热解法生产生物质油过程中水相成份的研究
摘要
生物质能是新型的可再生能源,将生物质热解生成生物油,不仅可以用做能源燃料,而且还可以作为生产化工产品的原料。在生物质油的生产过程中会产生油相和水相,油相主要用作能源燃料,水相的利用目前研究很少。经过我们的初步研究,发现水相中有许多化合物是工业生产中的基本原料,因此深入研究生物质油生产过程中水相的组成并加以开发利用对降低整个生物质油的生产成本,增加其附加值是很有意义的。具体的研究内容和结论如下：
一.在前期GC-MS初步定性结果的基础上主要从流动相及其梯度、色谱柱类型等方面优化高效液相(HPLC)分析条件,在保持分离度的前提下在色谱上得到尽量多的色谱峰,并通过标准物对几种主要的化合物进行了定性,为进一步的定量分析打下了基础；并在此基础上研究了生物油水相的稳定性。
二.利用HPLC对上述经过定性的水相中的化合物进行了色谱方法系统适用性研究和定量分析。HPLC分析方法系统适用性研究表明我们采用的分析方法具有良好的重复性及准确性。通过对生产过程正交试验样品的定量分析判定出较优生物质油水相的生产条件。
三.利用HPLC和LC-MS目结合的手段确定了水相中的一个含量很高的未知物为邻苯二酚,并经标准物对照得到了确认。在此基础上对其进行了进一步的定量分析方法研究,结果表明其含量较高,具有极大的开发价值。
总之,本文在GC-MS初步研究的基础上建立并优化了HPLC分析方法,结合LC-MS确定了具有确切开发价值的组份,进一步建立了它们的定量分析方法,并将该方法用于指导生物质油生产过程中催化氢化的正交实验结果判定,筛选出了可减少水相组份的种类,提高具有开发价值的组份的含量的最佳生产条件。
Biomass is a new type of renewable energy resource. Bio-oil, which is produced by the pyrolysis of biomass, not only could be used as fuel energy, but also as raw material in the chemical industry. Two phases of oil and aqueous could be acquired during the producting procedure of bio-oil. The oil phase is mainly used as fuel energy. In the aqueous phase, a great deal of compounds which are the basic raw materials of chemical industrial were found by our primarily studies. So the determination of what and how many these substances were is helpful to reduce the production cost of bio-oil and increase its added value.
Firstly, high-performance liquid chromatography (HPLC) analytical method of the aqueous phase had been studied and optimized. Then some components of the aqueous phase had been determinded based on the results of GC-MS and compared with their standard substances as well. Furthermore, the stabilities of the components of the aqueous phase were studied.
Secondly, studies on systematical suitabilities of HPLC analytical methods for the above-mentioned compositions of the aqueous phase showed that our quantitative methods were accuracy and stability. The optimized production procedure of the bio-oil aqueous phase was comfirmed by the analysis the products from different condition. It is confirmed that the types and amoumts of the main components got from the optimized procedure by the analytical results of dozens of products.
Finally, an unknown compound of Catechol with high content in the aqueous phase was determined by the method of HPLC coupled with LC-MS and compared with its standard substance. Also, its quantitive analytical method was studied. It was worthy to be got with its high content by our result.
In conclusion, HPLC methods had been established for the analytical of the aqueous phase from the production of bio-oil. Several components were studied by the method.
一.在前期GC-MS初步定性结果的基础上主要从流动相及其梯度、色谱柱类型等方面优化高效液相(HPLC)分析条件,在保持分离度的前提下在色谱上得到尽量多的色谱峰,并通过标准物对几种主要的化合物进行了定性,为进一步的定量分析打下了基础；并在此基础上研究了生物油水相的稳定性。
二.利用HPLC对上述经过定性的水相中的化合物进行了色谱方法系统适用性研究和定量分析。HPLC分析方法系统适用性研究表明我们采用的分析方法具有良好的重复性及准确性。通过对生产过程正交试验样品的定量分析判定出较优生物质油水相的生产条件。
三.利用HPLC和LC-MS目结合的手段确定了水相中的一个含量很高的未知物为邻苯二酚,并经标准物对照得到了确认。在此基础上对其进行了进一步的定量分析方法研究,结果表明其含量较高,具有极大的开发价值。
总之,本文在GC-MS初步研究的基础上建立并优化了HPLC分析方法,结合LC-MS确定了具有确切开发价值的组份,进一步建立了它们的定量分析方法,并将该方法用于指导生物质油生产过程中催化氢化的正交实验结果判定,筛选出了可减少水相组份的种类,提高具有开发价值的组份的含量的最佳生产条件。
Biomass is a new type of renewable energy resource. Bio-oil, which is produced by the pyrolysis of biomass, not only could be used as fuel energy, but also as raw material in the chemical industry. Two phases of oil and aqueous could be acquired during the producting procedure of bio-oil. The oil phase is mainly used as fuel energy. In the aqueous phase, a great deal of compounds which are the basic raw materials of chemical industrial were found by our primarily studies. So the determination of what and how many these substances were is helpful to reduce the production cost of bio-oil and increase its added value.
Firstly, high-performance liquid chromatography (HPLC) analytical method of the aqueous phase had been studied and optimized. Then some components of the aqueous phase had been determinded based on the results of GC-MS and compared with their standard substances as well. Furthermore, the stabilities of the components of the aqueous phase were studied.
Secondly, studies on systematical suitabilities of HPLC analytical methods for the above-mentioned compositions of the aqueous phase showed that our quantitative methods were accuracy and stability. The optimized production procedure of the bio-oil aqueous phase was comfirmed by the analysis the products from different condition. It is confirmed that the types and amoumts of the main components got from the optimized procedure by the analytical results of dozens of products.
Finally, an unknown compound of Catechol with high content in the aqueous phase was determined by the method of HPLC coupled with LC-MS and compared with its standard substance. Also, its quantitive analytical method was studied. It was worthy to be got with its high content by our result.
In conclusion, HPLC methods had been established for the analytical of the aqueous phase from the production of bio-oil. Several components were studied by the method.
引文
[1].薄洁萍.寻找新能源一二十一世纪能源问题展望.http://home.163.com/science/item-print/0,1257,1345,00.html.
[2].张新华,蔡文之,戈特瓦尔德.能源之重-能源形势、能源安全和能源革命.社会观察,2004,9
[3].中国科学院生物质资源领域战略研究组.中国至2050年生物质资源科技发展路线图.科学出版社,2009
[4].骆仲映,刘妮,高翔等.中国能源与可持续发展[A].中国动力工程学会第二界青年学术年会论文集[C].湖北宜昌：1999
[5].王丽红.生物质闪速热裂解挥发特性的研究与生物油的组分分析[D].硕士论文,山东理工大学,2004,6
[6].廖艳芬,王树荣,谭洪等.生物质热裂解制取液体燃料技术的发展[J].能源工程,2002,(2)：125-130
[7].田雅林,王革华.国家可再生能源的发展[J].可再生能源,2003,5：42-44
[8]. Everett A. Sondreal, Steven A. Benson, John P, Fuel Proeessing Teehnology,2001,71:7
[9]. Forest volume-to-biomass models and estimates of mass for live and standing dead trees of U.S. forests
[10].陈和平.关于编制“十五”新能源计划的思考.新能源,1999,12(100)：1-5
[11].郭艳,王鑫,魏飞等.生物质快速裂解液化技术的研究进展.化工进展,2001,(8)：13-17
[12].雏廷亮,许庆利,刘国际等.生物质能的应用前景分析.能源研究与信息,2003,19(4)：194-197
[13]. http://www.hwcc.com.cm
[14]. MeKendry P. Bioresource Technology,2002,83:37
[15]. MOA, DOE Project Expert Team. Biomass Energy Conversion Technologies in China:Development and Evaluation. Beijing, China Environmental Science Press,1998
[16].国家发展和改革委员会能源局,国家发展和改革委员会能源研究所,中国资源综合利用协会可再生能源专业委员会中国可再生能源学会产业工作委员会.中国可再生能源产业发展报告[R].北京2007
[17].孙永明,孙振钧,袁振宏.中国生物质能源与生物质利用现状与展望[J].可再生能源,2006,2：78-82
[18]. Gross R, Leach.M, Bauen.A. Progress in renewable energy [J].EnvironmentalInte nation-nal,2003,29(1):105-122
[19].卢凌霄,周应恒.借鉴国外经验,发展生物质能[J].生态经济,学术版,2007,2：437-439
[20].王树荣.生物质热裂解制油的试验与机理研究.博士论文.浙江大学,1999
[21]. Bemard.Delmon, Etienne Lauren. Applied catalysis.1994,109:19
[22]. D.C.Elliott, Liquid fuels by low-severity hydrotreating of bioerude, Developments in thermochemical biomass conversion.Vol.1.1996, Blaekie Academic& Professional, London.611-621
[23].国家发展和改革委员会能源局.生物燃料发展有关情况及政策建议http://ww w.ndrc.gov.cn/nyjt/dcyyj/t20060421-67088.htm,2006
[24].孙培勤,臧哲学,孙绍晖等.生物质高压液化生物油的研究进展[J].现代化工,2008,28(3)：22-26.
[25]. C.U.Pittman, D.Mohan, P.H.Steele. Pyrolysis of wood/biomass for bio-oil:A critieal Review. Energy& Fuels.2OO6,20(3):848－889
[26]. A.V.Bridgwater. Principles and practicecof biomass fast pyrolysis processes for liquids. Journal of Analytical and Applied Pyrolysis.1999.51(1－2):3－22
[27]. A.V.Bridgwater. Production of high grade fuels and chemicals from catalytic Pyrolysis of biomass. Catalysis Today.1996,29(1－4):285-295
[28]. A.V.Bridgwater, M.L.Cottam. Opportunities for Biomass Pyrolysis Liquids Production and Upgrading. Energy& Fuels.1992,6(2):113-120
[29]. A.V.Bridgwater, G.V.C.Peacocke. Fast pyrolysis processes for biomass. Renewable and Sustainable Energy Reviews.2000,4(1):1-73
[30].朱锡锋,陆强,郑冀鲁等.生物质热解与生物油的特性研究.太阳能学报,2006.27(12)：1285-1289
[31].沈晨杰,刘荣厚,陈天举.不同贮存温度对木屑热裂解生物油理化性质稳定性的影响[J].农业工程学报2011,27(2)：276-281
[32].刘荣厚,王华,栾敬德.红松木屑在流化床中热裂解温度对生物油产率及性质的影响[J].农业工程学报
[33].刘荣厚,王华.生物质快速热裂解反应温度对生物油产率及特性的影响[J].农业工程学报,2006,22(6)：138-142
[34].武丽娟,李天舒等.生物质快速热裂解制取生物油的研究[J].中国农业工程学会,2005年学术年会论文集,2005：269
[35].刘荣厚等.生物质快速热裂解制取生物油技术的研究进展[J].沈阳农业大学学报,2007-2,38(1)：3-7
[36].李天舒等.生物质快速热裂解主要参数对生物油产率的影响[J].环境污染治理技术与设备,2006,7(11)：18-22
[37].吴汉靓,邓春健等.甜高粱茎杆残渣热裂解过程及其生物油成分分析[J].农机化研究2009,8：205-207
[38].栾敬德等.榆木木屑快速热裂解主要工艺参数优化及生物油成分的研究[J].农业工程学报,2008,24(5)：187-190
[39]. X.J.Guo, S.R.Wang. Properties of Bio-oil from Fast Pyrolysis of Rice Husk[J]. Chinese Journal of Chemical Engineering,2011,19(1):116－121
[40].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,2004,20(2)：246-249
[41].王琦,刘倩,贺博等.流化床生物质快速热裂解制取生物油试验研究[J].工程热物理学报,2008,29(5)：885-888
[42].王琦,王树荣,王乐等.生物质快速热裂解制取生物油试验研究[J].工程热物理学报,2007.28(1)：173-176
[43]. J.P.Diebold. A Review of the chemical and physical mechanisms of the storage stability of fast pyrolysis bio-oil[M].Fast Pyrolysis of Biomass:a handbook,2002.2:243-292
[44]. Chiaramonti D, Bonini.M etal. Development of emulsions from biornass pyrolysis liquid and diesel and their use in engines-Part I:Emulsion production. Biomass and Bioenergy. 2003.25 (1):85-99
[45]. Chiaralnonti.D etal.Development of emulsions from biomass pyrolysis liquid and diesel and their use in engines-Part2:tests in diesel engines, Biomass and Bioenergy.2003. 25(1):101－111
[46].李九如等.稻壳热解和生物油精制的研究[J].现代化工.2009.29(1)：39-42
[47]. Hogan.E. Emulsifieation of pyrolysis derived bio-oil in diesel fuel.Biomass Bioenergy, 2003,24:221-232
[48]. L.H.Wang, Z.Yin. Compoditional analysis of bio-oil and emulsification of bio-oil in diedel fuel[J]. International Conference on Biomass Energy Technologies,2008,3(5):37-41
[49]. Rajesh N.Patel, Santanu Bandyopadhyay, Anuradda Ganesh. Extraction of cardanol and phenol from bio-oils obtained through vacuum pyrolysis of biomass using supercritical fluid extraction [J]. Energy.2011,36:1535－1542
[50]. Q.Bu, H.W.Lei, Shoujie Ren etal. Phenol and phenolics from lignocellulosic biomass by catalytic microwave pyrolysis[J]. Bioresource Technology.2011,102:7004－7007
[51].崔洪友,魏书芹等.NiMoB/y-A12O3催化生物油加氢提质[J].可厚生能源,2011,29(2)：43-48
[52].李文志,黄锋,陆强等.Pd[P(C_6H_5)_3]4_均相催化精制生物油的试验研究[A].太阳能学报,2009,30(11)：1449-1453
[53].李文东,徐玉福,胡献国.二硫化钼催化加氢生物油的研究[A].化学工业与工程技术,2011,32(5)：11-13
[54].徐莹,王铁军,张琦等.镍基催化剂上生物油临氢催化改质的试验研究[A].太阳能学报,2009,30(2)：245-248
[55].吕鹏梅,常杰,吴创之等.生物质快速催化裂解的反应动力学[J].太阳能学报,2005,26(5)：647-653
[56].王铁军,付严,陈勇等.生物质焦油裂解催化剂制备及其催化裂解性能[J].煤炭转化,2003,26(1)：89-93
[57].郭晓亚,颜涌捷.生物质快速裂解油的催化裂解精制[J].化学反应工程与工艺,2005,21(3)：227-233
[58].郭晓亚,李庭琛,任铮伟等.生物质裂解油催化裂解精制[J].过程工程学报,2003,3(1)：91-95
[59].熊英,戴晓群.生物质制取燃油催化裂解的工艺研究[J].江西化工,2009,4：232-236
[60].周劲松,刘亚军,骆仲泱等.酸性、碱性催化剂对生物质焦油催化裂解影响分析.浙江大学学报(工业版),2005,39(7)：1047-1051
[61].胡勋,吕功煊.水蒸气重整生物质裂解油及其模型分子制氢[J].化学进展.2010,22(9)：1687-1700
[62].王兆祥,朱锡锋,潘越.C12A7-K_2O催化水蒸气重整生物油制氢[J].中国科学技术大学学报,2006,36(4)：458-460
[63].于建华,袁红艳,徐绍平等.Ni-Fe/坡缕石催化水蒸气重整杏核热解焦油制氢[J].西安交通大学学报,2008,42(8)：1049-1053
[64].蓝平,徐庆利,吴层等.生物质快速裂解油水蒸气催化重整制氢研究进展[J].化工进展,2009,28(10)：1719-1727
[65].隋淼.生物质油模拟物水蒸气催化重整制氢[J].石油化工,2009,38(5)：476-481
[66].王晨光等.固体碱催化剂上生物油催化酯化改质[J].石油化工,2006,35(7)：615-618
[67].张琦,常杰,王铁军等.固体酸催化剂SO_4~(2－)/SiO_2-TiO_2的制备及其催化酯化性能[J].催化学报,2006,27(11)：1033-1038
[68]王锦江,常杰,范娟.离子交换树脂催化酯化生物油的试验研究[J].燃群化学学报,2010,38(5)：560-564
[69].熊万明,傅尧,来大明.酸性离子交换树脂催化酯化改质生物油的研究[J].高等学校化学学报,2009,30(9)：1754-1758
[70].于荟,朱银华,刘畅等.新型介孔SO_4~27TiO_2固体酸的制备及其催化酯化性能[J].催化化学,2009,30(3)：265-271
[71]. Catherine Tessini, Mario Vega, Niels Muller etal. High performance thin layer chromato-graphy determination of cellobiosan and levoglucosan in bio-oil obtained by fast pyrolysis of sawdust[J]. Journal of Chromatography A.2011,1218:3811-3815
[72].左承基,钱叶剑,何建辉等.木质生物质直接液化产物的红外光谱分析[J].研究与试验,2006,125(AII)：10-13
[73].吴汉靓,刘荣厚,邓春健.甜高粱茎杆残渣热裂解过程及其生物油成分分析[J].农机化研究,2009,8：205-208
[74].何明明,景亮晶,李瑞等.4种不同原料生物油的主要化学组分分析[J].可再生能源,2010,26(8)：103-105
[75].衡明星,孙绍辉,陈俊武等.泡桐在水中无催化直接液化生物油的GC-MS分析研究[J].可再生能源,2010,28(6)：48-53
[76].杨昌炎,郑冬洁,丁一刚.生物油主要化学成分的定量分析[J].武汉工程大学学报,2011,33(11)：11-13
[77].殷哲,易维明,王丽红等.玉米秸秆热解生物油的主要成分分析[J].农机化研究,2010,1：33-36
[78].朱道飞.生物质在超临界水中的液化转化的实验研究[D].昆明理工大学,2004,50-54.
[79].常胜,赵增立,张伟等.不同种类生物油化学组成结构的对比研究[J].燃群化学学报,2011,39(10)：746-753
[2].张新华,蔡文之,戈特瓦尔德.能源之重-能源形势、能源安全和能源革命.社会观察,2004,9
[3].中国科学院生物质资源领域战略研究组.中国至2050年生物质资源科技发展路线图.科学出版社,2009
[4].骆仲映,刘妮,高翔等.中国能源与可持续发展[A].中国动力工程学会第二界青年学术年会论文集[C].湖北宜昌：1999
[5].王丽红.生物质闪速热裂解挥发特性的研究与生物油的组分分析[D].硕士论文,山东理工大学,2004,6
[6].廖艳芬,王树荣,谭洪等.生物质热裂解制取液体燃料技术的发展[J].能源工程,2002,(2)：125-130
[7].田雅林,王革华.国家可再生能源的发展[J].可再生能源,2003,5：42-44
[8]. Everett A. Sondreal, Steven A. Benson, John P, Fuel Proeessing Teehnology,2001,71:7
[9]. Forest volume-to-biomass models and estimates of mass for live and standing dead trees of U.S. forests
[10].陈和平.关于编制“十五”新能源计划的思考.新能源,1999,12(100)：1-5
[11].郭艳,王鑫,魏飞等.生物质快速裂解液化技术的研究进展.化工进展,2001,(8)：13-17
[12].雏廷亮,许庆利,刘国际等.生物质能的应用前景分析.能源研究与信息,2003,19(4)：194-197
[13]. http://www.hwcc.com.cm
[14]. MeKendry P. Bioresource Technology,2002,83:37
[15]. MOA, DOE Project Expert Team. Biomass Energy Conversion Technologies in China:Development and Evaluation. Beijing, China Environmental Science Press,1998
[16].国家发展和改革委员会能源局,国家发展和改革委员会能源研究所,中国资源综合利用协会可再生能源专业委员会中国可再生能源学会产业工作委员会.中国可再生能源产业发展报告[R].北京2007
[17].孙永明,孙振钧,袁振宏.中国生物质能源与生物质利用现状与展望[J].可再生能源,2006,2：78-82
[18]. Gross R, Leach.M, Bauen.A. Progress in renewable energy [J].EnvironmentalInte nation-nal,2003,29(1):105-122
[19].卢凌霄,周应恒.借鉴国外经验,发展生物质能[J].生态经济,学术版,2007,2：437-439
[20].王树荣.生物质热裂解制油的试验与机理研究.博士论文.浙江大学,1999
[21]. Bemard.Delmon, Etienne Lauren. Applied catalysis.1994,109:19
[22]. D.C.Elliott, Liquid fuels by low-severity hydrotreating of bioerude, Developments in thermochemical biomass conversion.Vol.1.1996, Blaekie Academic& Professional, London.611-621
[23].国家发展和改革委员会能源局.生物燃料发展有关情况及政策建议http://ww w.ndrc.gov.cn/nyjt/dcyyj/t20060421-67088.htm,2006
[24].孙培勤,臧哲学,孙绍晖等.生物质高压液化生物油的研究进展[J].现代化工,2008,28(3)：22-26.
[25]. C.U.Pittman, D.Mohan, P.H.Steele. Pyrolysis of wood/biomass for bio-oil:A critieal Review. Energy& Fuels.2OO6,20(3):848－889
[26]. A.V.Bridgwater. Principles and practicecof biomass fast pyrolysis processes for liquids. Journal of Analytical and Applied Pyrolysis.1999.51(1－2):3－22
[27]. A.V.Bridgwater. Production of high grade fuels and chemicals from catalytic Pyrolysis of biomass. Catalysis Today.1996,29(1－4):285-295
[28]. A.V.Bridgwater, M.L.Cottam. Opportunities for Biomass Pyrolysis Liquids Production and Upgrading. Energy& Fuels.1992,6(2):113-120
[29]. A.V.Bridgwater, G.V.C.Peacocke. Fast pyrolysis processes for biomass. Renewable and Sustainable Energy Reviews.2000,4(1):1-73
[30].朱锡锋,陆强,郑冀鲁等.生物质热解与生物油的特性研究.太阳能学报,2006.27(12)：1285-1289
[31].沈晨杰,刘荣厚,陈天举.不同贮存温度对木屑热裂解生物油理化性质稳定性的影响[J].农业工程学报2011,27(2)：276-281
[32].刘荣厚,王华,栾敬德.红松木屑在流化床中热裂解温度对生物油产率及性质的影响[J].农业工程学报
[33].刘荣厚,王华.生物质快速热裂解反应温度对生物油产率及特性的影响[J].农业工程学报,2006,22(6)：138-142
[34].武丽娟,李天舒等.生物质快速热裂解制取生物油的研究[J].中国农业工程学会,2005年学术年会论文集,2005：269
[35].刘荣厚等.生物质快速热裂解制取生物油技术的研究进展[J].沈阳农业大学学报,2007-2,38(1)：3-7
[36].李天舒等.生物质快速热裂解主要参数对生物油产率的影响[J].环境污染治理技术与设备,2006,7(11)：18-22
[37].吴汉靓,邓春健等.甜高粱茎杆残渣热裂解过程及其生物油成分分析[J].农机化研究2009,8：205-207
[38].栾敬德等.榆木木屑快速热裂解主要工艺参数优化及生物油成分的研究[J].农业工程学报,2008,24(5)：187-190
[39]. X.J.Guo, S.R.Wang. Properties of Bio-oil from Fast Pyrolysis of Rice Husk[J]. Chinese Journal of Chemical Engineering,2011,19(1):116－121
[40].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,2004,20(2)：246-249
[41].王琦,刘倩,贺博等.流化床生物质快速热裂解制取生物油试验研究[J].工程热物理学报,2008,29(5)：885-888
[42].王琦,王树荣,王乐等.生物质快速热裂解制取生物油试验研究[J].工程热物理学报,2007.28(1)：173-176
[43]. J.P.Diebold. A Review of the chemical and physical mechanisms of the storage stability of fast pyrolysis bio-oil[M].Fast Pyrolysis of Biomass:a handbook,2002.2:243-292
[44]. Chiaramonti D, Bonini.M etal. Development of emulsions from biornass pyrolysis liquid and diesel and their use in engines-Part I:Emulsion production. Biomass and Bioenergy. 2003.25 (1):85-99
[45]. Chiaralnonti.D etal.Development of emulsions from biomass pyrolysis liquid and diesel and their use in engines-Part2:tests in diesel engines, Biomass and Bioenergy.2003. 25(1):101－111
[46].李九如等.稻壳热解和生物油精制的研究[J].现代化工.2009.29(1)：39-42
[47]. Hogan.E. Emulsifieation of pyrolysis derived bio-oil in diesel fuel.Biomass Bioenergy, 2003,24:221-232
[48]. L.H.Wang, Z.Yin. Compoditional analysis of bio-oil and emulsification of bio-oil in diedel fuel[J]. International Conference on Biomass Energy Technologies,2008,3(5):37-41
[49]. Rajesh N.Patel, Santanu Bandyopadhyay, Anuradda Ganesh. Extraction of cardanol and phenol from bio-oils obtained through vacuum pyrolysis of biomass using supercritical fluid extraction [J]. Energy.2011,36:1535－1542
[50]. Q.Bu, H.W.Lei, Shoujie Ren etal. Phenol and phenolics from lignocellulosic biomass by catalytic microwave pyrolysis[J]. Bioresource Technology.2011,102:7004－7007
[51].崔洪友,魏书芹等.NiMoB/y-A12O3催化生物油加氢提质[J].可厚生能源,2011,29(2)：43-48
[52].李文志,黄锋,陆强等.Pd[P(C_6H_5)_3]4_均相催化精制生物油的试验研究[A].太阳能学报,2009,30(11)：1449-1453
[53].李文东,徐玉福,胡献国.二硫化钼催化加氢生物油的研究[A].化学工业与工程技术,2011,32(5)：11-13
[54].徐莹,王铁军,张琦等.镍基催化剂上生物油临氢催化改质的试验研究[A].太阳能学报,2009,30(2)：245-248
[55].吕鹏梅,常杰,吴创之等.生物质快速催化裂解的反应动力学[J].太阳能学报,2005,26(5)：647-653
[56].王铁军,付严,陈勇等.生物质焦油裂解催化剂制备及其催化裂解性能[J].煤炭转化,2003,26(1)：89-93
[57].郭晓亚,颜涌捷.生物质快速裂解油的催化裂解精制[J].化学反应工程与工艺,2005,21(3)：227-233
[58].郭晓亚,李庭琛,任铮伟等.生物质裂解油催化裂解精制[J].过程工程学报,2003,3(1)：91-95
[59].熊英,戴晓群.生物质制取燃油催化裂解的工艺研究[J].江西化工,2009,4：232-236
[60].周劲松,刘亚军,骆仲泱等.酸性、碱性催化剂对生物质焦油催化裂解影响分析.浙江大学学报(工业版),2005,39(7)：1047-1051
[61].胡勋,吕功煊.水蒸气重整生物质裂解油及其模型分子制氢[J].化学进展.2010,22(9)：1687-1700
[62].王兆祥,朱锡锋,潘越.C12A7-K_2O催化水蒸气重整生物油制氢[J].中国科学技术大学学报,2006,36(4)：458-460
[63].于建华,袁红艳,徐绍平等.Ni-Fe/坡缕石催化水蒸气重整杏核热解焦油制氢[J].西安交通大学学报,2008,42(8)：1049-1053
[64].蓝平,徐庆利,吴层等.生物质快速裂解油水蒸气催化重整制氢研究进展[J].化工进展,2009,28(10)：1719-1727
[65].隋淼.生物质油模拟物水蒸气催化重整制氢[J].石油化工,2009,38(5)：476-481
[66].王晨光等.固体碱催化剂上生物油催化酯化改质[J].石油化工,2006,35(7)：615-618
[67].张琦,常杰,王铁军等.固体酸催化剂SO_4~(2－)/SiO_2-TiO_2的制备及其催化酯化性能[J].催化学报,2006,27(11)：1033-1038
[68]王锦江,常杰,范娟.离子交换树脂催化酯化生物油的试验研究[J].燃群化学学报,2010,38(5)：560-564
[69].熊万明,傅尧,来大明.酸性离子交换树脂催化酯化改质生物油的研究[J].高等学校化学学报,2009,30(9)：1754-1758
[70].于荟,朱银华,刘畅等.新型介孔SO_4~27TiO_2固体酸的制备及其催化酯化性能[J].催化化学,2009,30(3)：265-271
[71]. Catherine Tessini, Mario Vega, Niels Muller etal. High performance thin layer chromato-graphy determination of cellobiosan and levoglucosan in bio-oil obtained by fast pyrolysis of sawdust[J]. Journal of Chromatography A.2011,1218:3811-3815
[72].左承基,钱叶剑,何建辉等.木质生物质直接液化产物的红外光谱分析[J].研究与试验,2006,125(AII)：10-13
[73].吴汉靓,刘荣厚,邓春健.甜高粱茎杆残渣热裂解过程及其生物油成分分析[J].农机化研究,2009,8：205-208
[74].何明明,景亮晶,李瑞等.4种不同原料生物油的主要化学组分分析[J].可再生能源,2010,26(8)：103-105
[75].衡明星,孙绍辉,陈俊武等.泡桐在水中无催化直接液化生物油的GC-MS分析研究[J].可再生能源,2010,28(6)：48-53
[76].杨昌炎,郑冬洁,丁一刚.生物油主要化学成分的定量分析[J].武汉工程大学学报,2011,33(11)：11-13
[77].殷哲,易维明,王丽红等.玉米秸秆热解生物油的主要成分分析[J].农机化研究,2010,1：33-36
[78].朱道飞.生物质在超临界水中的液化转化的实验研究[D].昆明理工大学,2004,50-54.
[79].常胜,赵增立,张伟等.不同种类生物油化学组成结构的对比研究[J].燃群化学学报,2011,39(10)：746-753