超临界甲醇法从煎炸废油制备生物柴油的研究
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摘要
生物柴油是一种新型的可再生能源,作为石化能源的最佳替代品,近年来受到人们的高度关注与期待。
本文采用超临界酯交换法,以煎炸废油(废大豆油和废色拉油)和甲醇为原料制备了生物柴油,并以酯交换反应过程中的甘油产率为评价指标,利用单因素实验和正交实验,研究了醇油体积比、反应温度、反应时间等因素对酯交换反应转化率的影响,进而确定了酯交换反应的最佳条件分别为废大豆油体系:330℃、醇油体积比25:5、反应15min;废色拉油体系:350℃、醇油体积比25:5、反应15min。
利用不同温度下酯交换反应的转化率随时间的变化曲线,对废色拉油酯交换反应的动力学进行了初步探讨,并最终建立酯交换反应的动力学模型。计算结果反应级数为2,活化能52.46kJ/mol。
对酯交换反应制备出的产物进行了气质联用和红外光谱表征,分析了其主要成分,证实酯交换反应的产物主要成分是C12到C24的甲酯,含量最多的是软脂酸甲酯和亚油酸甲酯。
对实验室制备的废色拉油生物柴油样品的部分燃料性能进行了测试,结果表明该生物柴油样品的体积热值与0#柴油相当,40℃运动粘度是6.38 mm2/s ,密度0.899g/ml ,比0#柴油燃烧得更完全,不冒黑烟,酸值0.51mgKOH/g油脂,总甘油含量为0.21wt%,铜片腐蚀等级为1级,凝点0℃左右。
Biodiesel is a new kind of renewable energy resources. It is exploited recently and researched zealously by researchers both at home and abroad as the best candidate for diesel fuels.
In this paper, biodiesel was prepared from fried oil (fried bean oil and fried salad oil) and methanol with supercritical transesterification reaction. The effects of the volume ratio of methanol to oil, reaction temperature and reaction time to the yield of glycerol during the transesterification reaction were investigated using simple factor experiment and orthogonal test. And then the optimal conditions for the transesterification reaction were obtained, which were 330℃, volume ratio of methanol to oil 25:5, 15min for the fried bean oil system and 350℃, volume ratio of methanol to oil 25:5, 15min for the fried salad oil system.
The kinetics of transesterification with fried salad oil was investigated by analyzing the relationship between percent conversion of transesterification and reaction time, and the kinetic model was established finally. The results showed that reaction order was 2, activation energy was 52.46kJ/mol.
The product of the transesterification reaction was detected by GC-MS and FTIR. The results showed that the constituents in the product were methyl ester with 12 carbon atoms to 24 carbon atoms, and the main constituents were methyl hexadecanoate and methyl linoleate.
Some fuel performances of the biodiesel sample prepared from fried salad oil were test. The results showed that the volume heat value of this biodiesel sample was equivalent to that of 0# diesel oil, the kinematic viscosity of this sample was 6.38 mm2/s, density 0.899g/ml, higher completeness of combustion, acid value 0.51mgKOH per gram oil, total glycerol content 0.21wt%, sheet copper corrosion grade 1, and solidifying point at about 0℃.
本文采用超临界酯交换法,以煎炸废油(废大豆油和废色拉油)和甲醇为原料制备了生物柴油,并以酯交换反应过程中的甘油产率为评价指标,利用单因素实验和正交实验,研究了醇油体积比、反应温度、反应时间等因素对酯交换反应转化率的影响,进而确定了酯交换反应的最佳条件分别为废大豆油体系:330℃、醇油体积比25:5、反应15min;废色拉油体系:350℃、醇油体积比25:5、反应15min。
利用不同温度下酯交换反应的转化率随时间的变化曲线,对废色拉油酯交换反应的动力学进行了初步探讨,并最终建立酯交换反应的动力学模型。计算结果反应级数为2,活化能52.46kJ/mol。
对酯交换反应制备出的产物进行了气质联用和红外光谱表征,分析了其主要成分,证实酯交换反应的产物主要成分是C12到C24的甲酯,含量最多的是软脂酸甲酯和亚油酸甲酯。
对实验室制备的废色拉油生物柴油样品的部分燃料性能进行了测试,结果表明该生物柴油样品的体积热值与0#柴油相当,40℃运动粘度是6.38 mm2/s ,密度0.899g/ml ,比0#柴油燃烧得更完全,不冒黑烟,酸值0.51mgKOH/g油脂,总甘油含量为0.21wt%,铜片腐蚀等级为1级,凝点0℃左右。
Biodiesel is a new kind of renewable energy resources. It is exploited recently and researched zealously by researchers both at home and abroad as the best candidate for diesel fuels.
In this paper, biodiesel was prepared from fried oil (fried bean oil and fried salad oil) and methanol with supercritical transesterification reaction. The effects of the volume ratio of methanol to oil, reaction temperature and reaction time to the yield of glycerol during the transesterification reaction were investigated using simple factor experiment and orthogonal test. And then the optimal conditions for the transesterification reaction were obtained, which were 330℃, volume ratio of methanol to oil 25:5, 15min for the fried bean oil system and 350℃, volume ratio of methanol to oil 25:5, 15min for the fried salad oil system.
The kinetics of transesterification with fried salad oil was investigated by analyzing the relationship between percent conversion of transesterification and reaction time, and the kinetic model was established finally. The results showed that reaction order was 2, activation energy was 52.46kJ/mol.
The product of the transesterification reaction was detected by GC-MS and FTIR. The results showed that the constituents in the product were methyl ester with 12 carbon atoms to 24 carbon atoms, and the main constituents were methyl hexadecanoate and methyl linoleate.
Some fuel performances of the biodiesel sample prepared from fried salad oil were test. The results showed that the volume heat value of this biodiesel sample was equivalent to that of 0# diesel oil, the kinematic viscosity of this sample was 6.38 mm2/s, density 0.899g/ml, higher completeness of combustion, acid value 0.51mgKOH per gram oil, total glycerol content 0.21wt%, sheet copper corrosion grade 1, and solidifying point at about 0℃.
引文
1胡宗泰,王英阁,李继香.生物柴油研究现状和发展趋势.粮食与油脂. 2006, (11): 11~14
2邵茂盛.我国生物柴油急需政策扶持.中国石化. 2006, 4: 23~25
3 M. H. Han, H. Chen and J. F. Wang. Advance in Research for Preparation of Biodiesel Oil. Petrochemical Technology. 2006, 35(12): 1119~1124
4 W. T. Tsai, C. C. Lin and C. W. Yeh. An Analysis of Biodiesel Fuel from Waste Edible Oil in Taiwan. Renewable and Sustainable Energy Reviews. 2007, 11(5): 838~857
5刘丹.生物柴油制备.南京工业大学硕士学位论文. 2005: 9~14
6 W. Du, L. Wang and D. H. Liu. Improved Methanol Tolerance during Novozym435-mediated Methanolysis of SODD for Biodiesel Production. Green Chemistry. 2007, 9: 173~176
7薄向利,夏代宽,邱添.超临界流体技术制备生物柴油的研究进展.化工时刊. 2005, 19 (12): 32~37
8 J.M. Marchetti, V.U. Miguel and A.F. Errazu. Possible Methods for Biodiesel Production. Renewable and Sustainable Energy Reviews. 2007, 11: 1300~1311
9安文杰,许德平,王海京.生物柴油化学制备方法.粮食与油脂, 2005, (7): 3~6
10 M. Diasakou, A. Louloudi and N. Papayannakos. Kinetics of the Non-catalytic Transesterification of Soybean Oil. Fuel, 1998, 77(12): 1297~1302
11陈和,王金福.强碱催化棉籽油酯交换制备生物柴油的动力学.化工学报. 2005, 56(10): 1972~1973
12张传龙,纪威,符太军.从废油脂中制取生物柴油的反应动力学及工艺研究.中国粮油学报. 2005, 20(5): 101~104
13 D. Kusidiana, S. Saka. Effect of Water on Biodiesel Fuel Production by Supercritical Methanol Treatment. Bioresource Technology. 2004, (91): 289~295
14朱海峰,程健,何寿林.超临界甲醇中的酯交换反应及其动力学.武汉化工学院学报. 2006, 28(1): 8~12
15 H. Y. He, S. Y. Sun and T. Wang. Transesterification Kinetics of Soybean Oil for Production of Biodiesel in Supercritical methanol. The American Oil Chemists Society. 2007, 84(4): 399~404
16 L. Y. Wang, J. C. Yang. Transesterification of Soybean Oil with Nano-MgO or not in Supercritical and Subcritical methanol. Fuel. 2007, 86(3): 328~333
17 H. Y. He, T. Wang and S. L. Zhu. Continuous Production of Biodiesel Fuel from Vegetable Oil using Supercritical Methanol Process. Fuel. 2007(86): 442~447
18肖建华,王存文,吴元欣.生物柴油的超临界制备工艺.中国油脂. 2005, 30(12): 57~60
19 S. Ruengwit, B. Kunchana and N. Somkiat. Effect of Co-solvents on Production of Biodiesel via Transesterification in Supercritical Methanol. Green Chemistry. 2007, 9: 679~685
20陈英明,常杰,吕鹏梅.生物柴油转化效果测定方法的研究.可再生能源. 2007, 25(2): 30~33
21 S. L. Tang, J. A. Zhang and H. T. Wu. Research Advances in Preparation of Biodiesel Fuel using Supercritical Techniques. Modern Chemical Industry. 2006, 26(2): 391~394
22王存文,周俊锋,陈文.连续化条件下超临界甲醇法制备生物柴油.化工科技. 2007, 15(5): 28~33
23杨建斌,陈明锴,汤世华.超临界流体技术制备生物柴油.中国油脂. 2008, 33(1): 40~42
24 V. Rathore, G. Madras. Synthesis of Biodiesel from Edible and Non-edible Oils in Supercritical Alcohols and Enzymatic Synthesis in Supercritical Carbon Dioxide. Fuel. 2007, (86): 2650~2659
25肖敏,银建中,宋吉彬.超临界甲醇法制备生物柴油.现代化工. 2006, 26(2): 301~303
26孙世尧,贺华阳,王连鸳.超临界甲醇中制备生物柴油.精细化工. 2005, 22(12): 916~919
27陈文,王存文,王为国.超临界甲醇法连续制备生物柴油.武汉工程大学学报, 2007, 29(2): 1~4
28刘启栋,王存文,王为国.超临界条件连续操作制备生物柴油的初步研究.化学与生物工程. 2006, 24(3): 26~28
29 D. Kusidiana, S. Saka. Two Step Preparation for Catalyst Free Biodiesel Fuel Production. Applied Biochemistry and Biotechnology. 2004, (113-116): 781~791
30 S. A. D’Ippolito, J. C. Yori and M. E. Iturria. Analysis of a Two-Step, Noncatalytic, Supercritical Biodiesel Production Process with Heat Recovery. Energy & Fuels. 2007, 21: 339~346
31 S. Saka. Biodiesel Fuel Production by Supercritical Methanol Technology. Nihon Enerugi Gakkaishi. 2005, 84(5): 413~419
32王瑞红,李淑芬,马鸿宾.超临界流体法制备生物柴油研究进展.精细石油化工进展. 2007, 8(2): 39~42
33向丽,程健.脂肪酸在超临界甲醇中的酯化反应研究.燃料化学学报. 2008, 36(1): 111-114
34 A. Demirbas. Biodiesel from Sunflower Oil in Supercritical Methanol with Calcium Oxide. Energy Conversion and Management. 2007, (48): 937~941
35 A. Demirbas. Comparison of Transesterification Methods for Production of Biodiesel from Vegetable Oils and Fats. Energy Conversion and Management. 2007: 1~6
36侯相林,乔欣刚,齐永琴等.亚临界甲醇相固体碱催化大豆油酯交换制备生物柴油.中国油脂. 2006, 31(10): 37~ 39.
37 N. Mahesh. Varma, G. Madras. Synthesis of Biodiesel from Castor Oil and Linseed Oil in Supercritical Fluids. Ind. Eng. Chem. Res. 2007, 46: 1~6
38 Y. Isayama, S. Saka. Biodiesel Production by Supercritical Process with Crude Bio-methanol Prepared by Wood Gasification. Bioresource Technology. 2007: 1~5
39 A. Demirbas. Progress and Recent Trends in Biofuels. Progress in Energy and Combustion Science. 2007, 33(1): 1~18
40 L. C. Meher, D. V. Sagar and S. N. Naik. Technical Aspects of Biodiesel Production by Transesterification-a review. Renewable and Sustainable Energy Reviews. 2006, (10): 248~268
41 D. Kusdiana, S. Saka. Effects of Water on Biodiesel Fuel Production bySupercritical Methanol Treatment. Bioresource Technology. 2004, (91): 289~295
42安文杰,许德平,杜显云.超临界甲醇法制备生物柴油工艺探讨.粮食与油脂. 2005,(8): 21~23
43李海涛,谢文磊,郭威.生物柴油质量分析检测的评价.粮食食品科技. 2006, 14(4): 64~66
44李美华.植物油脂酯交换法合成脂肪酸甲酯.中国石油大学硕士学位论文. 2007: 50~52
45王传申.生物柴油的生产方法及反应动力学研究.湘潭大学硕士学位论文. 2007: 43~47
46罗文,袁振宏,廖翠萍.生物柴油标准及质量评价.可再生能源. 2006, 4(128): 33~37
47聂小安,蒋剑春,高一苇.海滨锦葵油生物柴油的制备及性能分析.南京林业大学学报. 2008, 32(1): 72~74
48陈英军,梅德清,袁银南.单酯类燃料组成与结构对燃料特性的影响.小型内燃机与摩托车. 2006, 35(3): 39~41
49彭娜.超临界酯交换制取生物柴油及其燃烧反应机理研究.浙江大学硕士学位论文. 2007: 60~62
50刘伟伟,苏有勇,张无敌.生物柴油中甘油含量测定方法的研究.可再生能源. 2005, 3(121): 14~16
51何东平.油脂精炼与加工工艺学.化学工业出版社. 2005: 248~250 242~244
52邬国英,林西平,巫淼鑫.棉籽油间歇式酯交换反应动力学的研究.高等化学工程学报. 2003, 17(3):314-316
2邵茂盛.我国生物柴油急需政策扶持.中国石化. 2006, 4: 23~25
3 M. H. Han, H. Chen and J. F. Wang. Advance in Research for Preparation of Biodiesel Oil. Petrochemical Technology. 2006, 35(12): 1119~1124
4 W. T. Tsai, C. C. Lin and C. W. Yeh. An Analysis of Biodiesel Fuel from Waste Edible Oil in Taiwan. Renewable and Sustainable Energy Reviews. 2007, 11(5): 838~857
5刘丹.生物柴油制备.南京工业大学硕士学位论文. 2005: 9~14
6 W. Du, L. Wang and D. H. Liu. Improved Methanol Tolerance during Novozym435-mediated Methanolysis of SODD for Biodiesel Production. Green Chemistry. 2007, 9: 173~176
7薄向利,夏代宽,邱添.超临界流体技术制备生物柴油的研究进展.化工时刊. 2005, 19 (12): 32~37
8 J.M. Marchetti, V.U. Miguel and A.F. Errazu. Possible Methods for Biodiesel Production. Renewable and Sustainable Energy Reviews. 2007, 11: 1300~1311
9安文杰,许德平,王海京.生物柴油化学制备方法.粮食与油脂, 2005, (7): 3~6
10 M. Diasakou, A. Louloudi and N. Papayannakos. Kinetics of the Non-catalytic Transesterification of Soybean Oil. Fuel, 1998, 77(12): 1297~1302
11陈和,王金福.强碱催化棉籽油酯交换制备生物柴油的动力学.化工学报. 2005, 56(10): 1972~1973
12张传龙,纪威,符太军.从废油脂中制取生物柴油的反应动力学及工艺研究.中国粮油学报. 2005, 20(5): 101~104
13 D. Kusidiana, S. Saka. Effect of Water on Biodiesel Fuel Production by Supercritical Methanol Treatment. Bioresource Technology. 2004, (91): 289~295
14朱海峰,程健,何寿林.超临界甲醇中的酯交换反应及其动力学.武汉化工学院学报. 2006, 28(1): 8~12
15 H. Y. He, S. Y. Sun and T. Wang. Transesterification Kinetics of Soybean Oil for Production of Biodiesel in Supercritical methanol. The American Oil Chemists Society. 2007, 84(4): 399~404
16 L. Y. Wang, J. C. Yang. Transesterification of Soybean Oil with Nano-MgO or not in Supercritical and Subcritical methanol. Fuel. 2007, 86(3): 328~333
17 H. Y. He, T. Wang and S. L. Zhu. Continuous Production of Biodiesel Fuel from Vegetable Oil using Supercritical Methanol Process. Fuel. 2007(86): 442~447
18肖建华,王存文,吴元欣.生物柴油的超临界制备工艺.中国油脂. 2005, 30(12): 57~60
19 S. Ruengwit, B. Kunchana and N. Somkiat. Effect of Co-solvents on Production of Biodiesel via Transesterification in Supercritical Methanol. Green Chemistry. 2007, 9: 679~685
20陈英明,常杰,吕鹏梅.生物柴油转化效果测定方法的研究.可再生能源. 2007, 25(2): 30~33
21 S. L. Tang, J. A. Zhang and H. T. Wu. Research Advances in Preparation of Biodiesel Fuel using Supercritical Techniques. Modern Chemical Industry. 2006, 26(2): 391~394
22王存文,周俊锋,陈文.连续化条件下超临界甲醇法制备生物柴油.化工科技. 2007, 15(5): 28~33
23杨建斌,陈明锴,汤世华.超临界流体技术制备生物柴油.中国油脂. 2008, 33(1): 40~42
24 V. Rathore, G. Madras. Synthesis of Biodiesel from Edible and Non-edible Oils in Supercritical Alcohols and Enzymatic Synthesis in Supercritical Carbon Dioxide. Fuel. 2007, (86): 2650~2659
25肖敏,银建中,宋吉彬.超临界甲醇法制备生物柴油.现代化工. 2006, 26(2): 301~303
26孙世尧,贺华阳,王连鸳.超临界甲醇中制备生物柴油.精细化工. 2005, 22(12): 916~919
27陈文,王存文,王为国.超临界甲醇法连续制备生物柴油.武汉工程大学学报, 2007, 29(2): 1~4
28刘启栋,王存文,王为国.超临界条件连续操作制备生物柴油的初步研究.化学与生物工程. 2006, 24(3): 26~28
29 D. Kusidiana, S. Saka. Two Step Preparation for Catalyst Free Biodiesel Fuel Production. Applied Biochemistry and Biotechnology. 2004, (113-116): 781~791
30 S. A. D’Ippolito, J. C. Yori and M. E. Iturria. Analysis of a Two-Step, Noncatalytic, Supercritical Biodiesel Production Process with Heat Recovery. Energy & Fuels. 2007, 21: 339~346
31 S. Saka. Biodiesel Fuel Production by Supercritical Methanol Technology. Nihon Enerugi Gakkaishi. 2005, 84(5): 413~419
32王瑞红,李淑芬,马鸿宾.超临界流体法制备生物柴油研究进展.精细石油化工进展. 2007, 8(2): 39~42
33向丽,程健.脂肪酸在超临界甲醇中的酯化反应研究.燃料化学学报. 2008, 36(1): 111-114
34 A. Demirbas. Biodiesel from Sunflower Oil in Supercritical Methanol with Calcium Oxide. Energy Conversion and Management. 2007, (48): 937~941
35 A. Demirbas. Comparison of Transesterification Methods for Production of Biodiesel from Vegetable Oils and Fats. Energy Conversion and Management. 2007: 1~6
36侯相林,乔欣刚,齐永琴等.亚临界甲醇相固体碱催化大豆油酯交换制备生物柴油.中国油脂. 2006, 31(10): 37~ 39.
37 N. Mahesh. Varma, G. Madras. Synthesis of Biodiesel from Castor Oil and Linseed Oil in Supercritical Fluids. Ind. Eng. Chem. Res. 2007, 46: 1~6
38 Y. Isayama, S. Saka. Biodiesel Production by Supercritical Process with Crude Bio-methanol Prepared by Wood Gasification. Bioresource Technology. 2007: 1~5
39 A. Demirbas. Progress and Recent Trends in Biofuels. Progress in Energy and Combustion Science. 2007, 33(1): 1~18
40 L. C. Meher, D. V. Sagar and S. N. Naik. Technical Aspects of Biodiesel Production by Transesterification-a review. Renewable and Sustainable Energy Reviews. 2006, (10): 248~268
41 D. Kusdiana, S. Saka. Effects of Water on Biodiesel Fuel Production bySupercritical Methanol Treatment. Bioresource Technology. 2004, (91): 289~295
42安文杰,许德平,杜显云.超临界甲醇法制备生物柴油工艺探讨.粮食与油脂. 2005,(8): 21~23
43李海涛,谢文磊,郭威.生物柴油质量分析检测的评价.粮食食品科技. 2006, 14(4): 64~66
44李美华.植物油脂酯交换法合成脂肪酸甲酯.中国石油大学硕士学位论文. 2007: 50~52
45王传申.生物柴油的生产方法及反应动力学研究.湘潭大学硕士学位论文. 2007: 43~47
46罗文,袁振宏,廖翠萍.生物柴油标准及质量评价.可再生能源. 2006, 4(128): 33~37
47聂小安,蒋剑春,高一苇.海滨锦葵油生物柴油的制备及性能分析.南京林业大学学报. 2008, 32(1): 72~74
48陈英军,梅德清,袁银南.单酯类燃料组成与结构对燃料特性的影响.小型内燃机与摩托车. 2006, 35(3): 39~41
49彭娜.超临界酯交换制取生物柴油及其燃烧反应机理研究.浙江大学硕士学位论文. 2007: 60~62
50刘伟伟,苏有勇,张无敌.生物柴油中甘油含量测定方法的研究.可再生能源. 2005, 3(121): 14~16
51何东平.油脂精炼与加工工艺学.化学工业出版社. 2005: 248~250 242~244
52邬国英,林西平,巫淼鑫.棉籽油间歇式酯交换反应动力学的研究.高等化学工程学报. 2003, 17(3):314-316