木质类废弃物液化及其高效利用研究进展

doi:10.16085/j.issn.1000-6613.2016.06.032

摘要/Abstract

摘要： 木质类废弃物具有数量多、分布广、可再生等特点,采用热化学液化技术将其转变为具有反应活性的新的化学原料,能替代或部分替代化石产品制备高品质化学品。本文将不同生物质转化技术以及可利用途径进行归纳总结,回顾了近年来国内外常见的木质类废弃物液化技术如高温高压液化、快速热解液化和常压催化液化等,重点介绍了广为关注的常压催化液化及其高效利用研究现状。概述了不同的液化剂和催化剂所得液化物的性质及所制备胶黏剂、聚氨酯材料等高附加值生物质基树脂材料的性能。指出木质类生物质液化过程只有朝着低成本、绿色、高效反应方向发展,才有可能向大规模工业化转化。作者结合自己的科研实践,提出该领域目前存在的一些问题以及解决途径的建议,对液化生物质基高分子材料的产业化应用提出展望。

关键词: 木质类废弃物, 液化, 生物质基树脂材料, 高效利用

Abstract: Much widely distributed renewable lignocellulosic waste could be liquefied to synthesize high quality polymers such as adhesive,resins,and etc. The liquefactant could be used as a new kind activated chemical materials to replace,at least partly,the petroleum-based products. In this paper,various biomass conversion technologies and the available utilization pathways are summarized. Several conventional liquefaction technologies at different reaction conditions such as the high temperature and pressure,fast pyrolysis and atmospheric pressure in the presence of catalyst were reviewed,and the atmospheric catalytic liquefaction technology and its efficient utilization were particularly introduced. Properties of high value-added biomass-based resin polymer such as adhesives,polyurethane materials,and etc. which is prepared using different liquefaction solvents and catalysts,are illustrated. Based on years of authors' practical research,some difficulties and the suggestions in the liquefaction process were presented for the future industrialized application with low cost,environmental friendly and high-efficiency.

Key words: lignocellulosic waste, liquefaction, biomass-based resin, efficient application

中图分类号:

TQ351.9

孟繁蓉, 李瑞松, 张玉苍. 木质类废弃物液化及其高效利用研究进展[J]. 化工进展, 2016, 35(06): 1905-1913.

MENG Fanrong, LI Ruisong, ZHANG Yucang. Research progress on liquefaction of lignocellulosic waste and its efficient application[J]. Chemical Industry and Engineering Progree, 2016, 35(06): 1905-1913.

参考文献

[1] 吴创之,马隆龙. 生物质能现代化利用技术[M]. 北京:化学工业出版社,2003.
[2] 王崇杰,蔡洪彬,薛一冰. 可再生能源利用技术[M]. 北京:中国建材工业出版社,2014.
[3] 国家能源局关于印发生物质能发展“十二五”规划的通知[R]. 北京:中华人民共和国国家能源局,2012.
[4] BEHRENDT F,NEUBAUER Y,OEVERMANN M,et al. Direct liquefaction of biomass [J]. Chemical Enigineering and Technology,2008,31(5):667-677.
[5] MA L L,WANG T J,LIU Q Y,et al. A review of thermal-chemical conversion of lignocellulosic biomass in China[J]. Biotechnology Advances,2012 (30):859-873.
[6] TEKIN K,KARAGÖZ S,BEKTAS S. A review of hydrothermal biomass processing[J]. Renewable and Sustainable Energy Reviews,2014(40):673-687.
[7] NO Soo-Young. Application of bio-oils from lignocellulosic biomass to transportation,heat and power generation:a review[J]. Renewable and Sustainable Energy Reviews,2014,40:1108-1125.
[8] 张求慧,等. 生物质液化技术及应用[M]. 北京:化学工业出版社,2013.
[9] 徐鑫,陈骁,咸漠. 面向资源与环境的生物基化学品技术创新与展望[J]. 化工进展,2015,34 (11):3825-3831.
[10] JENKINS B M,BAXTER L L,KOPPEJAN J. Biomass combustion,thermochemical processing of biomass:conversion into fuels[M]// Brown R C,editor. Chemicals and power. Chichester,UK:John Wiley & Sons,Ltd.,2011:13-46.
[11] 朱晨杰,张会岩,肖睿,等. 木质纤维素高值化利用的研究进展[J]. 中国科学(化学),2015,45(5):454-478.
[12] HUANG H J,YUAN X Z,ZENG G M,et al. Thermochemical liquefaction characteristics of microalgae in sub- and supercritical ethanol[J]. Fuel Processing Techonology,2011,92:147-153.
[13] SHAO Q,PENG J,XIU S,et al. Analysis of oil products by pyrolysis of bamboo in superchitical methanol[J]. Acta Energlae Solaris Sin,2007,28:984-987.
[14] ZOU S,WU Y,YANG M,et al. Production and characterization of bio-oil from hydrothermal liquefaction of microalgae Dunaliella tertiolecta cake[J]. Energy,2010,35:5406-5411.
[15] 姜洪涛,李会泉,张懿. 生物质高压液化制生物原油研究进展[J]. 化工进展,2006,25(1):8-31.
[16] YUAN X,WANG J,ZENG G,et al. Comparative studies of thermochemical liquefaction characteristics of microalgae using different organic solvents[J]. Energy,2011,36:6406-6412.
[17] PETERSON A A,VOGEL F,LACHANCE R P,et al. Thermoche-mical biofuel production in hydrothermal media:a review of sub- and supercritical water technologies[J]. Energy Environm. Sci.,2008,1:32-65.
[18] SAVAGE P E. A perspective on catalysis in sub- and supercritical water[J]. J. Supercrit Fluids,2009,47:407-14.
[19] TEKIN K,KARAGÖZ S,BEKTAS S. Hydrothermal liquefaction of beech wood using a natural calcium borate mineral[J]. J. Supercrit Fluids,2012,72:134-139.
[20] TOOR S S,ROSENDAHL L,RUDOLF A. Hydrothermal liquefaction of biomass:a review of subcritical water technologies[J]. Energy,2011,36:2328-2342.
[21] JUNG S H,KANG B S,KIM J S. Production of bio-oil from rice straw and bamboo sawdust under various reaction conditions in a fast pyrolysis plant queipped with a fluidized bed and a char separation system[J]. J. Anal. Appl. Pyrolysis,2008,82:240-247.
[22] 刘荣厚,等. 生物质能工程[M]. 北京:化学工业出版社,2009.
[23] 张建安,刘德华,等. 生物质能源利用技术[M]. 北京:化学工业出版社,2009.
[24] 袁振宏,等. 生物质能高效利用技术[M]. 北京:化学工业出版社,2014.
[25] BUNCH A Y,WANG X Q,OZKAN U S. Adsorption characteristics of reduced Mo and Ni-Mo catalysts in the hydrodeoxygenation of benzofuran[J]. Applied Catalysis A,2008,346(1/2,31):96-103.
[26] IKURA M,STANCIULESCU M,HOGAN E. Emulsification of pyrolysis derived bio-oil in diesel Fuel[J]. Biomass Bioenergy,2003,24:221-32.
[27] KURIMOTO Y,DOI S,TAMURA Y. Species effects on wood – liquefaction in polyhydric alcohols[J]. Holzforschung,1999,53(6):617-622.
[28] HASSAN E M,SHUKRY N. Polyhydric alcohol liquefaction of some lignocellulosic agricultural residues[J]. Industrial Crops and Products,2008,27(1):33-38.
[29] LIANG L,MAO Z,LI Y,et al. Liquefaction of crop residues for polyol production[J]. BioResources,2006(1):248-256.
[30] 栾复友. 竹材树脂化的基础研究[D]. 杭州:浙江农林大学,2010.
[31] YU C Y,LEE W J. Characteristics of glycolysis products of polyurethane foams made with polyhydric alcohol liquefied Cryptomeria japonica wood[J]. Polymer Degradation and Stability,2014,101:60-64
[32] LEE S H ,TERAMOTO Y,SHIRAISHI N. Biodegradable polyurethane foam from liquefied waste paper and its thermal stability,biodegradability,and genotoxicity[J]. J. Applied Polymer. Sci.,2002,83(7):1482-1489.
[33] HU S J,LUO X L,LI Y B. Polyols and polyurethanes from the liquefaction of lignocellulosic biomass[J]. ChemSusChem.,2014,7:66-72.
[34] ZHANG Y C,IKEDA A,HORI N,et al. Characterization of liquefied product from cellulose with phenol in the presence of sulfuric acid[J]. Bioresource Technology,2006,97:313-321.
[35] ONO H,ZHANG Y C,YAMADA T. Dissolving behavior and fate of cellulose in phenol liquefaction[J]. Transactions of the Materials Research Society of Japan,2001,26(3):807-812.
[36] 张文明,孙岩峰,李阳,等. 秸秆苯酚液化的工艺[J]. 大连工业大学学报,2008,27(1):73-75.
[37] 张文明,孙岩峰,李阳,等. 秸秆液化物环氧树脂胶粘剂的制备与表征[J]. 高分子材料科学与工程,2009,25(6):139- 142.
[38] 李阳,孙岩峰,张玉苍,等. 玉米秸秆制乙醇预处理新工艺——“液化技术”[J]. 食品科技,2009,34(9):123-127.
[39] 谢双平,陈洪章. 秸秆苯酚选择性液化研究[J]. 生物质化学工程,2008,42(4):1-5.
[40] CHEN H Z,ZHANG Y Z,XIE S P. Selective liquefaction of wheat Straw in phenol and its fractionation[J]. Applied Biochemistry and Biotechnology,2012,167(9):250-258.
[41] KURIMOTO Y,SHIRAKAWA K,YOSHIOKA M,et al. Liquefaction of untreated wood with polyhydric alcohols and its application to polyurethane foams[EB]// New Zealand Forest Research Institute,1992,176:155-162.
[42] YAO Y G,YOSHIOKA M,SHIRAISHI N. Combined liquefaction of wood and starch in a polyethylene glycol/glycerin blended solvent[J]. Mokuzai Gakkaishi,1993,39(8):930-938.
[43] YAO Y,YOSHIOKA M, SHIRAISHI N. Rigid polyurethane foams starch [J]. Mokuzai Gakkaishi,1995,41(7):659-668.
[44] MALDAS D,SHIRAISHI N. Liquefaction of wood in the presence of polyol using NaOH as a catalyst and its application to polyurethane foams[J]. Int. J. Polym. Mater.,1996,33(1):61-71.
[45] YAMADA T,ONO H. Rapid liquefaction of lignocellulosic waste by using ethylene carbonate[J]. Bioresource Technology,1999,70(1):61-67.
[46] YAN Y B,PANG H,YANG X X,et al. Preparation and charact- erization of water-blown polyurethane foams from liquefied cornstalk polyol[J]. J. Applied Polymer. Sci., 2008,110:1099-1111.
[47] CHEN F G,LU Z M. Liquefaction of wheat straw and preparation of rigid polyurethane foam from the liquefaction products[J]. J. Applied Polymer. Sci.,2009,111:508-516.
[48] ZHANG H R,DING F,LUO C R,et al. Liquefaction and charact- erization of acid hydrolysis residue of corncob in polyhydric alcohols[J]. Industrial Crops and Products,2012,39:47-51.
[49] LI W,ZHANG Y C,LI J H,et al. Characterization of cellulose from banana pseudo-stem by heterogeneous liquefaction[J]. Carbohydrate Polymers,2015,132:513-519.
[50] HU S J,WAN C X,LI Y B. Production and characterization of biopolyols and polyurethane foams from crude glycerol based liquefaction of soybean straw[J]. Bioresource Technology,2012,103(1):227-233.
[51] WANG T P,LI D,WANG L J,et al. Effects of CS/EC ratio on structure and properties of polyurethane foams prepared from untreated liquefied corn stover with PAPI[J]. Chemical Engineering Research and Design,2008,86(4):416-421.
[52] 谌凡更,谢涛,卢卓敏.蔗渣液化产物改性环氧树脂的制备和性能研 [J]. 林业化学与工业,2007,27(3):111-115.
[53] XIE T,CHEN F G. Fast liquefaction of bagasse in ethylene carbonate and preparation of epoxy resin from the liquefied product[J].J. Applied Polymer. Sci.,2005,98:1961-1968.
[54] DEMIRBAS A. Mechanisms of liquefaction and pyrolysis reactions of biomass[J]. Energy Conversion and Management,2000,41(6):633-646.
[55] 邹局春,郑志锋,张宏健. 生物质苯酚液化产物在模塑材料中的应用 [J]. 林业科技开发,2007,21(2):15-17.
[56] HESSE W,JUNG A. Harderable binding agents and their use:EP,43097[P]. 1980.
[57] 郑志锋,郑云武,顾继友,等. 生物基木材胶粘剂[J]. 粘接,2015,2:32-40.
[58] 张文明,张玉苍,赵德丰. 四种生物质废弃物环氧树脂的合成及表征 [J]. 高分子材料科学与工程,2012,28(6):1-4.
[59] 张文明. 桔秆苯酚液化物环氧树脂的合成及其水性涂料的研究[D]. 大连:大连理工大学,2011.
[60] 张玉苍,迟青山,孙岩峰,等. 木材液化及其在聚氨酯胶黏剂上的应用研究[J]. 林产化学与工业,2007,27(5):73-77.
[61] 高振华,顾继友. 利用苯酚液化大豆粉制备耐水性木材胶黏剂[J]. 林业科学,2011,47(9):129-134.
[62] 张文明,李玲,刘志强,等. 麦秆液化物环氧树脂的制备与表征[J]. 信息记录材料,2013,14(1):47-50.
[63] 张茜. 花生壳液化及其胶黏剂制备技术[D]. 南京:南京林业大学,2009.
[64] 莫引优,李昆蔚,廖章兵,等. 玉米秸秆液化树脂化研究[J]. 南方农业学报,2013,44(9):1538-1542.
[65] 揭淑俊. 杉木苯酚液化物树脂的合成及应用[D]. 北京:北京林业大学,2007.
[66] KURIMOTO Y,TAKEDA M,KOIZUMI A,et al. Mechanical properties of polyurethane films prepared from liquefied wood with polymeric MDI[J]. Bioresource Technology,2000,74(2):151-157.
[67] KURIMOTO Y,KOIZUMI A,DOI S,et al. Wood species effects on the characteristics of liquefied wood and the properties of polyurethane films prepared from the liquefied wood[J]. Biomass and Bioenergy,2001,21(5):381-390.
[68] 王万雨,王敦,张玉苍. 水稻秸秆液化物制备聚氨酯泡沫的研究[J]. 林产化学与工业,2015,35(6):78-82.
[69] WANG H,CHEN H Z. A novel method of utilizing the biomass resource:rapid liquefaction of wheat straw and preparation of biodegradable polyurethane foam (PUF)[J]. Journal of the Chinese Institute of Chemical Engineers,2007,38(2):95-102.
[70] LEE S H,YOSHIOKA M,SHIRAISHI N. Liquefaction of corn bran (CB) in the presence of alcohols and preparation of polyurethane foam from its liquefied polyol[J]. J. Applied Polymer. Sci.,2000,78(2):319-325.
[71] YU F,LE Z P,CHEN P,et al. Atmospheric pressure liquefaction of dried distillers grains (ddg) and making polyurethane foams from liquefied DDG[J]. Applied Biochemistry and Biotechnology,2008,148(1):235-243.
[72] BRIONES R,SERRANO L,LABIDI J. Valorization of some lignocellulosic agro-industrial residues to obtain biopolyols[J]. J. Chemical Technology and Biotechnology,2012,87(2):244-249.
[73] BRIONES R,SERRANO L,LLANO-PONTE R,et al. Polyols obtained from solvolysis liquefaction of biodiesel production solid residues[J]. Chemical Engineering Journal,2011,175: 169-175.
[74] BRIONES R,SERRANO L,YOUNES R B,et al. Polyol production by chemical modification of date seeds[J]. Industrial Crops and Products,2011,34(1):1035-1040.
[75] LEE W J,LIN M S. Preparation and application of polyurethane adhesives made from polyhydric alcohol liquefied Taiwan acacia and China fir[J]. J. Applied Polymer. Sci.,2008,109(1):23-31.
[76] HU S J,LI Y B. Polyols and polyurethane foams from acid- catalyzed biomass liquefaction by crude glycerol:effects of crude glycerol impurities[J]. J. Applied Polymer. Sci.,2014,131(18):1-9.
[77] LI Wei,ZHANG Yucang,LAO Bangsheng. Preparation and properties of liquefied banana pseudostem based PVAc membrane[J]. BioResource,2015,10(3):4519-4529.
[78] 李崴,张玉苍,劳邦盛. 香蕉假茎液化物/聚醋酸乙烯酯共混膜的制备与性能[J]. 高分子材料科学与工程,2016,32(1):1-5.
[79] MORI Ryohei. Inorganic-organic hybrid biodegradable polyurethane resin derived from liquefied Sakura wood[J]. Wood Science and Technology,2015,49(3):507-516
[80] sXU S Y,TAN Z T,CAI G R,et al. Sulfonic acid catalyst based on silica foam supported copolymer for hydrolysis of cellulose[J]. Catalysis Communications,2015,71:56-60.