乌桕油脂成分作为生物柴油原料的研究进展

生物柴油本质上是长链脂肪酸甲酯,工业上多通过酯交换反应进行生产.乌桕是广泛分布于中国的油料树种,其种子油脂含量高达40%左右,是生物柴油的优质原料.本文在介绍能源植物的种类及生物柴油生产概况的同时综述了乌桕皮油和梓油的提取工艺、用于催化乌桕油生产生物柴油的催化剂以及乌桕油及种子中脂肪酸组成等方面的研究进展.规范乌桕种质资源的标准化与分子标记辅助遗传育种、油脂代谢途径机理的揭示及转基因技术创制高含油新品种、新型纳米催化剂及新型高效固定化抗逆脂肪酶的研制对推动乌桕生物柴油的发展具有重要作用.     

生物柴油研究进展

介绍了国内外生物柴油的发展现状,探讨了我国发展生物柴油的原料来源途径,包括木本油料植物、转基因油料作物、废弃油脂、微生物油脂和微藻油脂等,综述了制备生物柴油的化学法、酶法、超临界法等生产技术及其进展,概括了当前生物柴油主要的品质问题与改性对策,分析了生物柴油副产物的高值化利用策略,指出了我国生物柴油产业化面临的原料、技术和生物炼制方面的主要问题。     

白木通种子油的理化特性及制备生物柴油的研究

以白木通种子为实验材料,索氏提取法提取种子油,GC-MS测定脂肪酸组成,国标法测定理化性质,运用响应面法对碱催化白木通种子油酯交换制备生物柴油工艺进行优化。结果表明:白木通种子油含有5种脂肪酸,其中油酸含量最高,硬脂酸次之。白木通种子油的得率、含水量、碘值、酸值、皂化值、过氧化值、凝固点、闪点和冷滤点分别为32.76%、0.36%、67.89 g/100 g、8.85 mg KOH/g、235.03 mg KOH/g、47.08 mmol/kg、-12℃、215℃和-7℃。优化的生物柴油制备工艺为:反应时间80 min,醇油摩尔比6.7∶1,催化剂用量1.3%(按反应体系总质量计算)。白木通种子含油率高,可作为藤本油料作物开发利用。     

中国樟科非粮生物柴油能源植物资源的初步评价与筛选

通过调查我国现有樟科油脂植物资源,本研究对74份(9属47种)樟科油脂植物样品的含油率、脂肪酸甲酯组成、碘值及其油酸甲酯的理化性质进行了分析,并根据非粮生物柴油能源植物的评价标准,初步筛选出了19份(5属18种)具有开发利用价值的樟科非粮生物柴油能源植物,为樟科油脂植物资源的评价与筛选、深度开发与综合利用等提供参考依据。     

云南主要木本生物柴油原料植物的综合评价

选用含油量、油脂成分、结实性状、分布范围和繁殖性状作为评价指标,运用灰色关联度分析法对云南分布的、可作为生物柴油原料的188种主要木本油料植物（含油量≥30%）进行了综合评价。结果表明：滇新樟(Neocinnamomum caudatum)、西南红山茶(Camellia pitardii)等29种木本油料植物与理想种的关联度均超过0.6500,具有良好的综合性状,可以在研究开发的基础上作为云南生物柴油产业的原料植物来推广应用。此外,脉叶虎皮楠(Daphniphyllum paxianum)、牛紏吴萸(Evodia trichotoma)、长梗大花漆(Toxicodendron grangiflorum var. longipes)是这次新发现的3种具有开发潜力的木本生物柴油原料植物。     

碱性离子液体1-甲基-3-丁基咪唑氢氧化物催化地沟油制备生物柴油的研究

本研究合成了碱性离子液体1-甲基-3-丁基咪唑氢氧化物,通过红外光谱和核磁共振检测与文献报道一致,以此离子液体为制备生物柴油的催化剂,发现具有很高的催化活性.在生物柴油的合成过程中,考察了离子液体的用量、醇与油物质的量比、反应温度和反应时间对酯交换反应的影响.结果显示,以地沟油制备生物柴油的最佳工艺条件为:醇油摩尔比8:1、反应温度70 ℃、反应时间110 min、催化剂用量为原料油质量的3.0 %.在此条件下, 脂肪酸甲酯转化率为95.7 %.由地沟油制备的生物柴油,其低温流动性能好,闪点高,除碘值较高外,其他主要性能符合0# 柴油标准,并且可以和0# 柴油进行调和使用.     

用GC-MS分析不同采收和贮存时期的麻疯树种子油的脂肪酸

将采收于青果期、黄果期、黑果期及储存1a、2a的麻疯树种子提油,测定其理化性质,并利用GC-MS分析这5个不同时期的种子所提取的麻疯树种子油成分。结果表明:5个油样的水分、酸值、出油率有较大差异,主要化学成分、碘值、皂化值差异不大。青果的出油率为13.13%,水分为0.66%,酸值为69.21,不饱和脂肪酸含量最低。新采成熟果实的出油率为54.64%,水分为0.36%,酸值为1.51,不饱和脂肪酸含量也相对较高。因此,新采的成熟果实较为适合作生物柴油的原料。     

我国优势油脂类生物柴油植物蓖麻的种质资源发掘和生物柴油利用

发展可再生生物质能源是解决人类能源危机和环境污染的重要途径。利用边际土地发展油脂类生物质能是生物质能的重要组成部分。蓖麻因为适应性强和油脂成份独特被誉为"理想的生物柴油植物"。蓖麻是我国优势油脂类能源植物,利用边际土地,发展蓖麻产业为我国生物柴油产业化提供原料,是我国现阶段生物柴油产业化发展的相对理想而又现实的选择,而且具有重要的发展前景和巨大的发掘潜力。立足我国现阶段生物柴油产业化的瓶颈问题,着重阐述了蓖麻种质资源发掘的现状、优良品种培育的途径和发展前景,以及利用蓖麻种子油生产商业化生物柴油的现状,以期推动我国利用边际土地发展蓖麻产业以及生物柴油商业化生产。     

加快微生物油脂研究为生物柴油产业提供廉价原料

当前国内外致力于发展生物柴油,因其性能优良,成为化石柴油的替代品。由于以植物油脂生产生物柴油原料成本占总成本的70％-85％,所以亟待开发廉价油脂资源。微生物油脂主要是微生物利用碳水化合物合成的甘油脂,其脂肪酸组成和植物油相近。产油微生物具有资源丰富、油脂含量高、碳源利用谱广等特点,开发潜力大。然而,目前微生物油脂生产成本偏高,研究工作仍以富含多不饱和脂肪酸的高附加值菌油为目标。随着现代分子生物学和生物化工技术的发展,对产油微生物菌种筛选、改良、代谢调控和发酵工程的研究日趋深入,将降低微生物油脂生产成本,为未来生物柴油产业提供廉价原料。     

中国如何突破生物柴油产业的原料瓶颈

因应我国日益严峻的能源资源、能源环境和能源安全形势,国家大力倡导发展可再生能源。生物柴油是最重要的液体可再生燃料之一,在能源性质方面可以完全替代化石柴油,而且还具有安全环保等其它优良特性。当前利用动植物油脂生产生物柴油,原料成本偏高,而且稳定、充足的油脂原料供应体系尚未形成。我国是油脂资源短缺国家,近年来植物油进口量逐年增加。同时,我国耕地资源匮乏,粮食供应形势不容乐观,扩大油料作物种植的潜力非常有限。但是,我国宜林地丰富,农林废弃生物质资源量巨大。综合以上因素,我国应重点发展木本油料植物规模化种植和推广,加快微生物油脂发酵技术创新和产业化进程;同时,利用植物遗传育种技术提高油料作物产量以及选择性发展不与粮争地的油料作物。依靠各方面的进步,发展创新的油脂生产技术,保障我国生物柴油产业和油脂化工行业健康发展。     

Biodiesel Potential of Nonfood Plant Resources from Tsinling and Zhongtiao Mountains of China

Forty-nine wild oil plants which are abundant in the Tsinling and Zhongtiao Mountains were investigated and screened as raw material for biodiesel production. The oil content was tested and found to be greatly variable, ranging from 10 to 62.8 %. Fatty acid profiles of their vegetable oils were analyzed, and their acid value, saponification number, and iodine value were found to range from 1.6 to 61.3 mg KOH/g, 128.6 to 225.9 mg KOH/g, and 54.3 to 120.9 g I₂/100 g, respectively. Cetane number, kinematic viscosity, specific gravity, high heating values, and cold filter plugging point of the 49 vegetable-oil methyl esters (MEs) were empirically calculated and were found to vary from 38.8 to 66.6, 2.9 to 4.2 mm²/s, 841.4 to 883.8 kg/m³, 39.0 to 47.5 kJ/g, and ?14.3 to 13.2 °C, respectively. Almost half (25 species) of all the sampled resources were found to be suitable for biodiesel production since the profiles of their vegetable-oil MEs met the major specifications of Chinese and European Union biodiesel standards, GB/T20828 and EN-14214, respectively. Grey relational analysis was used during the optimum-species screening process. The difference between the individual species and the artificial designed ideal species (the best biodiesel plant type in this paper) was calculated and evaluated with the help of grey relational grade, which varied from 0.467 to 0.686. Finally, the selected plants, Prunus salicina Linn. and Amygdalus davidiana (C.) C. de Vos, were considered as the optimal feedstock for biodiesel production.     

Influence of fatty acid composition of raw materials on biodiesel properties

The aim of this work was the study of the influence of the raw material composition on biodiesel quality, using a transesterification reaction. Thus, ten refined vegetable oils were transesterificated using potassium methoxide as catalyst and standard reaction conditions (reaction time, 1h; weight of catalyst, 1 wt.% of initial oil weight; molar ratio methanol/oil, 6/1; reaction temperature, 60 degrees C). Biodiesel quality was tested according to the standard [UNE-EN 14214, 2003. Automotive fuels. Fatty acid methyl esters (FAME) for diesel engines. Requirements and test methods]. Some critical parameters like oxidation stability, cetane number, iodine value and cold filter plugging point were correlated with the methyl ester composition of each biodiesel, according to two parameters: degree of unsaturation and long chain saturated factor. Finally, a triangular graph based on the composition in monounsaturated, polyunsaturated and saturated methyl esters was built in order to predict the critical parameters of European standard for whatever biodiesel, known its composition.     

Moringa oleifera oil: a possible source of biodiesel

Biodiesel is an alternative to petroleum-based conventional diesel fuel and is defined as the mono-alkyl esters of vegetable oils and animal fats. Biodiesel has been prepared from numerous vegetable oils, such as canola (rapeseed), cottonseed, palm, peanut, soybean and sunflower oils as well as a variety of less common oils. In this work, Moringa oleifera oil is evaluated for the first time as potential feedstock for biodiesel. After acid pre-treatment to reduce the acid value of the M. oleifera oil, biodiesel was obtained by a standard transesterification procedure with methanol and an alkali catalyst at 60 degrees C and alcohol/oil ratio of 6:1. M. oleifera oil has a high content of oleic acid (>70%) with saturated fatty acids comprising most of the remaining fatty acid profile. As a result, the methyl esters (biodiesel) obtained from this oil exhibit a high cetane number of approximately 67, one of the highest found for a biodiesel fuel. Other fuel properties of biodiesel derived from M. oleifera such as cloud point, kinematic viscosity and oxidative stability were also determined and are discussed in light of biodiesel standards such as ASTM D6751 and EN 14214. The (1)H NMR spectrum of M. oleifera methyl esters is reported. Overall, M. oleifera oil appears to be an acceptable feedstock for biodiesel.     

Study on the effect of cultivation parameters and pretreatment on Rhizopus oryzae cell-catalyzed transesterification of vegetable oils for biodiesel production

Enzymatic methanolysis of vegetable oils for biodiesel production has become a hot point recently, in which study on whole cell as catalyst is an important field. In this paper, whole cell (Rhizopus oryzae IFO 4697) was adopted directly as biocatalyst for biodiesel production. Effects of carbon source on cell growth and whole cell-catalyzed methanolysis of vegetable oils for biodiesel production were studied. The results showed that different oils contained in the cultivation medium had varied effects on the whole cell-catalyzed methanolysis of oils; with some specified oil as the carbon source for cell cultivation, those cells expressed higher catalytic activity in catalyzing the transesterification of the same oil for biodiesel production. The initial reaction rate was increased notably (204%) with oil pretreatment on the cells before catalyzing the reaction, which was possibly due to the improved mass transferring of substrates. Under the optimized conditions, the maximum methyl ester yield could reach 86%.     

Lipase-catalysed production of biodiesel fuel from some Nigerian lauric oils

Fatty acids esters were produced from two Nigerian lauric oils, palm kernel oil and coconut oil, by transesterification of the oils with different alcohols using PS30 lipase as a catalyst. In the conversion of palm kernel oil to alkyl esters (biodiesel), ethanol gave the highest conversion of 72%, t-butanol 62%, 1-butanol 42%, n-propanol 42% and iso-propanol 24%, while only 15% methyl ester was observed with methanol. With coconut oil, 1-butanol and iso-butanol achieved 40% conversion, 1-propanol 16% and ethanol 35%, while only traces of methyl esters were observed using methanol. Studies on some fuel properties of palm kernel oil and its biodiesel showed that palm kernel oil had a viscosity of 32.40 mm2/s, a cloud point of 28 degrees C and a pour point of 22 degrees C, while its biodiesel fuel had a viscosity of 9.33 mm2/s, a cloud point of 12 degrees C and a pour point of 8 degrees C. Coconut oil had a viscosity of 28.58 mm(2)/s, a cloud point of 27 degrees C and a pour point of 20 degrees C, while its biodiesel fuel had a viscosity of 7.34 mm2/s, a cloud point of 5 degrees C and a pour point of -8 degrees C. Some of the fuel properties compared favourably with international biodiesel specifications.     

高含游离脂肪酸的香果树籽油制备生物柴油的方法

目前生物柴油因其环保和可再生利用资源的特性备受关注。多数生物柴油是通过甲醇和碱催化食用油得到的,而大量非食用油也可以制备生物柴油。本文报道用高含游离酸脂肪油快速高效低成本制备成其单酯的二步法工艺。先用1% H2SO4以少于1.5%量对甲醇和云南特产香果树（Lindera communis）籽的粗原料油以10∶1摩尔比组成的混合液酸催化酯化游离脂肪酸;之后再对醇和得到的油脂产品按摩尔比15∶1的混合液碱催化转化为单甲酯和甘油。本方法是一个直接甲脂化制备生物柴油的工艺简洁、降低成本的新技术。文中还讨论了该工艺影响转化效率的主要因素,如摩尔比,催化量,温度,反应时间和酸度。香果树生物柴油不重蒸,而其生物柴油的主要特性,如粘度、热值、比重、闪点、冷滤点等与生物柴油标准的匹配度,也做了报道,研究结果将为香果树生物柴油以非重蒸油料制备生物柴油产品,作为潜在的柴油燃料替代产品提供技术支撑。     

Oil content,fatty acid composition and biodiesel properties among natural provenances of Siberian apricot (Prunus sibirica L.) from China

Siberian apricot (Prunus sibirica L.), an excellent woody oil plant unique to Asia, is well known for its ability to produce high‐oil seeds for use as a promising feedstock of biodiesel. Based on the investigation of natural Siberian apricot resources in China in the early stage, seeds of Siberian apricot from 74 geographic provenances which can fully reflect the overall information were collected. In this research, seeds oil content, fatty acid composition and biodiesel properties were evaluated, and the key environmental factors that caused the variation of these in different geographic provenance were analyzed. The oil content of Siberian apricot seeds is 45.48%–61.07%, and the average was 50.95% for all provenances. The characteristics of oil can identify and quantify eight fatty acids. The most abundant fatty acids were oleic acid (C18:1; 54.02%–76.54%), followed by linoleic acid (C18:2; 16.78%–38.49%) and erucic acid (C16:0; from 3.27% to 6.12%). Monounsaturated fatty acids are the most abundant in 54.75%–77.03% compared with saturated fatty acids and polyunsaturated fatty acids. The biodiesel properties of most provenance seeds meet the standards of the ASTM D6751 and GB/T 20828, and a few meet the standards of the EN14214. Through the clustering of oil content and fatty acid composition and the analysis of biodiesel properties indexes, it is concluded that KSK provenance is the most suitable for biodiesel production. The XBZ, HHE, AES, ZLQ and LD provenances may be preserved as potential biodiesel. RDA and VPA showed that the effects of environmental factors on the oil properties of Siberian apricot were ranked as terrain factor > climate factor > soil factor, among which longitude, latitude and altitude are the main terrain indicators. These evaluations can provide reference for the effective utilization and further development of Siberian apricot as a bioenergy feedstock.     

Biodiesel production from Jatropha oil by catalytic and non-catalytic approaches: an overview

Biodiesel (fatty acids alkyl esters) is a promising alternative fuel to replace petroleum-based diesel that is obtained from renewable sources such as vegetable oil, animal fat and waste cooking oil. Vegetable oils are more suitable source for biodiesel production compared to animal fats and waste cooking since they are renewable in nature. However, there is a concern that biodiesel production from vegetable oil would disturb the food market. Oil from Jatropha curcas is an acceptable choice for biodiesel production because it is non-edible and can be easily grown in a harsh environment. Moreover, alkyl esters of jatropha oil meet the standard of biodiesel in many countries. Thus, the present paper provides a review on the transesterification methods for biodiesel production using jatropha oil as feedstock.     

Biodiesel production using heterogeneous catalysts

The production and use of biodiesel has seen a quantum jump in the recent past due to benefits associated with its ability to mitigate greenhouse gas (GHG). There are large number of commercial plants producing biodiesel by transesterification of vegetable oils and fats based on base catalyzed (caustic) homogeneous transesterification of oils. However, homogeneous process needs steps of glycerol separation, washings, very stringent and extremely low limits of Na, K, glycerides and moisture limits in biodiesel. Heterogeneous catalyzed production of biodiesel has emerged as a preferred route as it is environmentally benign needs no water washing and product separation is much easier. The present report is review of the progress made in development of heterogeneous catalysts suitable for biodiesel production. This review shall help in selection of suitable catalysts and the optimum conditions for biodiesel production.     

Biodiesel production—current state of the art and challenges

Biodiesel is a clean-burning fuel produced from grease, vegetable oils, or animal fats. Biodiesel is produced by transesterification of oils with short-chain alcohols or by the esterification of fatty acids. The transesterification reaction consists of transforming triglycerides into fatty acid alkyl esters, in the presence of an alcohol, such as methanol or ethanol, and a catalyst, such as an alkali or acid, with glycerol as a byproduct. Because of diminishing petroleum reserves and the deleterious environmental consequences of exhaust gases from petroleum diesel, biodiesel has attracted attention during the past few years as a renewable and environmentally friendly fuel. Since biodiesel is made entirely from vegetable oil or animal fats, it is renewable and biodegradable. The majority of biodiesel today is produced by alkali-catalyzed transesterification with methanol, which results in a relatively short reaction time. However, the vegetable oil and alcohol must be substantially anhydrous and have a low free fatty acid content, because the presence of water or free fatty acid or both promotes soap formation. In this article, we examine different biodiesel sources (edible and nonedible), virgin oil versus waste oil, algae-based biodiesel that is gaining increasing importance, role of different catalysts including enzyme catalysts, and the current state-of-the-art in biodiesel production. JIMB 2008: BioEnergy—special issue.