固定化脂肪酶催化麻疯树油与碳酸二甲酯制备生物柴油的研究

以介孔硅材料(MPS)为载体将脂肪酶固定化,以碳酸二甲酯为酰基受体,对固定化酶催化碳酸二甲酯进行了反应路径(原料油)、反应条件(反应温度、碳酸二甲酯的用量、加水量)的优化,在最佳的条件下对实验过程中所用的固定化酶进行重复使用性的考察。实验结果表明,不同种油与碳酸二甲酯反应在固定化酶的催化下制备生物柴油的产率以麻疯树油为最高,最佳反应条件是碳酸二甲酯的浓度为16m L/g、不加水,在50℃下反应24h,生物柴油得率达81.6%。     

固定化扩展青霉脂肪酶的制备及其在玉米油转酯反应中的应用

采用吸附法对来源于扩展青霉Penicillium expansum的脂肪酶进行了固定化.从20种不同来源的树脂中筛选出固定化效率高且价格低廉的D4020树脂作为载体,系统研究了固定化条件对固定化效率及固定化酶转酯活力的影响.结果表明,最适加酶量、缓冲液pH和吸附时间分别为0.7 g/g、9.4和4 h.冻干时添加0.5%的半乳糖有助于提高固定化酶的转酯活力.在上述优化条件下,固定化酶的转酯活力为404.0 U/g,而所用的游离酶不能催化该转酯反应.利用该固定化酶催化玉米油转酯反应生产生物柴油时,叔戊醇为适宜的反应介质,其最适添加量为0.5 ml/g;适宜的酶量、加水量和反应温度分别为60.6 U/g、油重的1.2%和35℃.按醇/油摩尔比为1的比例分别在反应0、2和6 h时加入甲醇,在优化反应条件下,反应24 h后甲酯产率达85.0%;固定化脂肪酶具有较好的操作稳定性,反应10批次时,相对酶活力为62.8%.     

基于氯化镁饱和溶液中固定化脂肪酶Lipozyme TL IM催化光皮树油脂合成生物柴油

基于氯化镁饱和溶液反应体系中,对采用固定化脂肪酶Lipozyme TL IM催化光皮树油脂转化为生物柴油的工艺进行了研究。考察了固定化脂肪酶Lipozyme TL IM催化光皮树油转酯化的工艺中甲醇的用量、固定化脂肪酶的添加量、摇床的转速和反应时间对生物柴油产率的影响。实验结果表明,采用氯化镁饱和溶液反应体系,在醇油摩尔比为3∶1,固定化酶Lipozyme TL IM用量为光皮树油质量的20%,摇床转速为150 r/min,反应8 h时,生物柴油产率最高,达到86.5%。与传统的三步甲醇醇解或者有机溶剂反应体系比较,采用的氯化镁饱和溶液体系的酶稳定性更好,反应效率更高,有效地解决了酶在甲醇中失活的问题,生产成本低,可成为生产生物柴油的新工艺。     

无溶剂系统中固定化脂肪酶催化废油脂转酯生产生物柴油

 探讨了无溶剂系统中固定化脂肪酶Novozym 435催化餐饮业废油脂转酯生产生物柴油. 反应副产物甘油可吸附在固定化酶载体表面,采用丙酮洗涤除去甘油可提高酶的稳定性. 适宜的醇/油摩尔比、酶用量、反应温度和摇床转速分别为1, 6.6 U/g, 35～40 ℃和150 r/min,不宜加水到反应体系中. 采用分步加入甲醇的方式可减轻甲醇对酶的毒害作用. 分别在反应进行到6和14 h时用丙酮除去酶表面的甘油,然后按醇/油摩尔比为1的比例加入甲醇继续反应,反应30 h后产物中的脂肪酸甲酯含量为88.6%. 连续反应300 h后,酶活性基本没有下降.     

华根霉全细胞脂肪酶催化合成生物柴油

比较了5种不同商品化脂肪酶和自制的华根霉CCTCCM201021全细胞脂肪酶(RCL)催化油脂合成生物柴油的转化效果,结果表明,RCL能有效应用于无溶剂体系催化合成生物柴油.在无溶剂体系中对该酶催化生物柴油的转酯化反应工艺进行优化,考察了甲醇用量、体系含水量、酶的添加量和反应温度对生物柴油收率的影响,使生物柴油最终收率大于86.0%.在有机溶剂体系中选择不同有机溶剂作为助溶剂进行转酯化反应,发现logP值在4.0～4.5的有机溶剂具有较好的转化效果.其中以正庚烷为助溶剂的转酯化反应具有最高的生物柴油收率86.7%.在无溶剂体系中RCL催化转化油酸和模拟高酸价油脂合成脂肪酸甲酯的研究表明,该酶具有很好的催化合成生物柴油的潜力.     

玉米秸秆催化液化制备生物油实验研究

以玉米秸秆为原料,添加分子筛催化剂在体积为500 mL的高温高压反应釜中进行催化液化制备生物油实验研究。选取反应温度、催化剂含量和反应时间三个主要因素为变量,探究其对玉米秸秆催化液化产物分布的影响。利用气相色谱-质谱联用仪(GC-MS)和傅里叶红外光谱仪(FT-IR)对玉米秸秆生物油的成分和官能团结构进行分析。结果表明,玉米秸秆的最佳催化液化条件为,反应温度为340 ℃,玉米秸秆15 g,FeHZSM-5催化剂含量为6.67%,反应时间为30 min。在此条件下,生物油产率为28.03%,催化液化整体转化率为81.73%。生物油的主要成分为酚类和长链酯类,生物油的热值达30.08 MJ/kg。     

双层固定化酵母催化还原4-氯-乙酰乙酸乙酯的研究

以海藻酸钠为内层载体,利用机械强度良好的聚乙烯醇(PVA)改性海藻酸钠混合物作为外层载体,双层固定化高活性酵母,得到固载的生物催化剂,用于由磷酸缓冲溶液和环己烷组成的双相体系,对4-氯-乙酰乙酸乙酯(COBE,ethyl 4-cloro-3-oxobutyrate)进行不对称催化加氢合成(S)-4-氯-3-羟基丁酸乙酯[(S)-CHBE],ethyl[(S)-4-chloro-3-hydro butanoate].在最适条件下,双层固定化酵母的不对称催化还原反应优于游离细胞和单层固定化细胞.在底物COBE的最佳浓度和进料速率分别为170mmol/L,125mL/h的连续操作条件下,最高(S)-CHBE转化率为94.2%,最高对映体过量值为98%.与游离细胞催化COBE相比,反应转化率提高3%,最佳底物浓度比游离细胞增加1倍;与单层固定化细胞催化还原相比,对映体过量值提高8%.连续性实验表明,双层固定化酵母细胞在连续使用5d,其转化率和对映选择性没有明显下降.     

琼脂固定化过氧化氢酶的催化活性

采用琼脂包埋法对过氧化氢酶进行固定化,考察了固定化过氧化氢酶催化过氧化氢降解的活性,确定了最佳催化反应条件.结果表明,经琼脂包埋法固定化后,过氧化氢酶仍保留较高的催化活性,其催化过氧化氢分解反应的最佳条件为温度35℃、pH 9.0.与此同时,固定化过氧化氢酶具有更强的温度适应能力和更宽的pH作用范围,并具有一定的重复使用性能.     

有机相中固定化脂肪酶催化合成植物甾醇酯

酶法合成植物甾醇酯具有反应条件温和、产物纯度和产量高等优点,但非水相酶催化的活性和稳定性普遍较低.本文以大孔树脂固定化脂肪酶为催化剂,并在催化过程中添加乳糖的类似物,构建了有机相高效合成植物甾醇酯的工艺过程.以酯化率为考察指标,对脂肪酶和反应溶剂进行筛选,对酯化条件进行优化,同时考察了糖的种类及添加量对酶催化性能的影响.结果表明,大孔树脂NKA吸附固定化的褶皱假丝酵母(Candida rugosa)脂肪酶(NKA-CRL)为最适宜的催化剂,以正己烷为反应介质,在酸醇摩尔比为2和添加酶蛋白质量7.5%的海藻糖的条件下,40°C反应10 h,酯化率达到96.6%.连续6次催化后,植物甾醇的酯化率仍维持在85.0%以上.     

磁性氧化石墨烯固定化氯过氧化物酶及其在奥酸性蓝45脱色中的应用

以氧化石墨烯和Fe_3O_4为原料制备磁性氧化石墨烯,采用吸附法将氯过氧化物酶固定在磁性氧化石墨烯上,考察了固定化体系缓冲溶液p H值、固定化时间及反应温度对固定效果的影响.以氯过氧化物酶催化氧化奥酸性蓝45染料脱色反应为模型反应,探讨了固定化氯过氧化物酶的操作稳定性.实验结果表明,p H=3.5,反应15 min、反应温度15℃为固定化氯过氧化物酶的最佳催化条件;采用共沉淀法制备载体,加入的NH_4Fe(SO_4)_2·12H_2O与氧化石墨烯(GO)质量比为10.7∶1时,得到的磁性氧化石墨烯(TMGO)的酶固载量大于二者质量比为5.35∶1时得到的磁性氧化石墨烯(FMGO),这可能与FMGO氧化石墨烯表面的Fe_3O_4含量不足有关;与游离酶相比,固定化氯过氧化物酶表现出更好的酸碱稳定性、H_2O_2稳定性、热稳定性和储存稳定性,在35~50℃,聚集或堆积的磁性氧化石墨烯(TMGO)片层打开,导致固定化酶活损失率明显小于游离酶.重复使用5次后,TMGO-氯过氧化物酶(CPO)的相对活性仍然保持在60%以上.     

废茶油的精制及其合成生物柴油的研究

本文以废茶油为原料,经过脱胶脱酸等预处理后与甲醇进行酯交换反应制取生物柴油.探讨了反应时间、反应温度、醇-油摩尔比和催化剂用量等因素对废茶油-甲醇酯交换反应的影响,并且采用正交实验优化合成条件,确定了反应的最佳操作条件以及影响反应的关键因素.研究结果表明,酯交换反应进行的最佳反应条件为:醇油摩尔比为25:1、催化剂用量为油重的1.0%、反应时间为30min、反应温度为60℃,茶油酸甲酯产率77.34%.     

Improved Enzyme Stability in Lipase-Catalyzed Synthesis of Fatty Acid Ethyl Ester from Soybean Oil

In this work, we describe the optimization of the ethanolysis of soybean oil by the enzyme Lipozyme™ TL-IM in the lipase-catalyzed biodiesel synthesis and the improvement of the enzyme stability over repeated batches. The studied process variables were: reaction temperature, substrate molar ratio, enzyme content, and volume of added water. Fractional factorial design was used to analyze the variables so as to select those with higher influence on the reaction and then perform a central composite design to find the optimal reaction conditions. The optimal conditions found were: temperature, 26 °C; substrate molar ratio, 7.5:1 (ethanol/oil); enzyme content, 25% in relation to oil weight; and added water, 4% in relation to oil weight. Under these conditions, the yield conversion obtained was 69% in 12 h. The enzyme stability assessment in repeated batches was carried out by washing the immobilized enzyme with different solvents (n-hexane, water, ethanol, and propanol) after each batch. In the treatment with n-hexane, around 80% of the enzyme activity still remains after seven cycles of synthesis, suggesting its economical application on biodiesel production.     

The use of impregnated perlite as a heterogeneous catalyst for biodiesel production from marula oil

In this study, biodiesel was produced from marula (Sclerocarya birrea) oil using impregnated perlite with potassium hydroxide (KOH) as a heterogeneous catalyst. The effect of experimental variables such as temperature (°C), reaction time (h), methanol to oil ratio (mass %), and catalyst to oil ratio (mass %) on the transesterification process were investigated. Using a central composite design (CCD), a mathematical model was developed to correlate the experimental variables with the percentage yield of biodiesel. The model showed that optimum conditions for biodiesel production were as follows: catalyst to oil ratio of 4.7 mass %, temperature of 70.4°C, methanol to oil ratio of 29.9 mass %, and reaction time of 3.6 h. The yield of 91.4 mass % of biodiesel was obtained. It was also possible to recycle and reuse the modified perlite up to three times without any significant change in its catalytic activity. The X-ray diffraction (XRD) and the Brunauer-Emmett-Teller (BET) surface area showed no modifications in the perlite structure. The results show that the important fuel properties of marula biodiesel meet the American Society for Testing and Materials (ASTM) biodiesel standard properties.     

A novel method for the synthesis of biodiesel from soybean oil and urea

The increasing demand for energy has encouraged the development of renewable resources and environmentally benign fuel such as biodiesel. In this study, ethyl fatty esters (EFEs), a major component of biodiesel fuel, were synthesized from soybean oil using sodium ethoxide as a catalyst. By-products were glycerol and difatty acyl urea (DFAU), which has biological characteristics, as antibiotics and antifungal medications. Both EFEs and DFAU have been characterized using Fourier transform infrared (FTIR) spectroscopy, and ¹H nuclear magnetic resonance (NMR) technique. The optimum conditions were studied as a function of reaction time, reactant molar ratios, catalyst percentage and the effect of organic solvents. The conversion ratio of soybean oil into pure EFEs was 76% after 10 h of reaction. The highest conversion yield of EFEs is obtained when the urea/soybean oil ratio was from 6.2 mmol to 1 mmol, while the highest production of DFAU is obtained when the ethoxide (as a catalyst)/soybean oil ratio is from 6.4 mmol to 1 mmol in hexane as the reaction medium.     

Montmorillonite-supported KF/CaO: a new solid base catalyst for biodiesel production

Biodiesel is an alternative to petroleum-derived diesel fuel; development of a high-efficiency base catalyst to be used in heterogeneous biodiesel production is still a challenge. In this paper, a novel solid base catalyst, KF- and CaO-supported montmorillonite (KCa/MMT) was successfully synthesized by a facile impregnation method, and used for producing biodiesel in transesterification of commercial soybean oil with methanol. The catalysts were characterized by X-ray diffraction, carbon dioxide temperature-programmed desorption and scanning electron microscopy. Effects of the parameters, such as the loading amount of KF, the amount of KCa/MMT, and the methanol to oil molar ratios, on the yield of biodiesel were investigated. A maximum biodiesel yield of 98 % was obtained under the optimal reaction conditions. The separated catalyst can be directly used in the next round of reactions and gave a satisfactory yield. Furthermore, analysis of the catalyst's tolerance to oil-containing water or free fatty acids, and a kinetic study were also carried out. Koros–Nowak tests were designed and conducted, and it was proven that the heat and mass transfer were not limited by the reaction rate.     

Coupling transesterifications for no-glycerol biodiesel production catalyzed by calcium oxide

In this study, a method consisting in coupling transesterifications for no-glycerol biodiesel production catalyzed by CaO was put forward. The transesterification between rapeseed oil and methanol was greatly improved by integrating glycerol and dimethyl carbonate (DMC) transesterification. From this result, it was found that the high fatty acid methyl ester (FAME) yield of 92.6% (with ultra-traces of glycerol as a by-product) was obtained at 65 °C under normal pressure, which is as high as the previously reported supercritical DMC method for no-glycerol biodiesel production at a reaction temperature of 350 °C and under pressures up to 17.8 MPa. Moreover, this new method has high water tolerance, and a yield of over 82% of FAME is still achieved in the presence of 0.2% of water. The optimized reaction conditions, such as the molar ratio of DMC to methanol, the catalyst dosage and the reaction time, were investigated to produce high-quality biodiesel. The fuel properties determined and discussed in light of EN 14214 (European standards) demonstrate that the biodiesel produced using this new method has good flow properties with a cloud filter plugging point of –10 °C and a pour point of –9.4 °C. Furthermore, the amount of free glycerol was found to be as low as 0.018% in the biodiesel obtained directly from this new method without any further processing. The results of this study indicate the feasibility of producing quality biodiesel fuels without glycerol by coupling transesterifications.     

Promotion of Ionic Liquid to Dimethyl Carbonate Synthesis from Methanol and Carbcn Dioxide

Promotion of ionic liquid, 1-ethyl-3-methylimidazolium bromide (emimBr), to the synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the presence of potassium carbonate and less amount of methyl iodide under mild conditions was investigated. The results showed that the high selectivity and raised yield of DMC was achieved due to the addition of emimBr in the reaction system. And effect of several reaction conditions such as temperature, pressure and amount of emimBr was discussed.     

酸化油固定床酶法合成生物柴油研究

酸化油是油脂工作中以皂脚、油脚经酸化处理得到的产品.它的主要成份是游离脂肪酸及中性油,是生产脂肪酸的重要原料,但生产过程中有水解废水的产生,若将其直接排放,既污染了环境又浪费了资源.     

柴油溶剂中脂肪酶催化高酸值废油脂酯化制备生物柴油

采用0＃柴油作为反应溶剂,利用固定化脂肪酶催化高酸值废油脂与甲醇酯化反应制备生物柴油。来源于Candida antarctica的固定化脂肪酶Novozym435在0＃柴油溶剂中具有极高的催化活性。以酸价高达157×10-3的废油脂为原料,废油脂质量比10%的Novozym435,甲醇与废油脂初始摩尔比2∶1,0＃柴油与废油脂质量比5∶1,摇床摇速170r/min,50℃下反应2h甲酯化率可达95.10%。0＃柴油作为反应溶剂有效地溶解了高酸值废油脂和甲醇,降低了反应体系的黏度和消除了甲醇对Novozym435的负面影响,提高了Novozym435的稳定性。同时,0＃柴油溶剂对未脱胶废油脂中残留的对脂肪酶有害的磷脂等胶类物质具有一定的稀释作用。该工艺省却了溶剂蒸馏的繁琐工序,直接得到脂肪酸甲酯和石化柴油的混合燃料。