玉米油基无甘油副产的生物柴油的制备及燃烧性能研究
|
摘要
随着全世界经济的快速持续发展,化石能源需求量不断增加,而作为不可再生的化石能源将会逐渐枯竭,原有的产能过剩将消失。因此,开发新的石油替代燃料迫在眉睫。生物柴油具有原料可再生、善点高、使用安全性好等特征,成为大家公认的理想的石化柴油替代燃料,由此引起了关于生物柴油生产和研发的热潮。传统的甲醇基生物柴油,会副产低附加值粗甘油,不仅降低了原料的利用率,而且会由于副产甘油的随意丢弃和简单燃烧引起新的环境问题,因此,在生产生物柴油——脂肪酸甲酯的同时联产高附加值甘油下游产品成为生物柴油能否得到持续发展的关键所在。本论文以碳酸二甲酯(DMC)为酯交换试剂与玉米油进行酯交换反应来制备生物柴油脂肪酸甲酯,同时联产甘油下游产品甘油碳酸酯。此种工艺不仅解决了传统甲醇基生物柴油制备工艺中均相催化剂无法分离,反应结束后废酸、废碱洗液排放污染环境的问题,而且联产的甘油下游产品可以作为燃料直接使用,提高了原料的利用率,缓解了粗甘油过剩所引起的环境问题,成为非常具有前途的生物柴油发展方向。通过对制备工艺条件、反应过程以及产物燃烧性能的详细研究,本文得出以下结论：
首先,本文采用气质联用、模拟合成标准物验证、外标等多种方法对无甘油副产的生物柴油的组分进行了定性和定量分析,确定保留时间为4min和8-13min的峰分别对应副产物甘油一碳酸酯GC和主产物脂肪酸甲酯FAMEs；保留时间为14-17min的峰为反应中间体脂肪酸甘油碳酸酯FAGC的峰；保留时间为21-27min的峰分别对应原料甘油三酯和甘油二酯(甘油二酯的保留时间为21.5-22.3min,甘油三酯的保留时间为23.5-26.5min)。并且,脂肪酸甲酯在棕榈酸甲酯59-354μg/ml、油酸亚油酸甲酯50-304μg/ml和硬脂酸甲酯5.6-33.71μg/ml的浓度范围内都具有良好的线性关系,甘油二酯和甘油三酯在5-50μg/ml的浓度范围内具有良好的线性关系。
其次,在对无甘油副产的生物柴油产物进行定性和定量分析的基础上,本文对非均相固体碱氢氧化钾和固定化脂肪酶所催化的酯交换反应过程进行了研究。发现,在以氢氧化钾为催化剂时,当酯油摩尔比为9：1,KOH催化剂添加量为原料油质量16.2%,反应温度为85℃,反应时间为9h时,脂肪酸甲酯的收率可以达到90.4%；在以固定化脂肪酶为催化剂时,在反应温度为60℃,酯油摩尔比为10：1,固定化脂肪酶催化剂用量为原料油质量的20%,反应时间为24h时,脂肪酸甲酯的收率可以达到95.4%。并且,氢氧化钾催化剂催化的酯交换反应过程分反应增长阶段和平衡阶段两个过程进行。其中,甘油三酯和甘油二酯的酯交换增长阶段均为2级反应；甘油三酯的酯交换反应活化能为83.3KJ/mol,频率因子为4.48×10'L/(mol·min)；甘油二酯的酯交换反应活化能为89.8KJ/mol,频率因子为7.98×1010L/(mol·min)。均高于油脂与甲醇进行酯交换反应的活化能,表明本论文所设计的酯交换反应较难进行,需要在较长的反应时间下进行,与实验条件的探索吻合。
再次,在发动机未作任何调整的情况下,将脂肪酸甲酯、副产物甘油一碳酸酯以及过量的酯交换试剂与0号柴油进行混合,进行了其对发动机的动力和经济性能以及排放性能的影响研究,探究了酯交换试剂DMC、副产物甘油一碳酸酯GC的存在对生物柴油与0号柴油混合燃料燃烧性能的影响,发现：脂肪酸甲酯、副产甘油一碳酸酯以及过量的酯交换试剂可以与0号柴油直接混合而用于发动机,此时发动机的动力性略有降低,燃料油耗略有升高；一氧化碳、碳氢化合物、醛类、二氧化硫的排放量略有增加,氮氧化物、烟度、二氧化碳排放量略有降低；小颗粒排放物数量增加,大颗粒排放物数量降低,排放物颗粒分布向小粒径方向移动；总颗粒质量和聚集态颗粒质量的排放降低,核模态颗粒的质量排放量增加。副产物甘油一碳酸酯和过量的酯交换试剂DMC的添加对混合燃料的燃烧性能的影响非常小。
最后,为了使得玉米得到更充分的利用,变废为宝,本文还对制取乙醇后的玉米胚芽废渣进行了脂肪和油脂的分离,并以提取出来的油脂为原料进行了无甘油副产的生物柴油的制备探索,发现,体系当中水分的有效移除是保证生物酶催化剂足够催化活性的关键,当硅胶作为吸水剂添加在体系当中时,在反应温度为60℃、酯油摩尔比为15：1、催化剂用量为油脂质量20%、硅胶用量为油脂质量40%,反应时间12h的情况下,脂肪酸甲酯的收率可以达到83.6%；在高吸水树脂存在的情况下,当其用量仅为硅胶用量1/4时,其就可以达到与硅胶存在条件下相同的脂肪酸甲酯收率,并且催化剂和吸水树脂均可重复使用,重复五次收率没有明显下降；此外,通过单纯将反应时间从12h延长至24h,即可使得收率达到90%以上。并且,此无甘油副产的生物柴油制备工艺的脂肪酸甲酯收率明显高于相同原料的甲醇基生物柴油制备工艺的脂肪酸甲酯收率。说明,以从玉米胚芽残渣当中提取的玉米废油为原料进行无甘油副产的生物柴油的制备是一条理想的生物柴油制备路线,其对于玉米的充分利用具有非常重要的意义。
Surplus production of petroleum will disappear with the sustain development of economy in the whole world. It is estimated that the backorder of petroleum will reach about1million barrels per day till2015. So it is very imperative to develop the new fuels which can replace petroleum. Biodiesel is concered as a satisfactory fuel that can replace petroleum. Because it is prepared from renewable materials and it is used safety due to the higher flashing point. Under the conditions, more and more scientists and technical persons are engaging in the development of biodiesel. The biodiesel will be named as methol-biodisel when methanol was used as esterification reagent. Glycerol was produced as by product in the preparation of methol-biodiesel, and more and more glycerols were produced with the increase development of methol-biodiesel. More and more glycerols were discared or sincered directly due to the lower price of glycerol, which will induce the new economical and environmental problems. It is becoming more and more important that the downsteam products of glycrol, which have high addational value, are prepared in the production of biodiesel. In this thesis, dimethyl carbonate was used as a new esterfication reagent, and the glycerol carbonate monoesters (FAGC), who can be used directly as additive of fules, are produced in the preparation of fatty acid methyl esters (FAMEs). In the reaction, all raw materials can be transfered as fuels, so the usage rate of raw material is very high. Furthermore, there is no glycerol in products, and the problems concerning the glycerol were resolved efficiently. The main research results were as followed:
First, the GC-MS, verication of model compound, external standard and internal standard methods are all used in the quality and quantity analyses of reactant products in the preparation of biodiesel without glycerol as by product. The retention times of glycerol carbonate (GC), fatty acid methyl esters (FAMEs), acid glycerol carbonate monoesters (FAGC), triglycerides (TG) and diglycerides (DG) are4min,8-13min,14-17min,21.5-22.3min and23.5-26.5min, respectively. Furthermore, the GC peak area of methyl palmitate shows linear change in the concertration range of59-354μg/ml. The concertraction linear ranges of methyl oleate and methyl linoleate are50-304μg/ml and5.6-33.7μg/ml, respectively. And the GC peak areas of triglycerides (TG) and diglycerides (DG) changes linearly when the concertration is in the range of5-50μg/ml.
Second, the reaction processes catalysed by KOH and lipase-catalyzed were studied in detail. The results showed that:For the KOH-catalyzed esterification, the yield of FAMEs can reach90.4%, when the molar ratio of DMC to oil is9, the loading amount of catalyst is16.2%(based on the weight of oil), the reaction temperature is85℃and the reaction time is9h. When immobilized-lipases Novozym435was as catalyst, the yield of FAMEs can reach95.4%, with the molar ratio of DMC to oil of10:1, the loading of catalyst of20%, the reaction temperature of85℃and the reaction time of24h. Further, the kinetics of KOH-catalyzed transesterification of corn oil and DMC was researched. The reaction process can be divided into two stages including reaction growth stage and reaction equilibration stage. The transesterification kinetics of TG and DG are all agreeed with2-order model. The reaction energy of TG and DG are83.3KJ/mol and89.8KJ/mol, respectively, which are all bigger than that of esterification used for the preparation of methol-biodiesel. Frequency factor of TG and DG are4.48×1010L/(mol·min) and7.98×1010L/(mol·min).
Then, the study on engine performance, economic property and emission characteristics were conducted in a diesel engine fuelled with blends of corn oil methyl esters and diesel oil (the mixed ratio was10:90, named B10). And the effects of the additional DMC and glycerol carbonate (GC) on the engine fuel consumption were further investigated. The results showed the blend fuel can be directly used in diesel engine.The power performance and fuel consumption display a little increase when FAMEs, DMC and GC wered added in the fuel. CO, HC, aldehydes and SO2emissions were slightly increased. And the small particle emission increased, and the big particle emission reduced. The article distrabution had a tendency to small particles. Total particles quality emussions and gatherated particles quality emussions were reduced, and nuclear state particles quality emussions were increased. In a word, the GC by-product and the ester esterification reagent DMC have a little effect on the combustion performances of the biodiesel fuel.
Finally, the oil and fat in germ residue of corn were separated using solvent extraction method, and the oil was then used to prepare the biodiesel without glycerol as by-product. It was found that there are more free fatty acids in the residue oil. And the free fatty acids can react with esterification regeant DMC easily to produce some water, which will inhibit the catalyst activity of immobilized-lipases Novozym435. So for the esterification of residue oil, the removal of water produce due to the esterification of fatty acid is very important. Under the conditions, blue silical gel and super absorbent polymer were added in the system to absorb the water, respectively. The yield of FAMEs can reach about83.6%, when the reaction temperature is60℃, molar ratio of DMC to oil is15:1, the amount of blue silical gel is40%(based on oil) and the reaction time is12h. Furthermore, if the super absorbent polymer replaced the blue silical gel, only one quarterly amout of super absorbent polymer was needed to obtain the yield of85.0%. And the yield will reach above90%if the reaction time is extended from12h to24h under no change of other experimental conditions. The yield of biodiesel without glycerol as by-product is much higher than that of methol-biodiesel prepared using solid acid as catalyst. In a word, for the comprehensive utilization of corn, the preparation of biodiesel without glycerol as by-product is a very promising direction.
首先,本文采用气质联用、模拟合成标准物验证、外标等多种方法对无甘油副产的生物柴油的组分进行了定性和定量分析,确定保留时间为4min和8-13min的峰分别对应副产物甘油一碳酸酯GC和主产物脂肪酸甲酯FAMEs；保留时间为14-17min的峰为反应中间体脂肪酸甘油碳酸酯FAGC的峰；保留时间为21-27min的峰分别对应原料甘油三酯和甘油二酯(甘油二酯的保留时间为21.5-22.3min,甘油三酯的保留时间为23.5-26.5min)。并且,脂肪酸甲酯在棕榈酸甲酯59-354μg/ml、油酸亚油酸甲酯50-304μg/ml和硬脂酸甲酯5.6-33.71μg/ml的浓度范围内都具有良好的线性关系,甘油二酯和甘油三酯在5-50μg/ml的浓度范围内具有良好的线性关系。
其次,在对无甘油副产的生物柴油产物进行定性和定量分析的基础上,本文对非均相固体碱氢氧化钾和固定化脂肪酶所催化的酯交换反应过程进行了研究。发现,在以氢氧化钾为催化剂时,当酯油摩尔比为9：1,KOH催化剂添加量为原料油质量16.2%,反应温度为85℃,反应时间为9h时,脂肪酸甲酯的收率可以达到90.4%；在以固定化脂肪酶为催化剂时,在反应温度为60℃,酯油摩尔比为10：1,固定化脂肪酶催化剂用量为原料油质量的20%,反应时间为24h时,脂肪酸甲酯的收率可以达到95.4%。并且,氢氧化钾催化剂催化的酯交换反应过程分反应增长阶段和平衡阶段两个过程进行。其中,甘油三酯和甘油二酯的酯交换增长阶段均为2级反应；甘油三酯的酯交换反应活化能为83.3KJ/mol,频率因子为4.48×10'L/(mol·min)；甘油二酯的酯交换反应活化能为89.8KJ/mol,频率因子为7.98×1010L/(mol·min)。均高于油脂与甲醇进行酯交换反应的活化能,表明本论文所设计的酯交换反应较难进行,需要在较长的反应时间下进行,与实验条件的探索吻合。
再次,在发动机未作任何调整的情况下,将脂肪酸甲酯、副产物甘油一碳酸酯以及过量的酯交换试剂与0号柴油进行混合,进行了其对发动机的动力和经济性能以及排放性能的影响研究,探究了酯交换试剂DMC、副产物甘油一碳酸酯GC的存在对生物柴油与0号柴油混合燃料燃烧性能的影响,发现：脂肪酸甲酯、副产甘油一碳酸酯以及过量的酯交换试剂可以与0号柴油直接混合而用于发动机,此时发动机的动力性略有降低,燃料油耗略有升高；一氧化碳、碳氢化合物、醛类、二氧化硫的排放量略有增加,氮氧化物、烟度、二氧化碳排放量略有降低；小颗粒排放物数量增加,大颗粒排放物数量降低,排放物颗粒分布向小粒径方向移动；总颗粒质量和聚集态颗粒质量的排放降低,核模态颗粒的质量排放量增加。副产物甘油一碳酸酯和过量的酯交换试剂DMC的添加对混合燃料的燃烧性能的影响非常小。
最后,为了使得玉米得到更充分的利用,变废为宝,本文还对制取乙醇后的玉米胚芽废渣进行了脂肪和油脂的分离,并以提取出来的油脂为原料进行了无甘油副产的生物柴油的制备探索,发现,体系当中水分的有效移除是保证生物酶催化剂足够催化活性的关键,当硅胶作为吸水剂添加在体系当中时,在反应温度为60℃、酯油摩尔比为15：1、催化剂用量为油脂质量20%、硅胶用量为油脂质量40%,反应时间12h的情况下,脂肪酸甲酯的收率可以达到83.6%；在高吸水树脂存在的情况下,当其用量仅为硅胶用量1/4时,其就可以达到与硅胶存在条件下相同的脂肪酸甲酯收率,并且催化剂和吸水树脂均可重复使用,重复五次收率没有明显下降；此外,通过单纯将反应时间从12h延长至24h,即可使得收率达到90%以上。并且,此无甘油副产的生物柴油制备工艺的脂肪酸甲酯收率明显高于相同原料的甲醇基生物柴油制备工艺的脂肪酸甲酯收率。说明,以从玉米胚芽残渣当中提取的玉米废油为原料进行无甘油副产的生物柴油的制备是一条理想的生物柴油制备路线,其对于玉米的充分利用具有非常重要的意义。
Surplus production of petroleum will disappear with the sustain development of economy in the whole world. It is estimated that the backorder of petroleum will reach about1million barrels per day till2015. So it is very imperative to develop the new fuels which can replace petroleum. Biodiesel is concered as a satisfactory fuel that can replace petroleum. Because it is prepared from renewable materials and it is used safety due to the higher flashing point. Under the conditions, more and more scientists and technical persons are engaging in the development of biodiesel. The biodiesel will be named as methol-biodisel when methanol was used as esterification reagent. Glycerol was produced as by product in the preparation of methol-biodiesel, and more and more glycerols were produced with the increase development of methol-biodiesel. More and more glycerols were discared or sincered directly due to the lower price of glycerol, which will induce the new economical and environmental problems. It is becoming more and more important that the downsteam products of glycrol, which have high addational value, are prepared in the production of biodiesel. In this thesis, dimethyl carbonate was used as a new esterfication reagent, and the glycerol carbonate monoesters (FAGC), who can be used directly as additive of fules, are produced in the preparation of fatty acid methyl esters (FAMEs). In the reaction, all raw materials can be transfered as fuels, so the usage rate of raw material is very high. Furthermore, there is no glycerol in products, and the problems concerning the glycerol were resolved efficiently. The main research results were as followed:
First, the GC-MS, verication of model compound, external standard and internal standard methods are all used in the quality and quantity analyses of reactant products in the preparation of biodiesel without glycerol as by product. The retention times of glycerol carbonate (GC), fatty acid methyl esters (FAMEs), acid glycerol carbonate monoesters (FAGC), triglycerides (TG) and diglycerides (DG) are4min,8-13min,14-17min,21.5-22.3min and23.5-26.5min, respectively. Furthermore, the GC peak area of methyl palmitate shows linear change in the concertration range of59-354μg/ml. The concertraction linear ranges of methyl oleate and methyl linoleate are50-304μg/ml and5.6-33.7μg/ml, respectively. And the GC peak areas of triglycerides (TG) and diglycerides (DG) changes linearly when the concertration is in the range of5-50μg/ml.
Second, the reaction processes catalysed by KOH and lipase-catalyzed were studied in detail. The results showed that:For the KOH-catalyzed esterification, the yield of FAMEs can reach90.4%, when the molar ratio of DMC to oil is9, the loading amount of catalyst is16.2%(based on the weight of oil), the reaction temperature is85℃and the reaction time is9h. When immobilized-lipases Novozym435was as catalyst, the yield of FAMEs can reach95.4%, with the molar ratio of DMC to oil of10:1, the loading of catalyst of20%, the reaction temperature of85℃and the reaction time of24h. Further, the kinetics of KOH-catalyzed transesterification of corn oil and DMC was researched. The reaction process can be divided into two stages including reaction growth stage and reaction equilibration stage. The transesterification kinetics of TG and DG are all agreeed with2-order model. The reaction energy of TG and DG are83.3KJ/mol and89.8KJ/mol, respectively, which are all bigger than that of esterification used for the preparation of methol-biodiesel. Frequency factor of TG and DG are4.48×1010L/(mol·min) and7.98×1010L/(mol·min).
Then, the study on engine performance, economic property and emission characteristics were conducted in a diesel engine fuelled with blends of corn oil methyl esters and diesel oil (the mixed ratio was10:90, named B10). And the effects of the additional DMC and glycerol carbonate (GC) on the engine fuel consumption were further investigated. The results showed the blend fuel can be directly used in diesel engine.The power performance and fuel consumption display a little increase when FAMEs, DMC and GC wered added in the fuel. CO, HC, aldehydes and SO2emissions were slightly increased. And the small particle emission increased, and the big particle emission reduced. The article distrabution had a tendency to small particles. Total particles quality emussions and gatherated particles quality emussions were reduced, and nuclear state particles quality emussions were increased. In a word, the GC by-product and the ester esterification reagent DMC have a little effect on the combustion performances of the biodiesel fuel.
Finally, the oil and fat in germ residue of corn were separated using solvent extraction method, and the oil was then used to prepare the biodiesel without glycerol as by-product. It was found that there are more free fatty acids in the residue oil. And the free fatty acids can react with esterification regeant DMC easily to produce some water, which will inhibit the catalyst activity of immobilized-lipases Novozym435. So for the esterification of residue oil, the removal of water produce due to the esterification of fatty acid is very important. Under the conditions, blue silical gel and super absorbent polymer were added in the system to absorb the water, respectively. The yield of FAMEs can reach about83.6%, when the reaction temperature is60℃, molar ratio of DMC to oil is15:1, the amount of blue silical gel is40%(based on oil) and the reaction time is12h. Furthermore, if the super absorbent polymer replaced the blue silical gel, only one quarterly amout of super absorbent polymer was needed to obtain the yield of85.0%. And the yield will reach above90%if the reaction time is extended from12h to24h under no change of other experimental conditions. The yield of biodiesel without glycerol as by-product is much higher than that of methol-biodiesel prepared using solid acid as catalyst. In a word, for the comprehensive utilization of corn, the preparation of biodiesel without glycerol as by-product is a very promising direction.
引文
[1]潘宁.对世界石油供需基本面的解读.世界经济情况.2011,12：11-15
[2]Altin R, Cetinkaya S, Yiicesu HS. The potential of using vegetable oil fuels as fuel for diesel engines [J]. Energy Conversion and Management.2001,42:529-538
[3]Kralova I, Sjoblom J. Biofuels-renewable energy sources:a review [J]. Journal of Dispersion Science and Technology.2010,31:409-425
[4]Demirbas A. Biofuels securing the planet's future energy needs [J]. Energy Conversion and Management.2009,50:2239-2249
[5]Demirbas A. Progress and recent trends in biofuels [J]. Progress in Energy and Combustion Science.2007,33:1-18
[6]Pramanik T, Tripathi S. Biodiesel:clean fuel of the future [J]. Hydrocarbon Processing.2005,84:649
[7]王琦,梁冲冲,吕宇.中国能源发展趋势：石油危机与煤清洁技术[J].企业技术开发.2011,30(6)：6
[8]Li S, Wang Y, Dong S, Chen Y, Cao F, Chai F, Wang X. Biodiesel production from Eruca Sativa Gars vegetable oil and motor, emissions properties [J]. Renewable Energy. 2009,34:1871-1876
[9]Gerpen JV. Biodiesel processing and production [J]. Fuel Process Technology.2005, 86:1097-1107
[10]Shahid EM, Jamal Y. A review of biodiesel as vehicular fuel [J]. Renewable and Sustainable Energy Reviews.2008,12:2484-2494
[11]Vivek, Gupta AK. Biodiesel production from karanja oil [J]. Journal of scientific and Industrial Research.2004,63:39-47
[12]Demirbas A, Karslioglu S. Biodiesel production facilities from vegetable oils and animal fats [J]. Energy Sources Part A.2007,29:133-141
[13]Liu Y, Wang L. Biodiesel production from rapeseed deodorizer distillate in a packed column reactor [J]. Chemical Engineering and Processing:Process Intensification.2009, 48:1152-1156
[14]Phan AN, Phan TM. Biodiesel production from waste cooking oils [J]. Fuel.2008, 87:3490-3496
[15]汪多仁.生物柴油的开发与应用进展[J].增塑剂.2012,23(1)：12-22
[16]Korbitz W. Biodiesel production in Europe and North America, an encouraging prospect [J]. Renewable Energy.16:1078-1083
[17]Shimada Y, Watanabe Y, Sugihara A, Tominaga Y. Enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing [J]. Journal Molcular Catalysis B:Enzymatic.2002,17:133-142
[18]Kose O, Tuter M, Aksoy HA. Immobilized Candida antarctica lipase-catalyzed alcoholysis of cotton seed oil in a solvent-free medium [J]. Bioresource Technology.2002, 83:125-129
[19]Iso M, Chen B, Eguchi M, Kudo T, Shrestha S. Production of biodiesel fuel from triglycerides and alcohol using immobilized lipase [J]. Journal of Molecular Catalysis B: Enzymatic.2001,16:53-58
[20]宁守俭.生物柴油产业步入跨越发展——2011年回顾与2012年展望[J].中国生物柴油.2012,(1)：1-4
[21]王成,刘忠义,陈于陇,徐玉娟,吴继军.生物柴油制备技术研究进展[J].广东农业科学.2012,(1)：107-112
[22]闵恩泽院士.解码生物质燃料的DNA——访中国科学院、中国工程院院士闵恩泽[J].中国石化.2012,(1)：40-42
[23]Dunn RO, Bagby MO, Knothe G et al. The use of vegetable oils and their derivatives as alternative diesel fuels [J]. Fuels and Chemicals from Biomass.1997,666:172-208
[24]Schober S, Mittelbach M. Influence of diesel particulate filter Additives on biodiesel quality [J]. European Journal of Lipid Science and Technology.2005,107:268-271
[25]Johnson LA, Hammond EG, Lee I. Use of branched-chainesters to reduce the crystallization temperature of biodiesel [J]. Oil Chemistry.1995,72:1155-1160
[26]Wichmann H, Sahlabji T, Dieckmann H, et al. Chemical aspects of fractional crystallization of fatty acid methyl esters produced from waste fats [J]. Clean.2007,35: 323-328
[27]Rinke G, Schubert K, Kerschbaum S. Winterization of biodiesel by micro process engineering[J]. Fuel.2008,87:2590-2597
[28]郑王娜,周丽凤.玉米油的专家视角——访中国粮油学会油脂分会副秘书长、研究员周丽凤[J].全球食品工业.2011,(10)：32-33
[29]张春波,白雯,张丽静.生物柴油的发展现状[J].广州化工.2008,36(1)：4-6
[30]吕玮,陈顺玉.生物柴油制备方法的研究进展[J].福建师范大学福清分校学报.2008,(1)：7-11
[31]Fangrui M. Biodiesel production:a review [J]. Bioresource Technology.1999,70: 1-15
[32]Prasad R, Srivastava A. Triglyceride-based diesel fuels [J]. Renewable and Sustainable Energy Review.2000,4:111-133
[33]Stloukal R, Komers K, Machek J. Biodiesel fuel from rapaseed oil, methanol and KOH:analytical methods in research and production [J]. European Journal of Lipid Science and Technolog.2001,103:359-362
[34]Demirbas A. Progress and recent trends in biodiesel fuels [J]. Energy Conversion and Management.2009,501:14-34
[35]Balat M, Balat H. A critical review of bio-diesel as a vehicular fuel [J]. Energy Conversion and Management.2008,49(10):2727-2741
[36]王效华,颜培兵.生物柴油催化合成技术研究进展[J].农业工程学报.2007,23(1)：286-289
[37]Narasimharao K, Lee A, Wilson K. Catalysts in production of biodiesel:A review [J]. Journal of Biobased Materials and Bioenerg.2007,1:19-30
[38]Leung DYC, Wu X, Leung MKH. A review on biodiesel production using catalyzed transesterification [J]. Applied Energy.2010,87:1083-1095
[39]Siler-Marinkovic S, Tomasevic A. Transesterification of sunflower oil in situ [J]. Fuel.1998,77:1389-1391
[40]Jitputti J, Kitiyanan B, Rangsunvigit P, Bunyakiat K, Attanatho L, Jenvanitpanjakul P. Transesterification of crude palm kernel oil and crude coconut oil by different solid catalysts [J]. Chemical Engineering Journal.2006,116:61-66
[41]Lotero E, Liu Y, Lopez DE, Suwannakarn K, Bruce DA, Goodwin JG Synthesis of biodiesel via acid catalysis [J]. Industrial Engineering Chemistry Research.2005,44: 5353-5363
[42]Lopez DE, Goodwin JJG, Bruce DA, Lotero E. Transesterification of triacetin with methanol on solid acid and base catalysts [J]. Applied Catalysis:A General.2005,295: 97-105
[43]李为民,邬国英,林西平,薛长庚.采用固体碱法制备生物柴油的方法[P].CN 1664072,2005
[44]Ebiura T, Echizen T, Ishikawa A, Murai K, Baba T. Selective transesterification of triolein with methanol to methyl oleate and glycerol using alumina loaded with alkali metal salt as a solid-base catalyst [J]. Applied Catalysis:A General.2005,283:111-116
[45]Xie W, Peng H, Chen L. Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst [J]. Applied Catalysis A:General.2006,300: 67-74
[46]孟鑫,辛忠KF/CaO催化剂催化大豆油酯交换反应制备生物柴油[J].石油化工.2005,34：282-286
[47]Su EZ, Xu WQ, Gao KL, Zheng Y, Wei DZ. Lipase-catalyzed in situ reactive extraction of oilseeds with short-chained alkyl acetates for fatty acid esters production [J]. Journal of Molecular Catalysis B:Enzymatic.2007,48:28-32
[48]Ilham Z, Saka S. Dimethyl carbonate as potential reactant in non-catalytic biodiesel production by supercritical method [J]. Bioresource Technology.2009,100:1793-1796
[49]Huang Y, Yan YJ. Lipase-catalyzed biodiesel production with methyl acetate as acyl acceptor [J]. Zeitschrift fur naturforschung c-a journal of biosciences.2008,63:297-302
[50]Du W, Xu YY, Liu DH, Zeng J. Comparative study on lipase-catalyzed transformation of soybean oil for biodiesel production with different acyl acceptors [J]. Journal of Molecular Catalysis B:Enzymatic.2004,30:125-129
[51]Kim SJ, Jung SM, Park YC, Park K. Lipase catalyzed transesterification of soybean oil using ethyl acetate, an alternative acyl acceptor [J]. Biotechnology and Bioprocess Engineering.2007,12:441-445
[52]Saka S, Isayama Y. A new process for catalyst-free production of biodiesel using supercritical methyl acetate [J]. Fuel.2009,88:1307-1313
[53]Modi MK, Reddy JRC, Rao BVSK, Prasad RBN. Lipase-mediated conversion of vegetable oils into biodiesel using ethyl acetate as acyl acceptor [J]. Bioresource Technology.2007,98:1260-1264
[54]Su EZ, You PY, Wei DZ. In situ lipase-catalyzed reactive extraction of oilseeds with short-chained dialkyl carbonates for biodiesel production [J]. Bioresource Technology. 2009,100:5813-5817
[55]Rusch G, Klaas M, Warwel S. Reactive extraction of oilseeds with dialkyl carbonates [J]. European Journal of Lipid Science and Technology.2001,103:810-814
[56]Pioch D, Lozano P, Graille J. First lipase-catalyzed synthesis of fatty carbonate esters [J]. Biotechnology Letter.1991,13:633-635
[57]Fabbri D, Bevoni V, Notari M, Rivetti F. Properties of a potential biofuel obtained from soybean oil by transmethylation with dimethyl carbonate [J]. Fuel.2007,86: 690-697
[58]Ilham Z, Saka S. Dimethyl carbonate as potential reactant in non-catalytic biodiesel production by supercritical method [J]. Bioresource Technology.2009,100:1793-1796
[59]Freedman B, Butterfield RO, Pryde EH. Transesterification kinetics of soybean oil [J]. Journal of the American Oil Chemists'Society.1986,63:1375-1380
[60]Encinar JM, Gonzalez JF, Sabio E, Ramiro MJ. Preparation and properties of biodiesel from cynara cardunculusl oil [J]. Industrial Engineering Chemistry Research. 1999,38:2927-2931
[61]Vicente G, Martinez M, Aracil J. Integrated biodiesel production:a comparison of different homogeneous catalysts system [J].s. Bioresource Technology,2004,92:297-305
[62]Fukuda H, Kondo A, Noda H. Biodiesel fuel production by transesterification of oils [J]. Journal of bioscience and bioengineering.2001,92:405-416
[63]Warabi Y, Kusdiana D, Saka S. Reactivity of triglycerides and fatty acids of rapeseed oil in supercritical alcohols [J]. Bioresource Technology.2004,91:283-287
[64]Fjerbaek L, Christensen KV, Norddahl B. A review of the current state of biodiesel production using enzymatic transesterification [J]. Biotechnology and Bioengineering. 2009,102:1298-1315
[65]Shah S, Sharma S, Gupta MN. Biodiesel preparation by lipase-catalyzed transesterification of Jatropha oil [J]. Energy and Fuel.2004,18:154-159
[66]Watanabe Y, Shimada Y, Sugihara A, Tominaga Y. Enzymatic conversion of waste edible oil to biodiesel fuel in a fixed-bed bioreactor [J]. Journal of the American Oil Chemists Society.2001,78:703-707
[67]Chang HM, Liao HF, Lee CC, Shieh CJ. Optimized synthesis of lipase-catalyzed biodiesel by Novozym 435 [J]. Journal of Chemical Technology and Biotechnology.2005, 80:307-312
[68]Xu YY, Du W, Liu DH, Zeng J. A novel enzymatic route for biodiesel production from renewable oils in a solvent-free medium [J]. Biotechnology Letter.2003,25: 1239-1241
[69]Du W, Xu YY, Liu DH, Zeng J. Comparative study on lipase-catalyzed transformation of soybean oil for biodiesel production with different acyl acceptors [J]. Journal of Molecular Catalysis B:Enzymatic.2004,30:125-129
[70]Darnoko D, Cheryan M. Kinetics of palm oil transesterification in a batch reactor [J]. Journal of the American Oil Chemists'Society.2000,77:1263-1267
[71]张静雅,邬国英,林西平,魏斌.助溶剂法制备生物柴油的动力学研究[J].中国油脂.2008,33：46-48
[72]邬国英,林西平.棉籽油间歇式酯交换反应动力学的研究[J].高校化学工程学报.2003,17：314-318
[73]袁旦,韩德奇,王尽涛等.生物柴油的现状与发展前景[J].石油化工技术经济.2002,(4)：32-36
[74]Chase CL. Final report on the cat/ken worth 200,000-mile over-the-road project with hysee biodiesel. ASAE Annual International Meeting.2000
[75]Lowe G A, Peterson CL, Thompson JC et al. Producing hysee biodiesel from used French fry oil and ethanol fur an over-the road truck. ASAE Annual International Meeting.1998
[76]颜文胜,林玉珍,申立中等.小型内燃机与摩托车[J].柴油机燃用100%生物柴油的性能与排放.2010,39(2)：75-77
[77]Abdul M, Jan H, Van G. The effect of biodiesel oxidation on engine performance and emissions [J]. Biomass and Bioenergy.2001,20:317-325
[78]Mustafa C, Jan H, Van G. The performance and emissions of a diesel engine fueledwith biodiesel from yellow grease and soybean oil. ASAE Annual International Meeting.2001
[79]Dorado MP, Ballesteros E, Arnal JM, Gomez J, Lopez FJ et al. Exhaust emissions from a diesel engine fueled with transesterifiedwaste olive oil. Fuel.2003,82:1311-1315
[80]黄忠水,纪威.柴油机燃用生物柴油的研究.内燃机高新技术发展研讨会-安徽.2003,305-307
[81]宋建桐,张春化,杨烜.燃用生物柴油增压柴油机的性能和排放[J].交通运输工程学报.2008,8(2)：18-22
[82]耿莉敏,陈昊,祁东辉等.单缸直喷式柴油机燃用生物柴油性能研究[J].西北农林科技大学学报：自然科学版.2008,36(7)：219-223
[83]陈波水,吴江,方建华等.生物柴油对柴油机油氧化、清净和抗磨性能的影响[J].石油学报：石油加工.2009,25(B09)：62-66
[84]许广举,王忠,黄慧龙等.发动机燃用生物柴油的可靠性[J].农业工程学报.2009,11：169-172
[85]孙树祯,张丽萍,孟鑫,辛忠.无甘油副产生物柴油的组分分析及燃烧性能[J].石油化工,2012,41：335-341
[86]Rokicki G, Rakoczy P, Parzuchowski P, Sobiecki M. Hyperbranched aliphatic polyethers obtained from environmentally benign monomer:glycerol carbonate [J]. Green Chemistry.2005,7:529-539
[87]ASTM D6584-10 standard test method for determination of total monoglyceride, yotal diglyceride, total triglyceride, and free and total glycerin in B-100 biodiesel methyl esters by gas chromatography.
[88]SN/T 1945-2007,食品中反式脂肪酸含量的测定方法,毛细管气相色谱法[S]
[89]Liping Z, Boyang S, Zhong X et al. Kinetics of transesterification of palm oil and dimethyl carbonate for biodiesel production at the catalysis of heterogeneous base catalyst [J]. Bioresource Technology.2010,101(21):8144-8150
[90]张杰等.多变量统计过程控制[M].2008年化学工业出版社出版
[91]Davis OL工业试验的设计与分析(第二版)[M].1985年化学工业出版社出版
[92]刘成江,吴宏,郭安民,吴洪斌,王俊钢,武冬梅.响应曲面法研究干酪乳杆菌产酸性能的试验[J].乳品加工.2011(11)：60-63
[93]张丽平.基于非均相催化制备生物柴油的过程研究.华东理工大学博士学位论文[D].上海：华东理工大学,2010
[94]Noureddini H, Zhu D. Kinetics of transesterification of soybean oil[J]. Journal of the American Oil Chemists' Society.1997,74(11):1457-1463
[95]Hsu AF. Immobilized lipase—catalysed production of alkyl esters of restaurant greaseas biodiesel[J]. Biotechnology and Applied Biochemistry.2002,36(3):181-186
[96]Oznur K. Immobilized candida antarctica lipase—catalyzed alcoholysis of cotton seed oil in a solvent—free medium[J]. Bioresource Technology.2002,83(6):125-129
[97]Xu YY. A novel enzymatic route for biodiesel production from renewable oils in a solvent-free medium[J]. Biotechnology Letters.2003,25(5):1239-1241.
[98]Shieh. Optimization of lipase-catalyzed biodiesel by response surface methodology [J]. Bioresource Technology.2003,88(9):103-106
[99]Su E-Z, Zhang M-J, Zhang J-G, et al. Lipase-catalyzed irreversible transesterification of vegetable oils for fatty acid methyl esters production with dimethyl carbonate as the acyl acceptor[J]. Biochemical Engineering Journal.2007,36(2):167-173
[100]田雪,周斌,李鑫,陈芳,高剑峰.固定化脂肪酶催化棉籽油与碳酸二甲酯反应制备生物柴油.石油化工.2009,38(6)：677-681
[101]蒋德明.内燃机燃烧与排放学[M].西安：西安交通大学出版社.2001
[102]刘撰君.内燃机排放与控制[M].北京：机械工业出版社.2005
[103]严云祥.生物柴油发动机工作性能研究[D].扬州大学硕士学位论文.2010
[104]王鑫.喷式柴油机燃用黄连木籽生物柴油的燃烧及排放特性研究[D].河南科技大学硕士学位论文.2010
[105]江清阳.生物柴油的试制及其在柴油机中排放特性的研究[D].江苏大学硕士学位论文.2003
[106]Bona S, Mosca G, Valtleralj T. Energy and CO2 balance in biodiesel fuel production. Renewable Energy,16:1053-1056
[107]Bernard F, Royden O, Butterfield et al. Transesterification kinetics of soybean oil [J]. Journal of the American Oil Chemists'Society.1986,63(10):1375-1379
[108]Mark W, Majewski et al. Diphenylammonium salt catalysts for microwave assisted triglyceride transesterification of corn and soybean oil for biodiesel production [J]. Tetrahedron Letters.2009,50:5175-5177
[109]Prafulla D, Patil, Shuguang D. Optimization of biodiesel production from edible and non-edible vegetable oils [J]. Fuel.2009,88:1302-1306
[110]Yanlan B, Dongyou D, Donghai W. Low-melting-point biodiesel derived from corn oil via urea complexation [J]. Bioresource Technology.2010,101:1220-1226
[111]Aimin S, Zhenyi D, Xiaochen M et al. Production and evaluation of biodiesel and bioethanol from high oil corn using three processing routes [J]. Bioresource Technology. 2012, Available online 22 October
[112]Douglas SQ, Ana LdL. Thermal expansion coefficient and algebraic models to correct values of specific mass as a function of temperature for corn biodiesel [J]. Fuel. 2012, Available online 10 November
[113]Yong W, Shun M, Mourning Z et al. Improving the cold flow properties of biodiesel from waste cooking oil by surfactants and detergent fractionation [J]. Fuel. 2011,90:1036-1040
[114]Jinyong Y, Yunjun Y, Sanxiong L et al. Preparation of cross-linked lipase-coated micro-crystals for biodiesel production from waste cooking oil [J]. Bioresource Technology.2011,102:4755-4758
[115]Srilatha K, Prabhavathi DBLA et al. Biodiesel production from used cooking oil by two-step heterogeneous catalyzed process [J]. Bioresource Technology.2012,119: 306-311
[116]程国强.全球粮食供需格局发生深刻变化.《人民日报》2011年9月19日
[117]倪红艳,鲁靖.发展生物乙醇对我国玉米需求结构的影响分析[J].价格月刊,2011,8：12-15
[118]胡震.玉米油制备生物柴油的研究[J].辽宁化工.2010,39(3)：240-242.
[119]Nan-Wei L et al. Highly efficient transformation of waste oil to biodiesel by immobilized lipase from Penicillium expansum [J]. Process Biochemistry,2009(44): 685-688
[120]Li W, Wei D, Dehua L, Lilin L, Ningmei D. Lipase-catalyzed biodiesel production from soybean oil deodorizer distillate with absorbent present in tert-butanol system [J]. Journal of Molecular Catalysis B:Enzymatic.2006,43:29-32
[121]Liping Z et al.Synthesis and component confirmation of biodiesel from palm oil and dimethyl carbonate catalyzed by immobilized-lipase in solvent-free system [J]. Fuel, 2010(89):3960-3965
[122]Mahabubur MD et al. Novozym 435 for production of biodiesel from unrefined palm oil:Comparison of methanolysis methods [J]. Journal of Molecular Catalysis B: Enzymatic.2009,60:106-112
[123]Hajar M, Shokrollahzadehb S. Solvent-free methanolysis of canola oil in a packed-bed reactor with use of Novozym 435 plus loofa [J]. Enzyme and Microbial Technology.2009,45:188-194
[124]Maceiras R, Vega M, Costa C et al. Effect of methanol content on enzymatic production of biodiesel from waste frying oil [J]. Fuel.2009,88:2130-2134
[125]Dahai Y, Tian L, Hao W, Song W et al. Ultrasonic irradiation with vibration for biodiesel production from soybean oil by Novozym 435 [J]. Process Biochemistry.2010, 45:519-525
[126]Laura A, Gustavo C, Hermann J et al. Lipase-catalyzed process in an anhydrous medium with enzyme reutilization to produce biodiesel with low acid value [J]. Journal of Bioscience and Bioengineering.2011,112(6):583-589
[127]龚吉安.李倩,赵彦生.高吸水性树脂的发展及研究现状[J].应用化工.2012. 41(5)：895-897
[2]Altin R, Cetinkaya S, Yiicesu HS. The potential of using vegetable oil fuels as fuel for diesel engines [J]. Energy Conversion and Management.2001,42:529-538
[3]Kralova I, Sjoblom J. Biofuels-renewable energy sources:a review [J]. Journal of Dispersion Science and Technology.2010,31:409-425
[4]Demirbas A. Biofuels securing the planet's future energy needs [J]. Energy Conversion and Management.2009,50:2239-2249
[5]Demirbas A. Progress and recent trends in biofuels [J]. Progress in Energy and Combustion Science.2007,33:1-18
[6]Pramanik T, Tripathi S. Biodiesel:clean fuel of the future [J]. Hydrocarbon Processing.2005,84:649
[7]王琦,梁冲冲,吕宇.中国能源发展趋势：石油危机与煤清洁技术[J].企业技术开发.2011,30(6)：6
[8]Li S, Wang Y, Dong S, Chen Y, Cao F, Chai F, Wang X. Biodiesel production from Eruca Sativa Gars vegetable oil and motor, emissions properties [J]. Renewable Energy. 2009,34:1871-1876
[9]Gerpen JV. Biodiesel processing and production [J]. Fuel Process Technology.2005, 86:1097-1107
[10]Shahid EM, Jamal Y. A review of biodiesel as vehicular fuel [J]. Renewable and Sustainable Energy Reviews.2008,12:2484-2494
[11]Vivek, Gupta AK. Biodiesel production from karanja oil [J]. Journal of scientific and Industrial Research.2004,63:39-47
[12]Demirbas A, Karslioglu S. Biodiesel production facilities from vegetable oils and animal fats [J]. Energy Sources Part A.2007,29:133-141
[13]Liu Y, Wang L. Biodiesel production from rapeseed deodorizer distillate in a packed column reactor [J]. Chemical Engineering and Processing:Process Intensification.2009, 48:1152-1156
[14]Phan AN, Phan TM. Biodiesel production from waste cooking oils [J]. Fuel.2008, 87:3490-3496
[15]汪多仁.生物柴油的开发与应用进展[J].增塑剂.2012,23(1)：12-22
[16]Korbitz W. Biodiesel production in Europe and North America, an encouraging prospect [J]. Renewable Energy.16:1078-1083
[17]Shimada Y, Watanabe Y, Sugihara A, Tominaga Y. Enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing [J]. Journal Molcular Catalysis B:Enzymatic.2002,17:133-142
[18]Kose O, Tuter M, Aksoy HA. Immobilized Candida antarctica lipase-catalyzed alcoholysis of cotton seed oil in a solvent-free medium [J]. Bioresource Technology.2002, 83:125-129
[19]Iso M, Chen B, Eguchi M, Kudo T, Shrestha S. Production of biodiesel fuel from triglycerides and alcohol using immobilized lipase [J]. Journal of Molecular Catalysis B: Enzymatic.2001,16:53-58
[20]宁守俭.生物柴油产业步入跨越发展——2011年回顾与2012年展望[J].中国生物柴油.2012,(1)：1-4
[21]王成,刘忠义,陈于陇,徐玉娟,吴继军.生物柴油制备技术研究进展[J].广东农业科学.2012,(1)：107-112
[22]闵恩泽院士.解码生物质燃料的DNA——访中国科学院、中国工程院院士闵恩泽[J].中国石化.2012,(1)：40-42
[23]Dunn RO, Bagby MO, Knothe G et al. The use of vegetable oils and their derivatives as alternative diesel fuels [J]. Fuels and Chemicals from Biomass.1997,666:172-208
[24]Schober S, Mittelbach M. Influence of diesel particulate filter Additives on biodiesel quality [J]. European Journal of Lipid Science and Technology.2005,107:268-271
[25]Johnson LA, Hammond EG, Lee I. Use of branched-chainesters to reduce the crystallization temperature of biodiesel [J]. Oil Chemistry.1995,72:1155-1160
[26]Wichmann H, Sahlabji T, Dieckmann H, et al. Chemical aspects of fractional crystallization of fatty acid methyl esters produced from waste fats [J]. Clean.2007,35: 323-328
[27]Rinke G, Schubert K, Kerschbaum S. Winterization of biodiesel by micro process engineering[J]. Fuel.2008,87:2590-2597
[28]郑王娜,周丽凤.玉米油的专家视角——访中国粮油学会油脂分会副秘书长、研究员周丽凤[J].全球食品工业.2011,(10)：32-33
[29]张春波,白雯,张丽静.生物柴油的发展现状[J].广州化工.2008,36(1)：4-6
[30]吕玮,陈顺玉.生物柴油制备方法的研究进展[J].福建师范大学福清分校学报.2008,(1)：7-11
[31]Fangrui M. Biodiesel production:a review [J]. Bioresource Technology.1999,70: 1-15
[32]Prasad R, Srivastava A. Triglyceride-based diesel fuels [J]. Renewable and Sustainable Energy Review.2000,4:111-133
[33]Stloukal R, Komers K, Machek J. Biodiesel fuel from rapaseed oil, methanol and KOH:analytical methods in research and production [J]. European Journal of Lipid Science and Technolog.2001,103:359-362
[34]Demirbas A. Progress and recent trends in biodiesel fuels [J]. Energy Conversion and Management.2009,501:14-34
[35]Balat M, Balat H. A critical review of bio-diesel as a vehicular fuel [J]. Energy Conversion and Management.2008,49(10):2727-2741
[36]王效华,颜培兵.生物柴油催化合成技术研究进展[J].农业工程学报.2007,23(1)：286-289
[37]Narasimharao K, Lee A, Wilson K. Catalysts in production of biodiesel:A review [J]. Journal of Biobased Materials and Bioenerg.2007,1:19-30
[38]Leung DYC, Wu X, Leung MKH. A review on biodiesel production using catalyzed transesterification [J]. Applied Energy.2010,87:1083-1095
[39]Siler-Marinkovic S, Tomasevic A. Transesterification of sunflower oil in situ [J]. Fuel.1998,77:1389-1391
[40]Jitputti J, Kitiyanan B, Rangsunvigit P, Bunyakiat K, Attanatho L, Jenvanitpanjakul P. Transesterification of crude palm kernel oil and crude coconut oil by different solid catalysts [J]. Chemical Engineering Journal.2006,116:61-66
[41]Lotero E, Liu Y, Lopez DE, Suwannakarn K, Bruce DA, Goodwin JG Synthesis of biodiesel via acid catalysis [J]. Industrial Engineering Chemistry Research.2005,44: 5353-5363
[42]Lopez DE, Goodwin JJG, Bruce DA, Lotero E. Transesterification of triacetin with methanol on solid acid and base catalysts [J]. Applied Catalysis:A General.2005,295: 97-105
[43]李为民,邬国英,林西平,薛长庚.采用固体碱法制备生物柴油的方法[P].CN 1664072,2005
[44]Ebiura T, Echizen T, Ishikawa A, Murai K, Baba T. Selective transesterification of triolein with methanol to methyl oleate and glycerol using alumina loaded with alkali metal salt as a solid-base catalyst [J]. Applied Catalysis:A General.2005,283:111-116
[45]Xie W, Peng H, Chen L. Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst [J]. Applied Catalysis A:General.2006,300: 67-74
[46]孟鑫,辛忠KF/CaO催化剂催化大豆油酯交换反应制备生物柴油[J].石油化工.2005,34：282-286
[47]Su EZ, Xu WQ, Gao KL, Zheng Y, Wei DZ. Lipase-catalyzed in situ reactive extraction of oilseeds with short-chained alkyl acetates for fatty acid esters production [J]. Journal of Molecular Catalysis B:Enzymatic.2007,48:28-32
[48]Ilham Z, Saka S. Dimethyl carbonate as potential reactant in non-catalytic biodiesel production by supercritical method [J]. Bioresource Technology.2009,100:1793-1796
[49]Huang Y, Yan YJ. Lipase-catalyzed biodiesel production with methyl acetate as acyl acceptor [J]. Zeitschrift fur naturforschung c-a journal of biosciences.2008,63:297-302
[50]Du W, Xu YY, Liu DH, Zeng J. Comparative study on lipase-catalyzed transformation of soybean oil for biodiesel production with different acyl acceptors [J]. Journal of Molecular Catalysis B:Enzymatic.2004,30:125-129
[51]Kim SJ, Jung SM, Park YC, Park K. Lipase catalyzed transesterification of soybean oil using ethyl acetate, an alternative acyl acceptor [J]. Biotechnology and Bioprocess Engineering.2007,12:441-445
[52]Saka S, Isayama Y. A new process for catalyst-free production of biodiesel using supercritical methyl acetate [J]. Fuel.2009,88:1307-1313
[53]Modi MK, Reddy JRC, Rao BVSK, Prasad RBN. Lipase-mediated conversion of vegetable oils into biodiesel using ethyl acetate as acyl acceptor [J]. Bioresource Technology.2007,98:1260-1264
[54]Su EZ, You PY, Wei DZ. In situ lipase-catalyzed reactive extraction of oilseeds with short-chained dialkyl carbonates for biodiesel production [J]. Bioresource Technology. 2009,100:5813-5817
[55]Rusch G, Klaas M, Warwel S. Reactive extraction of oilseeds with dialkyl carbonates [J]. European Journal of Lipid Science and Technology.2001,103:810-814
[56]Pioch D, Lozano P, Graille J. First lipase-catalyzed synthesis of fatty carbonate esters [J]. Biotechnology Letter.1991,13:633-635
[57]Fabbri D, Bevoni V, Notari M, Rivetti F. Properties of a potential biofuel obtained from soybean oil by transmethylation with dimethyl carbonate [J]. Fuel.2007,86: 690-697
[58]Ilham Z, Saka S. Dimethyl carbonate as potential reactant in non-catalytic biodiesel production by supercritical method [J]. Bioresource Technology.2009,100:1793-1796
[59]Freedman B, Butterfield RO, Pryde EH. Transesterification kinetics of soybean oil [J]. Journal of the American Oil Chemists'Society.1986,63:1375-1380
[60]Encinar JM, Gonzalez JF, Sabio E, Ramiro MJ. Preparation and properties of biodiesel from cynara cardunculusl oil [J]. Industrial Engineering Chemistry Research. 1999,38:2927-2931
[61]Vicente G, Martinez M, Aracil J. Integrated biodiesel production:a comparison of different homogeneous catalysts system [J].s. Bioresource Technology,2004,92:297-305
[62]Fukuda H, Kondo A, Noda H. Biodiesel fuel production by transesterification of oils [J]. Journal of bioscience and bioengineering.2001,92:405-416
[63]Warabi Y, Kusdiana D, Saka S. Reactivity of triglycerides and fatty acids of rapeseed oil in supercritical alcohols [J]. Bioresource Technology.2004,91:283-287
[64]Fjerbaek L, Christensen KV, Norddahl B. A review of the current state of biodiesel production using enzymatic transesterification [J]. Biotechnology and Bioengineering. 2009,102:1298-1315
[65]Shah S, Sharma S, Gupta MN. Biodiesel preparation by lipase-catalyzed transesterification of Jatropha oil [J]. Energy and Fuel.2004,18:154-159
[66]Watanabe Y, Shimada Y, Sugihara A, Tominaga Y. Enzymatic conversion of waste edible oil to biodiesel fuel in a fixed-bed bioreactor [J]. Journal of the American Oil Chemists Society.2001,78:703-707
[67]Chang HM, Liao HF, Lee CC, Shieh CJ. Optimized synthesis of lipase-catalyzed biodiesel by Novozym 435 [J]. Journal of Chemical Technology and Biotechnology.2005, 80:307-312
[68]Xu YY, Du W, Liu DH, Zeng J. A novel enzymatic route for biodiesel production from renewable oils in a solvent-free medium [J]. Biotechnology Letter.2003,25: 1239-1241
[69]Du W, Xu YY, Liu DH, Zeng J. Comparative study on lipase-catalyzed transformation of soybean oil for biodiesel production with different acyl acceptors [J]. Journal of Molecular Catalysis B:Enzymatic.2004,30:125-129
[70]Darnoko D, Cheryan M. Kinetics of palm oil transesterification in a batch reactor [J]. Journal of the American Oil Chemists'Society.2000,77:1263-1267
[71]张静雅,邬国英,林西平,魏斌.助溶剂法制备生物柴油的动力学研究[J].中国油脂.2008,33：46-48
[72]邬国英,林西平.棉籽油间歇式酯交换反应动力学的研究[J].高校化学工程学报.2003,17：314-318
[73]袁旦,韩德奇,王尽涛等.生物柴油的现状与发展前景[J].石油化工技术经济.2002,(4)：32-36
[74]Chase CL. Final report on the cat/ken worth 200,000-mile over-the-road project with hysee biodiesel. ASAE Annual International Meeting.2000
[75]Lowe G A, Peterson CL, Thompson JC et al. Producing hysee biodiesel from used French fry oil and ethanol fur an over-the road truck. ASAE Annual International Meeting.1998
[76]颜文胜,林玉珍,申立中等.小型内燃机与摩托车[J].柴油机燃用100%生物柴油的性能与排放.2010,39(2)：75-77
[77]Abdul M, Jan H, Van G. The effect of biodiesel oxidation on engine performance and emissions [J]. Biomass and Bioenergy.2001,20:317-325
[78]Mustafa C, Jan H, Van G. The performance and emissions of a diesel engine fueledwith biodiesel from yellow grease and soybean oil. ASAE Annual International Meeting.2001
[79]Dorado MP, Ballesteros E, Arnal JM, Gomez J, Lopez FJ et al. Exhaust emissions from a diesel engine fueled with transesterifiedwaste olive oil. Fuel.2003,82:1311-1315
[80]黄忠水,纪威.柴油机燃用生物柴油的研究.内燃机高新技术发展研讨会-安徽.2003,305-307
[81]宋建桐,张春化,杨烜.燃用生物柴油增压柴油机的性能和排放[J].交通运输工程学报.2008,8(2)：18-22
[82]耿莉敏,陈昊,祁东辉等.单缸直喷式柴油机燃用生物柴油性能研究[J].西北农林科技大学学报：自然科学版.2008,36(7)：219-223
[83]陈波水,吴江,方建华等.生物柴油对柴油机油氧化、清净和抗磨性能的影响[J].石油学报：石油加工.2009,25(B09)：62-66
[84]许广举,王忠,黄慧龙等.发动机燃用生物柴油的可靠性[J].农业工程学报.2009,11：169-172
[85]孙树祯,张丽萍,孟鑫,辛忠.无甘油副产生物柴油的组分分析及燃烧性能[J].石油化工,2012,41：335-341
[86]Rokicki G, Rakoczy P, Parzuchowski P, Sobiecki M. Hyperbranched aliphatic polyethers obtained from environmentally benign monomer:glycerol carbonate [J]. Green Chemistry.2005,7:529-539
[87]ASTM D6584-10 standard test method for determination of total monoglyceride, yotal diglyceride, total triglyceride, and free and total glycerin in B-100 biodiesel methyl esters by gas chromatography.
[88]SN/T 1945-2007,食品中反式脂肪酸含量的测定方法,毛细管气相色谱法[S]
[89]Liping Z, Boyang S, Zhong X et al. Kinetics of transesterification of palm oil and dimethyl carbonate for biodiesel production at the catalysis of heterogeneous base catalyst [J]. Bioresource Technology.2010,101(21):8144-8150
[90]张杰等.多变量统计过程控制[M].2008年化学工业出版社出版
[91]Davis OL工业试验的设计与分析(第二版)[M].1985年化学工业出版社出版
[92]刘成江,吴宏,郭安民,吴洪斌,王俊钢,武冬梅.响应曲面法研究干酪乳杆菌产酸性能的试验[J].乳品加工.2011(11)：60-63
[93]张丽平.基于非均相催化制备生物柴油的过程研究.华东理工大学博士学位论文[D].上海：华东理工大学,2010
[94]Noureddini H, Zhu D. Kinetics of transesterification of soybean oil[J]. Journal of the American Oil Chemists' Society.1997,74(11):1457-1463
[95]Hsu AF. Immobilized lipase—catalysed production of alkyl esters of restaurant greaseas biodiesel[J]. Biotechnology and Applied Biochemistry.2002,36(3):181-186
[96]Oznur K. Immobilized candida antarctica lipase—catalyzed alcoholysis of cotton seed oil in a solvent—free medium[J]. Bioresource Technology.2002,83(6):125-129
[97]Xu YY. A novel enzymatic route for biodiesel production from renewable oils in a solvent-free medium[J]. Biotechnology Letters.2003,25(5):1239-1241.
[98]Shieh. Optimization of lipase-catalyzed biodiesel by response surface methodology [J]. Bioresource Technology.2003,88(9):103-106
[99]Su E-Z, Zhang M-J, Zhang J-G, et al. Lipase-catalyzed irreversible transesterification of vegetable oils for fatty acid methyl esters production with dimethyl carbonate as the acyl acceptor[J]. Biochemical Engineering Journal.2007,36(2):167-173
[100]田雪,周斌,李鑫,陈芳,高剑峰.固定化脂肪酶催化棉籽油与碳酸二甲酯反应制备生物柴油.石油化工.2009,38(6)：677-681
[101]蒋德明.内燃机燃烧与排放学[M].西安：西安交通大学出版社.2001
[102]刘撰君.内燃机排放与控制[M].北京：机械工业出版社.2005
[103]严云祥.生物柴油发动机工作性能研究[D].扬州大学硕士学位论文.2010
[104]王鑫.喷式柴油机燃用黄连木籽生物柴油的燃烧及排放特性研究[D].河南科技大学硕士学位论文.2010
[105]江清阳.生物柴油的试制及其在柴油机中排放特性的研究[D].江苏大学硕士学位论文.2003
[106]Bona S, Mosca G, Valtleralj T. Energy and CO2 balance in biodiesel fuel production. Renewable Energy,16:1053-1056
[107]Bernard F, Royden O, Butterfield et al. Transesterification kinetics of soybean oil [J]. Journal of the American Oil Chemists'Society.1986,63(10):1375-1379
[108]Mark W, Majewski et al. Diphenylammonium salt catalysts for microwave assisted triglyceride transesterification of corn and soybean oil for biodiesel production [J]. Tetrahedron Letters.2009,50:5175-5177
[109]Prafulla D, Patil, Shuguang D. Optimization of biodiesel production from edible and non-edible vegetable oils [J]. Fuel.2009,88:1302-1306
[110]Yanlan B, Dongyou D, Donghai W. Low-melting-point biodiesel derived from corn oil via urea complexation [J]. Bioresource Technology.2010,101:1220-1226
[111]Aimin S, Zhenyi D, Xiaochen M et al. Production and evaluation of biodiesel and bioethanol from high oil corn using three processing routes [J]. Bioresource Technology. 2012, Available online 22 October
[112]Douglas SQ, Ana LdL. Thermal expansion coefficient and algebraic models to correct values of specific mass as a function of temperature for corn biodiesel [J]. Fuel. 2012, Available online 10 November
[113]Yong W, Shun M, Mourning Z et al. Improving the cold flow properties of biodiesel from waste cooking oil by surfactants and detergent fractionation [J]. Fuel. 2011,90:1036-1040
[114]Jinyong Y, Yunjun Y, Sanxiong L et al. Preparation of cross-linked lipase-coated micro-crystals for biodiesel production from waste cooking oil [J]. Bioresource Technology.2011,102:4755-4758
[115]Srilatha K, Prabhavathi DBLA et al. Biodiesel production from used cooking oil by two-step heterogeneous catalyzed process [J]. Bioresource Technology.2012,119: 306-311
[116]程国强.全球粮食供需格局发生深刻变化.《人民日报》2011年9月19日
[117]倪红艳,鲁靖.发展生物乙醇对我国玉米需求结构的影响分析[J].价格月刊,2011,8：12-15
[118]胡震.玉米油制备生物柴油的研究[J].辽宁化工.2010,39(3)：240-242.
[119]Nan-Wei L et al. Highly efficient transformation of waste oil to biodiesel by immobilized lipase from Penicillium expansum [J]. Process Biochemistry,2009(44): 685-688
[120]Li W, Wei D, Dehua L, Lilin L, Ningmei D. Lipase-catalyzed biodiesel production from soybean oil deodorizer distillate with absorbent present in tert-butanol system [J]. Journal of Molecular Catalysis B:Enzymatic.2006,43:29-32
[121]Liping Z et al.Synthesis and component confirmation of biodiesel from palm oil and dimethyl carbonate catalyzed by immobilized-lipase in solvent-free system [J]. Fuel, 2010(89):3960-3965
[122]Mahabubur MD et al. Novozym 435 for production of biodiesel from unrefined palm oil:Comparison of methanolysis methods [J]. Journal of Molecular Catalysis B: Enzymatic.2009,60:106-112
[123]Hajar M, Shokrollahzadehb S. Solvent-free methanolysis of canola oil in a packed-bed reactor with use of Novozym 435 plus loofa [J]. Enzyme and Microbial Technology.2009,45:188-194
[124]Maceiras R, Vega M, Costa C et al. Effect of methanol content on enzymatic production of biodiesel from waste frying oil [J]. Fuel.2009,88:2130-2134
[125]Dahai Y, Tian L, Hao W, Song W et al. Ultrasonic irradiation with vibration for biodiesel production from soybean oil by Novozym 435 [J]. Process Biochemistry.2010, 45:519-525
[126]Laura A, Gustavo C, Hermann J et al. Lipase-catalyzed process in an anhydrous medium with enzyme reutilization to produce biodiesel with low acid value [J]. Journal of Bioscience and Bioengineering.2011,112(6):583-589
[127]龚吉安.李倩,赵彦生.高吸水性树脂的发展及研究现状[J].应用化工.2012. 41(5)：895-897