3-羟基丁酸甲酯作为新型汽油添加剂的性能研究
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摘要
聚羟基脂肪酸酯是一种已被证实的可生物降解的聚酯类生物材料,其单体酯化物具有与生物柴油组分类似的结构。本研究中,以甲醇为酯化剂,通过硫酸催化水解的方法,将聚-3-羟基丁酸酯转化成为3-羟基丁酸甲酯。利用核磁共振波谱仪(NMR)和气相色谱仪(GC)对制得的3-羟基丁酸甲酯分别进行定性和定量测定,HBME纯度达到96.4%。依据美国ASTM标准对HBME及其不同比例HBME-汽油混合物的理化性质和燃料相关性能进行了测定,测定结果表明HBME有可能被用作生物燃料或燃料添加剂。当HBME分别以5%、8.5%、10%、15%、20%的体积比与97#汽油混合时,我们发现HBME作为燃料添加剂在氧含量、动力粘度、闪点、沸点、凝固点和馏程等方面具有比乙醇更优异的性能。HBME-汽油混合物在辛烷值和燃烧热上只与97#汽油有微小的差别,特别是HBME以8.5%-10%体积比与汽油混合的时候,辛烷值的减少在5%范围内,燃烧热超过汽油的93%。各项研究结果都表明HBME具有作为燃料添加剂应用于生物燃料领域的潜能。
Polyhydroxyalkanoate (PHA) was demonstrated to be a family of biopolyester with good biodegradability. The structure of hydroxyalkanoate methyl ester was similar to biodiesel. In this study, 3-Hydroxybutyrate methyl ester (HBME) was prepared from hydrolysis of bacterial poly-3-hydroxybutyrate (PHB) using methanol as an esterification agent in the presence of sulfuric acid. nuclear magnetic resonance spectrometer (NMR) and Gas chromatography (GC) were used to have qualitative and quantitative analysis of the produced HBME. It was found that purity of HBME was 96.4%. Physicochemical and fuel related properties of HBME were studied for the possibility of using HBME as a biofuel or fuel additive according to the standard of ASTM. When HBME was blended with 97# gasoline in volume ratios of 5%, 8.5%, 10%, 15% and 20%, respectively, it was found that HBME had similar or better properties as a fuel additive compared with ethanol in terms of oxygen content, dynamic viscosity, flash point, boiling point, freezing point and distillation ranges. The blending of HBME and gasoline showed only little difference compared with the 97# gasoline in terms of octane number (RON) and heat of combustion, especially for the HBME 8.5% and 10% blends, which demonstrated an over 93% combustion heat of gasoline with less than 5% reduction in RON. HBME can be regarded as a fuel additive for developing into biofuel.
Polyhydroxyalkanoate (PHA) was demonstrated to be a family of biopolyester with good biodegradability. The structure of hydroxyalkanoate methyl ester was similar to biodiesel. In this study, 3-Hydroxybutyrate methyl ester (HBME) was prepared from hydrolysis of bacterial poly-3-hydroxybutyrate (PHB) using methanol as an esterification agent in the presence of sulfuric acid. nuclear magnetic resonance spectrometer (NMR) and Gas chromatography (GC) were used to have qualitative and quantitative analysis of the produced HBME. It was found that purity of HBME was 96.4%. Physicochemical and fuel related properties of HBME were studied for the possibility of using HBME as a biofuel or fuel additive according to the standard of ASTM. When HBME was blended with 97# gasoline in volume ratios of 5%, 8.5%, 10%, 15% and 20%, respectively, it was found that HBME had similar or better properties as a fuel additive compared with ethanol in terms of oxygen content, dynamic viscosity, flash point, boiling point, freezing point and distillation ranges. The blending of HBME and gasoline showed only little difference compared with the 97# gasoline in terms of octane number (RON) and heat of combustion, especially for the HBME 8.5% and 10% blends, which demonstrated an over 93% combustion heat of gasoline with less than 5% reduction in RON. HBME can be regarded as a fuel additive for developing into biofuel.
引文
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[2] Yokoyama S Y, Ogi T, Nalampoon A. Biomass energy potential in Thailand. Biomass and Bioenergy 2000; 18(5): 405-410.
[3] Antoni D, Zverlov VV, Schwarz WH. Biofuels from microbes. Appl Microbiol Biotechnol 2007; 77:23–35.
[4] Hill J, Nelson E, Tilman D, Polasky S, Tiffany D. Environmental, economic, and energetic costs and benefits of biodiesel and ethanol biofuels. PNAS 2006; 103(30): 6–10.
[5] Kevin N Rask. Clean air and renewable fuels: the market for fuel ethanol in the US from 1984 to 1993. Energy Economics 1998; 20:325-345.
[6]傅学政,朱薇,管天球.我国红薯生产燃料乙醇的综合效益分析.湖南科技学院学报2006; 27(11): 183-185.
[7]刘翔,何国庆.利用木素纤维素生产燃料乙醇的微生物代谢工程.粮油加工与食品机械2003; 8: 67-69.
[8]刘铁男.中国燃料乙醇产业发展.中国能源2002; 3: 6-10.
[9] Ma F, Hanna M A, Biodiesel production : a review. Bioresour Technol 1999; 70(1): 1-15.
[10] Harrington K J. Chemical and physical properties of vegetable oil esters and their effect on diesel fuel performance. Biomass 1996; 9: 1- 3.
[11]苏有勇,戈振扬,施卫省.皂脚制备生物柴油的试验研究.农业工程学报2007; 23(2): 183-187.
[12] Laureano Canoira, Ramon Alcantara, Jesus Carrasc, et al. Biodiesel from Jojoba oil - wax : Transesterification with methanol and properties as a fuel. Biomass and Bioenergy 2006; 30: 76-81.
[13]徐桂转,刘会丽,张百良.响应面法优化酶催化酯交换反应研究.化学工程2007; 35(3): 63-67.
[14] Madras G, Kolluru C, Kumar R. Synthesis of Biodiesel in Supereritical Fuids. Fuel 2004; 83: 2029-2033.
[15] Anderson AJ, Dawes EA. Occurrence, metabolism, metabolic role, and industrial use of bacterial polyhydroxyalkanoates. Microbiol Rev 1990; 54: 450-472.
[16] Madison LL, Huisman GW. Metabolic engineering of poly(3-hydroxyalkanoates): from DNA to plastic. Microbiol Mol Biol Rev 1999; 63: 21-53.
[17] Dowes EA, Senior PJ. The role and regulation of energy reserve polymers in microorganisms. Adv Microb Physiol 1973; 10: 135-266.
[18] Jendrossek D. Microbial degradation of polyesters. Adv Biochem Eng Biotechnol 2001; 71: 293-325.
[19] Reusch RN, Hiske TW, Sadoff HL. Poly-β-hydroxybutyrate membrane structure and its relationship to genetic transformability in Escherichia coli. J Bacteriol 1986; 168: 553-562.
[20] Huang R, Reusch RN. Poly(3-hydroxybutyrate) is associated with specific proteins in the cytoplasm and membranes of Escherichia coli. J Biol Chem 1996; 271: 22196-22202.
[21] Steinbüchel A, Valentin HE. Diversity of bacterial polyhydroxyalkanoic acids. FEMS Microbiol Lett 1995; 128: 219-228.
[22] Matsusaki H, Manji S, Taguchi K, Kato M, Fukui T, Doi Y. Cloning and molecular analysis of the poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate- co-3-hydroxyalkanoate) biosynthesis genes in Pseudomonas sp. strain 61-3. J. Bacteriol 1998; 180: 6459-6467.
[23] Matsusaki H, Abe H, Doi Y. Biosynthesis and properties of poly(3-hydroxy- butyrate-co-3-hydroxyalkanoates) by recombinant strains of Pseudomonas sp. 61-3. Biomacromolecules 2000; 1: 17-22.
[24] Wallen LL, Rohwedder WK. Poly-β-hydroxyalkanoate from activated sludge. Environ Sci Technol 1974; 8: 576-9.
[25] Findlay RH, White DC. Polymeric beta-hydroxyalkanoates from environmental samples and Bacillus megaterium. Appl Environ Microbiol 1983; 45: 71-8.
[26] Smet MJ, Eggink G, Witholt B, Kingma J, Wynberg H. Characterization of intracellular inclusions formed by Pseudomonas oleovorans during growth on octane. J Bacteriol 1983; 154: 870-8.
[27] Lageveen RG, Huisman GW, Preusting H, Ketelaar P, Eggink G, Witholt B. Formation of polyesters by Pseudomonas oleovorans: effect of substrates on formation and composition of poly-(R)-3-hydroxyalkanoates and poly-(R)-3-hydroxyalkanoates. Appl Environ Microbiol 1988; 54: 2924-32.
[28] Brandl H, Gross RA, Lenz RW, Fuller RC. Pseudomonas oleovorans as a source of poly (β-hydroxyalkanoates) for potential applications as biodegradable polyesters. Appl Environ Microbiol 1988; 54: 1977-82.
[29] Fritsche K, Lenz RW, Fuller RC. Bacterial polyesters containing branched poly (β-hydroxyalkanoates) units. Int J Biol Macromol 1990; 12: 92-101.
[30] He W, Tian W, Zhang G, Chen GQ, Zhang Z. Production of novel polyhydroxyal- kanoates by Pseudomonas stutzeri 1317 from glucose and soybean oil. FEMS Microbiol Lett 1998; 169: 45-9.
[31]陈国强,赵锴.生物工程与生物材料.中国生物工程杂志2002; 22: 1-8.
[32] Lee S Y. Bacterial polyhydroxyalkanoates. Biotechnol Bioeng 1996; 49: 1-14.
[33] Kunioka M, Doi Y. Thermal degradation of microbial copolyesters: poly (3-hy- droxybutyrate-co-4-hydroxybutyrate). Macromolecules 1990; 23: 1933-1936.
[34] Avella M, Martuscelli E, Orsello G. et al. Poly (3-hydroxybutyrate)/poly (methyleneoxide) blends: thermal, crystallization and mechanical behaviour. Polymer 1997; 38(25): 6135-6143.
[35] Iwata T, Tsunoda K, Aoyagi Y, et al. Mechanical properties of uniaxially cold-drawn films of poly([R]-3-hydroxybutyrate). Polym. Degrad. Stab 2003; 79(2): 217-224.
[36] Kusaka S, Iwata T, Doi Y. Properties and biodegradability of ultra-high- molecular-weight poly [(R)-3-hydroxybutyrate] produced by a recombinant Escherichia coli. Int. J. Biol. Macromolecules 1999; 25: 87-94.
[37] Doi Y, Kitamura S, Abe H. Microbial synthesis and characterization of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate). Macromolecules 1995; 28: 4822-4828.
[38] Abe H, Kikkawa Y, Aoki H, et al. Crystallization behavior and thermal properties of melt-crystallized poly [(R)-3-hydroxybutyric acid-co-6-hydroxyhexanoic acid]. Int. J. Biol. Macromolecules 1999; 25: 177-183.
[39] Ageveen R G, Huisman G W,Preusting H et al. Formation of polysters by Pseudomona oleovorans: effect of substrates on formation and composition of poly-(R)-3-hydroxyalakanoates and poly-(R)-3-hydroxyalkenoates. Appl. Environ. Microbiol 1988; 54: 2924-2932.
[40] Haywood G.W, Anderson A.J., Dawes E.A. Characterization of two 3-ketothiolases possessing differering substrates specificities in the polyhydroxyalkanoate synthesizing oganism Alcaligenus eutrophus. FEMS Microbiol. Lett 1988; 57: 1-6.
[41] Williamson D.H. and Wilkinson J.F. The Isolation and Estimation of Poly-β- hydroxybutyrate Inclusions of Bacillus Species. J gen. Microbiol 1958; 19: 198-209.
[42] Ward A. C. and Dawes E. A. A Disk Assay of Poly-?-hydroxyburate. Biochem. 1973; 52: 607-613.
[43] Kato M, Bao HJ, Kang CK, Fukui T and Doi Y. Production of a novel copolyester of 3- hydroxybutyric acid and medium chain length 3- hydroxyalkanoatic acids by Pseudomonas sp.61-3 from sugars. Appl. Microbiol
[44] Tadahisa Iwata, Yoshiharu Doi, Fumiaki Kokubu, Shinya Teramachi, Alkaline hydrolysis of solution-grown poly[(R)-3-hydroxybutyrate] single crystals, Macromolecules 1999; 32: 8325-8330.
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