生物柴油原料资源开发及深加工技术研究进展

生物柴油（脂肪酸甲酯）是一种绿色清洁的再生能源。我国生物柴油产业发展速度很快,但受原料价格高及产品多元化程度低等因素的影响,生物柴油价格高,产业缺乏竞争力。开发多样化的原料资源,进行产品深加工,对于生物柴油产业的发展具有重要的意义。本文综述了国内外生物柴油原料开发利用进展,介绍了国外生物柴油原料资源分布、资源特点及不同原料生物柴油的特点。简述了我国生物柴油原料资源现状及发展策略。介绍了生物柴油深加工技术研究进展,重点阐述了在制备第二代生物柴油、生物降解润滑油基础油、脂肪醇、烷醇酰胺、脂肪酸甲酯磺酸盐及绿色增塑剂等方面的研究进展及面临的问题,指出开发高效催化剂是发展生物柴油深加工技术的关键。     

我国生物柴油原料可获性及成本分析

分析了我国生物柴油原料的可获性及原料成本，提出了我国生物柴油原料供应的特点及建议。     

生物柴油研究进展

综述了生物柴油主要生产国欧盟和美国的生物柴油发展状况及中国发展现状.总结了世界各国生产生物柴油所用原料,提出了劣质植物油及其油脚,利用贫瘠土地种植油料植物,废食用油(地沟油)为原料的适合我国国情的原料方案.对生产生物柴油的各种方法发展状况和优缺点进行了对比和总结,重点讨论了酸碱催化剂和生物酶催化剂在酯交换过程中的应用,并指出了生物柴油合成研究的方向.     

我国生物柴油产业链发展前景

分析国内外石油基柴油和生物柴油市场后指出,发展生物柴油已势在必行.分析了生物柴油原料来源与生产成本,通过两个生物柴油项目投资效益分析,提出了投资建议.     

中国生物柴油大规模发展应首先解决的问题

随着原油价格高企,生物柴油产业应出现良好的发展前景,可为什么中国生物柴油生产企业开工率普遍较低?本文从原料来源及生物柴油制备技术发展趋势两方面分析,提出了我国生物柴油大规模发展应首先解决的两个重要问题-原料与技术.     

世界生物柴油产业发展现状及我国生物柴油发展建议

生物柴油具有安全、环保和可再生等优点。欧盟、美国和巴西等原料充足,出台多项扶持政策,在生物柴油发展方面走在世界前列。我国生物柴油产业由于原料供应问题,近年来发展缓慢。我国生物柴油产业发展应以地沟油为主要原料,建立稳定廉价的原料来源;加强宏观调控和政府监管,确保有计划稳步实施;加强微藻制生物柴油技术攻关,解决原料瓶颈。     

我国生物柴油产业链发展前景

分析国内外石油基柴油和生物柴油市场后指出,发展生物柴油已势在必行。分析了生物柴油原料来源与生产成本,通过两个生物柴油项目投资效益分析,提出了投资建议。     

生物柴油市场分析

生物柴油是一种可再生燃料资源,目前在世界各国正掀起开发利用生物柴油的热潮,本文对生物柴油的原料、成本、竞争力和投资风险进行深入分析,并指出了我国生物柴油在能源作物的种植、原料的收集、废弃油脂管理方面存在的问题。     

地沟油制备生物柴油的研究进展

生物柴油是一种原料广泛的可再生性燃料资源,目前世界各国正掀起开发利用生物柴油资源的热潮,与矿物柴油相比,它具有低含硫和低排放污染,可再生,优良的生物可降解性等特点,有广阔的发展前景,而原料问题是制约生物柴油产业发展的瓶颈。地沟油来源广泛,廉价易得,是制备生物柴油的良好原料。利用地沟油制备生物柴油不但可以缓解能源危机、环境污染等社会问题,还提供了废弃食用油脂的合理化利用方式、防止废弃食用油脂再次返回餐桌。文章综述了地沟油的来源及特点、生物柴油的生产技术和应用现状以及我国生物柴油行业存在的问题,并提出了相应的合理化建议。     

生物柴油原料与反应装置的研究进展

作为一种清洁、可再生的替代能源,生物柴油近年来备受关注。酯交换反应广泛应用于生物柴油制备工艺。为了降低生产成本、提高产品质量,生物柴油研究的关键在于选取低廉的制备原料和优化的反应装置。综述了生物柴油的原料,包括第一代食用植物油、第二代非食用植物油和动物油脂以及第三代微藻油,在此基础上,总结了生物柴油的间歇与连续反应装置,并对生物柴油发展前景进行了展望。     

废旧油脂的精制及酯交换制备生物柴油的研究

采用除杂、脱水、萃取、脱色等操作对废油脂如废煎炸油、地沟油、橡胶籽油进行了精制;对大豆油和精制处理前后的上述废油脂的各种物理化学性质进行了测定和评价;采用共沉淀法制备了Mg/Al类水滑石,450℃焙烧得到复合氧化物并以其催化各种油脂和甲醇合成生物柴油;分别用1H NMR法和仲裁法分析对比酯交换反应的产率。结果表明,大豆油制备生物柴油的产率高达96.9%,而精制后的地沟油、煎炸油和橡胶籽油制备生物柴油的收率分别达38.6%、40.2%和82.0%,可有效降低生物柴油生产成本。尤其是橡胶籽油,有望成为大豆油的替代原料用于生物柴油生产工业。     

Non-Edible Plant Oils as New Sources for Biodiesel Production

Due to the concern on the availability of recoverable fossil fuel reserves and the environmental problems caused by the use those fossil fuels, considerable attention has been given to biodiesel production as an alternative to petrodiesel. However, as the biodiesel is produced from vegetable oils and animal fats, there are concerns that biodiesel feedstock may compete with food supply in the long-term. Hence, the recent focus is to find oil bearing plants that produce non-edible oils as the feedstock for biodiesel production. In this paper, two plant species, soapnut (Sapindus mukorossi) and jatropha (jatropha curcas, L.) are discussed as newer sources of oil for biodiesel production. Experimental analysis showed that both oils have great potential to be used as feedstock for biodiesel production. Fatty acid methyl ester (FAME) from cold pressed soapnut seed oil was envisaged as biodiesel source for the first time. Soapnut oil was found to have average of 9.1% free FA, 84.43% triglycerides, 4.88% sterol and 1.59% others. Jatropha oil contains approximately 14% free FA, approximately 5% higher than soapnut oil. Soapnut oil biodiesel contains approximately 85% unsaturated FA while jatropha oil biodiesel was found to have approximately 80% unsaturated FA. Oleic acid was found to be the dominant FA in both soapnut and jatropha biodiesel. Over 97% conversion to FAME was achieved for both soapnut and jatropha oil.     

An enzymatic/acid-catalyzed hybrid process for biodiesel production from soybean oil

The present study is aimed at developing an enzymatic/acid-catalyzed hybrid process for biodiesel production using soybean oil as feedstock. In the enzymatic hydrolysis, 88% of the oil taken initially was hydrolyzed by binary immobilized lipase after 5 h under optimal conditions. The hydrolysate was further used in acid-catalyzed esterification for biodiesel production and the effects of temperature, catalyst concentration, feedstock to methanol molar ratio, and reaction time on biodiesel conversion were investigated. By using a feedstock to methanol molar ratio of 1:15 and a sulfuric acid concentration of 2.5%, a biodiesel conversion of 99% was obtained after 12 h of reaction at 50 °C. The biodiesel produced by this process met the American Society for Testing and Materials (ASTM) standard. This hybrid process may open a way for biodiesel production using unrefined and used oil as feedstock.     

生物柴油联产化工产品中试工艺研究

以菜籽油或酸化油为原料,进行了菜籽油及酸化油合成生物柴油工艺中试;得出了较理想的合成工艺条件;利用气相色谱及化学分析法,对生物柴油的燃烧特性进行了分析。通过材料成本核算,探讨了油脂合成生物柴油制备路线的经济可行性。结果表明,采用生物柴油与化工产品综合生产线,主要技术指标达到甚至超过德国生物柴油标准DINV51606,所得生物柴油十六烷值达60,硫含量为0.005%,具有广阔的应用前景。     

菜籽油制备生物柴油的研究现状和发展趋势

综述了国内外以菜籽油制备生物柴油的研究现状和发展趋势,通过对各种制备方法的系统比较和国内外发展现状的考察,提出了用常压、连续反应-分离一体化的生产技术,以纳米固体酸、碱催化法制备生物柴油的研发方向,指出了以菜籽油为原料制备生物柴油的发展优势。     

生物柴油全生命周期资源和能源消耗分析

针对以菜籽油、麻疯树油和地沟油为原料制取生物柴油过程,应用生命周期评价方法,对原料种植、收集运输、原料预处理、生物柴油生产、产品配送等子过程的土地资源占用、水资源和能源消耗进行了计算,并对能量消耗进行了参数敏感性分析. 结果表明,3种原料生产1 t生物柴油占用土地资源分别为13132, 3333和5 m2,水资源消耗分别为9063.55, 12306.62和1.97 m3,化石能源消耗分别为0.9, 0.67和0.25 MJ. 由于水资源消耗和土地占用主要源于种植环节,能源消耗主要发生在种植和转化环节,在我国适合以地沟油和麻疯树油为原料生产生物柴油. 开发耐旱、高产、高含油率的油料植物品种和新型高效酯交换反应催化剂及优化反应工艺是降低生物柴油全生命周期资源占用和能源消耗的有效措施.     

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.     

Optimization of biodiesel production process in a continuous microchannel using response surface methodology

We assessed the biodiesel production process in a continuous microchannel through preparation of a heterogeneous catalyst (CaO/MgO) from demineralized water plant sediment. This mixed oxide catalyst was used for transesterification of rapeseed oil as feedstock by methanol to produce biodiesel fuel at various conditions. A microchannel, utilized as a novel reactor, was applied to convert rapeseed oil into biodiesel in multiple steps. The effects of the process variables, such as catalyst concentration, methanol to oil volume ratio, n-hexane to oil volume ratio, and reaction temperature on the purity of biodiesel, were carefully investigated. Box-Behnken experimental design was employed to obtain the maximum purity of biodiesel response surface methodology. The optimum condition for the production of biodiesel was the following: catalyst concentration of 7.875 wt%, methanol to oil volume ratio of 1.75: 3, n-hexane to oil volume ratio of 0.575: 1, and reaction temperature of 70 °C.     

Obtaining and characterization of biodiesel from jupati (Raphia taedigera Mart.) oil

The search for alternative triglyceride sources for biodiesel production is a widely discussed issue in Brazil because of the initiation of the Brazilian biofuel program. The viability of biodiesel production from the oil of Raphia taedigeraMart., commonly known as jupati, is studied in this work. This paper presents the obtention and characterization of biodiesel from jupati using an ethylic route with a methane sulfonic acid reaction catalyst. The alcohol:oil molar ratio was 9:1, and the catalyst concentration was 2% of the oil mass. The yield of the process was 92% by mass, and the oil conversion into jupati ethylic biodiesel was 99.6%. The physical and chemical parameters of jupati ethylic biodiesel were within the limits set by the National Agency of Petroleum, Natural Gas and Biofuels (ANP).     

Characterization of ionic liquid‐based biocatalytic two‐phase reaction system for production of biodiesel

The property of a variety of ionic liquids (ILs) as reaction media was evaluated for the production of biodiesel by enzymatic methanolysis of rapeseed oil. The IL Ammoeng 102, containing tetraaminum cation with C₁₈ acyl and oligoethyleneglycol units, was found to be capable of forming oil/IL biphasic reaction system by mixing with substrates, which is highly effective for the production of biodiesel with more than 98% biodiesel yield and nearly 100% conversion of oil. Conductor‐like screening model for real solvent (COSMO‐RS) in silico prediction of substrate solubility and simulation of partition coefficient change vs. reaction evolution indicated that the amphiphilic property of Ammoeng 102 might be responsible for creating efficient interaction of immiscible substrates; while big difference of partition coefficients of generated biodiesel and glycerol between the two phases suggests a large chemical potential to move reaction equilibrium for maximum oil conversion and yield of target biodiesel. The reaction behavior and specificity of oil/IL biphasic system for enzymatic production of biodiesel were theoretically delineated through COSMO‐RS computation with experimental validation. © 2010 American Institute of Chemical Engineers AIChE J, 2011