Progress in formation mechanism and selective production of anhydrosugar derivatives from pyrolysis of cellulose/biomass

doi:10.16085/j.issn.1000-6613.2016.05.018

Abstract

Abstract: During the fast pyrolysis of cellulose/biomass, various anhydrosugar derivatives are produced, including levoglucosenone (LGO), 1, 4:3, 6-dianhydro-α-D-glucopyranose (DGP), 1, 5-anhydro-4-deoxy-D-glycero-hex-1-en-3-ulose (APP) and 1-hydroxy-3, 6-dioxabicyclo[3.2.1]octan-2-one (LAC). The four anhydrosugar derivatives all have high application values in chemical industry. However, for the conventional pyrolysis process, the yields of them are very low, which makes their separation very difficult. Whereas, under proper catalytic pyrolysis conditions, the yields can be greatly improved, so as to achieve their selective production. This paper firstly summarizes the experimental and theoretical studies on the formation mechanism of the four anhydrosugar derivatives, and then describes the selective production techniques of the LGO and LAC, including the best catalysts and the catalytic pyrolysis reaction conditions. Finally, future researches are proposed to disclose the formation mechanism and optimize the selective production techniques of the anhydrosugar derivatives.

Key words: cellulose, biomass, pyrolysis, selectivity

摘要： 纤维素/生物质快速热解过程中会形成多种脱水糖衍生物,包括左旋葡萄糖酮(LGO)、1,4:3,6-二脱水-α-D-吡喃葡萄糖(DGP)、1,5-脱水-4-脱氧-D-甘油基-己-1-烯-3-阿洛酮糖(APP)和1-羟基-3,6-二氧二环[3.2.1]辛-2-酮(LAC)等,这些脱水糖衍生物均具有很高的化工应用价值。然而在常规热解过程中,这些产物的产率都非常低,使得后续的分离提取十分困难;而在适当的催化热解条件下,其产率可以大幅提升,从而实现目标产物的选择性制备。基于此,本文首先概述了国内外学者对这4种脱水糖衍生物热解生成机理的实验以及密度泛函理论研究;随后总结了针对LGO和LAC这两种产物,现阶段已开发的选择性热解制备技术,包括最佳的催化剂以及催化热解反应条件;最后提出了未来在脱水糖衍生物生成机理以及选择性制备技术方面需要开展的工作。

关键词: 纤维素, 生物质, 热解, 选择性

CLC Number:

DONG Xiaochen, YE Xiaoning, ZHANG Zhibo, HU Bin, LU Qiang, DONG Changqing. Progress in formation mechanism and selective production of anhydrosugar derivatives from pyrolysis of cellulose/biomass[J]. Chemical Industry and Engineering Progree, 2016, 35(05): 1387-1395.

董晓晨, 叶小宁, 张智博, 胡斌, 陆强, 董长青. 纤维素/生物质热解生成脱水糖衍生物的机理以及选择性制备技术研究进展[J]. 化工进展, 2016, 35(05): 1387-1395.

References

[1] 林木森, 蒋剑春. 生物质快速热解技术现状[J]. 生物质化学工程, 2006, 40(1): 21-26.
[2] SHEN Dekui, WEI Jin, JUN Hu, et al. An overview on fast pyrolysis of the main constituents in lignocellulosic biomass to valued-added chemicals: structures, pathways and interactions[J]. Renewable and Sustainable Energy Reviews, 2015, 51: 761-774.
[3] 李军, 魏海国, 杨维军, 等. 生物质热解液化制油技术进展[J]. 化工进展, 2010, 29(s1): 43-47.
[4] 朱锡峰. 生物质热解液化技术研究与发展趋势[J]. 新能源进展, 2013, 1(1): 32-37.
[5] 黄金保, 刘朝, 魏顺安. 纤维素单体热解机理的热力学研究[J]. 化学学报, 2009, 67(18): 2081-2086.
[6] MA Longlong, WANG Tiejun, LIU Qiying, et al. A review of thermal-chemical conversion of lignocellulosic biomass in China[J]. Biotechnology Advances, 2012, 30(4): 859-873.
[7] SHEN Dekui, GU Sai, BRIDGWATER A V. The thermal performance of the polysaccharides extracted from hardwood: cellulose and hemicellulose[J]. Carbohydrate Polymers, 2010, 82(1): 39-45.
[8] PATWARDHAN P R, SATRIO J A, BROWN R C, et al. Product distribution from fast pyrolysis of glucose-based carbohydrates[J]. Journal of Analytical and Applied Pyrolysis, 2009, 86(2): 323-330.
[9] DONG Changqing, ZHANG Zhifei, LU Qiang, et al. Characteristics and mechanism study of analytical fast pyrolysis of poplar wood[J]. Energy Conversion and Management, 2012, 57: 49-59.
[10] LU Qiang, YANG Xiaochu, DONG Changqing, et al. Influence of pyrolysis temperature and time on the cellulose fast pyrolysis products: analytical Py-GC/MS study[J]. Journal of Analytical and Applied Pyrolysis, 2011, 92(2): 430-437.
[11] HALPERN Y, RIFFER R, BROIDO A. Levoglucosenone (1, 6-anhydro-3, 4-dideoxy-△³-β-D-pyranosen-2-one). A major product of the acid-catalyzed pyrolysis of cellulose and related carbohydrates[J]. The Journal of Organic Chemistry, 1973, 38: 204-209.
[12] 卫新来, 隋先伟, 俞志敏, 等. 生物质催化热解制备左旋葡萄糖酮的研究进展[J]. 化工进展, 2014, 33(4): 873-877.
[13] URABE D, NISHIKAWA T, ISOBE M. An efficient total synthesis of optically active tetrodotoxin from levoglucosenone[J]. Chemistry: An Asian Journal, 2006, 1(1/2): 125-135.
[14] OHNISHI A, KATO K, TAKAGI E. Curie-point pyrolysis of cellulose[J]. Polymer Journal, 1975, 7(4): 431-437.
[15] SHAFIZADEH F. Saccharification of lignocellulosic materials[J]. Pure and Applied Chemistry, 1983, 55(4): 705-720.
[16] SHAFIZADEH F, FURNEAUX R H, STEVENON T T, et al. Acid-catalyzed pyrolytic synthesis and decomposition of 1, 4: 3, 6-dianhydro-α-D-glucopyranose[J]. Carbohydrate Research, 1978, 61: 519-528.
[17] LIN Yuchuan, CHO J, TOMPSETT G A, et al. Kinetics and mechanism of cellulose pyrolysis[J]. The Journal of Physical Chemistry C, 2009, 113: 20097-20107.
[18] LU Qiang, ZHANG Yang, DONG Cangqing, et al. The mechanism for the formation of levoglucosenone during pyrolysis of β-D-glucopyranose and cellobiose: a density functional theory study[J]. Journal of Analytical and Applied Pyrolysis, 2014, 110: 34-43.
[19] FURNEAUX R H, MASON J M, MILLER I J. A novel hydroxylactone from the Lewis acid catalysed pyrolysis of cellulose[J]. Journal of the Chemical Society Perkin Transactions, 1988, 1(1): 49-51.
[20] SHAFIZADEH F, FURNEAUX R H, STEVENON T T, et al. 1, 5-Anhydro-4-deoxy-d-glycero-hex-1-en-3-ulose and other pyrolysis products of cellulose[J]. Carbohydrate Research, 1978, 67(2): 433-447.
[21] OHTANI H, KOMURA T, SONODA N, et al. Evaluation of acidic paper deterioration in library materials by pyrolysis-gas chromatography[J]. Journal of Analytical and Applied Pyrolysis, 2009, 85(1): 460-464.
[22] RUTKOWSKI P. Pyrolysis of cellulose, xylan and lignin with the K₂CO₃ and ZnCl₂ addition for bio-oil production[J]. Fuel Processing Technology, 2011, 9(3): 517-522.
[23] BLABI C D, BRANCA C, GALGANO A. Products and global weight loss rates of wood decomposition catalyzed by zinc chloride[J]. Energy and Fuels, 2008, 22(1): 663-670.
[24] RUTKOWSKI P. Chemical composition of bio-oil produced by co-pyrolysis of biopolymer/polypropylene mixtures with K₂CO₃ and ZnCl₂ addition[J]. Journal of Analytical and Applied Pyrolysis, 2012, 95(5): 38-47.
[25] SCHWARZINGER C, BREUER G, KLAMPFL C, et al. Investigations on the effect of metal ions on the products obtained from the pyrolysis of cellulose[J]. Acta Chimica Slovenica, 2006, 53(4): 437-443.
[26] LU QIANG, DONG Changqing, ZHANG Xuming, 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.
[27] LU Qiang, WANG Zhi, DONG Changqing, et al. Selective fast pyrolysis of biomass impregnated with ZnCl₂: furfural production together with acetic acid and activated carbon as by-products[J]. Journal of Analytical and Applied Pyrolysis, 2011, 91(1): 273-279.
[28] 陆强, 张栋, 朱锡锋. 四种金属氯化物对纤维素快速热解的影响(Ⅱ)机理分析[J]. 化工学报, 2010, 4(4): 1025-1032.
[29] PIOTR R. Chemical composition of bio-oil produced by co-pyrolysis of biopolymer/polypropylene mixtures with K₂CO₃ and ZnCl₂ addition[J]. Journal of Analytical and Applied Pyrolysis, 2012, 95: 38-47.
[30] PIOTR R. Catalytic effects of copper (Ⅱ) chloride and aluminum chloride on the pyrolytic behavior of cellulose[J]. Journal of Analytical and Applied Pyrolysis, 2012, 98: 86-97.
[31] DOBELE G, ROSSINSKAJA G, DIZHBITE T, et al. Application of catalysts for obtaining 1, 6-anhydrosaccharides from cellulose and wood by fast pyrolysis[J]. Journal of Analytical and Applied Pyrolysis, 2005, 74(1/2): 401-405.
[32] DOBELE G, ROSSINSKAJA G, TELYSHEYA G, et al. Cellulose dehydration and depolymerization reactions during pyrolysis in the presence of phosphoric acid[J]. Journal of Analytical and Applied Pyrolysis, 1999, 49(1): 307-317.
[33] DOBELE G, MEIER D, FAIX O, et al. Volatile products of catalytic flash pyrolysis of celluloses[J]. Journal of Analytical and Applied Pyrolysis, 2001, 58(2): 453-463.
[34] DOBELE G, DIZHBITE T, ROSSINSKAJA G, et al. Pre-treatment of biomass with phosphoric acid prior to fast pyrolysis: a promising method for obtaining 1, 6-anhydrosaccharides in high yields[J]. Journal of Analytical and Applied Pyrolysis, 2003, 3: 197-211.
[35] FU Q, ARGYROPOULOS D S, TILOTTA D C, et al. Understanding the pyrolysis of CCA-treated wood: Part Ⅱ. Effect of phosphoric acid[J]. Journal of Analytical and Applied Pyrolysis, 2008, 82(1): 140-144.
[36] NOWAKOWSKI D J, WOODBRIDGE C R, JONES J M. Phosphorus catalysis in the pyrolysis behaviour of biomass[J]. Journal of Analytical and Applied Pyrolysis, 2008, 83(2): 197-204.
[37] ZHANG Zhibo, LU Qiang, YE Xiaoning, et al. Selective production of levoglucosenone from catalytic fast pyrolysis of biomass mechanically mixed with solid phosphoric acid catalysts[J]. Bioenergy Research, 2015, 8(3): 1-12.
[38] BRANCA C, GALGANO A, BLASI C, et al. H₂SO₄-catalyzed pyrolysis of corncobs[J]. Energy Fuels, 2010, 25(1): 359-369.
[39] SUI Xianwei, WANG Zhi, LIAO Bing, et al. Preparation of levoglucosenone through sulfuric acid promoted pyrolysis of bagasse at low temperature[J]. Bioresource Technology, 2012, 103: 466-469.
[40] KAWAMOTO H, SAITO S, HATANAKA W, et al. Catalytic pyrolysis of cellulose in sulfolane with some acidic catalysts[J]. Journal of Wood Science, 2007, 53(2): 127-133.
[41] KUDO S, ZHOU Z, NORINAGA K, et al. Efficient levoglucosenone production by catalytic pyrolysis of cellulose mixed with ionic liquid[J]. Green Chemistry, 2011, 13(11): 3306-3311.
[42] TORRI C, LESCI I G, FABBRI D. Analytical study on the pyrolytic behaviour of cellulose in the presence of MCM-41 mesoporous materials[J]. Journal of Analytical and Applied Pyrolysis, 2009, 85: 192-196.
[43] PIOTR R. Pyrolytic behavior of cellulose in presence of montmorillonite K10 as catalyst[J]. Journal of Analytical and Applied Pyrolysis, 2012, 98: 115-122.
[44] FU Q, ARGYROPOULOS D S, TILOTTA D C, et al. Understanding the pyrolysis of CCA-treated wood: Part I. effect of metal ions[J]. Journal of Analytical and Applied Pyrolysis, 2008, 81(1): 60-64.
[45] FABBRI D, TORRI C, MANCINI I. Pyrolysis of cellulose catalysed by nanopowder metal oxides: production and characterisation of a chiral hydroxylactone and its role as building block[J]. Green Chemistry, 2007, 9(9): 1374-1379.
[46] FABBRI D, TORRI C, BARAVELLI V. Effect of zeolites and nanopowder metaloxides on the distribution of chiral anhydrosugars evolved from pyrolysis of cellulose: an analytical study[J]. Journal of Analytical and Applied Pyrolysis, 2007, 80(1): 24-29.
[47] WANG Zhi, LU Qiang, ZHU Xifeng, et al. Catalytic fast pyrolysis of cellulose to prepare levoglucosenone using sulfated zirconia[J]. ChemSusChem, 2011, 4(1): 79-84.
[48] LU Q, ZHANG Xuming, ZHANG Zhibo, et al. Catalytic fast pyrolysis of cellulose mixed with sulfated titania to produce levoglucosenone: analytical Py-GC/MS sdtdy[J]. Bioresources, 2012, 7(3): 2820-2834.
[49] LU Q, YE Xiaoning, ZHANG Zhibo, et al. Catalytic fast pyrolysis of cellulose and biomass to produce levoglucosenone using magnetic SO₄^2-/TiO₂-Fe₃O₄[J]. Bioresource Technology, 2014, 171(171C): 10-15.
[50] MARSHALL J A. An improved preparation of levoglucosenone from cellulose[D]. US, Iowa: Iowa State University, 2008.
[51] TORRI C, LESCI I G, FABBRI D. Analytical study on the production of a hydroxylactone from catalytic pyrolysis of carbohydrates with nanopowder aluminium titanate[J]. Journal of Analytical and Applied Pyrolysis, 2009, 84(1): 25-30.
[52] EIBONER S, FRANCOIS B, JOEL B, et al. Catalytic effect of metal nitrate salts during pyrolysis of impregnated biomass[J]. Journal of Analytical and Applied Pyrolysis, 2015, 113: 143-152.
[53] RUTKOWSKI P. Pyrolytic behavior of cellulose in presence of montmorillonite K10 as catalyst[J]. Journal of Analytical and Applied Pyrolysis, 2012, 98(10): 115-122.
[54] MANCINI I, DOSI F, DEFANT A, et al. Upgraded production of (1R, 5S)-1-hydroxy-3, 6-dioxa-bicyclo[3.2.1]octan-2-one from cellulose catalytic pyrolysis and its detection in bio-oils by spectroscopic methods[J]. Journal of Analytical and Applied Pyrolysis, 2014, 110: 285-290.