碳基固体酸催化剂的制备及其应用研究
|
摘要
生物柴油是一种新型绿色能源,生产原料主要是来自于动植物油脂和回收的废油脂。因其具有含硫量低、对环境污染较小、可再生等优势而备受关注。利用餐饮废油为原料是我国生产生物柴油的优势,我国每年产生大量餐饮废油,如果以其作为原料生产生物柴油,一定能够产生很好的经济效益。目前,在我国生产生物柴油主要以酯交换反应法为主。餐饮废油的酸值较高,酯交换法制备生物柴油需要原料油的酸值必须小于1,因此需降酸处理。降酸过程在酯化反应中进行,一般采用强酸(硫酸)作为催化剂,但对设备有腐蚀,并会产生大量的废水,而且催化剂不能回收。
碳基固体酸催化剂是一种新型固体酸催化剂,使用此种催化剂可以避免酸腐蚀及产生大量废水等不利环境的因素,还能够显著的降低生产成本。本文首先对新型碳基固体酸催化剂的制备进行了探索式的研究,以生物质块状竹料(杆径为0.3～0.5cm)合成了碳基固体酸催化剂。采用扫描电镜(SEM)、红外光谱(FT-IR)对催化剂进行了表征。利用油酸模拟高酸值生物柴油原料进行气相酯化降酸应用研究,并考察了碳化温度、磺化时间、磺化温度对催化活性的影响。酯化反应温度92℃,反应时间3h,催化剂用量为油酸质量的6%,甲醇蒸气为75℃。实验结果表明：以碳化温度在210℃,磺化时间7h,磺化温度70℃时所制备的碳基固体酸催化剂参与气相酯化反应,反应结束后测得油酸的转化率为86.93%。催化剂在重复使用4次,转化率仍能达到60%以上。试验还对催化剂再生利用进行了试验研究,实验结果催化剂的活性基本得到恢复。
在此基础上以新方法制备出磁性碳基固体酸催化剂。此种催化剂带有磁性,在制备生物柴油的过程中如在反应器皿以外添加磁场,可以影响催化剂在反应器内的分布及反应后的回收。对制备的磁性催化材料采用扫描电镜(SEM)、红外光谱(FT-IR)、X-射线衍射(XRD)进行了表征,并考察了催化剂制备条件中磺化温度及时间、磺化酸量对反应转化率的影响。实验选用温度为500℃,活性炭与三氧化二铁质量比1：3混合,高温加热8h,得到的磁性材料经磺化温度70℃,磺化时间6h,磺化酸量7ml制成的磁性碳基固体酸催化剂参与生物柴油气相酯化降酸试验；酯化反应温度95℃,反应时间为3h,催化剂用量定为油酸质量的6%,甲醇蒸气75℃。反应后油酸转化率为85.82%。催化剂回收率为96.37%,且回收方法简单。催化剂重复使用4次后,反应中油酸的转化率仍能达到55%以上。磁性碳基固体酸催化剂具有较好稳定性及催化活性。在生物柴油生产中,应用碳基固体酸催化剂催化高酸值生物柴油原料降酸过程,具有很好的应用前景和经济价值。
Biodiesel is a kind of green renewable energy, because of has the sulphur content lowly, renewable, merits and so on environmental protection to receive the attention. The Biodiesel production are mainly the zoology and botany fat and the recycling waste fat.Our country makes biodiesel with a superiority raw material of the dining- used oil, its not only fruitful in resources, moreover the price is cheap. At present, in industrial production mainly by transesterification preparation for biodiesel. But, the dining used oil's acid value is very high, the transesterification preparation for biodiesel that request raw oil acid value to be smaller than 1, must therefore fall the oil acid value treatment. Falls the sour process, in the esterification carries on, generally uses the strong acid (sulfuric acid) to take the catalyst, but has the corrosion to the equipment, and will produce the massive waste water, and the catalyst cannot be recycled.
The carbon base solid acid catalyst is one new kind of the solid acid catalyst, may avoid the acid corrosion and the waste of water and disadvantageous environmental factor, can reduce the production cost. This article first has conducted the exploration-like experimental study to the new carbon base solid acid catalyst's preparation, take lived the material bamboo (pole diameter is 0.3～0.5cm) synthesized the carbon base solid acid catalyst as raw material. The catalyst samples were characterized by scanning electron microscopey (SEM), Fourier transform infrared (FT-IR) spectroscopy.The experiment simulates the high acid value of biodiesel raw material using the oleic acid to carry on the gaseous esterification to fall the acid experiment, and inspected the carbonization temperature, the sulfonation time, the sulfonation temperature to the catalytic activity influence. Esterification reaction temperature 92℃, reaction time 3h, catalyst amount used for oleic acid quality 6%, vaporization temperature for 75℃. The experimental result indicated:Carbonization temperature 210℃, sulfonation time 7h, sulfonation temperature 70℃prepares the carbon base solid acid catalyst uses in the esterification responding that the conversion rate is 86.93%. The catalyst after repeatedly uses use 4 times, the oleic acid conversion rate still could achieve above 60%. Meanwhile has conducted the exploration type experimental study to the catalyst regeneration use, the experiment result that activities of the catalyst can be recovery.
On the foundation in new way preparation the magnetic carbon base solid acid catalyst. This catalyst has magnetism, in the process preparation of biodiesel that toward outside increase the magnetic field, it can be control distribution of the catalyst in the reactor and the catalyst recycling. The preparation materialof magnetic catalyst with the scanning electron microscope (SEM), Fourier transform infrared (FT-IR) spectroscopy, and the X-ray diffractometer (XRD) to carry on the characterized,, simultaneously inspected the sulfonation temperature, the sulfonation time, the sulphur acidify quantity to the esterification's conversion rate influence. The experiment selects the temperature for 500℃, the activated carbon and the ferric oxide quantity compare 1:3, heat up 8h, obtains the magnetic material after the sulfonation temperature 70℃, sulfonation time 6h, the sulfuric acid 7ml. Uesd the magnetic carbon base solid acid catalyst makes to fall the acid experiment by participation the gaseous esterification, the esterification's conversion rate 85.82%. The catalyst of recycle rate is 96.37%, and the recycling method is very simple. The esterification reaction temperature at 95℃,reaction time3h, the catalyst amount used for the oleic acid quality 6%, the vaporization temperature for 75℃. The catalyst after repeatedly uses use 4 times, that the oleic acid conversion rate still could achieve above 55%.The catalyst stability and the activity are good. In the production of biodiesel, high acid value of raw material was explored to reduce the acid value that using the carbon base solid acid catalyst, has the very good application prospect and the economic value.
碳基固体酸催化剂是一种新型固体酸催化剂,使用此种催化剂可以避免酸腐蚀及产生大量废水等不利环境的因素,还能够显著的降低生产成本。本文首先对新型碳基固体酸催化剂的制备进行了探索式的研究,以生物质块状竹料(杆径为0.3～0.5cm)合成了碳基固体酸催化剂。采用扫描电镜(SEM)、红外光谱(FT-IR)对催化剂进行了表征。利用油酸模拟高酸值生物柴油原料进行气相酯化降酸应用研究,并考察了碳化温度、磺化时间、磺化温度对催化活性的影响。酯化反应温度92℃,反应时间3h,催化剂用量为油酸质量的6%,甲醇蒸气为75℃。实验结果表明：以碳化温度在210℃,磺化时间7h,磺化温度70℃时所制备的碳基固体酸催化剂参与气相酯化反应,反应结束后测得油酸的转化率为86.93%。催化剂在重复使用4次,转化率仍能达到60%以上。试验还对催化剂再生利用进行了试验研究,实验结果催化剂的活性基本得到恢复。
在此基础上以新方法制备出磁性碳基固体酸催化剂。此种催化剂带有磁性,在制备生物柴油的过程中如在反应器皿以外添加磁场,可以影响催化剂在反应器内的分布及反应后的回收。对制备的磁性催化材料采用扫描电镜(SEM)、红外光谱(FT-IR)、X-射线衍射(XRD)进行了表征,并考察了催化剂制备条件中磺化温度及时间、磺化酸量对反应转化率的影响。实验选用温度为500℃,活性炭与三氧化二铁质量比1：3混合,高温加热8h,得到的磁性材料经磺化温度70℃,磺化时间6h,磺化酸量7ml制成的磁性碳基固体酸催化剂参与生物柴油气相酯化降酸试验；酯化反应温度95℃,反应时间为3h,催化剂用量定为油酸质量的6%,甲醇蒸气75℃。反应后油酸转化率为85.82%。催化剂回收率为96.37%,且回收方法简单。催化剂重复使用4次后,反应中油酸的转化率仍能达到55%以上。磁性碳基固体酸催化剂具有较好稳定性及催化活性。在生物柴油生产中,应用碳基固体酸催化剂催化高酸值生物柴油原料降酸过程,具有很好的应用前景和经济价值。
Biodiesel is a kind of green renewable energy, because of has the sulphur content lowly, renewable, merits and so on environmental protection to receive the attention. The Biodiesel production are mainly the zoology and botany fat and the recycling waste fat.Our country makes biodiesel with a superiority raw material of the dining- used oil, its not only fruitful in resources, moreover the price is cheap. At present, in industrial production mainly by transesterification preparation for biodiesel. But, the dining used oil's acid value is very high, the transesterification preparation for biodiesel that request raw oil acid value to be smaller than 1, must therefore fall the oil acid value treatment. Falls the sour process, in the esterification carries on, generally uses the strong acid (sulfuric acid) to take the catalyst, but has the corrosion to the equipment, and will produce the massive waste water, and the catalyst cannot be recycled.
The carbon base solid acid catalyst is one new kind of the solid acid catalyst, may avoid the acid corrosion and the waste of water and disadvantageous environmental factor, can reduce the production cost. This article first has conducted the exploration-like experimental study to the new carbon base solid acid catalyst's preparation, take lived the material bamboo (pole diameter is 0.3～0.5cm) synthesized the carbon base solid acid catalyst as raw material. The catalyst samples were characterized by scanning electron microscopey (SEM), Fourier transform infrared (FT-IR) spectroscopy.The experiment simulates the high acid value of biodiesel raw material using the oleic acid to carry on the gaseous esterification to fall the acid experiment, and inspected the carbonization temperature, the sulfonation time, the sulfonation temperature to the catalytic activity influence. Esterification reaction temperature 92℃, reaction time 3h, catalyst amount used for oleic acid quality 6%, vaporization temperature for 75℃. The experimental result indicated:Carbonization temperature 210℃, sulfonation time 7h, sulfonation temperature 70℃prepares the carbon base solid acid catalyst uses in the esterification responding that the conversion rate is 86.93%. The catalyst after repeatedly uses use 4 times, the oleic acid conversion rate still could achieve above 60%. Meanwhile has conducted the exploration type experimental study to the catalyst regeneration use, the experiment result that activities of the catalyst can be recovery.
On the foundation in new way preparation the magnetic carbon base solid acid catalyst. This catalyst has magnetism, in the process preparation of biodiesel that toward outside increase the magnetic field, it can be control distribution of the catalyst in the reactor and the catalyst recycling. The preparation materialof magnetic catalyst with the scanning electron microscope (SEM), Fourier transform infrared (FT-IR) spectroscopy, and the X-ray diffractometer (XRD) to carry on the characterized,, simultaneously inspected the sulfonation temperature, the sulfonation time, the sulphur acidify quantity to the esterification's conversion rate influence. The experiment selects the temperature for 500℃, the activated carbon and the ferric oxide quantity compare 1:3, heat up 8h, obtains the magnetic material after the sulfonation temperature 70℃, sulfonation time 6h, the sulfuric acid 7ml. Uesd the magnetic carbon base solid acid catalyst makes to fall the acid experiment by participation the gaseous esterification, the esterification's conversion rate 85.82%. The catalyst of recycle rate is 96.37%, and the recycling method is very simple. The esterification reaction temperature at 95℃,reaction time3h, the catalyst amount used for the oleic acid quality 6%, the vaporization temperature for 75℃. The catalyst after repeatedly uses use 4 times, that the oleic acid conversion rate still could achieve above 55%.The catalyst stability and the activity are good. In the production of biodiesel, high acid value of raw material was explored to reduce the acid value that using the carbon base solid acid catalyst, has the very good application prospect and the economic value.
引文
[1]林晶,林金清.生物柴油及其催化合成技术研究进展[J].化学工程与装备,2009,33(1)：102-107.
[2]高寒,崔勇,郑晋军.生物柴油与石化柴油的性能对比研究[J].内燃机,2009,3(6)：35-42.
[3]燕来荣.我国生物柴油的发展状况及产业化前景[J].客车技术与研究,2009,(6)：1-3
[4]徐立清,于晓红.试论中国生物柴油的商业化[J].江南大学学报,2009,8(8)：85-88
[5]陈明华.生物柴油简介[J].化学教育,2009,(7)：8-10.
[6]周华,张道文.生物柴油发动机的排放特征研究[J].小型内燃机与摩托车,2009,38(6)：51-55.
[7]任洪娟,田永祥,张若平.生物柴油对柴油机性能的影响与发展前景[J].农机化研究,2009,(4)：204-206.
[8]李昌珠.生物柴油研究现状与商业化应用前景[N].中经BP社,2004.1.7.
[9]孙尚德,王兴国,单良.生物柴油研究与开发进展[J].粮食与油脂,2007,33(4)：8-14.
[10]Chanatip Samart, Chaiyan Chaiya, Prasert Reubroycharoen. Biodiesel production by methanolysis of soybean oil using calcium supported onmesoporous silica catalyst [J]. Energy Conversion and Management,2007, (51):1428-1431.
[1]]吴伟光,仇焕光,徐志刚.生物柴油发展现状、影响与展望[J].农业工程学报,2009,25(3)：298-302.
[12]Nicolae Sdrula..A study using classical or membrane separation in the biodiesel process[J].Desalination,2010, (250):1070-1072.
[13]孙剑萍,汤兆平.生物柴油的发展及其在发动机中的应用[J].小型内燃机与摩托车,2009,38(1)：92-96.
[14]崔十贞,刘纯山.固体碱催化大豆油酯交换反应的研究[J].工业催化,2005,13(7)：32-35.
[15]饯伯章.欧美加快推广应用生物柴油[J].精细石油化工进展,2003,(11)：3-7.
[16]刘鑫.生物柴油的特点及发展状况[J].高校理科研究科技信息,2009,(3)：82-86.
[17]宋玉春.中国生物柴油亟待产业化[J].化工文摘,2004,(3)：17-19.
[18]GuanHua Huang, Feng Chen, Dong Wei. Biodiesel production by microalgal biotechnology [J]. Applied Energy,2010, (87):38-46.
[19]Paul C.Smith, Yung Ngothai.Improving the low-temperature properties of biodiesel: Methodsand consequences [J].Renewable Energy,2010, (35):1145-1151.
[20]冀星,王璇.世界各国生物柴油应用情况[J].国际化工信息,2002,(9)：1-4.
[21]龚丽萍.生物柴油的优点与现状[J].太原大学学报,2007,4(8)：15-19.
[22]韩毅,邓宇.生物柴油的发展现状及新技术[J].2007,13(5)：10-12.
[23]嵇磊.利用藻类生物质制备生物燃料研究进展[J].石油学报,2007,23(5)：33-36.
[24]杨阳, 张楠.生物柴油的标准和调和性能[J].石油知识,2009,(3)：23-25.
[25]Aldara da SilvaCe'sar, Ma'rio Ota'vio Batalha.Biodiesel production from castor oil in Brazil:A difficult reality [J]. Energy Policy,2011, (38):4031-4039.
[26]张骥.日本生物柴油的发展[J].可再生能源,2009,27(1)：36-38.
[27]张道杰,杨翠玲,乔明宽.生物柴油的发展概况与应用前景[J].化学研究,2009,20(3)：108-112.
[28]张扬健,向威达,雷家锡.我国生物柴油经济效益和发展前景分析[J].能源及环境,2009,(22)：18-21.
[29]曾炜.我国生物柴油发展状况及对策[J].华中农业大学学报,2009,82(4)：45-48.
[30]柯路.我国生物柴油产业化前景诱人[J].节能减排,2009,16(4)：89-91.
[31]李晓辉.开发生物柴油势住必行[J].科技情报开发与经济,2009,(4)：145-147.
[32]李金萍,张小兵,李茜茜,李忠.中国生物柴油技术开发及应用进展[J].专论与综述,2008,(3)：327-330.
[33]吴伟光,李怒云.我国林业生物柴油的发展目标、现状及面临的挑战[J].林业科学,2009,45(11)：141-147.
[34]纪徐源.生物柴油的发展现状及其产业化[J].石油商技,2003,(5)：20-23.
[35]白雯,张春波,张丽静.生物柴油的发展现状[J].广东化工,2008,(5)：4-7.
[36]杨仕品.生物柴油生产发展的现状及发展前景[J].贵州农业科学,2009,(1)：157-160.
[37]侯元凯,刘松杨,黄琳等.生物柴油树种选择与评价[J].林业科学院,2009,22(1)：7-13.
[38]吴红,宗敏华,娄文勇等.无溶剂系统中固定化脂肪酶催化废油脂转酯生产生物柴油[J].催化学报,2004,25(11)：903-908.
[39]Metin Guru, Atilla Koca, Ozer Can. Biodiesel production from waste chicken fat based sources and evaluationwith Mg based additive in a diesel engine [J].Renewable Energy, 2010, (35):637-643.
[40]翼星,刘京顺,翼金平等.中国生物柴油产业化发展战略思考[J].中国能源,2006,(5)：25-30.
[41]郑风田,崔海兴.中国生物柴油发展的现状、潜力与障碍分析[J].林业经济,2009,(3)：65-70.
[42]王利宾,黄凤洪,李文林等.固体酸催化剂制备生物柴油的研究进展[J].化学与生物工程,2009,26(4)：12-15.
[43]Dennis Y.C. Leung, Xuan Wu, M.K.H. Leung.A review on biodiesel production using catalyzed transesterification [J]. Applied Energy,2010, (87),1083-1095.
[44]于世涛,刘福胜.固体酸与精细化工[M].北京：化学工业出版社,2005.
[45]Kok Tat Tan, Keat Teong Lee*.Abdul Rahman Mohamed A glycerol-free process to produce biodiesel by supercritical methyl acetate technology:An optimization study via Response Surface Methodology [J]. Bioresource Technology,2010, (101),965-969.
[46]张根旺.生物柴油的生产及发展前景[J].粮油食品科技,2009,17(4)：17-19.
[47]刘星火,李为民,姚超.固体酸在生物柴油生产中的应用[J].中国油脂,2009,34(3)：38-42.
[48]徐静莉,孙国富.固体酸催化剂在酯化反应中应用研究进展[J].林化工学院学报,2001,18(4)：87-90.
[49]唐建飞.生物柴油的生产方法[J].中国科学技术展望,2007,(6)：81-83.
[50]廖李,程微,王少华等.超声波强化甲醇—乙醇混合体系酯化反应制备生物柴油[J].农品加工,2009,188(10)：13-15.
[51]Le Tu Thanh, Kenji Okitsu, Yasuhiro Sadanaga. A two-step continuous ultrasound assisted production of biodiesel fuel from waste cooking oils:A practical and economical approach to produce high quality biodiesel fuel[J]. Bioresource Technology,2010, (101):5394-5401.
[52]任庆功,阎杰,丘泰球.超声强化酯交换制备生物柴油的研究进展[J].中国油脂,2009,34(1)：54-58.
[53]雍开东,苟科,张鹏.超声波制取生物柴油工艺技术探讨[J].中外能源,2009,14(5)：47-50.
[54]J.A. Siles, M.A. Martin. Anaerobic co-digestion of glycerol and wastewater derived from Biodiesel manufacturing [J].Bioresource Technology,2010, (101):6315-6321.
[55]SOUMANOU M M, BORNSCHEUER U T. Improvement in lipase—catalyzed synthesis of fatty acid methyl esters from sunflower oil [J].Enzyme and Microbial Technology,2003, 3314(1):97-103.
[56]张哲,魏海国.生物柴油生产技术进展[J].石油规划设计,2009,20(1)：23-27
[57]马震,银建中,商紫阳等.超临界酯交换法制备生物柴油工艺基础及其过程强化技术研究[J].化学与生物工程,2009,26(8)：1-7.
[58]邢存章,谭明臣,吕海亮等.超临界甲醇法制备生物柴油[J].石油化工高等学校学报,2009,22(3)：9-12.
[59]Kok Tat Tan, Meei Mei Gui, Keat Teong Lee. An optimized study of methanol and ethanol in supercritical alcohol technology for biodiesel production [J].The Journal ofSupercritical Fluids,2010, (53):82-87.
[60]赵贵兴.超临界甲醇法制备大豆生物柴油[J].大豆科技,2009,(2)：33-36.
[61]王桂茹.催化剂与催化作用[M].辽宁：大连理工大学出版社,2007.
[62]夏海涛.催化剂设计与制备工艺[M].北京：化学工业出版社,2003.
[63]张艺,柏子龙,金宏轩等.铌硅铝磷分子筛的合成及催化酯化性能研究[J].化学研究,2008,19(2)：9-12.
[64]Zhao Zhenhua.Synthesis of butyl propionate using novel alumin -ophosphate molecular sieve as catalyst[J].J Mol Catal,2000,154(1-2):131-135.
[65]沈文霞,王志斌,李春志等.固体酸催化剂的制备与应用研究[J].宁夏大学学报(自然科学版),2001,22(2)：123-124.
[66]Chai F, Cao F H, Zhai F Y,et al. Transesterification of vegetable oil to biodiesel using a heteropolyacid solid catalyst [J]. AdvSynth Catal,2007,349(7):1057-1065.
[67]曹宏远,曹维良,张敬畅.固体酸Zr(SO4)2-4H2O催化制备生物柴油[J].北京化工大学学报,2005,32(6)：61-63.
[68]万祯,张胜涛.复合固体酸催化餐饮废油合成生物柴油的研究[J].河北化工,2008,31(1)：37-39.
[69]Yin-Qing Zhang, Sheng-Jie Wang, Jun-Wei Wang. Synthesis and characterization of Zr-SBA-15 supported tungsten oxide as a new mesoporous solid acid [J].Solid State Sciences,2009, (11):1412-1418.
[70]张琦,常铁,王铁军等.固体酸催化改质生物柴油的研究[J].燃料化学学报,2006,34(6)：680-684.
[71]吴芹,王玲,吴谋成等.阳离子交换树脂催化制备生物柴油的工艺优化[J].中国油料作物学报,2008,30(1)：119-12.
[72]Chitralekha Khatri, Ashu Rani.Synthesis of a nano-crystalline solid acid catalyst from fly ash and its catalytic performance [J].Fuel,2008, (87):2886-2892.
[73]王督,苏有勇,王华.碳基固体酸催化高酸值生物柴油原料降酸效果[J].农业工程学报,2006,25(11)：274-277.
[74]周丽娜,刘可,华伟明等.碳基磺酸化固体酸材料的制备及其催化性能[J].催化学报,2009,30(3)：196-200.
[75]江文辉,文鹤林.碳基固体酸催化印楝树油与甲醇的酯交换反应[J].湖南工业大学学报,2009,23(3)：46-49.
[76]Daizo, Yamaguchi, Michikazu Hara.Starch saccharification by carbon-based solid acid catalyst[J]. Solid State Sciences,2010, (12):1018-1023.
[77]曾昌凤,陈军等.磺酸型固体酸催化剂的制备与应用研究进展[J].南京工业大学学报,2009,31(6)：104-110.
[78]Sato shi Suganuma, Kiyotaka Nakajima, Masaaki Kitano.Synthesis and derivedcarbon-based solid acid [J].Solid State Sciences,2010, (12):1029-1034.
[79]Beena Tyagi, Manish Kumar Mishra, Raksh Vir Jasra. Solvent free synthesis of acetyl salicylic acid over nano-crystalline sulfated zirconia solid acid catalyst [J].Journal of Molecular Catalysis A:Chemical,2010, (317):41-45.
[80]Qing Shu, Zeeshan Nawaz, Jixian Gao.Synthesis of biodiesel from a model waste oilfeedstock using a carbon-based solid acid catalyst:Reaction and separation[J]. Bioresource Technology, Bioresource Technology,2010, (101):5374-5384.
[81]复合碳基固体酸催化剂的制备及应用[D].宁夏：宁夏大学硕十毕业论文,2010年.
[82]高珊.新型碳基固体磺酸的合成及其在有机反应中的应用[D].上海：华东师范大学博十论文,2009年.
[83]覃兆海,金淑惠,李楠编著.基础有机化学[M].北京：科·学技术文献出版社,2004.
[2]高寒,崔勇,郑晋军.生物柴油与石化柴油的性能对比研究[J].内燃机,2009,3(6)：35-42.
[3]燕来荣.我国生物柴油的发展状况及产业化前景[J].客车技术与研究,2009,(6)：1-3
[4]徐立清,于晓红.试论中国生物柴油的商业化[J].江南大学学报,2009,8(8)：85-88
[5]陈明华.生物柴油简介[J].化学教育,2009,(7)：8-10.
[6]周华,张道文.生物柴油发动机的排放特征研究[J].小型内燃机与摩托车,2009,38(6)：51-55.
[7]任洪娟,田永祥,张若平.生物柴油对柴油机性能的影响与发展前景[J].农机化研究,2009,(4)：204-206.
[8]李昌珠.生物柴油研究现状与商业化应用前景[N].中经BP社,2004.1.7.
[9]孙尚德,王兴国,单良.生物柴油研究与开发进展[J].粮食与油脂,2007,33(4)：8-14.
[10]Chanatip Samart, Chaiyan Chaiya, Prasert Reubroycharoen. Biodiesel production by methanolysis of soybean oil using calcium supported onmesoporous silica catalyst [J]. Energy Conversion and Management,2007, (51):1428-1431.
[1]]吴伟光,仇焕光,徐志刚.生物柴油发展现状、影响与展望[J].农业工程学报,2009,25(3)：298-302.
[12]Nicolae Sdrula..A study using classical or membrane separation in the biodiesel process[J].Desalination,2010, (250):1070-1072.
[13]孙剑萍,汤兆平.生物柴油的发展及其在发动机中的应用[J].小型内燃机与摩托车,2009,38(1)：92-96.
[14]崔十贞,刘纯山.固体碱催化大豆油酯交换反应的研究[J].工业催化,2005,13(7)：32-35.
[15]饯伯章.欧美加快推广应用生物柴油[J].精细石油化工进展,2003,(11)：3-7.
[16]刘鑫.生物柴油的特点及发展状况[J].高校理科研究科技信息,2009,(3)：82-86.
[17]宋玉春.中国生物柴油亟待产业化[J].化工文摘,2004,(3)：17-19.
[18]GuanHua Huang, Feng Chen, Dong Wei. Biodiesel production by microalgal biotechnology [J]. Applied Energy,2010, (87):38-46.
[19]Paul C.Smith, Yung Ngothai.Improving the low-temperature properties of biodiesel: Methodsand consequences [J].Renewable Energy,2010, (35):1145-1151.
[20]冀星,王璇.世界各国生物柴油应用情况[J].国际化工信息,2002,(9)：1-4.
[21]龚丽萍.生物柴油的优点与现状[J].太原大学学报,2007,4(8)：15-19.
[22]韩毅,邓宇.生物柴油的发展现状及新技术[J].2007,13(5)：10-12.
[23]嵇磊.利用藻类生物质制备生物燃料研究进展[J].石油学报,2007,23(5)：33-36.
[24]杨阳, 张楠.生物柴油的标准和调和性能[J].石油知识,2009,(3)：23-25.
[25]Aldara da SilvaCe'sar, Ma'rio Ota'vio Batalha.Biodiesel production from castor oil in Brazil:A difficult reality [J]. Energy Policy,2011, (38):4031-4039.
[26]张骥.日本生物柴油的发展[J].可再生能源,2009,27(1)：36-38.
[27]张道杰,杨翠玲,乔明宽.生物柴油的发展概况与应用前景[J].化学研究,2009,20(3)：108-112.
[28]张扬健,向威达,雷家锡.我国生物柴油经济效益和发展前景分析[J].能源及环境,2009,(22)：18-21.
[29]曾炜.我国生物柴油发展状况及对策[J].华中农业大学学报,2009,82(4)：45-48.
[30]柯路.我国生物柴油产业化前景诱人[J].节能减排,2009,16(4)：89-91.
[31]李晓辉.开发生物柴油势住必行[J].科技情报开发与经济,2009,(4)：145-147.
[32]李金萍,张小兵,李茜茜,李忠.中国生物柴油技术开发及应用进展[J].专论与综述,2008,(3)：327-330.
[33]吴伟光,李怒云.我国林业生物柴油的发展目标、现状及面临的挑战[J].林业科学,2009,45(11)：141-147.
[34]纪徐源.生物柴油的发展现状及其产业化[J].石油商技,2003,(5)：20-23.
[35]白雯,张春波,张丽静.生物柴油的发展现状[J].广东化工,2008,(5)：4-7.
[36]杨仕品.生物柴油生产发展的现状及发展前景[J].贵州农业科学,2009,(1)：157-160.
[37]侯元凯,刘松杨,黄琳等.生物柴油树种选择与评价[J].林业科学院,2009,22(1)：7-13.
[38]吴红,宗敏华,娄文勇等.无溶剂系统中固定化脂肪酶催化废油脂转酯生产生物柴油[J].催化学报,2004,25(11)：903-908.
[39]Metin Guru, Atilla Koca, Ozer Can. Biodiesel production from waste chicken fat based sources and evaluationwith Mg based additive in a diesel engine [J].Renewable Energy, 2010, (35):637-643.
[40]翼星,刘京顺,翼金平等.中国生物柴油产业化发展战略思考[J].中国能源,2006,(5)：25-30.
[41]郑风田,崔海兴.中国生物柴油发展的现状、潜力与障碍分析[J].林业经济,2009,(3)：65-70.
[42]王利宾,黄凤洪,李文林等.固体酸催化剂制备生物柴油的研究进展[J].化学与生物工程,2009,26(4)：12-15.
[43]Dennis Y.C. Leung, Xuan Wu, M.K.H. Leung.A review on biodiesel production using catalyzed transesterification [J]. Applied Energy,2010, (87),1083-1095.
[44]于世涛,刘福胜.固体酸与精细化工[M].北京：化学工业出版社,2005.
[45]Kok Tat Tan, Keat Teong Lee*.Abdul Rahman Mohamed A glycerol-free process to produce biodiesel by supercritical methyl acetate technology:An optimization study via Response Surface Methodology [J]. Bioresource Technology,2010, (101),965-969.
[46]张根旺.生物柴油的生产及发展前景[J].粮油食品科技,2009,17(4)：17-19.
[47]刘星火,李为民,姚超.固体酸在生物柴油生产中的应用[J].中国油脂,2009,34(3)：38-42.
[48]徐静莉,孙国富.固体酸催化剂在酯化反应中应用研究进展[J].林化工学院学报,2001,18(4)：87-90.
[49]唐建飞.生物柴油的生产方法[J].中国科学技术展望,2007,(6)：81-83.
[50]廖李,程微,王少华等.超声波强化甲醇—乙醇混合体系酯化反应制备生物柴油[J].农品加工,2009,188(10)：13-15.
[51]Le Tu Thanh, Kenji Okitsu, Yasuhiro Sadanaga. A two-step continuous ultrasound assisted production of biodiesel fuel from waste cooking oils:A practical and economical approach to produce high quality biodiesel fuel[J]. Bioresource Technology,2010, (101):5394-5401.
[52]任庆功,阎杰,丘泰球.超声强化酯交换制备生物柴油的研究进展[J].中国油脂,2009,34(1)：54-58.
[53]雍开东,苟科,张鹏.超声波制取生物柴油工艺技术探讨[J].中外能源,2009,14(5)：47-50.
[54]J.A. Siles, M.A. Martin. Anaerobic co-digestion of glycerol and wastewater derived from Biodiesel manufacturing [J].Bioresource Technology,2010, (101):6315-6321.
[55]SOUMANOU M M, BORNSCHEUER U T. Improvement in lipase—catalyzed synthesis of fatty acid methyl esters from sunflower oil [J].Enzyme and Microbial Technology,2003, 3314(1):97-103.
[56]张哲,魏海国.生物柴油生产技术进展[J].石油规划设计,2009,20(1)：23-27
[57]马震,银建中,商紫阳等.超临界酯交换法制备生物柴油工艺基础及其过程强化技术研究[J].化学与生物工程,2009,26(8)：1-7.
[58]邢存章,谭明臣,吕海亮等.超临界甲醇法制备生物柴油[J].石油化工高等学校学报,2009,22(3)：9-12.
[59]Kok Tat Tan, Meei Mei Gui, Keat Teong Lee. An optimized study of methanol and ethanol in supercritical alcohol technology for biodiesel production [J].The Journal ofSupercritical Fluids,2010, (53):82-87.
[60]赵贵兴.超临界甲醇法制备大豆生物柴油[J].大豆科技,2009,(2)：33-36.
[61]王桂茹.催化剂与催化作用[M].辽宁：大连理工大学出版社,2007.
[62]夏海涛.催化剂设计与制备工艺[M].北京：化学工业出版社,2003.
[63]张艺,柏子龙,金宏轩等.铌硅铝磷分子筛的合成及催化酯化性能研究[J].化学研究,2008,19(2)：9-12.
[64]Zhao Zhenhua.Synthesis of butyl propionate using novel alumin -ophosphate molecular sieve as catalyst[J].J Mol Catal,2000,154(1-2):131-135.
[65]沈文霞,王志斌,李春志等.固体酸催化剂的制备与应用研究[J].宁夏大学学报(自然科学版),2001,22(2)：123-124.
[66]Chai F, Cao F H, Zhai F Y,et al. Transesterification of vegetable oil to biodiesel using a heteropolyacid solid catalyst [J]. AdvSynth Catal,2007,349(7):1057-1065.
[67]曹宏远,曹维良,张敬畅.固体酸Zr(SO4)2-4H2O催化制备生物柴油[J].北京化工大学学报,2005,32(6)：61-63.
[68]万祯,张胜涛.复合固体酸催化餐饮废油合成生物柴油的研究[J].河北化工,2008,31(1)：37-39.
[69]Yin-Qing Zhang, Sheng-Jie Wang, Jun-Wei Wang. Synthesis and characterization of Zr-SBA-15 supported tungsten oxide as a new mesoporous solid acid [J].Solid State Sciences,2009, (11):1412-1418.
[70]张琦,常铁,王铁军等.固体酸催化改质生物柴油的研究[J].燃料化学学报,2006,34(6)：680-684.
[71]吴芹,王玲,吴谋成等.阳离子交换树脂催化制备生物柴油的工艺优化[J].中国油料作物学报,2008,30(1)：119-12.
[72]Chitralekha Khatri, Ashu Rani.Synthesis of a nano-crystalline solid acid catalyst from fly ash and its catalytic performance [J].Fuel,2008, (87):2886-2892.
[73]王督,苏有勇,王华.碳基固体酸催化高酸值生物柴油原料降酸效果[J].农业工程学报,2006,25(11)：274-277.
[74]周丽娜,刘可,华伟明等.碳基磺酸化固体酸材料的制备及其催化性能[J].催化学报,2009,30(3)：196-200.
[75]江文辉,文鹤林.碳基固体酸催化印楝树油与甲醇的酯交换反应[J].湖南工业大学学报,2009,23(3)：46-49.
[76]Daizo, Yamaguchi, Michikazu Hara.Starch saccharification by carbon-based solid acid catalyst[J]. Solid State Sciences,2010, (12):1018-1023.
[77]曾昌凤,陈军等.磺酸型固体酸催化剂的制备与应用研究进展[J].南京工业大学学报,2009,31(6)：104-110.
[78]Sato shi Suganuma, Kiyotaka Nakajima, Masaaki Kitano.Synthesis and derivedcarbon-based solid acid [J].Solid State Sciences,2010, (12):1029-1034.
[79]Beena Tyagi, Manish Kumar Mishra, Raksh Vir Jasra. Solvent free synthesis of acetyl salicylic acid over nano-crystalline sulfated zirconia solid acid catalyst [J].Journal of Molecular Catalysis A:Chemical,2010, (317):41-45.
[80]Qing Shu, Zeeshan Nawaz, Jixian Gao.Synthesis of biodiesel from a model waste oilfeedstock using a carbon-based solid acid catalyst:Reaction and separation[J]. Bioresource Technology, Bioresource Technology,2010, (101):5374-5384.
[81]复合碳基固体酸催化剂的制备及应用[D].宁夏：宁夏大学硕十毕业论文,2010年.
[82]高珊.新型碳基固体磺酸的合成及其在有机反应中的应用[D].上海：华东师范大学博十论文,2009年.
[83]覃兆海,金淑惠,李楠编著.基础有机化学[M].北京：科·学技术文献出版社,2004.