast pyrolysis of biomass based on the effects of modified biochars. Energy, 2021, 229: 120818 doi: 10.1016/j.energy.2021.120818
[47]	Liang S, Tian B L, Guo F Q, et al. Porous silicon film overcoating biomass char-supported catalysts for improved activity and stability in biomass pyrolysis tar decomposition. Catal Sci Technol, 2021, 11(17): 5938 doi: 10.1039/D1CY00649E
[48]	Guo F Q, Peng K Y, Liang S, et al. Evaluation of the catalytic performance of different activated biochar catalysts for removal of tar from biomass pyrolysis. Fuel, 2019, 258: 116204 doi: 10.1016/j.fuel.2019.116204
[49]	Godina L I, Kirilin A V, Tokarev A V, et al. Sibunit-supported mono- and bimetallic catalysts used in aqueous-phase reforming of xylitol. Ind Eng Chem Res, 2018, 57(6): 2050 doi: 10.1021/acs.iecr.7b04937
[50]	Bu Q, Lei H W, Wang L, et al. Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons. Bioresour Technol, 2014, 162: 142 doi: 10.1016/j.biortech.2014.03.103
[51]	Yogalakshmi K N, Poornima D T, Sivashanmugam P, et al. Lignocellulosic biomass-based pyrolysis: A comprehensive review. Chemosphere, 2022, 286(2): 131824
[52]	Shi K Q, Yan J F, Menéndez J A, et al. Production of H₂-rich syngas from lignocellulosic biomass using microwave-assisted pyrolysis coupled with activated carbon enabled reforming. Front Chem, 2020, 8: 3 doi: 10.3389/fchem.2020.00003
[53]	Zhu L, Zhang Y Y, Lei H W, et al. Production of hydrocarbons from biomass-derived biochar assisted microwave catalytic pyrolysis. Sustainable Energy Fuels, 2018, 2(8): 1781 doi: 10.1039/C8SE00096D
[54]	Bu Q, Lei H W, Wang L, et al. Renewable phenols production by catalytic microwave pyrolysis of Douglas fir sawdust pellets with activated carbon catalysts. Bioresour Technol, 2013, 142: 546 doi: 10.1016/j.biortech.2013.05.073
[55]	Yerrayya A, Suriapparao D V, Natarajan U, et al. Selective production of phenols from lignin via microwave pyrolysis using different carbonaceous susceptors. Bioresour Technol, 2018, 270: 519 doi: 10.1016/j.biortech.2018.09.051
[56]	An Y, Tahmasebi A, Zhao X H, et al. Catalytic reforming of palm kernel shell microwave pyrolysis vapors over iron-loaded activated carbon: Enhanced production of phenol and hydrogen. Bioresour Technol, 2020, 306: 123111 doi: 10.1016/j.biortech.2020.123111
[57]	Zhang S P, Dong Q, Zhang L, et al. High quality syngas production from microwave pyrolysis of rice husk with char-supported metallic catalysts. Bioresour Technol, 2015, 191: 17 doi: 10.1016/j.biortech.2015.04.114
[58]	Dai L L, Zeng Z H, Yang Q, et al. Synthesis of iron nanoparticles-based hydrochar catalyst for ex-situ catalytic microwave-assisted pyrolysis of lignocellulosic biomass to renewable phenols. Fuel, 2020, 279: 118532 doi: 10.1016/j.fuel.2020.118532
[59]	Chellappan S, Aparna K, Chingakham C, et al. Microwave assisted biodiesel production using a novel Br?nsted acid catalyst based on nanomagnetic biocomposite. Fuel, 2019, 246: 268 doi: 10.1016/j.fuel.2019.02.104
[60]	Huang S S, Xu H L, Li H Y, et al. Preparation and characterization of char supported Ni-Cu nanoalloy catalyst for biomass tar cracking together with syngas-rich gas production. Fuel Process Technol, 2021, 218: 106858 doi: 10.1016/j.fuproc.2021.106858
[61]	Fidalgo B, Arenillas A, Menéndez J A. Mixtures of carbon and Ni/Al₂O₃ as catalysts for the microwave-assisted CO₂ reforming of CH₄. Fuel Process Technol, 2011, 92(8): 1531 doi: 10.1016/j.fuproc.2011.03.015
[62]	Li J, Tao J Y, Yan B B, et al. Microwave reforming with char-supported Nickel-Cerium catalysts: A potential approach for thorough conversion of biomass tar model compound. Appl Energy, 2020, 261: 114375 doi: 10.1016/j.apenergy.2019.114375
[63]	Chen G Y, Li J, Cheng Z J, et al. Investigation on model compound of biomass gasification tar cracking in microwave furnace: Comparative research. Appl Energy, 2018, 217: 249 doi: 10.1016/j.apenergy.2018.02.028
[64]	Dong Q, Li H J, Niu M M, et al. Microwave pyrolysis of moso bamboo for syngas production and bio-oil upgrading over bamboo-based biochar catalyst. Bioresour Technol, 2018, 266: 284 doi: 10.1016/j.biortech.2018.06.104
[65]	Luo H, Bao L W, Wang H, et al. Microwave-assisted in situ elimination of primary tars over biochar: Low temperature behaviours and mechanistic insights. Bioresour Technol, 2018, 267: 333 doi: 10.1016/j.biortech.2018.07.071
[66]	Bu Q, Lei H W, Ren S J, et al. Phenol and phenolics from lignocellulosic biomass by catalytic microwave pyrolysis. Bioresour Technol, 2011, 102(13): 7004 doi: 10.1016/j.biortech.2011.04.025
[67]	Omoriyekomwan J E, Tahmasebi A, Yu J L. Production of phenol-rich bio-oil during catalytic fixed-bed and microwave pyrolysis of palm kernel shell. Bioresour Technol, 2016, 207: 188 doi: 10.1016/j.biortech.2016.02.002
[68]	Zeng Z H, Tian X J, Wang Y P, et al. Microwave-assisted catalytic pyrolysis of corn cobs with Fe-modified Choerospondias axillaris seed-based biochar catalyst for phenol-rich bio-oil. J Anal Appl Pyrolysis, 2021, 159: 105306 doi: 10.1016/j.jaap.2021.105306
[69]	Dong Q, Li H J, Zhang S P, et al. Biomass tar cracking and syngas production using rice husk char-supported nickel catalysts coupled with microwave heating. RSC Adv, 2018, 8(71): 40873 doi: 10.1039/C8RA09045A
[70]	Bu Q, Lei H W, Wang L, et al. Biofuel production from catalytic microwave pyrolysis of Douglas fir pellets over ferrum-modified activated carbon catalyst. J Anal Appl Pyrolysis, 2015, 112: 74 doi: 10.1016/j.jaap.2015.02.019
[71]	Morgan H M Jr, Liang J H, Chen K, et al. Bio-oil production via catalytic microwave co-pyrolysis of lignin and low density polyethylene using zinc modified lignin-based char as a catalyst. J Anal Appl Pyrolysis, 2018, 133: 107 doi: 10.1016/j.jaap.2018.04.014
[72]	Chen C X, Bu X Y, Qi Q H, et al. Experimental study on microwave pyrolysis of Dunaliella salina using compound additives. Bioenerg Res, 2021, 14(4): 1300 doi: 10.1007/s12155-020-10222-8