超临界流体技术制备生物柴油进展及前景
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摘要
超临界流体技术制备生物柴油不使用催化剂,生产过程清洁环保,是极具发展潜力的绿色可再生能源生产技术。本文首先简述超临界流体的特点及其用于生物柴油制备的物理、化学基础;其次详细分析超临界流体技术制备生物柴油的过程中反应温度、反应压力、醇油摩尔比、低碳醇种类、水、脂肪酸、反应器及反应形式等工艺控制条件对反应的影响和原因,并介绍超临界流体制备生物柴油中的过程强化方法和技术经济性。尽管超临界流体制备生物柴油具有原料适应性好、投资和运行成本低、生产过程清洁等优点,但存在反应条件苛刻、甲醇用量高等问题,从工业化角度指出使用廉价废弃油脂原料降成本、调节原料酸值降低反应苛刻度、连续化和大型化是超临界流体制备生物柴油技术的重点提升方向。
As an environment-friendly biodiesel process, the catalyst-free supercritical f luids(SCF)technology shows great potential in green and renewable energy production. The physical and chemical foundation in SCF technology for biodiesel production was firstly discussed. The effects of process factors, including reaction temperature, pressure, alcohol, water, free fatty acid and reactor type, on the SCF transesterification were then discussed in detail. The intensification measures used in SCF biodiesel process and the techno-economic analysis were also presented. Though the SCF biodiesel process showed its merits of good feedstock adaptability, low equipment and operation cost, and catalyst-free feature, the shortcomings of harsh reaction condition and high methanol dosage hindered its industrialization. The future improvements should focus on the reduction of biodiesel cost, the decrease of reaction harshness, and continuity and industrialization.
As an environment-friendly biodiesel process, the catalyst-free supercritical f luids(SCF)technology shows great potential in green and renewable energy production. The physical and chemical foundation in SCF technology for biodiesel production was firstly discussed. The effects of process factors, including reaction temperature, pressure, alcohol, water, free fatty acid and reactor type, on the SCF transesterification were then discussed in detail. The intensification measures used in SCF biodiesel process and the techno-economic analysis were also presented. Though the SCF biodiesel process showed its merits of good feedstock adaptability, low equipment and operation cost, and catalyst-free feature, the shortcomings of harsh reaction condition and high methanol dosage hindered its industrialization. The future improvements should focus on the reduction of biodiesel cost, the decrease of reaction harshness, and continuity and industrialization.
引文
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[24] KING J W. Analytical supercritical fluid techniques and methodology:conceptualization and reduction to practice[J]. Journal of AOAC International,1998,81(1):9-17.
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[28] KUSDIANA D,SAKA S. Kinetics of transesterification in rapeseed oil to biodiesel fuel as treated in supercritical methanol[J]. Fuel,2001,80(5):693-698.
[29] KUSDIANA D,SAKA S. Effects of water on biodiesel fuel production by supercritical methanol treatment[J]. Bioresource Technology,2004,91(3):289-295.
[30]商紫阳,银建中,马震,等.超临界甲醇法制备生物柴油过程的热力学行为[J].应用科技,2011,38(1):5-9.
[31] SAKA S,KUSDIANA D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol[J]. Fuel,2001,80(2):225-231.
[32] DASARI M A,GOFF M J,SUPPES G J. Noncatalytic alcoholysis kinetics of soybean oil[J]. Journal of the American Oil Chemists Society,2003,80(2):189-192.
[33] DEMIRBAS A. Biodiesel from vegetable oils via transesterification in supercritical methanol[J]. Energy Conversion&Management,2002,43(17):2349-2356.
[34] DEMIRBAS A. Biodiesel fuels from vegetable oils via catalytic supercritical alcohol transesterification and other methods:a survey[J].Energy Conversion&Management,2003,44(13):2093-2109.
[35] HE H Y,SUN S Y,WANG T,et al. Transesterification kinetics of soybean oil for production of biodiesel in supercritical methanol[J].Journal of the American Oil Chemists Society,2007,84(4):399-404.
[36] NIK W B W,ANI F N,MASJUKI H H. Thermal stability evaluation of palm oil as energy transport media[J]. Energy Conversion&Management,2005,46(13/14):2198-2215.
[37] IMAHARA H,MINAMI E,HARI S,et al. Thermal stability of biodiesel in supercritical methanol[J]. Fuel,2008,87(1):1-6.
[38] JOAQUíN Q M,OLIVARES C P. Evidence of thermal decomposition of fatty acid methyl esters during the synthesis of biodiesel with supercritical methanol[J]. Journal of Supercritical Fluids,2011,56(1):56-63.
[39] MARULANDA V F,ANITESCU G,TAVLARIDES L L. Biodiesel fuels through a continuous flow process of chicken fat supercritical transesterification[J]. Energy&Fuels,2010,24(1):253-260.
[40] SONG E S,LIM J W,LEE H S,et al. Transesterification of rbd palm oil using supercritical methanol[J]. Journal of Supercritical Fluids,2008,44(3):356-363.
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