改性4A分子筛催化高酸值油脂制备生物柴油

以浓硫酸为改性剂,采用化学键合方法对固体分子筛4A表面进行磺化改性。以此为催化剂催化油酸-菜籽油模拟的高酸值油脂-甲醇酯交换反应制备生物柴油。结果表明,反应体系在65℃,醇/油摩尔比为16∶1条件下反应6h,生物柴油产率可达到88.39%,比相同条件下未改性的分子筛4A和浓硫酸催化高酸油脂制备的生物柴油产率明显提高。     

复合固定化脂肪酶催化餐厨废弃油脂合成生物柴油

探讨了复合固定化脂肪酶(Rhizopus oryzae lipase和Candida rugosa lipase)催化餐厨废弃油脂合成生物柴油的工艺条件。实验结果表明,单独使用1,3位专一性脂肪酶R.oryzae lipase催化餐厨废弃油脂,反应18h,生物柴油转化率达到70%;单独使用非专一性脂肪酶C.rugosa lipase,反应30h,生物柴油转化率可达20%。为了更有效提高生物柴油转化率,采用1,3位专一性脂肪酶R.oryzae lipase和非专一性脂肪酶C.rugosa lipase复合固定化脂肪酶催化合成生物柴油,反应21h,生物柴油转化率可达到96.5%。同时对该复合酶的稳定性进行了实验,在连续催化反应10个批次(300h)后,生物柴油转化率仍保持在80%以上。     

新型反应介质中脂肪酶催化多种油脂制备生物柴油

用叔丁醇作为反应介质,利用固定化脂肪酶催化油脂原料甲醇醇解反应制备生物柴油,消除了甲醇和甘油对酶的负面影响,酶的使用寿命显著延长. 用菜籽油作原料,叔丁醇和油脂的体积比为1:1,甲醇与油脂的摩尔比为4:1,3%的Lipozyme TLIM和1%的Novozym 435结合使用,35℃下130 r/min反应12 h,生物柴油得率可达95%. 该工艺在200 kg/d的规模下制得的生物柴油产品完全满足美国和德国生物柴油标准,脂肪酶重复使用200批次,酶活性基本没有下降. 且在叔丁醇介质体系中大豆油、桐籽油、棉籽油、乌桕油、泔水油、地沟油和酸化油都能被有效转化成生物柴油且脂肪酶保持很好的稳定性.     

氧化钙催化菜籽油酯交换制备生物柴油

以菜籽油和甲醇为原料,在固体碱催化剂的作用下,通过酯交换反应制得生物柴油(脂肪酸甲酯)。以氧化钙为催化剂,通过正交试验得到该反应的最佳工艺条件:温度60℃,催化剂用量为菜籽油质量的1%,醇油比为10∶1(物质的量比),反应时间3 h,甘油收率达80.8%。     

生物柴油的制备

通过正交试验得出了菜籽油在NaOH作用下与甲醇经转酯反应合成生物柴油的最适宜工艺条件:摩尔比6:1、反应温度40℃、反应时间1h、催化剂用量1%。考察了工业甲醇、搅拌速度等工艺条件对反应的影响,对脂肪酶催化反应进行了探索性研究。采用气相色谱(氢火焰)内标法分析产品中脂肪酸甲酯的含量,研究了生物柴油与O#柴油的调和油性质。结果表明,合成的生物柴油其各项性能指标基本达到国外同类产品的标准,与O#柴油调和后低温流动性得到明显改善。     

非水相脂肪酶催化大豆油脂合成生物柴油的研究

脂肪酶Lipozyme TL IM在非水相体系中能有效催化大豆油脂转化生成生物柴油.在优化条件下(醇油摩尔比41,反应温度40C,硅胶负载脂肪酶与油的质量比为60%),反应5h后产物脂肪酸甲酯得率可达92%.实验证明加入有机溶剂以及分批加入甲醇等均能有效提高本反应体系中脂肪酶的催化活性.     

棕榈油制备生物柴油研究

通过利用浓硫酸作催化剂对酸值较高的棕榈油进行预酯化,采用正交实验的方法来研究预酯化的最优工艺条件,预酯化反应温度为70℃,反应时间为1.0 h,催化剂H2SO4的用量为1.0%(油重),棕榈油的酸值降到2.4 mg KOH/g油。预酯化后的棕榈油与甲醇在氢氧化钾作为催化剂进行酯交换反应得到脂肪酸甲酯,采用正交实验的方法来研究酯交换反应的最优工艺条件,酯交换反应温度为60℃,反应时间为10 h,催化剂KOH的用量为1.0%(油重),酯交换反应的转化率为95.89%,生物柴油总得率为95.6%。以棕榈油为原料制备的生物柴油,其主要性能符合柴油标准,但倾点较高,需与柴油馏分调合或加降凝剂以达到柴油标准。     

生物酶法转化酵母油脂合成生物柴油

以一株高产油脂圆红冬孢酵母菌(Rhodosporidum toruloides Y4#)干菌粉为原料,利用酸热法提取了该酵母油脂,并对所得油脂进行了分析. 进一步利用该酵母油脂为原料分别研究了无溶剂体系中三步甲醇法及在叔丁醇介质体系中脂肪酶催化合成生物柴油,发现脂肪酶可以有效转化该酵母油脂制备生物柴油. 在优化反应条件下,生物柴油得率可达90%左右,略低于相同条件下利用精制大豆油合成生物柴油的得率.     

响应面法乌桕脂制备生物柴油研究

探讨了以乌桕脂为原料,叔丁醇体系利用脂肪酶催化制备生物柴油的工艺。通过响应面法优化,获得最佳工艺条件为:2.5 g乌桕脂中加入0.6 mL甲醇,0.75 mL叔丁醇和9%脂肪酶,50℃反应16 h,生物柴油得率为92.34%;脂肪酶回收利用10次,生物柴油得率仍能保持在85%以上。     

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。     

Effects of ultrasonification and mechanical stirring methods for the production of biodiesel from rapeseed oil

This study was conducted to compare the effects of ultrasonic energy and mechanical stirring methods in bio-diesel production from rapeseed oil under base catalysis conditions. With the transesterification of rapeseed oil, the molar ratio of methanol to vegetable oil was 6: 1, and the amount of catalysts added to the vegetable oil was 0.3, 0.5 and 1.0% (wt/wt). The main components of methyl esters from the transesterification of rapeseed oil were oleic acid (48.5%, C18:1) and linoleic acid (18.1%, C18:2). In addition, the optimum conditions to produce fatty acid methyl esters (96.6%) were 0.5% KOH after 25 min of ultrasonification at 40 °C as compared to mechanical stirring at 60 °C. The maximum conversion ratio was 75.6% with 1.0% NaOH after 40 min of ultrasonification at 40 °C. These results indicate that ultrasonic energy could be a valuable tool for transesterification of fatty acids from rapeseed oil in terms of the reaction time and temperature.     

固体碱法制备生物柴油及其性能

用共沉淀法制备了水滑石,焙烧后得到Mg-Al复合氧化物,以此为催化剂进行菜籽油的酯交换反应,正交实验表明该酯交换反应的小试最佳工艺条件为： 反应温度65 ℃、醇油摩尔比6∶1、反应时间为3 h,催化剂加入量为菜籽油质量的2%,脂肪酸甲酯（生物柴油）含量为95.7%.得到的生物柴油低温流动性能好,闪点高达170 ℃,氧化安定性好,主要性能指标符合0#柴油标准,可以和0#柴油以任何比例调和.     

Lipase biocatalysis in the production of esters

Lipase biocatalysis was investigated as a tool for the production of butyl oleate and rapeseed oil 2-ethyl-1-hexyl ester by esterification and transesterification, respectively. We screened 25 commercially available lipases and found that butyl oleate was produced at high yields from oleic acid and 1-butanol by lipases fromCandida rugosa, Chromobacterium viscosum, Rhizomucor miehei, and Pseudomonas fluorescens. The initial water content of the system, lipase quantity, and the molar ratio of 1-butanol to oleic acid were important factors in influencing the ester yield. In general, no ester was formed without the addition of water. The exception wasCh. viscosum lipase, which yielded 98% of ester in 12 h with 1-butanol excess without additional water. The addition of 3.2% water increased the initial rate of reaction. With an oleic acid excess and only 0.3% lipase,C. rugosa andR. miehei lipases yielded 94 and 100% esters with initial water contents of 3.2 and 14%, respectively. Lipase-catalyzed alcoholysis of low-erucic acid rapeseed oil and 2-ethyl-1-hexanol without additional organic solvent also was studied in stirred batch reactors. In this case,C. rugosa lipase was the best biocatalyst with an optimal 2-ethyl-1-hexanol to rapeseed oil molar ratio of 2.8, a minimum of 1.0% added water, and 37°C. An increase in temperature up to 55°C increased the rate of reaction but did not affect the final ester yield. The enzyme was inactivated at 60°C. Under optimal conditions, the ester yield increased from 88% in 7 h to nearly complete conversion in 1 h when the lipase content was increased from 0.3 to 14.6%. In a 2-kg small pilot scale, up to 90% conversion (97% of theoretical) was obtained in 8 h at 37°C with 3.4% lipase in the presence of Amberlite XAD-7 resin with 3% added water.     

Lipase-catalyzed transesterification of rapeseed oil and 2-ethyl-1-hexanol

Lipase-catalyzed transesterification (alcoholysis) of lowerucic acid rapeseed oil and 2-ethyl-1-hexanol without an additional organic solvent was studied in stirred batch reactors. Of a number of commercially available enzymes investigated, the best results were obtained with aCandida rugosa lipase. The optimal transesterification conditions were an oil/alcohol molar ratio of 1∶2.8, a minimum of 1.0% (w/w) added water, and with a temperature of 37–55°C. Under the optimal conditions, a nearly complete conversion was obtained in one hour with 14.6% (w/w) lipase, whereas 0.3% (w/w) lipase required 10 h for similar results. The enzyme was inactivated at 60°C.     

Enzymatic production of fatty acid alkyl esters with a lipase preparation from Candida sp. 99‐125

A lipase preparation developed from Candida sp. 99‐125 was used for fatty acid alkyl ester synthesis by both enzymatic esterification of fatty acids, and transesterification of oils and fats. The lipase preparation was chosen based on screening of lipases from commercial sources as well as those produced in the laboratory. The effects of enzyme dosage, solvent types, water absorbent additions, inhibition of short‐chain alcohols, alcohol and acid types, molar ratio of substrates, and reusability of the lipase preparation in esterification were studied. Degree of esterification between oleic acid and methanol under optimal conditions reached 92%. Purity of the methyl ester after washing with water and distillation was 98%. Half‐life of the lipase preparation was calculated to be approximately 340 h. For transesterification of rapeseed oil with the same lipase preparation, the amount of methanol and mode of methanol addition to the reaction were also conducted. Transesterification of the oil with stepwise methanol addition reached 83% after 36 h reaction time.     

Analysis of parameters and interaction between parameters of the microwave-assisted continuous transesterification process of Jatropha oil using response surface methodology

A simple continuous process was designed for the transesterification of Jatropha curcas (J. curcas) oil to alkyl esters using microwave-assisted method. The product with purity above 96.5% of alkyl ester is called the biodiesel fuel. Using response surface methodology, a series of experiments with three reaction factors at three levels were carried out to investigate the transesterification reaction in a microwave and conversion of alkyl ester from J. curcas oil with NaOH as the catalyst. The results showed that the ratio of methanol to oil, amount of catalyst and flow rate have significant effects on the transesterification and conversion of alkyl ester. Based on the response surface methodology using the selected operating conditions, the optimal ratio of methanol to oil, amount of catalyst and flow rate of transesterification process were 10.74, 1.26 wt% and 1.62 mL/min, respectively. The largest predicted and experimental conversions of alkyl esters (biodiesel) under the optimal conditions are 99.63% and 99.36%, respectively. Our findings confirmed the successful development of a two-step process for the transesterification reaction of Jatropha oil by microwave-assisted heating, which is effective and time-saving for alkyl ester production.     

Lipase‐catalyzed alcoholysis of vegetable oils

Fatty acid alkyl esters were produced from various vegetable oils by transesterification with different alcohols using immobilized lipases. Using n‐hexane as organic solvent, all immobilized lipases tested were found to be active during methanolysis. Highest conversion (97%) was observed with Thermomyces lanuginosa lipase after 24 h. In contrast, this lipase was almost inactive in a solvent‐free reaction medium using methanol or 2‐propanol as alcohol substrates. This could be overcome by a three‐step addition of methanol, which works efficiently for a range of vegetable oils (e.g. cottonseed, peanut, sunflower, palm olein, coconut and palm kernel) using immobilized lipases from Pseudomonas fluorescens (AK lipase) and Rhizomucor miehei (RM lipase). Repeated batch reactions showed that Rhizomucor miehei lipase was very stable over 120 h. AK and RM lipases also showed acceptable conversion levels for cottonseed oil with ethanol, 1‐propanol, 1‐butanol and isobutanol (50‐65% conversion after 24 h) in solvent‐free conditions. Methyl and isopropyl fatty acid esters obtained by enzymatic alcoholysis of natural vegetable oils can find application in biodiesel fuels and cosmetics industry, respectively.     

Biodiesel production using tetramethyl- and benzyltrimethyl ammonium hydroxides as strong base catalysts

In recent years, the acceptance of fatty acid methyl esters (biodiesel) as an alternative fuel has rapidly grown in EU. The most common method for biodiesel production is based on triglyceride transesterification to methyl esters with dissolved sodium hydroxide in methanol as catalyst. In this study, cottonseed oil and used frying oil were subjected to the transesterification reaction with tetramethyl ammonium hydroxide and benzyltrimethyl ammonium hydroxide as strong base catalysts. This work investigates the optimum conditions for biodiesel production using amine-based liquid catalysts. Biodiesel ester content was strongly related with the type of feedstock and the reaction variables, such as those of the catalyst concentration, methanol to oil molar ratio, and reaction time. The overall results suggested that the transesterification of cottonseed oil achieved high conversion rates with both catalysts, while the use of waste oil resulted in lower yields of methyl esters due to the possible formation of amides.     

Conversion of waste cooking oil to biodiesel using ferric sulfate and supercritical methanol processes

In this comparative study, conversion of waste cooking oil to methyl esters was carried out using the ferric sulfate and the supercritical methanol processes. A two-step transesterification process was used to remove the high free fatty acid contents in the waste cooking oil (WCO). This process resulted in a feedstock to biodiesel conversion yield of about 85-96% using a ferric sulfate catalyst. In the supercritical methanol transesterification method, the yield of biodiesel was about 50-65% in only 15 min of reaction time. The test results revealed that supercritical process method is probably a promising alternative method to the traditional two-step transesterification process using a ferric sulfate catalyst for waste cooking oil conversion. The important variables affecting the methyl ester yield during the transesterification reaction are the molar ratio of alcohol to oil, the catalyst amount and the reaction temperature. The analysis of oil properties, fuel properties and process parameter optimization for the waste cooking oil conversion are also presented.