超声强化酯交换制备生物柴油的工艺优化

为了获得超声强化酯交换反应制备生物柴油最佳工艺条件,为工业化生产提供借鉴。该文考察了超声功率密度、反应温度、催化剂用量和醇油摩尔比等因素对超声强化 KOH 催化酯交换反应过程的影响,并采用响应曲面分析方法（RSM）优化最佳工艺参数。研究结果表明：超声强化 KOH 催化酯交换反应制备生物柴油最佳工艺条件为：超声功率密度54.7 W/L、反应温度34℃、催化剂用量为大豆油质量的 1.3%、醇油摩尔比6︰1,此条件下酯交换反应甲酯质量分数为 99.68%,经验证试验得实测值为99.56%。RSM优化的试验结果适合于碱催化酯交换反应制备生物柴油工艺,并能够预测不同条件下碱催化酯交换反应中的甲酯质量分数。     

菜籽油碱催化酯交换法制备生物柴油工艺参数的优化

为获得最佳反应条件,在单因素试验的基础上,采用响应面法对菜籽油碱催化酯交换法制备生物柴油的工艺参数进行了优化试验,结果表明,预测酯交换反应过程中菜籽油转化率变化的回归方程拟合程度良好,最优工艺参数为：醇油摩尔比6.12︰1,催化剂用量0.9%,反应时间40 min,反应温度57.74℃,并且在最优工艺参数下进行了验证试验,得到菜籽油转化率为97.43%,与预测值的误差为0.4%,小于5%。对生物柴油的组成成分进行了气相色谱/质谱联用（GC/MS）分析,结果表明,脂肪酸甲酯质量分数达到99.54%。因此,利用响应面分析法得到的最优工艺参数真实可靠,制得的生物柴油品质较好。     

Ba(OH)2催化酯交换反应制备生物柴油

为简化酯交换法制备生物柴油工艺过程,实现生物柴油绿色生产.采用正交试验的方法研究了Ba(OH)2催化酯交换反应制备生物柴油过程中油醇摩尔比、Ba(OH)2用量、反应温度、反应时间等因素对生物柴油转化率的影响,并将Ba(OH)2与KOH的催化效果进行了简单比较.实验结果显示:最佳的工艺条件为油醇摩尔比1:6、Ba(OH)2用量2%、反应温度60℃.在此条件下以大豆油为原料90 min生物柴油转化率达到94.27%,花生油、亚麻油、菜籽油等相应转化率均超过95%,同时对比实验证明Ba(OH)2与KOH具有同样高的催化活性,反应产物成分相同,且Ba(OH)2可通过BaSO4沉淀的形式简单、完全回收.Ba(OH)2可作为一种有潜力的生物柴油制备催化剂.     

碳基固体酸催化高酸值生物柴油原料降酸效果

以淀粉和对甲苯磺酸合成的碳基固体酸为催化剂,油酸模拟高酸值生物柴油原料进行酯化降酸的试验研究,考察醇油比、催化剂用量、反应温度、反应时间及重复利用性等因素对转化率的影响。通过单因素与正交试验确定最佳工艺条件：醇油质量比为1︰4,催化剂用量为油酸质量的6.5%,反应时间6 h,反应温度85℃,在此条件下转化率可达80.21%,重复使用6次,转化率仍保持在70%以上。碳基固体酸催化剂对高酸值原料酯化降酸有很好的催化活性,易于分离且具有良好的稳定性。     

固体催化剂催化牛油制取生物柴油工艺优化

利用固体催化剂催化废弃动物油脂制取生物柴油可以实现催化剂的重复利用、降低原料成本,从而提高生物柴油的市场竞争力。该文以牛油为原料,在自制固体催化剂Cs2O/γ-Al2O3的催化作用下与甲醇酯交换反应制备生物柴油。采用响应面法对反应过程进行了优化,试验考察了醇油摩尔比、催化剂用量、反应时间和反应温度等操作条件对酯交换反应的影响,并得到了最优反应条件,即反应温度66℃,醇油摩尔比10.5：1,催化剂用量5.3%,反应时间120 min,生物柴油的酯交换率达到95.5%。反应后固体催化剂在400℃下灼烧4 h后可以重复利用,重复利用8次后酯交换率下降不到6%。研究结果将为固体催化剂催化废弃动物油脂制取生物柴油的连续和产业化生产提供试验基础,为提高生物柴油的市场竞争力提供参考。     

利用动物脂肪酯交换反应制备生物柴油的试验研究

该文以牛油为原料,在KOH的催化作用下与甲醇酯交换反应制备生物柴油.采用正交试验与人工神经网络相结合的试验方法,考察了醇油摩尔比、催化剂用量、反应时间和反应温度等操作条件对酯交换反应的影响,得到了最优工艺条件,即反应温度 70°C,醇油摩尔比10.5:1,催化剂用量1.1%(占油脂质量的百分数),反应时间90 min.经试验验证,利用神经网络优化后的酯交换率达到94.16%,高于正交试验的结果93.17%.     

菜籽油酯交换制备生物柴油的工艺研究

为提高生物柴油的转化率和纯度，以菜籽油为原料，研究在KOH催化剂作用下与甲醇进行酯交换反应制备生物柴油的工艺，考察了甲醇用量、催化剂用量、反应温度和反应时间等操作条件对酯交换反应的影响。结果表明，该反应最适宜的工艺条件为：甲醇用量为菜籽油质量的20%，催化剂用量为菜籽油质量的1.2%，反应温度为65℃，反应时间为90～120 min；菜籽油制备的生物柴油品质达到美国ASTM和德国DINE生物柴油标准，其生物柴油的转化率为94.89%。若充分开发中国南方可利用的冬闲田和边际土地约1000万hm²种植油菜，按照此工艺条件加工菜籽油，则每年可加工生产生物柴油740万t，具有广阔的发展前景。     

利用菜籽油酶法生产生物柴油的初步研究

生物柴油作为可再生能源，对环境友好，引起了世界范围内的广泛关注。该文利用固定化脂肪酶－Novo435，在无有机溶剂存在的情况下，催化菜籽油与甲醇酯交换反应制取生物柴油，对影响酯交换反应过程的因素：甲醇与油脂的摩尔比、反应温度、反应时间、脂肪酶用量、转速、水分等进行深入研究，得到了菜籽油间歇酯交换反应的适宜工艺条件：转速200 r/min、醇油摩尔比1.5∶1、反应温度50℃、酶用量10%(与油脂的质量比)、反应10 h后菜籽油的酯交换率达到47％。水分的存在不利于固定化酶在无有机溶剂系统下催化菜籽油的酯交换反应，使酯交换率降低到30％。反应所需理论甲醇量分两次加入，反应26 h后，油脂的酯交换率达到80％。     

碳基固体酸催化剂加压催化合成生物柴油

为了减少生物柴油制备过程中传统催化剂对环境的污染,开发新型固体催化剂具有重要意义。该文以纤维素为原料,采用碳化-磺化法制备了碳基固体酸催化剂,并利用SEM(scanning electron microscope)、BET比表面积测试法、XRD(X-ray diffraction)和NH3-TPD(NH3-temperature programmed desorption)对其结构进行表征。研究了碳基固体酸催化剂催化棕榈酸和甲醇通过酯化反应制备生物柴油的工艺条件,考察了不同醇酸摩尔比、反应时间、反应温度及催化剂用量对转化率的影响,并对比了加压条件下碳基固体酸催化剂与浓硫酸和对甲苯磺酸的催化活性。试验结果表明,当醇酸摩尔比10:1,反应温度110℃,反应时间2 h,碳基固体酸催化剂用量为棕榈酸质量的5%时,转化率可达到98.11%。在加压条件下,碳基固体酸的催化活性高于浓硫酸和对甲苯磺酸,且催化剂在使用4次后,转化率仍在60%以上。通过GC-MS分析得出制备的生物柴油甲酯质量分数为93.8%。该研究为纤维素基碳基固体酸制备生物柴油提供了依据。     

固定化细胞磁稳定流化床反应器制备生物柴油

为了探索生物酶法制备生物柴油新工艺,克服现有工艺的不足,采用超顺磁性全细胞催化剂在自制的磁稳定流化床中对废油脂连续生产生物柴油进行了试验研究。考察了改变磁场强度、进料醇油摩尔比、催化剂用量及流量等因素对连续酯交换反应的影响,进而得到单级磁流化床酯交换反应的最佳工艺条件：磁稳态操作,醇油摩尔比为1∶1,催化剂用量为原料油质量的12%,进料流量为42.6?mL/min。四级磁流化床连续系统最终转酯化率达到85%以上,连续反应200 h后四级出口的甲酯产率仍在80%以上。这说明全细胞催化剂在磁稳定流化床中活性较高,使用寿命较长,该系统具有良好的操作稳定性。     

利用Biopro型设备转化废弃油脂制备生物柴油

为开发适应中国废弃油脂生物柴油转化的成套技术与装备,结合美国Biopro 380型设备,对中国的4种典型废弃油脂生物柴油转化工艺进行了系统研究,结果表明,甲醇回流温度65℃下,酯化反应时间2.5h、浓硫酸加入量0.5%、甲醇与游离脂肪酸摩尔比2.7∶1时,酯化混合物的酸值降至1～2?mg/g;转酯化反应在醇油摩尔比6∶1、催化剂NaOH的加入量1.0%（与废弃油脂的质量百分比）、反应时间60 min时,转酯化效果最佳;将该工艺条件应用于Biopro 380型设备中进行验证试验,获得的生物柴油产品质量指标基本符合中国生物柴油标准GB/T 20828-2007。     

超声波辅助离子液体组合物直接制备微藻生物柴油

微藻生物柴油能够解决目前植物原料生物柴油面临的耕地不足、气候变化影响产量并引起农作物价格上涨等突出问题,但传统微藻生物柴油生产过程能源与化学品消耗大,将微藻油脂的提取-酯交换耦合成一个单元,具有较大应用潜力.该研究采用小球藻、甲醇为原料,离子液体组合物作为提取剂、催化剂,超声波辅助催化微藻直接提取-酯交换制备生物柴油.考察超声波频率、超声波功率、离子液体类型、离子液体用量、反应温度、反应时间、醇油摩尔比等因素对酯交换率的影响,并与传统水浴加热机械搅拌法比较,结果表明,超声波和离子液体对生物柴油的制备有协同促进作用,离子液体具有催化、提取与增溶的作用,能较好地消除醇油界面接触,超声波的引入强化了传质传热过程,与传统加热方式水浴加热机械搅拌法相比,可以缩短酯交换反应的时间,降低反应温度,减少离子液体、甲醇的用量.离子液体[BMIM][HCOO]为提取剂,微藻油脂提取率最高;酸性离子液体催化效果明显高于碱性离子液体,离子液体[SO3H-BMIM][HSO4]为催化剂,微藻油脂转化率最高.当超声波功率240W,频率28kHz,甲醇用量和藻粉质量比为61:,离子液体组合物和藻粉质量比为51:,离子液体[BMIM][HCOO]与[SO3H-BMIM][HSO4]体积比为12:1,反应温度为50℃,超声反应时间50min条件下,生物柴油的转化率可达69.6%.该方法将离子液体溶解提取性能、催化性能及超声波的空化效应相结合,将油脂的提取与油脂的转酯化合二为一,不需先从微藻粉中提取油脂,缩短了工艺,能够实现含油微藻到生物柴油的一步转化.     

Studies on the preparation of biodiesel from Zanthoxylum bungeanum Maxim seed oil

To reduce the cost of biodiesel production, the feasibility of Zanthoxylum bungeanum Maxim seed oil (ZBMSO) was studied to produce biodiesel. A methyl ester biodiesel was produced from ZBMSO using methanol, sulfuric acid, and potassium hydroxide in a two-stage process. The main variables that affect the process were investigated. The high level of free fatty acids in ZBMSO was reduced to < 1% by an acid-catalyzed (2% H2SO4) esterification with methanol to oil molar ratios of 20-25:1 for 1 h. A maximum yield of 96% of methyl esters in ZBMSO biodiesel was achieved using a 6.5:1 molar ratio of methanol to oil, 0.9% KOH (percent oil), and reaction time of 0.5 h at 55 degrees C. Further investigation has also been devoted to the assessment of some important fuel properties of ZBMSO biodiesel produced under the optimized conditions according to specifications for biodiesel as fuel in diesel engines. The fuel properties of the ZBMSO biodiesel obtained are similar to those of no. 0 petroleum diesel fuel, and most of the parameters comply with the limits established by specifications for biodiesel.     

NaHSO4催化椰子油皂脚油酯化降酸工艺优化

以椰子油皂脚油为原料的生物柴油酯化效率与催化剂和结合反应装置的操作方法有关。以硫酸氢钠为催化剂结合设计的反应装置,对高酸值椰子油皂脚油进行预酯化反应研究。通过单因子试验探讨适用于反应装置的反应条件,并讨论不同的操作方式对反应速率和反应进程的影响。结果表明:最佳条件为:反应温度105℃,甲醇通入流速为0.825 mL/min,催化剂用量为5.0%,反应2 h下转化率>95%。催化剂重复使用9次后转化率78.15%;改变操作方法,0.1 MPa条件下反应,采用通入甲醇1.32 mL/min反应30 min,后常压条件下通入甲醇量0.825 mL/min,反应30 min,椰子油皂脚油酸值由106变为1.2 mg/g,转化率98.9%,并可缩短酯化时间1 h,油脂成品满足酯交换工序要求。精制的生物柴油成品所测试的技术指标符合德国现行生物柴油标准(DIN V 51606)。     

脂肪酸甲酯生物柴油改善低硫柴油的润滑性能

生物柴油可作为改善低硫柴油润滑性能的天然添加剂。该文将豆蔻酸甲酯(C14:0)、棕榈酸甲酯(C16:0)、硬脂酸甲酯(C18:0)、油酸甲酯(C18:1)、亚油酸甲酯(C18:2)、亚麻酸甲酯(C18:3)、蓖麻醇酸甲酯(C18:1 OH)及蓖麻油甲酯和餐饮废油甲酯按照0.5%、1.0%、1.5%和3.0%的体积分数添加到低硫柴油中,在高频往复试验机(high-frequency reciprocating rig,HFRR)上进行润滑性能测试,探究脂肪酸甲酯的碳链长度、不饱和度及含羟基等结构特征对润滑性能的影响。结果表明,长碳链脂肪酸甲酯一般比短链润滑效果好;碳链长度为十八的脂肪酸酯中,不饱和程度即碳碳双键数目越高则润滑性能越好;而在相同碳链长度和不饱和度条件下,含羟基的蓖麻醇酸甲酯的润滑改善效果优于油酸甲酯。由多种脂肪酸酯构成的混合物生物柴油的润滑性能要优于某单一的纯脂肪酸甲酯。在低硫柴油中,当某饱和脂肪酸甲酯的体积分数比例达3.0%时,或不饱和酯的体积分数达到1.5%时,或生物柴油的体积分数达1.0%时,可使低硫柴油的润滑性能指标满足相关标准。研究脂肪酸甲酯的各种结构特征对其润滑性能的影响及作用机制,有助于筛选合适的生物柴油组分及其添加浓度作为低硫柴油的润滑添加剂。     

Eicosapentaenoic acid enrichment from sardine oil by argentation chromatography

Eicosapentaenoic acid (EPA) derived from chemically hydrolyzed sardine oil was concentrated by urea fractionation using methanol at different temperatures (2, 4, and 6 degrees C) and urea/fatty acid ratios (2:1, 3:1, and 4:1 w/w) and purified by argentation neutral alumina column chromatography. The individual fatty acids were determined as fatty acid methyl esters (FAME) by gas-liquid chromatography and gas chromatography-mass spectroscopy as FAME and N-acyl pyrrolidides. In the mass fragmentation pattern of FAME, the base peak was assigned to be the 1-methoxyethenol moiety (m/z = 74) obtained by McLafferty rearrangement. Formation of the cyclic tropylium ion (m/z = 91) in fatty acids with four or more double bonds was apparent in FAME-PUFAs. The base peak of N-acyl pyrrolidides was the McLafferty rearrangement ion, 1-(pyrrolidin-1-yl)ethenol (m/z = 113). The highest concentration of EPA (47.78%) was obtained at the crystallization temperature of 4 degrees C with a urea/fatty acid ratio of 4:1 (w/w) with 93.74% yield. After complexation of saturated and less unsaturated fatty acids by urea complexation, argentation chromatography resulted in an EPA of high purity (99.6%) with an overall recovery of 54.09% using 50% diethyl ether/n-hexane as eluting solvent. The peroxide (POV) and thiobarbituric acid (TBS) values were found to be highest (4.0 mequiv of O2/kg and 5.2 mg of malondialdehyde/kg, respectively) during urea fractionation at the higher crystallization temperature (6 degrees C) and higher urea/fatty acid ratio (4:1). Keywords: Sardine oil; eicosapentaenoic acid (EPA); fatty acid methyl esters (FAME); urea fractionation; argentation column chromatography.     

Application of ethyl esters and d3-methyl esters as internal standards for the gas chromatographic quantification of transesterified fatty acid methyl esters in food

Ethyl esters (FAEE) and trideuterium-labeled methyl esters (d3-FAME) of fatty acids were prepared and investigated regarding their suitability as internal standards (IS) for the determination of fatty acids as methyl esters (FAME). On CP-Sil 88, ethyl esters of odd-numbered fatty acids eluted approximately 0.5 min after the respective FAME, and only coelutions with minor FAME were observed. Depending on the problem, one or even many FAEE can be added as IS for the quantification of FAME by both GC-FID and GC-MS. By contrast, d3-FAME coeluted with FAME on the polar GC column, and the use of the former as IS requires application of GC-MS. In the SIM mode, m/z 77 and 90 are suggested for d3-methyl esters of saturated fatty acids, whereas m/z 88 and 101 are recommended for ethyl esters of saturated fatty acids. These m/z values give either no or very low response for FAME and can thus be used for the analysis of FAME in food by GC-MS in the SIM mode. Fatty acids in sunflower oil and mozzarella cheese were quantified using five saturated FAEE as IS. Gravimetric studies showed that the transesterification procedure could be carried out without of loss of fatty acids. GC-EI/MS full scan analysis was suitable for the quantitative determination of all unsaturated fatty acids in both food samples, whereas GC-EI/MS in the SIM mode was particularly valuable for quantifying minor fatty acids. The novel GC-EI/MS/SIM method using fatty acid ethyl esters as internal standards can be used to quantify individual fatty acids only, that is, without determination of all fatty acids (the common 100% method), although this is present. This was demonstrated by the exclusive quantification of selected fatty acids including methyl-branched fatty acids, erucic acid (18:1n-9trans), and polyunsaturated fatty acids in cod liver oil and goat's milk fat.     

Screening of the entire USDA castor germplasm collection for oil content and fatty acid composition for optimum biodiesel production

Castor has tremendous potential as a feedstock for biodiesel production. The oil content and fatty acid composition in castor seed are important factors determining the price for production and affecting the key fuel properties of biodiesel. There are 1033 available castor accessions collected or donated from 48 countries worldwide in the USDA germplasm collection. The entire castor collection was screened for oil content and fatty acid composition by nuclear magnetic resonance (NMR) and gas chromatography (GC), respectively. Castor seeds on the average contain 48.2% oil with significant variability ranging from 37.2 to 60.6%. Methyl esters were prepared from castor seed by alkaline transmethylation. GC analysis of methyl esters confirmed that castor oil was composed primarily of eight fatty acids: 1.48% palmitic (C16:0), 1.58% stearic (C18:0), 4.41% oleic (C18:1), 6.42% linoleic (C18:2), 0.68% linolenic (C18:3), 0.45% gadoleic (C20:1), 84.51% ricinoleic (C18:1-1OH), and 0.47% dihydroxystearic (C18:0-2OH) acids. Significant variability in fatty acid composition was detected among castor accessions. Ricinoleic acid (RA) was positively correlated with dihydroxystearic acid (DHSA) but highly negatively correlated with the five other fatty acids except linolenic acid. The results for oil content and fatty acid composition obtained from this study will be useful for end-users to explore castor germplasm for biodiesel production.