木化生物质的加氢液化
摘要
面对能源和环境的双重压力,开发洁净的可再生能源已经成为当今世界的紧迫课题。生物质能具有量大、分布广、易获得、易储存、环保等优势,因而生物质能源转化技术成为各国研究的热点。本文就木化生物质加氢液化进行了相关研究。
本实验选用具有代表性的的农林废弃物玉米秸秆和竹子为原料,以水作为溶剂,氢氧化钠做催化剂,通过氢气提供高压氛围,在一定温度下实现木化生物质液化,制取生物质油。通过考察反应温度、压力、时间、溶剂以及催化剂种类、用量等因素对液化率和生物质油产率及其产品性能的影响,寻找最佳的液化工艺条件,然后利用多种检测手段对液化产物进行检测分析,包括热值分析、红外色谱、扫描电镜、凝胶渗透色谱和气相色谱质谱联用,综合考察产物的物化性质和液化反应历程,为木化生物质加氢液化和产物利用提供实验室依据,丰富其理论体系。
通过大量实验,得出以玉米秸秆和竹子为原料的木化生物质加氢液化的最佳反应条件为:原料与溶剂质量比在1/10~1/6之间,反应温度210~240℃;氢气初始压力7~8MPa;反应停留时间20~30min;氢氧化钠用量为原料绝干质量的10~15%。在此条件下,木化生物质的液化率达到90%,生物质油产率达到50%。
所得生物质油为黑褐色沥青状液体,高位热值为30MJ/kg,比原料热值提高了66%~68%。对生物质油的GC-MS分析结果显示,生物质油成分复杂,多达几十种,以有机酸、酮和酚类物质居多,含氧量高。加氢液化后得到的生物质油要在实际中得以应用,还需进一步分离和提纯。
Under pressure of energy and environment, developing clean and reproducible energy becomes to be urgent problem all over the world. Biomass has large quantity, distribution, available to obtain and storage and environmentally, so biomass energy converting technology has been hot spot in many countries. Hydro-liquefaction of lignified biomass was studied in this article.
Corn stalk and bamboo was selected for material in this experiment, water as solvent, NaOH as catalyst, with hydrogen Providing high pressure, and then liquefaction was realized under proper temperature, to produce bio-oil. By reviewing the effect of reaction temperature, pressure, time, solvent and catalyst on liquefaction the optimal process condition was obtained. Then the physical and chemical character of liquefaction product and reaction mechanism was studied by using different detection method including calorific value analysis, IR, SEM, GPC and GC-MS so that the theory system was enriched.
Through lots of experiments the optimal condition of hydro-liquefaction of biomass was concluded: weight ratio of biomass and solvent was 1/10~1/6, reaction temperature was 210~240℃, initial pressure of hydrogen was 7~8MPa, remaining time was 20~30min, weight of NaOH was 10~15% of dried material. The liquefaction rate was up to 90%, and bio-oil yield was 50% under this condition. The bio-oil was black brawn liquid like tar. Its gross calorific value was 30MJ/kg, increasing by 66%~68%。GC-MS detection result shows that components of bio-oil were complex, up to 40 species or more, much of which was organic acid, ketone and phenolic and that oxygen ratio was high. The bio-oil obtained by hydro-liquefaction needed to be separated and purified further if applied in practice.
本实验选用具有代表性的的农林废弃物玉米秸秆和竹子为原料,以水作为溶剂,氢氧化钠做催化剂,通过氢气提供高压氛围,在一定温度下实现木化生物质液化,制取生物质油。通过考察反应温度、压力、时间、溶剂以及催化剂种类、用量等因素对液化率和生物质油产率及其产品性能的影响,寻找最佳的液化工艺条件,然后利用多种检测手段对液化产物进行检测分析,包括热值分析、红外色谱、扫描电镜、凝胶渗透色谱和气相色谱质谱联用,综合考察产物的物化性质和液化反应历程,为木化生物质加氢液化和产物利用提供实验室依据,丰富其理论体系。
通过大量实验,得出以玉米秸秆和竹子为原料的木化生物质加氢液化的最佳反应条件为:原料与溶剂质量比在1/10~1/6之间,反应温度210~240℃;氢气初始压力7~8MPa;反应停留时间20~30min;氢氧化钠用量为原料绝干质量的10~15%。在此条件下,木化生物质的液化率达到90%,生物质油产率达到50%。
所得生物质油为黑褐色沥青状液体,高位热值为30MJ/kg,比原料热值提高了66%~68%。对生物质油的GC-MS分析结果显示,生物质油成分复杂,多达几十种,以有机酸、酮和酚类物质居多,含氧量高。加氢液化后得到的生物质油要在实际中得以应用,还需进一步分离和提纯。
Under pressure of energy and environment, developing clean and reproducible energy becomes to be urgent problem all over the world. Biomass has large quantity, distribution, available to obtain and storage and environmentally, so biomass energy converting technology has been hot spot in many countries. Hydro-liquefaction of lignified biomass was studied in this article.
Corn stalk and bamboo was selected for material in this experiment, water as solvent, NaOH as catalyst, with hydrogen Providing high pressure, and then liquefaction was realized under proper temperature, to produce bio-oil. By reviewing the effect of reaction temperature, pressure, time, solvent and catalyst on liquefaction the optimal process condition was obtained. Then the physical and chemical character of liquefaction product and reaction mechanism was studied by using different detection method including calorific value analysis, IR, SEM, GPC and GC-MS so that the theory system was enriched.
Through lots of experiments the optimal condition of hydro-liquefaction of biomass was concluded: weight ratio of biomass and solvent was 1/10~1/6, reaction temperature was 210~240℃, initial pressure of hydrogen was 7~8MPa, remaining time was 20~30min, weight of NaOH was 10~15% of dried material. The liquefaction rate was up to 90%, and bio-oil yield was 50% under this condition. The bio-oil was black brawn liquid like tar. Its gross calorific value was 30MJ/kg, increasing by 66%~68%。GC-MS detection result shows that components of bio-oil were complex, up to 40 species or more, much of which was organic acid, ketone and phenolic and that oxygen ratio was high. The bio-oil obtained by hydro-liquefaction needed to be separated and purified further if applied in practice.
引文
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[3]袁振宏,吴创之,马隆龙.生物质能利用原理与技术.化学工业出版社,北京,2004
[4]白鲁刚,颜涌捷.废弃生物质的开发利用[J].新能源,2000,22(4):34-38
[5] Chuanmin Yuan, Jieyong Yan, Zhengwei Ren, et al. Kinetics of Sawdust Hydrolysis with Dilute Hydrochloric Acid and Ferrous Chloride. Chinese journal of process engineering, 2004, 4(1):64-68
[6] Haiping Yang, Rong Yan, Hanping Chen, et al. In-Depth Investigation of Biomass Pyrolysis Based on Three Major Components: Hemicellulose, Cellulose and Lignin. Energy&Fuels, 2006, 20:388-393
[7] COOK J, BEYEA J. Bioenergy in the United States: Progress and Possibilities. Biomass and Bioenerg, 2000,18(6),441
[8]姚福生,易维明,柏雪源.生物质快速热解液化技术.中国工程科学,2001,3(4):63-67
[9]徐冰燕等.中国生物质气化技术的发展与前景.太阳能学报,1999(10):162-168
[10]朱清时,阎立峰,郭庆祥.生物质洁净能源.北京:化学工业出版社,2002,35-74
[11] J E Miller, L Evans, A Littlewolf. Batch microreactor studies of lignin and lignin model compound depolymerization by bases in alcohol solvents [J]. Fuel,1999,78(1):1363-1366
[12] F Karaosmanoglu, E Tetik. Fuel properties of pyrolytic oil of the straw and stalk of rape plant [J]. Renewable Energy, 1999, 16(1):1090-1093
[13]闫桂焕,孙立,许敏等.生物质热化学转化制氢.可再生能源,2004,116:33~36
[14]姚向君,田宜水.生物质能资源清洁转化利用技术.北京:化学工业出版社,2005,108-115
[15] EUREC Agency. The future for renewable energy prospects and directions.London:James and James Science Publisher,1996,157-165
[16]应浩,蒋剑春.生物质气化技术及开发应用研究进展[J].林产化学与工业,2005,25(10):151-155.
[17] Schmieder H, Abeln J. Boukis N,Dinjus E,Kruse A,Kluth M. Hydrothermal gasification of biomass and organic wastes. J.Supercritical Fluids. 2000.17(1):145-153
[18] Appell H R, Wender I, Miller R D. Converting organic wastes to oil [R].Bureau of Mines Report of Inve.1971.7560-7568.
[19] Ogi T, Yokoyama S. Liquid fuel production from woody biomass by direct liquefaction [J].Sekiyu Gakkaishi, 1993, 36(20):73-84.
[20]温从科,乔旭,张进平等.生物质高压液化技术研究进展.生物质化学工程,2006,40(1):32-34
[21]赵胜利,开玉台,秦树仁.超临界流体技术在环境保护中的应用[J].石油化工高等学校学报,1999,12(1):48-53
[22] M Watanabe, H Inomata, K Arai. Catalytic hydrogen generation from biomass (glucose and cellulose) with ZrO2 in supercritical water [J]. Biomass and Bioenergy, 2002,22(1):405-410
[23]朱自强.超临界流体技术-原理和应用[M].北京:化学工业出版社,2003:56-60
[24] Ali sinag,Andrea Kruse et al. Influence of the Heating Rate and the Type of Catalyst on the Formation of Key Intermediates and on the Generation of Gases During Hydro Pyrolysis of Glueose in Supercritical Water in a Batch Reactor. Ind. Eng,Chem. Res.,2004,43:502-508
[25]方昭贤.不同种类生物质热裂解液化试验研究.[硕士论文],杭州,浙江大学,2008
[26]乔国朝.生物质热解液化技术研究现状及展望[J].林业机械与木工设备,2005,33(5):4-7
[27] Bridgwater A V,Peacocke G V C. Fast pyrolysis Processes for biomass [J]. Renewable and Sustainable Energy Reviews,2000,4(1),1-73.
[28]林木森,蒋剑春.生物质快速热解技术现状.生物质化学工程,2006,40(l),21-26.
[29]董良杰.生物质热裂解技术及其反应动力学研究.[博士学位论文],沈阳,沈阳农业大学,1997.
[30] Yamada T and Ono H. Characterization of the Products from ethylene glycol liquefaction of cellulose [J]. J Wood Sci,2001,47:458-464.
[31] Seung-Hwan Lee. Liquefaction and Product identification of corn bran(CB)in Phenol.J Appl Polym Sci. 2000,78:311-318.
[32] Sharypov V I, Marin N, Beregovtsova N G, et al. Co-pyrolysis of wood biomass and synthetic polymer mixtures. Part I: influence of experimental conditions on the evolution of solids, liquids and gases. J. Anal. Appl. Pyrolysis, 2002,64:15–28.
[33]王华.秸秆纤维的催化液化及其产物的初步研究.山西大学学报2004,27(1)48一53.
[34]戈进杰等.基于玉米棒的环境友好材料研究玉米棒的液化反应及植物多元醇的制备.高分子材料和科学.2003.5,19(3):23-26.
[35]白鲁刚,颜涌捷,李庭深等.煤与生物质共液化的催化反应[J].化工冶金, 2000,21(2):198-203
[36] Minowa T, Zhen F, Ogi T, et al. Liquefaction of cellulose in hot-compressed water using sodium carbonate: products distribution at different reaction temperatures. J. Chem. Eng. Japan,1997,30(1):186-190
[37] Appell H R, Fu Y C, Frideman S, et al. Converting organic wastes to oi1[J]. EnergyConversion and Management, 1972, 53(3): 17-19
[38] Shafiazdeh F, Stevenson T T. [J] Journal of applied Polymer Scienee.1982,27:4577
[39] Demirbas A. Mechanisms of liquefaction and Pyrolysis reactions of biomass.[J] Energy Conversion and Management.2000,41(6):633-646
[40] Vasilkaos N P,Austgen D M. Hydrogen-donor solvents in biomass liquefaction.[J] Industrial and Engineering Chemistry Process Design and Development.198524(2):304-311
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