脂肪酸在超临界甲醇中的酯化反应研究

超临界甲醇中的酯化和酯交换反应是利用植物油、动物油或废油脂制备生物柴油的新工艺.它的最大特点是不需要添加催化剂,超临界甲醇既是反应媒介,又是反应物.     

Phase and chemical equilibria in the transesterification reaction of vegetable oils with supercritical lower alcohols

Calculations of thermodynamic data are performed for fatty acid triglycerides, free fatty acids, and fatty acid methyl esters, participants of the transesterification reaction of vegetable oils that occurs in methanol. Using the obtained thermodynamic parameters, the phase diagrams for the reaction mixture are constructed, and the chemical equilibria of the esterification reaction of free fatty acids and the transesterification reaction of fatty acid triglycerides attained upon treatment with supercritical methanol are determined. Relying on our analysis of the obtained equilibria for the esterification reaction of fatty acids and the transesterification reaction of triglycerides attained upon treatment with lower alcohols, we select the optimum conditions for performing the reaction in practice.     

Fat content for nutritional labeling by supercritical fluid extraction and an on-line lipase catalyzed reaction

A method using sequential supercritical fluid extraction (SFE) and enzymatic transesterification has been developed for the rapid determination of total nutritional fat content in meat samples. SFE conditions of 12.16 MPa and 50°C were utilized to extract lipid species from the sample matrix. The enzymatic transesterification of the lipids by methanol was catalyzed by an immobilized lipase isolated from Candida antarctica. Conversion of the triglycerides to fatty acid methyl esters was monitored by supercritical fluid chromatography, while the fatty acid content of the extract was determined by capillary gas chromatography (GC). Total fat, saturated fat and monounsaturated fat contents were calculated from the GC data and compared to values from traditional extraction and lipid determination methods. Both off-line SFE and automated SFE followed by on-line GC analysis using two different instruments were utilized in this study. The enzymatic-based SFE method gave comparable results to the organic solvent extraction-based method followed by conventional BF₃-catalyzed esterification.     

亚铁锌双金属氰化络合物固体催化剂催化合成生物柴油

Fe(Ⅱ)-Zn双金属氰化络合物固体催化剂用于一步催化酯交换和酯化反应制备生物柴油,具有易分离、流程简单,不受水毒性影响的优点。将水溶性金属氰化络合物亚铁氰化钾和金属化合物氯化锌反应,并结合有机配体叔丁醇制备了基于亚铁氰化锌的双金属氰化物络合物(DMC)。并研究了DMC固体催化剂催化菜籽油合成生物柴油过程中,助络合剂种类、催化剂用量、反应温度、醇油摩尔比、反应时间、体系中水和脂肪酸含量等因素对反应过程的影响。研究结果表明,在最佳实验条件下,甲酯产率最高可达98%。催化剂可循环使用,6次循环使用后回收率仍达93.45%,适宜工业化生产。     

Clean synthesis of biodiesel over solid acid catalysts of sulfonated mesopolymers

FDU-15-SO₃H, a solid acid material prepared from the sulfonation of FDU-15 mesoporous polymer, has been demonstrated to serve as an efficient catalyst in the esterification of palmitic acid with methanol as well as in the transesterification of fatty acid-edible oil mixture. FDU-15-SO₃H achieved an acid conversion of 99.0% when the esterification was carried out at 343 K with a methanol/palmitic acid molar ratio of 6:1 and 5 wt% catalyst loading. It was capable of giving 99.0% yield of fatty acid methyl esters (FAME) when the transesterification of soybean oil was performed at 413 K and the methanol/oil weight ratio of 1:1. FDU-15-SO₃H was further applied to the transesterification/esterification of the oil mixtures with a varying ratio of soybean oil to palmitic acid, which simulated the feedstock with a high content of free fatty acids. The yield of FAME reached 95% for the oil mixtures containing 30 wt% palmitic acid. This indicated the sulfonated mesopolymer was a potential catalyst for clean synthesis of fuel alternative of biodiesel from the waste oil without further purification.     

Fatty and resin acid analysis in tall oil products via supercritical fluid extraction-supercritical fluid reaction using enzymatic catalysis

Supercritical fluid extraction (SFE) is combined with supercritical fluid reaction (SFR) in an analytical mode to assess tall oil products for their fatty or resin acid content or both. The SFR consists of an inline enzymatically catalyzed reaction in which a lipase transesterifies specific lipids with methanol. The SFE-SFR sequence is conducted employing commercially available extractors using supported lipases in the extraction cell to form methyl esters. In this study, six different commercially available lipases are screened for activity. The SFE-SFR extracts are analyzed by capillary gas chromatography and supercritical fluid chromatography and then compared with tall oil products derivatized by conventional chemical derivatization techniques.     

麻疯油转酯化产物的高效液相色谱分析

建立了高效液相色谱法同时测定麻疯油转酯化产物中4种主要脂肪酸甲酯的分析方法。样品经膜处理后用丙酮溶解,采用Hypersil ODS(C18)色谱柱进行分离。以乙腈为流动相进行等度洗脱,内标法定量,同时对色谱条件进行优化。结果表明,在优化的色谱条件下4种脂肪酸甲酯在10 min内得到良好的分离,标准曲线的线性相关系数均达到0.999以上,平均回收率为96%~98%,重现性相对标准偏差为7.2%~10.2%,重复性相对标准偏差为0.31%~2.02%。与气相色谱法相比,该方法具有较高的灵敏度,可用于麻疯油转酯化产物中脂肪酸甲酯含量的测定,为麻疯油转酯化反应制备生物柴油的定性定量分析提供了参考依据。     

大麻籽油合成生物柴油

大麻籽油;甲醇;甲酯化;生物柴油;酯交换     

Soybean biodiesel methyl esters,free glycerin and acid number quantification by 1H nuclear magnetic resonance spectroscopy

Production of alternative fuels, such as biodiesel, from transesterification of vegetable oil driven by heterogeneous catalysts is a promising alternative to fossil diesel. However, achieving a successful substitution for a new renewable fuel depends on several quality parameters. ¹H NMR spectroscopy was used to determine the amount of methyl esters, free glycerin and acid number in the transesterification of soybean oil with methanol in the presence of hydrotalcite‐type catalyst to produce biodiesel. Reaction parameters, such as temperature and time, were used to evaluate soybean oil methyl esters rate conversion. Temperatures of 100 to 180 °C and times of 20 to 240 min were tested on a 1 : 12 molar ratio soybean oil/methanol reaction. At 180 °C/240 min conditions, a rate of 94.5 wt% of methyl esters was obtained, where free glycerin and free fatty acids were not detected. Copyright © 2012 John Wiley & Sons, Ltd.     

Supercritical fluid assisted, integrated process for the synthesis and separation of different lipid derivatives

The partial synthesis of ethyl esters from corn and fish oil was carried out in a stirred tank at supercritical conditions and the products were separated from the reaction mixture using the supercritical fluid. Corn oil can be almost completely converted to ethyl esters under optimized conditions and the rate of reaction is comparable to atmospheric pressure conditions. Some concentration of polyunsaturates occurs in the partially converted glyceride fraction of fish oil, as the enzyme used, Lipozyme TL-IM, allows preferential esterification of the saturates and mono-unsaturates that are concentrated in positions 1 and 3 of the triglycerides. By judicious selection of the processing conditions, good separation of ethyl esters from the partially reacted glycerides was achieved.     

气相色谱质谱法测定植物油中脂肪酸

建立了气相色谱质谱法测定食用植物性油中脂肪酸检测的方法。植物油中的脂肪酸甘油酯在碱性条件下被水解为游离脂肪酸,随后采用三氟化硼将其转化为脂肪酸甲酯。采用同位素标记脂肪酸进行加标回收试验,回收率在94%以上。通过质谱的选择离子检测模式对硬脂酸、油酸、亚油酸等10种目标脂肪酸进行了检测,结果显示,该方法可用于油品的质量检测和日常分析。     

Calculations of phase equilibria for mixtures of triglycerides,fatty acids,and their esters in lower alcohols

The objects of study were mixtures containing triglycerides and lower alcohols and also the products of the transesterification of triglycerides, glycerol and fatty acid esters. The Redlich-Kwong-Soave equation of state was used as a thermodynamic model for the phase state of the selected mixtures over wide temperature, pressure, and composition ranges. Group methods were applied to determine the critical parameters of pure substances and their acentric factors. The parameters obtained were used to calculate the phase diagrams and critical parameters of mixtures containing triglycerides and lower alcohols and the products of the transesterification of triglycerides, glycerol and fatty acid esters, at various alcohol/oil ratios. The conditions of triglyceride transesterification in various lower alcohols providing the supercritical state of reaction mixtures were selected.     

Comparison and optimisation of biodiesel production from <Emphasis Type="Italic">Jatropha curcas</Emphasis> oil using supercritical methyl acetate and methanol

In this study, biodiesel has been successfully produced by transesterification using non-catalytic supercritical methanol and methyl acetate. The variables studied, such as reaction time, reaction temperature and molar ratio of methanol or methyl acetate to oil, were optimised to obtain the optimum yield of fatty acid methyl ester (FAME). Subsequently, the results for both reactions were analysed and compared via Response Surface Methodology (RSM) analysis. The mathematical models for both reactions were found to be adequate to predict the optimum yield of biodiesel. The results from the optimisation studies showed that a yield of 89.4 % was achieved for the reaction with supercritical methanol within the reaction time of 27 min, reaction temperature of 358°C, and methanol-to-oil molar ratio of 44. For the reaction in the presence of supercritical methyl acetate, the optimum conditions were found to be: reaction time of 32 min, reaction temperature of 400°C, and methyl acetate-to-oil molar ratio of 50 to achieve 71.9 % biodiesel yield. The differences in the behaviour of methanol and methyl acetate in the transesterification reaction are largely due to the difference in reactivity and mutual solubility of Jatropha curcas oil and methanol/methyl acetate.     

棉籽现场碱催化转酯化联产生物柴油和无毒棉粕

通过棉籽现场碱催化转酯化联产生物柴油和无毒棉粕,考察了棉仁中水的质量分数、粒径对产物中脂肪酸甲酯（FAME）的质量分数和棉粕中游离棉酚（FG）质量分数的影响;对反应过程中的醇油摩尔比、反应时间、催化剂用量、反应温度进行了单因素和正交实验考察。实验得到的反应适宜条件为,棉仁含水量在1.92%左右,棉仁粒径小于0.335mm,反应醇油摩尔比135∶1,反应3h,甲醇中氢氧化钠浓度0.10mol/L,反应温度30℃。在上述反应条件下,反应产物中甲酯的质量分数可达97%,棉粕中游离棉酚的质量分数为0.031%,低于FAO规定的国际标准。     

Bismuth(III) Triflate: A Safe and Easily Handled Precursor for Triflic Acid: Application to the Esterification Reaction

A series of carboxylic acids were converted into their corresponding methyl esters using bismuth(III) triflate as a catalyst in methanol. Good to excellent yields were obtained for different aliphatic or aromatic starting materials. In the reaction, bismuth triflate acts as a precursor that, upon hydrolysis, liberates sufficient triflic acid to catalyze the esterification.     

两相溶剂萃取黄连木籽油制备生物柴油

以黄连木籽为原料,采用乙醇/异己烷两相不互溶溶剂对其进行萃取处理.考察了乙醇／异己烷体积比、萃取温度和萃取时间对萃取过程的影响.通过实验确定最佳的萃取条件为,黄连木仁粉50 g,乙醇异己烷总体积300 mL,乙醇/异己烷体积比为50∶50,萃取温度40℃,萃取时间30 min.在此条件下,黄连木籽油出油率达到99.5％...     

Production and Characterization of Biodiesel from Tung Oil

The feasibility of biodiesel production from tung oil was investigated. The esterification reaction of the free fatty acids of tung oil was performed using Amberlyst-15. Optimal molar ratio of methanol to oil was determined to be 7.5:1, and Amberlyst-15 was 20.8wt% of oil by response surface methodology. Under these reaction conditions, the acid value of tung oil was reduced to 0.72mg KOH/g. In the range of the molar equivalents of methanol to oil under 5, the esterification was strongly affected by the amount of methanol but not the catalyst. When the molar ratio of methanol to oil was 4.1:1 and Amberlyst-15 was 29.8wt% of the oil, the acid value decreased to 0.85mg KOH/g. After the transesterification reaction of pretreated tung oil, the purity of tung biodiesel was 90.2wt%. The high viscosity of crude tung oil decreased to 9.8mm²/s at 40 °C. Because of the presence of eleostearic acid, which is a main component of tung oil, the oxidation stability as determined by the Rancimat method was very low, 0.5h, but the cold filter plugging point, −11 °C, was good. The distillation process did not improve the fatty acid methyl ester content and the viscosity.     

Determination of fatty acid methyl esters derived from algae Scenedesmus dimorphus biomass by GC–MS with one‐step esterification of free fatty acids and transesterification of glycerolipids

Algae can synthesize, accumulate and store large amounts of lipids in its cells, which holds immense potential as a renewable source of biodiesel. In this work, we have developed and validated a GC–MS method for quantitation of fatty acids and glycerolipids in forms of fatty acid methyl esters derived from algae biomass. Algae Scenedesmus dimorphus dry mass was pulverized by mortar and pestle, then extracted by the modified Folch method and fractionated into free fatty acids and glycerolipids on aminopropyl solid‐phase extraction cartridges. Fatty acid methyl esters were produced by an optimized one‐step esterification of fatty acids and transesterification of glycerolipids with boron trichloride/methanol. The matrix effect, recoveries and stability of fatty acids and glycerolipids in algal matrix were first evaluated by spiking stable isotopes of pentadecanoic‐2,2‐d₂ acid and glyceryl tri(hexadecanoate‐2,2‐d₂) as surrogate analytes and tridecanoic‐2,2‐d₂ acid as internal standard into algal matrix prior to sample extraction. Later, the method was validated in terms of lower limits of quantitation, linear calibration ranges, intra‐ and inter‐assay precision and accuracy using tridecanoic‐2,2‐d₂ acid as internal standard. The method developed has been applied to the quantitation of fatty acid methyl esters from free fatty acid and glycerolipid fractions of algae Scenedesmus dimorphus .     

Gas chromatography/mass spectrometry of oils and oil binders in paintings

A GC/MS procedure has been developed, optimized, and applied to characterization of oil binders in paintings. The procedure involves hydrolysis of lipids to fatty acids (FAs) and derivatization of FAs to fatty acid methyl esters (FAMEs) by a solution of sodium methanolate in methanol at an elevated temperature. FAMEs are analyzed by temperature-programed GC followed by full-scan MS. Old and dried samples are subjected to extraction of nonpolymerized FAMEs into dichloromethane prior to hydrolysis. The method provides a good repeatability of results and has been applied to the characterization of common plant oils used in paintings, to commercial oil and tempera paints, to model painting samples, and to samples taken from real paintings. The fresh oils and binders can readily be identified and characterized. The ratio of the methyl esters of palmitic and stearic acids can be used to characterize oil binders in old works of art.     

Enzyme catalyzed production of biodiesel from olive oil

Biodiesel (fatty acid methyl esters) was produced by transesterification of triglycerides (triolein) present in olive oil with methanol and Novozym435. The effect of the molar ratio of methanol to triolein, semibatch (stepwise addition of methanol) vs batch operation, enzyme activity, and reaction temperature on overall conversion was determined. Stepwise methanolysis with a 3:1 methanol to triolein molar ratio and an overall ratio of 8:1 gave the best results. The final conversion and yield of biodiesel were unaffected by initial enzyme concentrations greater than 500 U/mL olive oil. The optimum reaction temperature was 60 degrees C. Comparison of conversion data between a test-tube scale reactor and a 2-L batch reactor revealed that the difference in conversion was within 10%. Experiments were also carried out with used cooking oil; the conversion with used cooking oil was slightly lower but no major differences were observed. The efficacy of Novozym435 was determined by reusing the enzyme; although the enzyme's relative activity decreased with reuse, it still retained 95% of its activity after five batches and more than 70% after as many as eight batches.