酯化及转酯化法制备生物柴油过程中催化剂的研究进展

酯化及转酯化法是目前研究最多、最具优势的生物柴油制备方法,根据原料特性选择合适的催化刺是该法成功的重要保证.在简述生物柴油制备原理的基础上,重点综述了目前研究较多的各种酸催化剂、碱催化剂、脂肪酶催化剂、离子液体及无催化剂过程的优缺点,并对生物柴油催化剂的发展方向进行了展望.     

固定酶法生产生物柴油

探讨了利用本实验室自制的Candidasp.99-125脂肪酶转酯化合成生物柴油的过程。深入研究了甲醇对反应的抑制作用,酶用量、溶剂、底物浓度、反应温度、时间、水含量、pH值对生物柴油合成的影响,以及反应中固定化酶的寿命等问题。试验结果表明,采用最佳转酯化反应条件和分批加入甲醇的工艺条件下,最高单批转化率可以达到96%,固定化酶的使用半衰期可达到200h以上。     

生物柴油发展的技术切入探究

主要介绍生物柴油的生产工艺及新进展,重点分析生产生物柴油的化学转酯法和生物转酯法在实际工程中存在的制约因素及技术发展的切人探究.     

催化酯化技术与生物柴油产业化

介绍了生物柴油的生产工艺新进展以及国内近期对生物柴油研究所取得的一些新成果;重点叙述生产生物柴油的化学转酯法和生物转酯法的应用情况;特别针对近期国内对生物柴油工业化生产研究提出的一些新技术作了详细叙述。生物柴油以其优良的环境友好和可再生性已引起世界广泛关注。     

Biodiesel production using immobilized enzyme-current state and future perspective

近年来由于化石燃料的全球性短缺、原油价格的过度上涨和环境问题的加剧致使生物柴油的生产迅速增长。生物柴油生产的关键反应是化学或生物催化的转酯反应,酶催化的转酯反应与化学催化相比有相对节能、副产物甘油易回收及适合高含量游离脂肪酸油脂作为底物等明显优势。本文综述了固定化脂肪酶生产生物柴油的现状及最新进展,包括生物柴油的原料、脂肪酶的来源、酶的固定化技术、甲（乙）醇及甘油对脂肪酶的失活作用,展望了固定化脂肪酶生产生物柴油的未来前景。     

废弃生物油资源化利用国内外技术进展

介绍了废弃生物油制备肥皂和洗衣粉,脂肪酸,生物柴油,生物破乳剂,PHA的五个主要资源化用途,就制备生物柴油的方法主要介绍了微乳化法、热裂解法、酯交换法、超临界甲醇法,其中酯交换法是利用废弃油脂与甲醇等小分子醇在催化剂下进行转酯化反应制得生物柴油的一种方法,该方法由于工艺简单,效率较高,经济可行,是国内外工业生产生物柴油的主要方法。并在最后总结了目前我国废弃生物油资源化利用的现状和面临的问题。     

酶促泔水油生产生物柴油条件的研究

以泔水油资源转化为宗旨,利用中性脂肪酶催化泔水油与甲醇反应制备生物柴油。通过50g泔水油正交实验获得最佳转酯化反应条件：油醇摩尔比1∶3,油酶质量比1∶1,温度45℃,油溶剂质量比1∶0.6,反应时间10h后,生物柴油产率可达89.7%以上。对生物柴油密度、黏度、馏程、凝固点、硫含量、残碳、十六烷值等多项指标进行检测,油品的质量符合我国生物柴油的标准。在优化条件的基础上进行10L和50L反应釜实验,10h生物柴油的产率达到80%以上。     

Candida sp. 99-125脂肪酶及其在化学品合成中的应用

传统的酯化或转酯化产品的合成通常需要高温、强酸、强碱等相对苛刻的条件,脂肪酶由于其生物催化过程具有高效、高选择性、条件温和和环境友好等特点,在化学品的合成中越来越受到人们的关注。本课题组开发了一种可以用于酯类合成的新脂肪酶,并且实现了该酶的工业化生产。来源于Candida sp. 99-125的脂肪酶在非水相中对酯化和转酯化反应具有高效的催化活性和稳定性。本文介绍了该脂肪酶的发酵生产及其在中长链脂肪酸酯、二元酸酯、维生素A棕榈酸酯、手性化合物以及生物柴油等多种化学品的合成中的应用。     

叔戊醇体系酶促大豆油制备生物柴油

叔戊醇作为反应介质,固定化脂肪酶Novozym 435催化大豆油与甲醇的转酯反应制备生物柴油。叔戊醇消除了反应底物甲醇及反应副产物甘油对酶活的负面影响。定量分析表明,叔戊醇与油脂的体积比为1,甲醇与油脂的摩尔比为3,2%脂肪酶,反应体系含水量2%,40 ℃、180 r/min条件下反应15 h,生物柴油得率可达97%。在最适条件下反应进行160批次,酶仍保持了较高的活性和良好的稳定性。     

全细胞生物催化麻疯树油制备生物柴油的研究

利用石油醚直接浸提法抽提得到含油率达到55.84%的麻疯树籽油作为原料,采用米根霉(Rizopus oryzae)菌株和聚氨酯泡沫制备成固定化全细胞生物催化剂,通过对全细胞生物催化法制备生物柴油的主要工艺参数进行了优化,获得最佳工艺条件为:当甲酯化反应的醇油比为6:1,转酯化温度为35℃,转酯化体系中2%～20%质量分数的含水率,菌体量相当于油质量的4%,每12 h加入一次甲醇的条件下转酯化效果最好,甲酯得率达到82.29%.同时固定化全细胞生物催化剂的重复使用性达4次,具有较高的催化性能.     

Production of Biodiesel Using Liquid Lipase Formulations

Looking back at the literature for enzymatic biodiesel, it is evident that the research has been focused on using immobilized lipase to enable re‐use of the enzyme due to price constraints on lipases used for catalyzing the transesterification process. The use of liquid formulations of lipase for biodiesel has recently been implemented in the industry. Technology for using liquid formulated lipases for enzymatic biodiesel production is new and, since enzyme prices have been reduced, it is now possible to simplify the process considerably and apply it for very low‐quality oils. In this paper, the use of liquid lipase formulations for enzymatic biodiesel will be described along with a general proposal for an industrial‐scale enzymatic biodiesel process with >95 % yield.     

Free Lipase-Catalyzed Esterification of Oleic Acid for Fatty Acid Ethyl Ester Preparation with Response Surface Optimization

Free lipase-mediated alcoholysis for biodiesel production has drawn increasing attention in recent years due to its advantages of lower cost and faster reaction rate compared to immobilized lipase. Ethanol, derived from renewable biomass, has a great potential for biodiesel production. A previous study showed that free lipase NS81006 could effectively catalyze the ethanolysis of triglycerides for biodiesel preparation. Since most crude plant oils always contain an amount of free fatty acids, oleic acid was used as the model substrate for this study on lipase-mediated esterification for biodiesel production. The central composite design of the response surface methodology was adopted for process optimization. A biodiesel yield of over 90 % was achieved under optimal reaction conditions and the repeated use of the free lipase was easily realized through phase separation either by natural gravity force or centrifugation.     

游离脂肪酶NS81006催化含酸油脂制备生物柴油的应用研究

与固定化脂肪酶相比,游离脂肪酶具有反应速率快、成本较低的优势,成为制备生物柴油新的研究方向。前期研究结果表明,游离脂肪酶NS81006可以高效催化大豆油甲醇解制备生物柴油,进一步研究其对含酸油脂的催化,对于促进游离脂肪酶在生物柴油领域中的应用具有重要意义。本文系统研究了甲醇添加策略对游离脂肪酶NS81006催化油酸制备生物柴油的影响,进而考察了NS81006催化模拟酸化油以及实际含酸油脂制备生物柴油的转化情况。研究表明,在优化的甲醇添加策略下,游离脂肪酶NS81006可有效催化油酸、不同含酸量(0~100%,基于总质量)模拟酸化油以及实际含酸油脂进行生物柴油的制备;离心分离可有效实现NS81006的回复使用,连续回用5个批次,游离脂肪酶活性未出现明显下降。     

Study on Free Lipase-Catalyzed Ethanolysis for Biodiesel Preparation in an Oil/Water Biphasic System

Using free lipase as the catalyst for biodiesel production has drawn increasing attention in recent years due to its advantages of lower cost and faster reaction rate compared to immobilized lipase. Our previous study showed that free lipase NS81006 could effectively catalyze the methanolysis of renewable oil. Ethanol, derived from renewable biomass, has a greater potential for biodiesel production. In this paper, ethanol was explored for the first time as the acyl acceptor for free lipase-mediated biodiesel preparation. The effect of stirring rate, water content, molar ratio of ethanol to oil and ethanol adding strategy was investigated systematically during the process of free lipase NS81006-catalyzed ethanolysis. An ethyl ester yield of 90% was obtained under the optimized conditions. Further study showed that the free lipase could be repeatedly used by simple separation of the water phase from the oil phase and there was no obvious loss in lipase activity after five repeated uses.     

Kinetics of glycerol effect on biodiesel production for optimal feeding of methanol

The enzymatic production of biodiesel has been considered as an eco-friendly process. Candida antarctica lipase B (CalB) has been studied for its application for biodiesel production because of its high activity and stability. Enzyme deactivation caused by alcohol and effect of glycerol has to be resolved for the industrial application of this process. In traditional kinetic studies of biodiesel production, the effects of alcohol and oil were only considered in the kinetic equation, while the effect by glycerol was neglected. A new kinetic model incorporating glycerol effect is proposed in this paper. The proposed kinetic equation is applied by predicting the supplying rate of methanol in a fed-batch addition of methanol. The conversion rate was improved from 59.7% to 94.6% in a fed-batch by considering glycerol effect.     

固定化脂肪酶催化制备香叶树籽生物柴油研究

研究了Novozym 435和Lipozyme TLIM混合脂肪酶催化香叶树籽油制备生物柴油,2种酶按1:3质量比混合使用时,既可提高反应转化率,又可降低酶的使用成本.应用响应面优化法确定了固定化酶催化香叶树籽生物柴油的最优工艺参数,采用叔丁醇作为反应体系的溶剂,最优反应条件为反应温度38.5℃、甲醇与油摩尔比4:1、叔丁醇与油体积比1:1.5、酶用量为油质量的4%,此时反应转化率达90.09%.分析表明香叶树籽油的甘油三酯主要由短链脂肪酸甘油酯组成,生物柴油中原油的甘油三酯已完全转变成脂肪酸甲酯.     

Towards continuous sustainable processes for enzymatic synthesis of biodiesel in hydrophobic ionic liquids/supercritical carbon dioxide biphasic systems

The excellent suitability of immobilized Candida antarctica lipase B (Novozym 435) catalyst to carry out the synthesis of methyl oleate (biodiesel) by methanolysis of triolein in ILs based on imidazolium cations with large alkyl side chain (from C₁₂ to C₁₈) has been demonstrated at 60 and 85 °C. The phase behaviour of IL/triolein/methanol and IL/methyl oleate mixtures were studied at different concentrations and temperatures, the best results (up to 98.6% biodiesel yield after 6 h) being obtained for ILs able to provide monophasic reaction systems, i.e. 1-methyl-3-octadecylimidazolium bis(trifluoromethylsulfonyl)imide). A continuous enzymatic reactor, based on biocatalysts particles coated with hydrophobic ILs, for biodiesel synthesis in supercritical carbon dioxide was studied at 60 °C and 180 bar. The operational stability of the immobilized lipase was improved by its coating with ILs, i.e. 1-methyl-3-octadecylimidazolium hexafluorophosphate, leading to a two-phase systems with respect to the biodiesel product, which showed an excellent catalytic behaviour in continuous operation under supercritical conditions (up to 82% biodiesel yield after 12 cycles of 4 h).     

Effect of methanol content on enzymatic production of biodiesel from waste frying oil

The enzymatic production of biodiesel from waste frying oil with methanol has been studied using immobilized lipase Novozym 435 as catalyst. The effects of methanol to oil molar ratio, dosage of enzyme and reaction time were investigated. The optimum reaction conditions were methanol to oil molar ratio of 25:1, 10% of Novozym 435 based on oil weight and reaction period of 4 h at 50 °C obtaining a biodiesel yield of 89.1%. Moreover, the reusability of the lipase over repeated cycles was also investigated under standard conditions.     

Lipase‐catalyzed transesterification to remove saturated MAG from biodiesel

Saturated MAG (SMG) are known to be present in FAME intended to be used as biodiesel. These SMG can strongly affect the properties of biofuels such as the cloud point (CP), and they have been implicated in engine failure due to filter plugging. It is shown here that lipase G from Penicillium camemberti can be efficiently used for the transesterification of SMG to fatty acid methyl ester and glycerol even in the presence of the bulk biodiesel. Thus, in samples of commercial biodiesel to which glycerol monostearate (GMS) and glycerol monopalmitate (GMP) had been added, their levels were enzymatically reduced from 2% (w/v) to 0.22% (w/v) for GMP and 0.14% (w/v) for GMS as confirmed by GC‐MS analysis. Practical applications: SMG present in biodiesel can have a pronounced negative effect on the CP, and/or filterability and in‐field performance of the fuel. The lipase‐catalyzed transesterification shown in this paper enables a significant reduction in the amount of SMG, leading to superior biodiesel quality.