生物柴油冷滤点与其化学组成的定量关系
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摘要
生物柴油的低温流动性主要取决于化学组成。为了量化表征生物柴油组成与其冷滤点的关系,采用气相色谱-质谱与冷滤点分析技术和多元线性回归分析方法,分析了生物柴油的脂肪酸甲酯组成和冷滤点,研究了脂肪酸甲酯组成对冷滤点的影响规律。研究表明:生物柴油主要由14～24个偶数碳原子组成的长链脂肪酸甲酯组成,其中饱和脂肪酸甲酯主要为C14:0～C24:0,不饱和脂肪酸甲酯主要为C16:1～C22:1、C18:2～C20:2和C18:3。120种生物柴油油样中,乌桕梓油生物柴油的冷滤点最低,为-14℃,花生油生物柴油的冷滤点最高,为13℃。生物柴油的脂肪酸甲酯的含量与分布不同,冷滤点差异较大。冷滤点随饱和脂肪酸甲酯含量的增加呈线性升高,且碳链长的较短的增加显著;随不饱和脂肪酸甲酯含量的增加而呈线性降低,且不饱和度高的较低的降低略明显。建立了线性相关性非常显著(R=0.971)的基于组成的冷滤点预测模型。研究结果为不同环境下生物柴油的推广应用提供参考。
Biodiesel has become one of the comparatively ideal partial alternative fuels for diesel engines because of its environmental benefits and the fact that it is a product made from renewable resources. However the less favorable cold flow properties or the low temperature operability of biodiesel fuel compared to conventional diesel is a major drawback limiting its use. The poor flow properties of biodiesel at cold temperatures are mainly due to fatty acid methyl ester composition. In order to quantify the relation between biodiesel composition and its cold filter plugging point (CFPP), fatty acid methyl ester composition, CFPP, and the influence of composition on CFPP were analyzed by gas chromatography-mass spectrometry and a cold filter plugging point test method. Correlation between fatty acid methyl ester composition and CFPP was studied with multivariate linear regression. The study shows that biodiesel is mainly fatty acid methyl ester (FAME) that is composed of 14-24 even number carbon atoms. Saturated fatty acid methyl esters (SFAMEs) are mainly C 14:0 ~C 24:0 and unsaturated fatty acid methyl ester (UFAMEs) are mainly C 16:1 ~C 22:1 , C 18:2 ~C 20:2 and C 18:3 . The cold flow property of biodiesel is mainly determined by the content and distribution of FAME. The CFPP increases linearly with increasing SFAME, and the longer the carbon chains are, the greater the increase will be. In addition, CFPP decreases linearly with the increasing unsaturated fatty acid methyl esters (UFAME), and the higher the degree of unsaturation, the greater the decrease. Among the 120 kinds of biodiesel we studied, the CFPP of sapium sebiferum methyl ester (SSME) was the lowest (-14℃ ) and the CFPP of peanut methyl ester (PNME) was the highest (13℃ ). Considering SFAMEC≤18 , SFAMEC≥20 , mono-unsaturated fatty acid methyl ester (MUFAME) and di-unsaturated fatty acid methyl ester (DUFAME) in biodiesel as independent variables, and CFPP as dependent variable, we built a CFPP quaternary linear regression prediction model. The significance of the linear regression and deviation analysis were both analyzed. The regression correlation coefficient R=0.971 shows that the CFPP of biodiesel has a very significant linear dependence with SFAMEC≤18 , SFAMEC≥20 , MUFAME and DUFAME. The variance analysis F=471.65 and significance F=2.53E-70 show that our regression equation is very significant. The deviation analysis indicates that the regression prediction model has a high accuracy. At a significance level of α=0.05, the deviation between the measured and predicted values of CFPP was ≤3 ℃. The result indicated that the regression model can predict well.
Biodiesel has become one of the comparatively ideal partial alternative fuels for diesel engines because of its environmental benefits and the fact that it is a product made from renewable resources. However the less favorable cold flow properties or the low temperature operability of biodiesel fuel compared to conventional diesel is a major drawback limiting its use. The poor flow properties of biodiesel at cold temperatures are mainly due to fatty acid methyl ester composition. In order to quantify the relation between biodiesel composition and its cold filter plugging point (CFPP), fatty acid methyl ester composition, CFPP, and the influence of composition on CFPP were analyzed by gas chromatography-mass spectrometry and a cold filter plugging point test method. Correlation between fatty acid methyl ester composition and CFPP was studied with multivariate linear regression. The study shows that biodiesel is mainly fatty acid methyl ester (FAME) that is composed of 14-24 even number carbon atoms. Saturated fatty acid methyl esters (SFAMEs) are mainly C 14:0 ~C 24:0 and unsaturated fatty acid methyl ester (UFAMEs) are mainly C 16:1 ~C 22:1 , C 18:2 ~C 20:2 and C 18:3 . The cold flow property of biodiesel is mainly determined by the content and distribution of FAME. The CFPP increases linearly with increasing SFAME, and the longer the carbon chains are, the greater the increase will be. In addition, CFPP decreases linearly with the increasing unsaturated fatty acid methyl esters (UFAME), and the higher the degree of unsaturation, the greater the decrease. Among the 120 kinds of biodiesel we studied, the CFPP of sapium sebiferum methyl ester (SSME) was the lowest (-14℃ ) and the CFPP of peanut methyl ester (PNME) was the highest (13℃ ). Considering SFAMEC≤18 , SFAMEC≥20 , mono-unsaturated fatty acid methyl ester (MUFAME) and di-unsaturated fatty acid methyl ester (DUFAME) in biodiesel as independent variables, and CFPP as dependent variable, we built a CFPP quaternary linear regression prediction model. The significance of the linear regression and deviation analysis were both analyzed. The regression correlation coefficient R=0.971 shows that the CFPP of biodiesel has a very significant linear dependence with SFAMEC≤18 , SFAMEC≥20 , MUFAME and DUFAME. The variance analysis F=471.65 and significance F=2.53E-70 show that our regression equation is very significant. The deviation analysis indicates that the regression prediction model has a high accuracy. At a significance level of α=0.05, the deviation between the measured and predicted values of CFPP was ≤3 ℃. The result indicated that the regression model can predict well.
引文
[1]ChuangWei Chiu.Biodiesel synthesis and impact of cold flow additives[D].Columbia:the Faculty of the Graduate School University of Missouri-Columbia,2004,50.
[2]Ernesto C Zuleta,Luis A Rios,Pedro N Benjumea.Oxidative stability and cold flow behavior of palm,sacha-inchi,jatropha and castor oil biodiesel blends[J].Fuel Processing Technology,2012,102(10):96-101.
[3]Hoekman S Kent,Amber Broch,et al.Review of biodiesel composition,properties,and specifications[J].Renewable and Sustainable Energy Reviews,2012,16(1):143-169.
[4]Evangelos G Giakoumis.A statistical investigation of biodiesel physical and chemical properties,and theircorrelation with the degree of unsaturation[J].Renewable Energy,2013,50(2):858-878.
[5]ángel Pérez,Abraham Casas,Carmen María Fernández,et al.Winterization of peanut biodiesel to improve the cold flow properties[J].Bioresource Technology,2010,101(19):7375-7381.
[6]Suzana Yusup,Modhar Khan.Basic properties of crude rubber seed oil and crude palm oil blend as a potential feedstock for biodiesel production with enhanced cold flow characteristics[J].Biomass and Bioenergy,2010,34(10):1523-1526.
[7]Paul C Smith,Yung Ngothai,Nguyen Q Dzuy,et al.Improving the low-temperature properties of biodiesel methods and consequences[J].Renewable Energy,2010,35(6):1145-1151.
[8]Usta N,Aydo an B,on AH,et al.Properties and quality verification of biodiesel produced from tobacco seed oil[J].Energy Conversion and Management,2011,52(5):2031-2039.
[9]Bryan R Moser,Steven F Vaughn.Efficacy of fatty acid profile as a tool for screening feedstocks for biodiesel production[J].Biomass and Bioenergy,2012,37(2):31-41.
[10]Lécia MS Freire,JoséRC Filho,Carla VR Moura,et al.Evaluation of the oxidative stability and flow properties of quaternary mixtures of vegetable oils for biodiesel production[J].Fuel,2012,95(5):126-130.
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[12]巫淼鑫.生物柴油低温流动性能影响因素的研究[D].南京:南京理工大学,2008.Wu Miaoxin.Study on influencing factors of low-temperature flowing properties of biodiesel fuel[D].Najin:Nanjing University of Science and Technology,2008.
[13]李泓,沈本贤,卡巴罗.生物柴油低温流动性能的研究[J].中国油脂,2008,33(9):44-46.Li Hong,Shen Benxian,KABALU.Low temperature fluidity of biodiesel[J].China Oils and Fats,2008,33(9):44-46.(in Chinese with English abstract)
[14]孙玉秋,陈波水,孙玉丽,等.生物柴油低温凝固机理探讨[J].石油炼制与化工,2009,40(5):57-60.Sun Yuqiu,Chen Boshui,Sun Yuli,et al.A preliminary study of the solidification mechanism of biodiesel at low temperature[J].Petroleum Processing and Petrochemicals,2009,40(5):57-60.(in Chinese with English abstract)
[15]陈秀,袁银男,王利平,等.脂肪酸甲酯结构对生物柴油低温流动性的影响[J].江苏大学学报(自然科学版),2010,31(1):31-34.Chen Xiu,Yuan Yinnan,Wang LiPing,et al.Impact of fatty acid methyl ester upon cold flow properties for biodiesel[J].Journal of Jiangsu University(Natural Science Edition),2010,31(1):31-34.(in Chinese with English abstract)
[16]胡健华.生物柴油的脂肪酸组成对其性能的影响[J].武汉工业学院学报,2010,29(4):26-28.Hu Jianhua.The effect of fatty acid components of biodiesel on its performance[J].Journal of Wuhan Polytechnic University,2010,29(4):26-28.(in Chinese with English abstract)
[17]陈秀,来永斌.改善棉子油生物柴油低温流动性的研究[J].棉花学报,2011,23(1):75-79.Chen Xiu,Lai Yongbin.Study on Cold Flow Properties of Biodiesel Derived from Cottonseed Oil[J].Cotton Science,2011,23(1):75-79.(in Chinese with English abstract)
[18]吕涯,李骏,欧阳福生.生物柴油调合对其低温流动性能的改善[J].燃料化学学报,2011,39(3):189-193.Lv Ya,Li Jun,Ouyang Fusheng.Effect of biodiesels blending on their low-temperature fluidity[J].Journal of Fuel Chemistry and Technology,2011,39(3):189-193.(in Chinese with English abstract)
[19]马顺.生物柴油制备及低温流动性改善研究[D].广州:暨南大学,2011.Ma Shun.Preparation of Biodiesel and Improving its Cold Flow Properties[D].Guangzhou:Jinan University,2011.
[20]Camelia Echim,Jeroen Maes,Wim De Greyt.Improvement of cold filter plugging point of biodiesel from alternative feedstocks[J].Fuel,2012,93(3):642-648.
[21]陈秀,袁银南,来永斌,王利平.生物柴油的组成与组分结构对其低温流动性的影响[J].石油学报(石油加工),2009,25(5):50-52.Chen Xiu,Yuan Yinnan,Lai Yongbin,et al.Impact of composition and molecular structure upon the cold flow properties for biodiesel[J].Acta Petrolei Sinica(PetroleumProcessing Section),2009,25(5):50-52.(in Chinese with English abstract)
[22]Ji-Yeon Park,Deog-Keun Kim,Joon-Pyo Lee,et al.Blending effects of biodiesels on oxidation stability and low temperature flow properties[J].Bioresource Technology,2008,99(5):1196-1203.
[23]María Jesús Ramos,Carmen María Fernández,Abraham Casas,et al.Influence of fatty acid composition of raw materials on biodiesel properties[J].Bioresource Technology,2009,100(1):261-268.
[24]Wang Libing,Yu Haiyan,He Xiaohui,et al.Influence of fatty acid composition of woody biodiesel plants on the fuel properties[J].Journal of Fuel Chemistry and Technology,2012,40(4):397-404.
[25]Pinz S i,Leiva D,Arzamendi G,et al.Multiple response optimization of vegetable oils fatty acid composition toimprove biodiesel physical properties[J].Bioresource Technology,2011,102(15):7280-7288.
[26]Gerhard Knothe.Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters[J].Fuel Processing Technology,2005,86(10):1059-1070.
[27]吴谋成.生物柴油[M].北京:化学工业出版社,2008.Wu Mouchen.Biodiesel[M].Beijing:Chemical Industry Press,2008.
[28]陈秀,袁银男,来永斌.生物柴油的低温流动特性及其改善[J].农业工程学报,2010,26(3):277-280.Chen Xiu,Yuan Yinnan,Lai Yongbin.Flow properties of biodiesel at low temperature and its improvement[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2010,26(3):277-280.(in Chinese with English abstract)
[2]Ernesto C Zuleta,Luis A Rios,Pedro N Benjumea.Oxidative stability and cold flow behavior of palm,sacha-inchi,jatropha and castor oil biodiesel blends[J].Fuel Processing Technology,2012,102(10):96-101.
[3]Hoekman S Kent,Amber Broch,et al.Review of biodiesel composition,properties,and specifications[J].Renewable and Sustainable Energy Reviews,2012,16(1):143-169.
[4]Evangelos G Giakoumis.A statistical investigation of biodiesel physical and chemical properties,and theircorrelation with the degree of unsaturation[J].Renewable Energy,2013,50(2):858-878.
[5]ángel Pérez,Abraham Casas,Carmen María Fernández,et al.Winterization of peanut biodiesel to improve the cold flow properties[J].Bioresource Technology,2010,101(19):7375-7381.
[6]Suzana Yusup,Modhar Khan.Basic properties of crude rubber seed oil and crude palm oil blend as a potential feedstock for biodiesel production with enhanced cold flow characteristics[J].Biomass and Bioenergy,2010,34(10):1523-1526.
[7]Paul C Smith,Yung Ngothai,Nguyen Q Dzuy,et al.Improving the low-temperature properties of biodiesel methods and consequences[J].Renewable Energy,2010,35(6):1145-1151.
[8]Usta N,Aydo an B,on AH,et al.Properties and quality verification of biodiesel produced from tobacco seed oil[J].Energy Conversion and Management,2011,52(5):2031-2039.
[9]Bryan R Moser,Steven F Vaughn.Efficacy of fatty acid profile as a tool for screening feedstocks for biodiesel production[J].Biomass and Bioenergy,2012,37(2):31-41.
[10]Lécia MS Freire,JoséRC Filho,Carla VR Moura,et al.Evaluation of the oxidative stability and flow properties of quaternary mixtures of vegetable oils for biodiesel production[J].Fuel,2012,95(5):126-130.
[11]徐鸽,巫淼鑫,邬国英.生物柴油低温流动性能研究[J].江苏工业学院学报,2004,16(4):14-16.Xu Ge,Wu Miaoxing,Wu Guoying.Study of the low temperature flowing properties of biodiesel[J].Journal of Jiangsu Polytechnic University,2004,16(4):14-16.(in Chinese with English abstract)
[12]巫淼鑫.生物柴油低温流动性能影响因素的研究[D].南京:南京理工大学,2008.Wu Miaoxin.Study on influencing factors of low-temperature flowing properties of biodiesel fuel[D].Najin:Nanjing University of Science and Technology,2008.
[13]李泓,沈本贤,卡巴罗.生物柴油低温流动性能的研究[J].中国油脂,2008,33(9):44-46.Li Hong,Shen Benxian,KABALU.Low temperature fluidity of biodiesel[J].China Oils and Fats,2008,33(9):44-46.(in Chinese with English abstract)
[14]孙玉秋,陈波水,孙玉丽,等.生物柴油低温凝固机理探讨[J].石油炼制与化工,2009,40(5):57-60.Sun Yuqiu,Chen Boshui,Sun Yuli,et al.A preliminary study of the solidification mechanism of biodiesel at low temperature[J].Petroleum Processing and Petrochemicals,2009,40(5):57-60.(in Chinese with English abstract)
[15]陈秀,袁银男,王利平,等.脂肪酸甲酯结构对生物柴油低温流动性的影响[J].江苏大学学报(自然科学版),2010,31(1):31-34.Chen Xiu,Yuan Yinnan,Wang LiPing,et al.Impact of fatty acid methyl ester upon cold flow properties for biodiesel[J].Journal of Jiangsu University(Natural Science Edition),2010,31(1):31-34.(in Chinese with English abstract)
[16]胡健华.生物柴油的脂肪酸组成对其性能的影响[J].武汉工业学院学报,2010,29(4):26-28.Hu Jianhua.The effect of fatty acid components of biodiesel on its performance[J].Journal of Wuhan Polytechnic University,2010,29(4):26-28.(in Chinese with English abstract)
[17]陈秀,来永斌.改善棉子油生物柴油低温流动性的研究[J].棉花学报,2011,23(1):75-79.Chen Xiu,Lai Yongbin.Study on Cold Flow Properties of Biodiesel Derived from Cottonseed Oil[J].Cotton Science,2011,23(1):75-79.(in Chinese with English abstract)
[18]吕涯,李骏,欧阳福生.生物柴油调合对其低温流动性能的改善[J].燃料化学学报,2011,39(3):189-193.Lv Ya,Li Jun,Ouyang Fusheng.Effect of biodiesels blending on their low-temperature fluidity[J].Journal of Fuel Chemistry and Technology,2011,39(3):189-193.(in Chinese with English abstract)
[19]马顺.生物柴油制备及低温流动性改善研究[D].广州:暨南大学,2011.Ma Shun.Preparation of Biodiesel and Improving its Cold Flow Properties[D].Guangzhou:Jinan University,2011.
[20]Camelia Echim,Jeroen Maes,Wim De Greyt.Improvement of cold filter plugging point of biodiesel from alternative feedstocks[J].Fuel,2012,93(3):642-648.
[21]陈秀,袁银南,来永斌,王利平.生物柴油的组成与组分结构对其低温流动性的影响[J].石油学报(石油加工),2009,25(5):50-52.Chen Xiu,Yuan Yinnan,Lai Yongbin,et al.Impact of composition and molecular structure upon the cold flow properties for biodiesel[J].Acta Petrolei Sinica(PetroleumProcessing Section),2009,25(5):50-52.(in Chinese with English abstract)
[22]Ji-Yeon Park,Deog-Keun Kim,Joon-Pyo Lee,et al.Blending effects of biodiesels on oxidation stability and low temperature flow properties[J].Bioresource Technology,2008,99(5):1196-1203.
[23]María Jesús Ramos,Carmen María Fernández,Abraham Casas,et al.Influence of fatty acid composition of raw materials on biodiesel properties[J].Bioresource Technology,2009,100(1):261-268.
[24]Wang Libing,Yu Haiyan,He Xiaohui,et al.Influence of fatty acid composition of woody biodiesel plants on the fuel properties[J].Journal of Fuel Chemistry and Technology,2012,40(4):397-404.
[25]Pinz S i,Leiva D,Arzamendi G,et al.Multiple response optimization of vegetable oils fatty acid composition toimprove biodiesel physical properties[J].Bioresource Technology,2011,102(15):7280-7288.
[26]Gerhard Knothe.Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters[J].Fuel Processing Technology,2005,86(10):1059-1070.
[27]吴谋成.生物柴油[M].北京:化学工业出版社,2008.Wu Mouchen.Biodiesel[M].Beijing:Chemical Industry Press,2008.
[28]陈秀,袁银男,来永斌.生物柴油的低温流动特性及其改善[J].农业工程学报,2010,26(3):277-280.Chen Xiu,Yuan Yinnan,Lai Yongbin.Flow properties of biodiesel at low temperature and its improvement[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2010,26(3):277-280.(in Chinese with English abstract)