生物质热解制备高品质生物油研究进展

doi:10.16085/j.issn.1000-6613.2020-0486

摘要/Abstract

摘要：

生物质热解制备生物油是能源富集的有效途径，是实现碳闭路循环的重要方式，作为一种环境友好型技术受到广泛关注和研究。然而，生物质热解反应过程复杂，生成的生物油热值低、含氧量高及强酸性等特点，制约了生物油的分离提纯、制备合成气以及燃烧等方面的应用，生物油品质的提升迫在眉睫。本文从生物质三组分、原料预处理、反应参数、催化剂、反应器等方面综述了影响生物油品质的主要因素，分析了生物油的特点，不同预处理下生物质特性的变化与生物油的关系，催化剂参与的热解行为对提升生物油品质的导向作用以及常用生物质热解反应器的特点，并对影响生物油品质的主要因素进行了总结。最后，针对影响制备高品质生物油的诸多因素提出建议，以期为制备高品质生物油提供参考和借鉴。

关键词: 生物质, 热解, 生物油, 预处理, 催化剂, 失活

Abstract:

Preparation of bio-oil by biomass pyrolysis is an effective way to enrich energy and realize the closed cycle of carbon, which has been widely concerned and studied as an environmental friendly technology. However, the process of biomass pyrolysis is very complex, and the resulting bio-oil shows low heat value, high oxygen content and strong acidity, which restricts the separation and purification, producing syngas and combustion. Therefore, the improvement of bio-oil quality is more urgent. In this paper, the main factors affecting the quality of bio-oil are reviewed from the aspects of three components, raw material pretreatment, reaction parameters, catalysts and reactors. In addition, this article analyzes characteristics of bio-oil and the relationship to the change of biomass properties under different pretreatment, the guiding effect of improving bio-oil quality in pyrolysis behavior involving catalysts, and the advantages and disadvantages of commonly used biomass pyrolysis reactors. Finally, it summarizes the main factors that affects the quality of bio-oil. Then, some suggestions for affecting the production of high quality bio-oil are put forward, which is expected to provide reference for the production of high quality bio-oil.

Key words: biomass, pyrolysis, bio-oil, pretreatment, catalyst, deactivation

中图分类号:

仉利, 姚宗路, 赵立欣, 李志合, 易维明, 付鹏, 袁超. 生物质热解制备高品质生物油研究进展[J]. 化工进展, 2021, 40(1): 139-150.

Li ZHANG, Zonglu YAO, Lixin ZHAO, Zhihe LI, Weiming YI, Peng FU, Chao YUAN. Research progress on preparation of high quality bio-oil by pyrolysis of biomass[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 139-150.

图/表 6

参考文献 119

1	DEMIRBAS A. The social, economic, and environmental importance of biofuels in the future[J]. Energy Sources Part B: Economics Planning and Policy, 2017, 12(1): 47-55.
2	HEW K L, TAMIDI A M, YUSUP S, et al. Catalytic cracking of bio-oil to organic liquid product (OLP)[J]. Bioresource Technology, 2010, 101(22): 8855-8858.
3	CHEN D, MEI J, LI H, et al. Combined pretreatment with torrefaction and washing using torrefaction liquid products to yield upgraded biomass and pyrolysis products[J]. Bioresource Technology, 2017, 228: 62-68.
4	YANG Z, KUMAR A, HUHNKE R L. Review of recent developments to improve storage and transportation stability of bio-oil[J]. Renewable and Sustainable Energy Reviews, 2015, 50: 859-870.
5	ANTONAKOU E, LAPPAS A, NILSEN M H, et al. Evaluation of various types of Al-MCM-41 materials as catalysts in biomass pyrolysis for the production of bio-fuels and chemicals[J]. Fuel, 2006, 85(14/15): 2202-2212.
6	浮爱青, 谌伦建, 杨洁, 等. 小麦与玉米秸秆的热解过程及其动力学分析[J]. 化学工业与工程, 2009, 26(4): 350-353.
	FU A Q, SHEN L J, YANG J, et al. Pyrolysis process and kinetics analysis of corn stalk and wheat straw[J]. Chemical Industry and Engineering, 2009, 26(4): 350-353.
7	胡二峰, 赵立欣, 吴娟, 等. 生物质热解影响因素及技术研究进展[J]. 农业工程学报, 2018, 34(14): 212-220.
	HU E F, ZHAO L X, WU J,et al. Research advance on influence factors and technologies of biomass pyrolysis[J]. Transactions of the Chinese Society of Agricultural Engineering, 2018, 34(14): 212-220.
8	周芳磊, 胡雨燕, 陈德珍. 不同种类生物质热解残焦的CO₂气化研究[J]. 太阳能学报, 2017, 38(5): 1440-1446.
	ZHOU F L, HU Y Y, CHEN D Z. Production of CO by CO₂ gasification of biomass-derived char[J]. Acta Energiae Solaris Sinica, 2017, 38(5): 1440-1446.
9	田宜水, 王茹. 基于多升温速率法的典型生物质热动力学分析[J]. 农业工程学报, 2016, 32(3): 234-240.
	TIAN Y S, WANG R. Thermokinetics analysis of biomass based on model-free different heating rate method[J]. Transactions of the Chinese Society of Agricultural Engineering, 2016, 32(3): 234-240.
10	杨选民, 王雅君, 邱凌, 等. 温度对生物质三组分热解制备生物炭理化特性的影响[J]. 农业机械学报, 2017, 48(4): 284-290.
	YANG X M, WANG Y J, QIU L, et al. Effect of temperature on physicochemical properties of biochar prepared by pyrolysis of three components of biomass[J]. Transactions of the Chinese Society for Agricultural Machinery, 2017, 48(4): 284-290.
11	姬文心, 曾鸣, 丛宏斌, 等. 生物质热解反应装置研究现状及展望[J].生物质化学工程, 2019, 53(3): 46-58.
	JI W X, ZENG M, CONG H B, et al. Research status and prospects of biomass pyrolysis reactor[J]. Biomass Chemical Engineering, 2019, 53(3): 46-58.
12	LU Q, LI W Z, ZHU X F. Overview of fuel properties of biomass fast pyrolysis oils[J]. Energy Conversion and Management, 2009, 50(5): 1376-1383.
13	GARCIAPEREZ M, CHAALA A, PAKDEL H, et al. Vacuum pyrolysis of softwood and hardwood biomass: comparison between product yields and bio-oil properties[J]. Journal of Analytical and Applied Pyrolysis, 2007, 78(1): 104-116.
14	罗泽军, 胡永华, 王雨松, 等. 重质生物油理化性质及其热解特性研究[J]. 化工学报, 2019, 70(8): 3196-3201.
	LUO Z J, HU Y H, WANG Y S, et al. Physicochemical properties and pyrolysis characteristics of heavy bio-oil[J]. CIESC Journal, 2019, 70(8): 3196-3201.
15	OASMAA A, MEIER D. Norms and standards for fast pyrolysis liquids: 1. Round robin test[J]. Journal of Analytical and Applied Pyrolysis, 2005, 73(2): 323-334.
16	王昕. 生物质选择性热解制备酚类化合物的研究[D]. 北京: 华北电力大学, 2018.
	WANG X. Selective fast pyrosis of biomass to produce phenolic compounds[D]. Beijing: North China Electric Power University, 2018.
17	陆强. 生物质选择性热解液化的研究[D]. 北京: 中国科学技术大学, 2010.
	LU Q. Selective fast pyrosis of biomas[D]. Beijing: University of Science and Technology of China, 2010.
18	李毅, 张哲民, 渠红亮, 等. 生物喷气燃料制备技术研究进展[J]. 石油学报(石油加工), 2013, 29(2): 359-367.
	LI Y, ZHANG Z M, QU H L, et al. Reviewon the progress of producing bio-jet fuel[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2013, 29(2): 359-367.
19	POPOV A, KONDRATIEVA E, MARIEY L, et al. Bio-oil hydrodeoxygenation: adsorption of phenolic compounds on sulfided (Co) Mo catalysts[J]. Journal of Catalysis, 2013, 297: 176-186.
20	KUMAR R, STREZOV V, WELDEKIDAN H, et al. Lignocellulose biomass pyrolysis for bio-oil production: a review of biomass pre-treatment methods for production of drop-in fuels[J]. Renewable and Sustainable Energy Reviews, 2020, 123: 109763.
21	WANG S, DAI G, YANG H, et al. Lignocellulosic biomass pyrolysis mechanism: a state-of-the-art review[J]. Progress in Energy and Combustion Science, 2017, 62: 33-86.
22	HOSOYA T, KAWAMOTO H, SAKA S. Pyrolysis behaviors of wood and its constituent polymers at gasification temperature[J]. Journal of Analytical and Applied Pyrolysis, 2007, 78(2): 328-336.
23	FAN Y, CAI Y, LI X, et al. Effects of the cellulose, xylan and lignin constituents on biomass pyrolysis characteristics and bio-oil composition using the Simplex Lattice Mixture Design method[J]. Energy Conversion and Management, 2017, 138: 106-118.
24	CHANG G, HUANG Y, XIE J, et al. The lignin pyrolysis composition and pyrolysis products of palm kernel shell, wheat straw, and pine sawdust[J]. Energy Conversion & Management, 2016, 124: 587-597.
25	SAHA B C, QURESHI N, KENNEDY G J, et al. Biological pretreatment of corn stover with white-rot fungus for improved enzymatic hydrolysis[J]. International Biodeterioration & Biodegradation, 2016, 109: 29-35.
26	DAI L, WANG Y, LIU Y, et al. Integrated process of lignocellulosic biomass torrefaction and pyrolysis for upgrading bio-oil production: a state-of-the-art review[J]. Renewable and Sustainable Energy Reviews, 2019, 107: 20-36.
27	HAO N, BEZERRA T L, WU Q, et al. Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process[J]. Fuel, 2017, 206: 494-503.
28	ZHENG A, ZHAO Z, HUANG Z, et al. Overcoming biomass recalcitrance for enhancing sugar production from fast pyrolysis of biomass by microwave pretreatment in glycerol[J]. Green Chemistry, 2015, 17(2): 1167-1175.
29	BHATIA S K, JAGTAP S S, BEDEKAR A A, et al. Recent developments in pretreatment technologies on lignocellulosic biomass: effect of key parameters, technological improvements, and challenges[J]. Bioresource Technology, 2020, 300: 122724.
30	ALVIRA P, TOMASPEJO E, BALLESTEROS M, et al. Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: a review[J]. Bioresource Technology, 2010, 101(13): 4851-4861.
31	SHEN J, WANG X S, GARCIAPEREZ M, et al. Effects of particle size on the fast pyrolysis of oil mallee woody biomass[J]. Fuel, 2009, 88(10): 1810-1817.
32	GARG R, ANAND N, KUMAR D. Pyrolysis of babool seeds (acacia nilotica) in a fixed bed reactor and bio-oil characterization[J]. Renewable Energy, 2016, 96: 167-171.
33	KERSTEN S R A, WANG X, PRINS W, et al. Biomass pyrolysis in a fluidized bed reactor. Part 1: Literature review and model simulations[J]. Industrial & Engineering Chemistry Research, 2005, 44(23): 8773-8785.
34	WRIGHT M M, DAUGAARD D E, SATRIO J A, et al. Techno-economic analysis of biomass fast pyrolysis to transportation fuels[J]. Fuel, 2010, 89: S2-S10.
35	CHEN D, GAO A, CEN K, et al. Investigation of biomass torrefaction based on three major components: hemicellulose, cellulose, and lignin[J]. Energy Conversion and Management, 2018, 169: 228-237.
36	REN S, LEI H, WANG L, et al. Microwave torrefaction of Douglas fir sawdust pellets[J]. Energy & Fuels, 2012, 26(9): 5936-5943.
37	REN S, LEI H, WANG L, et al. The effects of torrefaction on compositions of bio-oil and syngas from biomass pyrolysis by microwave heating[J]. Bioresource Technology, 2013, 135: 659-664.
38	陈登宇, 张鸿儒, 刘栋, 等. 烘焙预处理对秸秆热解产物品质及能量分布的影响[J]. 太阳能学报, 2017, 38(2): 565-570.
	CHEN D Y, ZHANG H R, LIU D, et al. Effect of torrefaction pretreatment on properties of pyrolysis product and energy distribution of corn stalk[J]. Acta Energiae Solaris Sinica, 2017, 38(2): 565-570.
39	CHEN D, CEN K, JING X, et al. An approach for upgrading biomass and pyrolysis product quality using a combination of aqueous phase bio-oil washing and torrefaction pretreatment[J]. Bioresource Technology, 2017, 233: 150-158.
40	李攀. 生物质催化热解制备高选择性芳香烃生物油的实验研究[D]. 武汉: 华中科技大学, 2016.
	LI P. Highly selective aromatics by catalytic pyrolysis of biomass[D]. Wuhan: Huazhong University of Science and Technology, 2016.
41	FENG Y, LI G, LI X, et al. Enhancement of biomass conversion in catalytic fast pyrolysis by microwave-assisted formic acid pretreatment[J]. Bioresource Technology, 2016, 214: 520-527.
42	MOHAMMED I Y, ABAKR Y A, KAZI F K, et al. Effects of pretreatments of Napier grass with deionized water, sulfuric acid and sodium hydroxide on pyrolysis oil characteristics[J]. Waste and Biomass Valorization, 2017, 8(3): 755-773.
43	SHI W, LI S, JIA J, et al. Highly efficient conversion of cellulose to bio-oil in hot-compressed water with ultrasonic pretreatment[J]. Industrial & Engineering Chemistry Research, 2013, 52(2): 586-593.
44	TARVES P C, SERAPIGLIA M J, MULLEN C A, et al. Effects of hot water extraction pretreatment on pyrolysis of shrub willow[J]. Biomass and Bioenergy, 2017, 107: 299-304.
45	LE R É, DIOUF P N, STEVANOVIC T. Analytical pyrolysis of hot water pretreated forest biomass[J]. Journal of Analytical and Applied Pyrolysis, 2015, 111: 121-131.
46	HUANG Z, WUFUER A, WANG Y, et al. Hydrothermal liquefaction of pretreated low-lipid microalgae for the production of bio-oil with low heteroatom content[J]. Process Biochemistry, 2018, 69: 136-143.
47	DICKERSON T, SORIA J. Catalytic fast pyrolysis: a review[J]. Energies, 2013, 6(1): 514-538.
48	LOU R, WU S, LV G. Fast pyrolysis of enzymatic/mild acidolysis lignin from moso bamboo[J]. Bioresources, 2010, 5(2): 827-837.
49	LOU R, WU S, LV G. Effect of conditions on fast pyrolysis of bamboo lignin[J]. Journal of Analytical and Applied Pyrolysis, 2010, 89(2): 191-196.
50	REN X Y, ZHANG Z T, WANG W L, et al. Transformation and products distribution of moso bamboo and derived components during pyrolysis[J]. Bioresources, 2013, 8(3): 3685-3698.
51	WANG P, ZHAN S, YU H, et al. The effects of temperature and catalysts on the pyrolysis of industrial wastes (herb residue)[J]. Bioresource Technology, 2010, 101(9): 3236-3241.
52	典平鸽, 张乐观, 江程程. 裂解温度对生物质热解焦油成分的影响[J]. 可再生能源, 2012, 30(5): 54-58.
	DIAN P G, ZHANG L G, JIANG C C. The influence of pyrolysis temperature on the component of biomass pyrolytic tar[J]. Renewable Energy Resources, 2012, 30(5): 54-58.
53	王敬茹,姚宗路,丛宏斌, 等. 生物质炭催化玉米秸秆热解气重整提质研究[J].农业工程学报, 2019, 35(16): 258-264.
	WANG J R, YAO Z L, CONG H B, et al. Upgrading biomass pyrolysis gas from corn stalk by charcoal catalytic reforming[J]. Transactions of the Chinese Society of Agricultural Engineering, 2019, 35(16): 258-264.
54	ZHANG H, XIAO R, WANG D, et al. Biomass fast pyrolysis in a fluidized bed reactor under N₂, CO₂, CO, CH₄ and H₂ atmospheres[J]. Bioresource Technology, 2011, 102(5): 4258-4264.
55	MANTE O D, AGBLEVOR F A, OYAMA S T, et al. The influence of recycling non-condensable gases in the fractional catalytic pyrolysis of biomass[J]. Bioresource Technology, 2012, 111: 482-490.
56	李永玲, 吴占松. 秸秆热解特性及热解动力学研究[J]. 热力发电, 2008(7):1-5.
	LI Y L, WU Z S. Study on charicters and dynamics concerning pyrolysis of corn stalks[J]. Thermal Power Generation, 2008(7): 1-5.
57	王树荣, 骆仲泱, 董良杰, 等. 几种农林废弃物热裂解制取生物油的研究[J]. 农业工程学报, 2004(2): 246-249.
	WANG S R, LUO Z Y, DONG L J, et al. Experimental study on bio-oil production from biomass of some agricultural and forestry residues[J]. Transactions of the Chinese Society of Agricultural Engineering, 2004(2): 246-249.
58	王雅君, 李丽洁, 邓媛方, 等. 变速升温对玉米秸秆热解产物特性的影响[J]. 农业机械学报, 2018, 49(4): 337-342, 350.
	WANG Y J, LI L J, DENG Y F, et al. Effect of variable heating rate on pyrolysis process and product characteristics of corn stalk[J]. Transactions of the Chinese Society for Agricultural Machinery, 2018, 49(4): 337-342, 350.
59	WANG K, KIM K H, BROWN R C. Catalytic pyrolysis of individual components of lignocellulosic biomass[J]. Green Chemistry, 2014, 16(2): 727-735..
60	STEFANIDIS S D, KALOGIANNIS K G, LLIOPOULOU E F, et al. In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor[J]. Bioresource Technology, 2011, 102(17): 8261-8267.
61	ADAM J, BLAZSO M, MESZAROS E, et al. Pyrolysis of biomass in the presence of Al-MCM-41 type catalysts[J]. Fuel, 2005, 84(12/13): 1494-1502.
62	ADAM J, ANTONAKOU E, LAPPAS A, et al. In situ catalytic upgrading of biomass derived fast pyrolysis vapours in a fixed bed reactor using mesoporous materials[J]. Microporous and Mesoporous Materials, 2006, 96(1/2/3): 93-101.
63	NILSEN M H, ANTONAKOU E, BOUZGA A, et al. Investigation of the effect of metal sites in Me-Al-MCM-41 (Me= Fe, Cu or Zn) on the catalytic behavior during the pyrolysis of wooden based biomass[J]. Microporous and Mesoporous Materials, 2007, 105(1/2): 189-203.
64	LLIOPOULOU E F, STEFANIDIS S D, KALOGIANNIS K G, et al. Catalytic upgrading of biomass pyrolysis vapors using transition metal-modified ZSM-5 zeolite[J]. Applied Catalysis B: Environmental, 2012, 127: 281-290.
65	CHEN X, CHEN Y, YANG H, et al. Catalytic fast pyrolysis of biomass: selective deoxygenation to balance the quality and yield of bio-oil[J]. Bioresource Technology, 2019, 273: 153-158.
66	ARORA J S, CHEW J W, MUSHRIF S H. Influence of alkali and alkaline-earth metals on the cleavage of glycosidic bond in biomass pyrolysis: a DFT study using cellobiose as a model compound[J]. The Journal of Physical Chemistry A, 2018, 122(38): 7646-7658.
67	RAYMUNDO L M, MULLEN C A, STRAHAN G D, et al. Deoxygenation of biomass pyrolysis vapors via in situ and ex situ thermal and biochar promoted upgrading[J]. Energy & Fuels, 2019, 33(3): 2197-2207.
68	JAE J, TOMPSETT G A, FOSTER A J, et al. Investigation into the shape selectivity of zeolite catalysts for biomass conversion[J]. Journal of Catalysis, 2011, 279(2): 257-268.
69	WILLIAMS P T, NUGRANAD N. Comparison of products from the pyrolysis and catalytic pyrolysis of rice husks[J]. Energy, 2000, 25(6): 493-513.
70	TANG S, ZHANG C, XUE X, et al. Catalytic pyrolysis of lignin over hierarchical HZSM-5 zeolites prepared by post-treatment with alkaline solutions[J]. Journal of Analytical and Applied Pyrolysis, 2019, 137: 86-95.
71	YU N, CAI Y, LI X, et al. Catalytic pyrolysis of rape straw for upgraded bio-oil production using HZSM-5 zeolite[J]. Transactions of the Chinese Society of Agricultural Engineering, 2014, 30(15): 264-271.
72	MENDES F L, XIMENES V L, ALMEIDA M D, et al. Catalytic pyrolysis of sugarcane bagasse and pinewood in a pilot scale unit[J]. Journal of Analytical and Applied Pyrolysis, 2016, 122: 395-404.
73	CHEN X, CHE Q, LI S, et al. Recent developments in lignocellulosic biomass catalytic fast pyrolysis: strategies for the optimization of bio-oil quality and yield[J]. Fuel Processing Technology, 2019, 196: 106180.
74	LI J, LI X, ZHOU G, et al. Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared by desilication with NaOH solutions[J]. Applied Catalysis A: General, 2014, 470: 115-122.
75	ZHENG Y, WANG F, YANG X, et al. Study on aromatics production via the catalytic pyrolysis vapor upgrading of biomass using metal-loaded modified H-ZSM-5[J]. Journal of Analytical and Applied Pyrolysis, 2017, 126: 169-179.
76	CHENG Y T, JAE J, SHI J, et al. Production of renewable aromatic compounds by catalytic fast pyrolysis of lignocellulosic biomass with bifunctional Ga/ZSM-5 catalysts[J]. Angewandte Chemie International Edition, 2012, 51(6): 1387-1390.
77	ENGTRAKUL C, MUKARAKATE C, STARACE A K, et al. Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors[J]. Catalysis Today, 2016, 269: 175-181.
78	杨雅, 郭庆杰, 杨林, 等. 碱脱硅改性的HZSM-5分子筛催化裂解小球藻的研究[J]. 太阳能学报, 2016, 37(1): 171-177.
	YANG Y, GUO Q J, YANG L, et al. Catalytic cracking of chlorella over HZSM-5 zeolite modified by desilication in alkalilie medium[J]. Acta Energiae Solaris Sinica, 2016, 37(1): 171-177.
79	ZHANG H, WANG Y, SHAO S, et al. Catalytic conversion of lignin pyrolysis model compound-guaiacol and its kinetic model including coke formation[J]. Scientific Reports, 2016, 6: 37513.
80	ZGANG H, SHAO S, XIAO R, et al. Characterization of coke deposition in the catalytic fast pyrolysis of biomass derivates[J]. Energy & Fuels, 2014, 28(1): 52-57.
81	YANG H, COOLMAN R, KARANJKAR P, et al. The effects of contact time and coking on the catalytic fast pyrolysis of cellulose[J]. Green Chemistry, 2017, 19(1): 286-297.
82	DU S, VALLA J A, BOLLAS G M. Characteristics and origin of char and coke from fast and slow, catalytic and thermal pyrolysis of biomass and relevant model compounds[J]. Green Chemistry, 2013, 15(11): 3214-3229.
83	STANTON A R, LISA K, MUKARAKATE C, et al. Role of biopolymers in the deactivation of ZSM-5 during catalytic fast pyrolysis of biomass[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(8): 10030-10038.
84	SHAO S, ZHANG H, WANG Y, et al. Catalytic pyrolysis of biomass-derived compounds: coking kinetics and formation network[J]. Energy & Fuels, 2015, 29(3): 1751-1757.
85	ZHANG H, MA Y, SHAO S, et al. The effects of potassium on distributions of bio-oils obtained from fast pyrolysis of agricultural and forest biomass in a fluidized bed[J]. Applied Energy, 2017, 208: 867-877.
86	HWANG H, OH S, CHO T S, et al. Fast pyrolysis of potassium impregnated poplar wood and characterization of its influence on the formation as well as properties of pyrolytic products[J]. Bioresource Technology, 2013, 150: 359-366.
87	BANKS S W, NOWAKOWSKI D J, BRIDGWATER A V. Impact of potassium and phosphorus in biomass on the properties of fast pyrolysis bio-oil[J]. Energy & Fuels, 2016, 30(10): 8009-8018.
88	PATWARDHAN P R, SATRIO J A, BROWN R C, et al. Influence of inorganic salts on the primary pyrolysis products of cellulose[J]. Bioresource Technology, 2010, 101(12): 4646-4655.
89	SADDAWI A, JONES J M, WILLIAMS A. Influence of alkali metals on the kinetics of the thermal decomposition of biomass[J]. Fuel Processing Technology, 2012, 104: 189-197.
90	PENG C, ZHANG G, YUE J, et al. Pyrolysis of lignin for phenols with alkaline additive[J]. Fuel Processing Technology, 2014, 124: 212-221.
91	DALLUGE D L, KIM K H, BROWN R C. The influence of alkali and alkaline earth metals on char and volatile aromatics from fast pyrolysis of lignin[J]. Journal of Analytical and Applied Pyrolysis, 2017, 127: 385-393.
92	CARVALHO W S, CUNHA I F, PEREIRA M S, et al. Thermal decomposition profile and product selectivity of analytical pyrolysis of sweet sorghum bagasse: effect of addition of inorganic salts[J]. Industrial Crops and Products, 2015, 74: 372-380.
93	BRANCA C, DI BLASI C, GALGANO A. Pyrolysis of corncobs catalyzed by zinc chloride for furfural production[J]. Industrial & Engineering Chemistry Research, 2010, 49(20): 9743-9752.
94	LU Q, DONG C, ZHANG X, et al. Selective fast pyrolysis of biomass impregnated with ZnCl₂ to produce furfural: analytical Py-GC/MS study[J]. Journal of Analytical and Applied Pyrolysis, 2011, 90(2): 204-212.
95	MOCHIZUKI T, ATONG D, CHEN S Y, et al. Effect of SiO₂ pore size on catalytic fast pyrolysis of Jatropha residues by using pyrolyzer-GC/MS[J]. Catalysis Communications, 2013, 36: 1-4.
96	KAEWPENGKROW P, ATONG D, SRICHAROENCHAIKUL V. Effect of metal oxide/alumina on catalytic deoxygentation of biofuel from physic nut residues pyrolysis[J]. International Journal of Hydrogen Energy, 2017, 42(31): 19629-19640.
97	LU Q, XIONG W M, LI W Z, et al. Catalytic pyrolysis of cellulose with sulfated metal oxides: a promising method for obtaining high yield of light furan compounds[J]. Bioresource Technology, 2009, 100(20): 4871-4876.
98	PUTUN E. Catalytic pyrolysis of biomass: effects of pyrolysis temperature, sweeping gas flow rate and MgO catalyst[J]. Energy, 2010, 35(7): 2761-2766.
99	STEFANIDIS S D, KARAKOULIA S A, KALOGIANNIS K G, et al. Natural magnesium oxide (MgO) catalysts: a cost-effective sustainable alternative to acid zeolites for the in situ upgrading of biomass fast pyrolysis oil[J]. Applied Catalysis B: Environmental, 2016, 196: 155-173.
100	EL-RUB Z A, BRAMER E A, BREM G. Experimental comparison of biomass chars with other catalysts for tar reduction[J]. Fuel, 2008, 87(10/11): 2243-2252.
101	GAO X, ZHANG Y, XU F, et al. Experimental and kinetic studies on the intrinsic reactivities of rice husk char[J]. Renewable Energy, 2019, 135: 608-616.
102	向玲, 李立松, 李新, 等. 炭基催化剂比表面积、孔径与硫容关系研究[J]. 四川环境, 2014, 33(1): 18-21.
	XIANG L, LI L S, LI X, et al. Study on the relationship between specific surface area, pore volume and sulfur capacity of activated carbon catalyst[J]. Sichuan Environment, 2014, 33(1): 18-21.
103	GUO F, PENG K, LIANG S, et al. Evaluation of the catalytic performance of different activated biochar catalysts for removal of tar from biomass pyrolysis[J]. Fuel, 2019, 258: 116204.
104	LIU Y, PASKVICIUS M, WANG H, et al. Role of O-containing functional groups in biochar during the catalytic steam reforming of tar using the biochar as a catalyst[J]. Fuel, 2019, 253: 441-448.
105	张纯. 外热式内构件移动床低阶碎煤热解技术研究[D]. 北京: 中国科学院研究生院（过程工程研究所), 2015.
	ZHANG C. Pyrolysis of small-size low coal in heated moving bed with internals[D]. Beijing: Graduate School of Chinese Academy of Sciences (Institute of Process Engineering), 2015.
106	HU E, ZENG X, MA D, et al. Characterization of coal pyrolysis in indirectly heated fixed bed based on field effects[J]. Fuel, 2017, 200: 186-192.
107	辛子扬, 葛立超, 冯红翠, 等. 生物质微波热解利用技术综述[J]. 热力发电, 2019, 48(7): 19-31.
	XIN Z Y, GE L C, FENG H C, et al. Application of microwave technology in biomass pyrolysis: a review[J]. Thermal Power Generation, 2019, 48(7): 19-31.
108	WU C, BUDARIN V L, GRONNOW M J, et al. Conventional and microwave-assisted pyrolysis of biomass under different heating rates[J]. Journal of Analytical and Applied Pyrolysis, 2014, 107: 276-283.
109	MORGAN JR H M, BU Q, LIANG J, et al. A review of catalytic microwave pyrolysis of lignocellulosic biomass for value-added fuel and chemicals[J]. Bioresource Technology, 2017, 230: 112-121.
110	刘荣厚, 鲁楠, 曹玉瑞, 等. 旋转锥反应器生物质热裂解工艺过程及实验[J]. 沈阳农业大学学报, 1997(4): 307-311.
	LIU R H, LU N, CAO Y R, et al. Technolocical process and experimental research of the rotating cone reactor for biomass pyrolysis[J]. Journal of Shenyang Agricultural University, 1997(4): 307-311.
111	丛宏斌, 姚宗路, 赵立欣, 等. 生物质连续热解炭气油联产中试系统开发[J]. 农业工程学报, 2017, 33(18): 173-179.
	CONG H B, YAO Z L, ZHAO L X, et al. Development of carbon, gas and oil poly-generation pilot system based on biomass continuous pyrolysis[J]. Transactions of the Chinese Society of Agricultural Engineering, 2017, 33(18): 173-179.
112	高新源, 徐庆, 李占勇, 等. 生物质快速热解装置研究进展[J]. 化工进展, 2016, 35(10): 3032-3041.
	GAO X Y, XU Q, LI Z Y, et al. Progress in the study of biomass fast pyrolysis equipment[J]. Chemical Industry and Engineering Progress, 2016, 35(10): 3032-3041.
113	林木森. 国外生物质快速热解反应器现状[J]. 化学工业与工程技术, 2010, 31(5): 34-36.
	LIN M S. Status of reactors for fast pyrolysis of biomass in abroad[J]. Chemical Industry and Engineering, 2010, 31(5): 34-36.
114	BRIDGWATER A V. Fast pyrolysis of biomass for energy and fuels[J]. Thermochemical Conversion of Biomass to Liquid Fuels and Chemicals, 2010: 146-191.
115	FU P, YI W M, LI Z, et al. Evolution of char structural features during fast pyrolysis of corn straw with solid heat carriers in a novel V-shaped down tube reactor[J]. Energy Conversion and Management, 2017, 149: 570-578.
116	KALOGIANNI K G, STEFANIDIS S D, Lappas A A. Catalyst deactivation, ash accumulation and bio-oil deoxygenation during ex situ catalytic fast pyrolysis of biomass in a cascade thermal-catalytic reactor system[J]. Fuel Processing Technology, 2019, 186: 99-109.
117	LIU S, ZHANG Y, FAN L, et al. Bio-oil production from sequential two-step catalytic fast microwave-assisted biomass pyrolysis[J]. Fuel, 2017, 196: 261-268.
118	常全超, 杜玉凤, 戴敏, 等.太阳能热解制备生物炭及其对水中铜离子的吸附[J]. 环境工程学报， 2020， 14(11): 2946-2958.
	CHANG Q C, DU Y F, DAI M, et al. Properties of biochar prepared by solar pyrolysis and its adsorption of copper ions in water[J]. Chinese Journal of Environmental Engineering， 2020， 14(11): 2946-2958.
119	白章. 太阳能与生物质能热化学互补高效利用系统集成与方法[D]. 北京：中国科学院研究生院（工程热物理研究所）, 2016.
	BAI Z. Integration mechanism for thermochemical hybrid utilization of solar thermal energy and biomass[D]. Beijing: Chinese Academy of Sciences(Institute of Engineering Thermophysics), 2016.

反应器类型	优点	缺点
流化床热解反应器	不含运动部件；结构较为简单；工作可靠性大；处理量大；传热系数高；使用寿命长等	需要的流化气流量较多；损失能量较大
螺旋反应器	原理简单；能耗低；较高热效率；实现连续运行	温度分布不均；螺杆和壁面温差较大；热解原料易附着，造成堵塞
旋转锥反应器	结构紧凑；不需要载气，避免了热解气的稀释，降低了成本；加热效率高，减少生物质热解气二次催化裂解	原料粒径要求较小；设备复杂；工作可靠性难以保证（支撑外伸轴的轴承长时间在高温和高粉尘的条件下运行）
烧蚀式反应器	结构简单紧凑；运行能耗低；加热速率快（提高生物油的产率）	结构和操作复杂（反应物与高温壁面紧密接触，对材料和轴承的性能要求高），不利于大规模生产
真空热解反应器	系统内压力低；产生的生物质热解气停留时间短	油产率不高（生物质升温速率缓慢）；能耗高（真空泵功率较大），不利于大规模推广

反应器类型	优点	缺点
流化床热解反应器	不含运动部件；结构较为简单；工作可靠性大；处理量大；传热系数高；使用寿命长等	需要的流化气流量较多；损失能量较大
螺旋反应器	原理简单；能耗低；较高热效率；实现连续运行	温度分布不均；螺杆和壁面温差较大；热解原料易附着，造成堵塞
旋转锥反应器	结构紧凑；不需要载气，避免了热解气的稀释，降低了成本；加热效率高，减少生物质热解气二次催化裂解	原料粒径要求较小；设备复杂；工作可靠性难以保证（支撑外伸轴的轴承长时间在高温和高粉尘的条件下运行）
烧蚀式反应器	结构简单紧凑；运行能耗低；加热速率快（提高生物油的产率）	结构和操作复杂（反应物与高温壁面紧密接触，对材料和轴承的性能要求高），不利于大规模生产
真空热解反应器	系统内压力低；产生的生物质热解气停留时间短	油产率不高（生物质升温速率缓慢）；能耗高（真空泵功率较大），不利于大规模推广

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[8]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[9]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[10]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[11]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[12]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[13]	邵志国, 任雯, 许世佩, 聂凡, 许毓, 刘龙杰, 谢水祥, 李兴春, 王庆吉, 谢加才. 终温对油基钻屑热解产物分布和特性影响[J]. 化工进展, 2023, 42(9): 4929-4938.
[14]	李志远, 黄亚继, 赵佳琪, 于梦竹, 朱志成, 程好强, 时浩, 王圣. 污泥与聚氯乙烯共热解重金属特性[J]. 化工进展, 2023, 42(9): 4947-4956.
[15]	李由, 吴越, 钟禹, 林琦璇, 任俊莉. 酸性熔盐水合物预处理麦秆高效制备木糖及其对酶解效率的影响[J]. 化工进展, 2023, 42(9): 4974-4983.