棉籽油生物柴油制备的试验研究
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摘要
作者利用棉籽油为原料,利用亚临界水-超临界甲醇两步法制备生物柴油.第一步棉籽油在亚临界水中制备出棉籽油脂肪酸,第二步利用制备得出的棉籽油脂肪酸在超临界甲醇中制备脂肪酸甲酯,即生物柴油.本文详细的研究了物料配比、反应温度、反应压力、反应时间各单因素对制备生物柴油的影响.通过对产物的酸值测定和UPLC(超高效液相色谱)检测.
第一步水解反应中,结果表明该反应最适宜的操作条件为：油水体积比1：4,反应时间40min,反应温度290℃,在此条件下生物柴油的收率可达96.69%。通过进行动力学研究分析表明,棉籽油与水在亚临界状态下进行水解反应的平均反应级数为n=1.15,活化能Ea=108.63kJ/mol,频率因子A=2.696x109,动力学模型为：
第二步酯化反应中,结果表明该反应最适宜的操作条件为：油水体积比1：3,反应时间30min,反应温度290℃,在此条件下生物柴油的收率可达98.89%。通过UPLC(超高效液相色谱)对产物检测,分析了各影响因素对脂肪酸及脂肪酸甲酯含量的影响。结果表明：(1)不饱和脂肪酸甲酯如油酸甲酯(18：1),以及多聚不饱和脂肪酸甲酯如亚油酸甲酯(18：2)在280℃超临界甲醇下相对含量开始降低了。过高的温度使脂肪酸甲酯产生变化。(2)甲醇的过多的加入并不能使得产物脂肪酸甲酯的量也随着增加。一般在脂肪酸与甲醇体积比1：3为适宜。(3)反应时间的过多增长并不能提高其脂肪酸甲酯的量,因为生产出的脂肪酸甲酯会产生其他副反应。
Author use cottonseed oil as raw material to make the biodiesel in the sub-critical water and supercritical methanol. Cottonseed oil in the sub-critical first step in the preparation of cottonseed oil fatty acid in the water, and the second step the use of cottonseed oil fatty acid preparation derived from Supercritical Methanol in the preparation of fatty acid methyl ester, or biodiesel. Cottonseed oil fatty acid is made by cottonseed oil and water in the sub-critical first step,fatty acid methyl ester is made by cottonseed oil fatty acid and methanol in the Supercritical Methanol. In this paper, a detailed study on the single factor of material ratio, reaction temperature, reaction pressure and reaction time impacting in the preparation of biodiesel. The acid value and UPLC testing of the product of measured. The product are measured by the acid value of the product of measured and UPLC testing.
The best conditions that the cottonseed oil hydrolysis in sub-critical water is temperature 290℃, oil-water volume ratio 1:4, reaction time 40min, which yields 96.69% of fatty acids. Reaction kinetics analysis shows that the reaction order of hydrolysis reaction is 1.15; activation energy is 108.63kJ/mol, and kinetics equation the most appropriate conditions of esterification are reaction temperature 290℃, reaction time 30min, volume ratio of to methanol 1:3. With the conditions of the test, the yields of fatty acids methyl ester is 98.89%. The adoption of UPLC of tine product testing, analysis of the impact of factors on the fatty acid and fatty acid methyl ester content. The results show that:Unsaturated fatty acid methyl ester such as methyl oleate (18:1), and poly-unsaturated fatty acid methyl esters such as linoleic acid methyl ester (18:2) at 280℃under supercritical methanol relative content began to lower.fatty acid methyl ester changes in high temperature. Fatty acid methyl ester can not increase by adding excess methanol. General fatty acid and methanol in volume ratio 1:3 is Suitable. The excessive reaction time growth can not increase the fatty acid methyl ester, because the production of fatty acid methyl ester will have other side effects.
第一步水解反应中,结果表明该反应最适宜的操作条件为：油水体积比1：4,反应时间40min,反应温度290℃,在此条件下生物柴油的收率可达96.69%。通过进行动力学研究分析表明,棉籽油与水在亚临界状态下进行水解反应的平均反应级数为n=1.15,活化能Ea=108.63kJ/mol,频率因子A=2.696x109,动力学模型为：
第二步酯化反应中,结果表明该反应最适宜的操作条件为：油水体积比1：3,反应时间30min,反应温度290℃,在此条件下生物柴油的收率可达98.89%。通过UPLC(超高效液相色谱)对产物检测,分析了各影响因素对脂肪酸及脂肪酸甲酯含量的影响。结果表明：(1)不饱和脂肪酸甲酯如油酸甲酯(18：1),以及多聚不饱和脂肪酸甲酯如亚油酸甲酯(18：2)在280℃超临界甲醇下相对含量开始降低了。过高的温度使脂肪酸甲酯产生变化。(2)甲醇的过多的加入并不能使得产物脂肪酸甲酯的量也随着增加。一般在脂肪酸与甲醇体积比1：3为适宜。(3)反应时间的过多增长并不能提高其脂肪酸甲酯的量,因为生产出的脂肪酸甲酯会产生其他副反应。
Author use cottonseed oil as raw material to make the biodiesel in the sub-critical water and supercritical methanol. Cottonseed oil in the sub-critical first step in the preparation of cottonseed oil fatty acid in the water, and the second step the use of cottonseed oil fatty acid preparation derived from Supercritical Methanol in the preparation of fatty acid methyl ester, or biodiesel. Cottonseed oil fatty acid is made by cottonseed oil and water in the sub-critical first step,fatty acid methyl ester is made by cottonseed oil fatty acid and methanol in the Supercritical Methanol. In this paper, a detailed study on the single factor of material ratio, reaction temperature, reaction pressure and reaction time impacting in the preparation of biodiesel. The acid value and UPLC testing of the product of measured. The product are measured by the acid value of the product of measured and UPLC testing.
The best conditions that the cottonseed oil hydrolysis in sub-critical water is temperature 290℃, oil-water volume ratio 1:4, reaction time 40min, which yields 96.69% of fatty acids. Reaction kinetics analysis shows that the reaction order of hydrolysis reaction is 1.15; activation energy is 108.63kJ/mol, and kinetics equation the most appropriate conditions of esterification are reaction temperature 290℃, reaction time 30min, volume ratio of to methanol 1:3. With the conditions of the test, the yields of fatty acids methyl ester is 98.89%. The adoption of UPLC of tine product testing, analysis of the impact of factors on the fatty acid and fatty acid methyl ester content. The results show that:Unsaturated fatty acid methyl ester such as methyl oleate (18:1), and poly-unsaturated fatty acid methyl esters such as linoleic acid methyl ester (18:2) at 280℃under supercritical methanol relative content began to lower.fatty acid methyl ester changes in high temperature. Fatty acid methyl ester can not increase by adding excess methanol. General fatty acid and methanol in volume ratio 1:3 is Suitable. The excessive reaction time growth can not increase the fatty acid methyl ester, because the production of fatty acid methyl ester will have other side effects.
引文
[1]Adams C, Peter J F, Rand M C, et al, Investigation of soybean oil as a diesel fuel extender [J]. JAOCS,1983,60:1574.
[2]Ziejewski M, Kaufman K R. Diesel engine evaluation of a nonionic sunflower oil-aqueous ethanol micro emulsion [J]JAOCS,1984,61:1620-1626.
[3]Anon. Filtered used frying fat powers diesel fleet[J]. Journal of American O(?)l Che-mistry Society,1982,59:780-781.
[4]Georing A, Engine durability screening test of a diesel oil/soy oil/alcohol microemulsion fuel[J]. JAOCS,1984,61:1627-1632.
[5]Ziejewski M, Kaufman K R, Pratt G L. Vegetable Oil as Diesel Fuel[J]. Seminar Ⅱ,Northern Regional Research Center,Peoria.Illiois,1983.
[6]Neuma T, Silva A C, AAD Neto.[J]. Fuel,2001,80(8):75-81.
[7]Goefing. A. Engine durability screening test of a diesel oil/soy bean oil/alcohol microemulsion fuel[J]. Journal of American Oil Chemistry Society,1984,61: 1627-1632.
[8]Schwab A W, Bagby M O. FreedmanB.[J]. Fuel,1987,66(10):1372-1378.
[9]Pioch D, Biofuels from catalytic cracking of tropical vegetable oils [J]. Oleagineux, 1993,48:289-291.
[10]Pioch. Biofuels from catalytic cracking of tropical vegetable oils [J]. Journal of American Oil Chemistry Society,1993,48:289-291.
[11]Aaward Carbbe. Biodiesel production from crude palm oil and evaluation of butanol extraction and fuel properties[J]. Process Biochemistry,2001,37(1):65-71.
[12]Michael J, Haas Improving the economics of biodiesel production through the use of low value lipids as feedstocks:vegetable oil soapstock[J]. Fuel Processing Te-chnology,2005,86:1087-1096.
[13]Gems. Bioresource Technology,2004,92:197-305.
[14]H. J. Kim, et al. Transesterification of vegetable oil to biodiesel using heterog eneous base catalyst[J]. Catalysis Today,2004,93-95:315-320.
[15]Shieh, Optimization of lipase-catalyzed biodiesel by response surface methodol-ogy[J].Bioreseuree technology,200388:103-106.
[16]Saka S, Kundiana D. Biodiesel fuel from rapeseed oil as prepared in supercfitical methanol[J]. Fuel,2001,80(2):225-231.
[17]彭立风,赵汝琪,谭天伟.微生物脂肪酶的应用[J].食晶与发酵工业.2002,26(3)：68-73.
[18]徐秀丽.成立军,刘伦,等.分光光度法测定甘油合剂中甘油的含量[J].泰山医学院学报,2002,23(3)：247-248.
[19]申书昌,王文波.气相色谱法测定工业甘油禽量[J].齐齐哈尔轻工业学院学报,1994,10(4)：84-88.
[20]雷猛,许世海,魏小平.菜籽油制备生物柴油及其理化性能的研究[J].后勤工程学院学报,2004(4)：59-63.
[21]刘伟伟,苏有勇,张无敌,等.生物柴油中甘油含量测定方法的研究[J].可再生能源2005(3)：14-20.
[22]刘伟伟,苏有勇,张无敌,等.橡胶籽油制备生物柴油的研究[J].中国油脂,2005,30(10)：43-46.
[23]聂开立,王芳,邓利,等.间歇及连续式固定化酶反应生产生物柴油[J].生物加工过程,2005,3(1)：58-62.
[24]鲁明波,余龙江,薛勇,等.生物柴油的酶促合成研究[J].中国油脂,2005,30(11)：62-64.
[25]M A DUBE, A Y TREMBLAY, T LIU. Biodiesel production using membrane reactor[J]. Bioresourcce echnology,2006,98(3):639-647.
[26]ANDREA SALIS,MARCELLA pINNA, et al. Biodiesel production from triolein and short chain alcohols through biocatalysis [J]. Journal biotechnology, 2005,119(3):291-299.
[27]S ZHENG M KATE. Acid-catalyzed produetion of biodiesel from waste frying oil[J]. Biomasss and Bioenergy,2006,30(3):267-272.
[28]Anjana S, Ram P. Triglycerides-based diesel fuels[J]. Renewable and Sustainable Energy Reviews,2000,4(2):111-133
[29]赵沟,骆念军,曹发海.生物柴油制备方法的研究进展[J].石油化工技术经济,2007,23(3)：59-62
[30]Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol[J].2001,80(2):225-231.
[31]Holliday R L, King J W, List G R. Hydrolysis of vegetable oils in sub-and supercritical water. Ind. Eng. Chem. Res.,1997,36(3):932-935
[32]King J W, Holliday R L, List G R. Hydrolysis of soybean oil in a subcritical water flow reactor. Green Chem. Res,1999,1 (6):261-264
[33]KUSIDIANAD, SAKA S. Two-step preparation for catalyst-free biodiesel fuel production [J]. Applied Biochemistry and Biotechnology,2004,113: 781-791.
[34]孙辉,吕秀阳,陈良.不同植物油脂在近临界水中水解反应动力学的比较[J].化工学报,2007,58(4)：925-929
[35]LI Changzhu, JIANG Liq, CHENG Shuqi. Biodiesel—Green energy[M]. Beijing:Chemical industry press,2004.
[36]刘勤生、王群.油脂加热后理化指标变化的研究[J].粮食加工与食品机械,2003,(2)：41-43
[37]周华龙、张新申、陈家丽等.不饱和脂肪酸的氧化机理的研究与技术开发(Ⅱ)-油脂游离基的反应特点与技术开发[J].中国皮革,2003,32,(13)：4-9
[38]陈纪岳.关于反应级数的确定方法[J].大学化学,2000,15(6)：49-50.
[39]曹哓燕,满瑞林,刘小风等.生物柴油制备方法研究进展[J].化学工程师,2007,144(9)：27-31.
[40]Pedro Felizardo M, Joana Neiva Correia, et al. [J]. Waste Management,2006,26(5):487-494.
[41]Saka S,Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol[J].2001,80(2):225-231.
[42]Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol. Fuel 2001;80:225-31.
[43]Kusdiana D, Saka S. Kinetics of transesterification in rapeseed oil to biodiesel fuel as treated in supercritical methanol. Fuel 2001:80:693-8.
[44]Kusdiana D, Saka S. Kinetics of transesterification in rapeseed oil to biodiesel fuel as treated in supercritical methanol. Fuel 2001;80:693-8.
[45]Tabe A, Kusdiana D, Minami E, Saka S. Kinetics in transesterification of rapeseed oil by supercritical methanol treatment. Proc 2nd World Biomass Conf Exhib 2004:1553-6.
[46]Kusdiana D, Saka S. Two-step preparation for catalyst-free biodiesel fuel production:hydrolysis and methyl esterification. Appl Biochem Biotechnol 2004;115:781-91.
[47]LI Guihua. Test and analysis of oil and lipin[M]. Beijing:Chemical industry press,2006.
[2]Ziejewski M, Kaufman K R. Diesel engine evaluation of a nonionic sunflower oil-aqueous ethanol micro emulsion [J]JAOCS,1984,61:1620-1626.
[3]Anon. Filtered used frying fat powers diesel fleet[J]. Journal of American O(?)l Che-mistry Society,1982,59:780-781.
[4]Georing A, Engine durability screening test of a diesel oil/soy oil/alcohol microemulsion fuel[J]. JAOCS,1984,61:1627-1632.
[5]Ziejewski M, Kaufman K R, Pratt G L. Vegetable Oil as Diesel Fuel[J]. Seminar Ⅱ,Northern Regional Research Center,Peoria.Illiois,1983.
[6]Neuma T, Silva A C, AAD Neto.[J]. Fuel,2001,80(8):75-81.
[7]Goefing. A. Engine durability screening test of a diesel oil/soy bean oil/alcohol microemulsion fuel[J]. Journal of American Oil Chemistry Society,1984,61: 1627-1632.
[8]Schwab A W, Bagby M O. FreedmanB.[J]. Fuel,1987,66(10):1372-1378.
[9]Pioch D, Biofuels from catalytic cracking of tropical vegetable oils [J]. Oleagineux, 1993,48:289-291.
[10]Pioch. Biofuels from catalytic cracking of tropical vegetable oils [J]. Journal of American Oil Chemistry Society,1993,48:289-291.
[11]Aaward Carbbe. Biodiesel production from crude palm oil and evaluation of butanol extraction and fuel properties[J]. Process Biochemistry,2001,37(1):65-71.
[12]Michael J, Haas Improving the economics of biodiesel production through the use of low value lipids as feedstocks:vegetable oil soapstock[J]. Fuel Processing Te-chnology,2005,86:1087-1096.
[13]Gems. Bioresource Technology,2004,92:197-305.
[14]H. J. Kim, et al. Transesterification of vegetable oil to biodiesel using heterog eneous base catalyst[J]. Catalysis Today,2004,93-95:315-320.
[15]Shieh, Optimization of lipase-catalyzed biodiesel by response surface methodol-ogy[J].Bioreseuree technology,200388:103-106.
[16]Saka S, Kundiana D. Biodiesel fuel from rapeseed oil as prepared in supercfitical methanol[J]. Fuel,2001,80(2):225-231.
[17]彭立风,赵汝琪,谭天伟.微生物脂肪酶的应用[J].食晶与发酵工业.2002,26(3)：68-73.
[18]徐秀丽.成立军,刘伦,等.分光光度法测定甘油合剂中甘油的含量[J].泰山医学院学报,2002,23(3)：247-248.
[19]申书昌,王文波.气相色谱法测定工业甘油禽量[J].齐齐哈尔轻工业学院学报,1994,10(4)：84-88.
[20]雷猛,许世海,魏小平.菜籽油制备生物柴油及其理化性能的研究[J].后勤工程学院学报,2004(4)：59-63.
[21]刘伟伟,苏有勇,张无敌,等.生物柴油中甘油含量测定方法的研究[J].可再生能源2005(3)：14-20.
[22]刘伟伟,苏有勇,张无敌,等.橡胶籽油制备生物柴油的研究[J].中国油脂,2005,30(10)：43-46.
[23]聂开立,王芳,邓利,等.间歇及连续式固定化酶反应生产生物柴油[J].生物加工过程,2005,3(1)：58-62.
[24]鲁明波,余龙江,薛勇,等.生物柴油的酶促合成研究[J].中国油脂,2005,30(11)：62-64.
[25]M A DUBE, A Y TREMBLAY, T LIU. Biodiesel production using membrane reactor[J]. Bioresourcce echnology,2006,98(3):639-647.
[26]ANDREA SALIS,MARCELLA pINNA, et al. Biodiesel production from triolein and short chain alcohols through biocatalysis [J]. Journal biotechnology, 2005,119(3):291-299.
[27]S ZHENG M KATE. Acid-catalyzed produetion of biodiesel from waste frying oil[J]. Biomasss and Bioenergy,2006,30(3):267-272.
[28]Anjana S, Ram P. Triglycerides-based diesel fuels[J]. Renewable and Sustainable Energy Reviews,2000,4(2):111-133
[29]赵沟,骆念军,曹发海.生物柴油制备方法的研究进展[J].石油化工技术经济,2007,23(3)：59-62
[30]Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol[J].2001,80(2):225-231.
[31]Holliday R L, King J W, List G R. Hydrolysis of vegetable oils in sub-and supercritical water. Ind. Eng. Chem. Res.,1997,36(3):932-935
[32]King J W, Holliday R L, List G R. Hydrolysis of soybean oil in a subcritical water flow reactor. Green Chem. Res,1999,1 (6):261-264
[33]KUSIDIANAD, SAKA S. Two-step preparation for catalyst-free biodiesel fuel production [J]. Applied Biochemistry and Biotechnology,2004,113: 781-791.
[34]孙辉,吕秀阳,陈良.不同植物油脂在近临界水中水解反应动力学的比较[J].化工学报,2007,58(4)：925-929
[35]LI Changzhu, JIANG Liq, CHENG Shuqi. Biodiesel—Green energy[M]. Beijing:Chemical industry press,2004.
[36]刘勤生、王群.油脂加热后理化指标变化的研究[J].粮食加工与食品机械,2003,(2)：41-43
[37]周华龙、张新申、陈家丽等.不饱和脂肪酸的氧化机理的研究与技术开发(Ⅱ)-油脂游离基的反应特点与技术开发[J].中国皮革,2003,32,(13)：4-9
[38]陈纪岳.关于反应级数的确定方法[J].大学化学,2000,15(6)：49-50.
[39]曹哓燕,满瑞林,刘小风等.生物柴油制备方法研究进展[J].化学工程师,2007,144(9)：27-31.
[40]Pedro Felizardo M, Joana Neiva Correia, et al. [J]. Waste Management,2006,26(5):487-494.
[41]Saka S,Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol[J].2001,80(2):225-231.
[42]Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol. Fuel 2001;80:225-31.
[43]Kusdiana D, Saka S. Kinetics of transesterification in rapeseed oil to biodiesel fuel as treated in supercritical methanol. Fuel 2001:80:693-8.
[44]Kusdiana D, Saka S. Kinetics of transesterification in rapeseed oil to biodiesel fuel as treated in supercritical methanol. Fuel 2001;80:693-8.
[45]Tabe A, Kusdiana D, Minami E, Saka S. Kinetics in transesterification of rapeseed oil by supercritical methanol treatment. Proc 2nd World Biomass Conf Exhib 2004:1553-6.
[46]Kusdiana D, Saka S. Two-step preparation for catalyst-free biodiesel fuel production:hydrolysis and methyl esterification. Appl Biochem Biotechnol 2004;115:781-91.
[47]LI Guihua. Test and analysis of oil and lipin[M]. Beijing:Chemical industry press,2006.