Enzymatic biodiesel production: Technical and economical considerations

It is well documented in the literature that enzymatic processing of oils and fats for biodiesel is technically feasible. However, with very few exceptions, enzyme technology is not currently used in commercial‐scale biodiesel production. This is mainly due to non‐optimized process design and a lack of available cost‐effective enzymes. The technology to re‐use enzymes has typically proven insufficient for the processes to be competitive. However, literature data documenting the productivity of enzymatic biodiesel together with the development of new immobilization technology indicates that enzyme catalysts can become cost effective compared to chemical processing. This work reviews the enzymatic processing of oils and fats into biodiesel with focus on process design and economy.     

纳米催化剂在生物柴油合成中的应用

生物柴油作为一种可再生的绿色能源,是化石燃料理想的替代品.该文聚焦于纳米催化剂在生物柴油合成中的应用,对常见的纳米催化剂的设计、制备、物化性质、催化行为及重复使用性等方面进行了综述.提出了纳米催化剂在生物柴油合成中所面临的问题并展望其应用前景.     

Chemical reactions,thermal and mechanical properties of epoxy — Polycarbonate blends cured with aromatic amines

Bisphenol-A polycarbonate (PC) has been incorporated into epoxy resin cured with 4,4-diaminodiphenyl sulphone (DDS) and 4,4'-diaminodiphenyl methane (DDM). IR spectra reveal that transesterification and transamidation occur between the carbonate group of PC and the hydroxyl group of cured epoxy resin for the DDM-cured system, and that only transesterification occurs for the DDS-cured system. Scanning electron micrographs (SEM) show no evidence of phase separation in these cured systems, which is an indication of full miscibility between the bisphenol-A monomers and PC-oligomers with the copolymer network. The mechanical strength and glass transition temperature (T_g) fluctuate with PC content, whereas the flexural modulus shows a steadily increasing tendency.     

Transesterification in poly(ethylene terephthalate) and poly(ethylene naphthalate 2,6-dicarboxylate) blends: model compounds study

Kinetics of transesterification reaction in poly(ethylene terephthalate)-poly(ethylene naphthalate 2,6-dicarboxylate), PET-PEN, blends resulting from melt processing was simulated using model compounds of ethylene dibenzoate (BEB) and ethylene dinaphthoate (NEN). The exchange reaction between BEB and NEN was followed by ¹H NMR spectroscopy using signals from the aliphatic protons of ethylene glycol moieties at 4.66 and 4.78 ppm, respectively. The first-order kinetics was established under pseudo-first-order conditions for both reactants. Thus, the overall transesterification reaction was second order reversible. The reversibility was confirmed experimentally by heating a mixed sequence of 1-benzoate 2-naphthoate ethylene (BEN) under similar conditions. Both forward reaction of the equimolar amounts of the reagents and reverse reaction came to equilibrium at the same molar ratio of the reactants and reaction products of roughly 0.25:0.50:0.25 for BEB, BEN, and NEN, respectively. The rate equation for the transesterification reaction in the model system was modified using half-concentration of BEN, which is the only effective in the intermolecular exchange. Direct ester-ester exchange was deduced as a prevailing mechanism for the transesterification reaction under the conditions studied, and the values of equilibrium and rate constants, as well as other basic thermodynamic and kinetic parameters were determined. The use of Zn(OAc)₂ as a catalyst resulted in a significant decrease in the activation enthalpy of transesterification, which might be due to the partial switch of the reaction mechanism from primarily pseudo-homolytic to more heterolytic where Zn^II acts as a Lewis base which binds to the ester carbonyl oxygen.     

酯交换合成碳酸二苯酯催化剂的研究进展

对近年来碳酸二甲酯和苯酚酯交换合成碳酸二苯酯的催化剂体系进行了较为系统的概述,包括均相催化剂体系(碱或碱金属化合物、Lewis酸、锡和钛的有机化合物等)和多相催化剂体系(各种负载型、金属氧化物、水滑石等),认为开发有机锡、有机钛配合物催化剂以及将其固载化是碳酸二甲酯与苯酚酯交换反应合成碳酸二苯酯催化剂研究的重要方向.     

固体碱氧化钙催化蓖麻油酯交换制备生物柴油

制备了固体碱氧化钙催化剂,并用XRD技术、低温氮气吸附-脱附技术对其进行了表征。对固体碱氧化钙催化蓖麻油酯交换制备生物柴油进行了研究。考察了反应温度、醇油摩尔比、催化剂质量分数及反应时间对甲酯收率的影响。在反应温度为65℃、醇油摩尔比为9：1、催化剂质量分数为1．5％、反应时间为2．5h的优化工艺条件下,甲酯收率平均可达92％。用气相色谱法对产品进行了分析,甲酯质量分数为97．6％。产品后处理简单,对环境无污染且催化剂可活化再生,重复使用。     

Biodiesel production from inedible animal tallow and an experimental investigation of its use as alternative fuel in a direct injection diesel engine

In this study, a substitute fuel for diesel engines was produced from inedible animal tallow and its usability was investigated as pure biodiesel and its blends with petroleum diesel fuel in a diesel engine. Tallow methyl ester as biodiesel fuel was prepared by base-catalyzed transesterification of the fat with methanol in the presence of NaOH as catalyst. Fuel properties of methyl ester, diesel fuel and blends of them (5%, 20% and 50% by volume) were determined. Viscosity and density of fatty acid methyl ester have been found to meet ASTM D6751 and EN 14214 specifications. Viscosity and density of tallow methyl esters are found to be very close to that of diesel. The calorific value of biodiesel is found to be slightly lower than that of diesel. An experimental study was carried out in order to investigate of its usability as alternative fuel of tallow methyl ester in a direct injection diesel engine. It was observed that the addition of biodiesel to the diesel fuel decreases the effective efficiency of engine and increases the specific fuel consumption. This is due to the lower heating value of biodiesel compared to diesel fuel. However, the effective engine power was comparable by biodiesel compared with diesel fuel. Emissions of carbon monoxide (CO), oxides of nitrogen (NO_x), sulphur dioxide (SO₂) and smoke opacity were reduced around 15%, 38.5%, 72.7% and 56.8%, respectively, in case of tallow methyl esters (B100) compared to diesel fuel. Besides, the lowest CO, NO_x emissions and the highest exhaust temperature were obtained for B20 among all other fuels. The reductions in exhaust emissions made tallow methyl esters and its blends, especially B20 a suitable alternative fuel for diesel and thus could help in controlling air pollution. Based on this study, animal tallow methyl esters and its blends with petroleum diesel fuel can be used a substitute for diesel in direct injection diesel engines without any engine modification.     

Glycerolysis of Fatty Acid Methyl Esters: 1. Investigations in a Batch Reactor

The present work focused on the glycerolysis of fatty acid methyl esters. The aim was to develop and test a kinetic model that could be used to reliably simulate different process alternatives for this reaction. A prerequisite was the identification and characterization of the factors that affect the reaction kinetics. Experiments were carried out in a batch reactor with and without forced removal of methanol, which is one of the reaction products. Concentrations of all components in the two-phase system were measured. It was found that the methanol concentration has a strong effect on the reaction rate and equilibrium conversion. Near-complete conversions were obtained by stripping methanol with an inert gas. The glycerol concentration in the ester phase was found to increase as the reaction proceeds, which also accelerates the reaction. Effects of mass transfer on the reaction rate were not found to control the reaction rate under well-agitated conditions. A semi-empirical model was used to simulate the reaction. The results from the semi-empirical model show good agreement with experimental results.     

连续化条件下超临界甲醇法制备生物柴油

在连续操作的管式反应器中,以大豆油为原料在压力11～19MPa,温度240～400℃的超临界甲醇条件下进行连续化制备生物柴油的研究。考察了在连续反应条件下醇油摩尔比、压力、温度、停留时间及共溶剂对大豆油转化率的影响。实验结果表明:较高的醇油摩尔比有利于油脂转化率的提高,但当醇油摩尔比超过40:1后提高醇油摩尔比对提高油脂转化率的影响不大;在11～15MPa范围内,压力升高对油脂转化率影响很大,但高于15MPa后压力对转化率的影响减弱;反应温度对油脂转化率有着重要影响,在300℃以上随着温度的升高,油脂转化率有较大幅度的上升,但温度太高油脂会发生分解反应;醇油摩尔比40:1,温度350℃,压力15MPa,停留时间1000s是该实验获得的最佳反应条件,在该条件下油脂转化率可达89%。实验还研究了添加共溶剂四氢呋喃对油脂转化率的影响。     

In situ synthesis and characterization of Ca-Mg-Al hydrotalcite on ceramic membrane for biodiesel production☆

In situ surface synthesis of Ca–Mg–Al hydrotalcite (HT) on inorganic ceramic membrane (CM) was investigated with urea as precipitator. The effects of molar ratio of raw materials, crystallization time, and temperature on surface synthesis of HT were examined. The as-prepared HT/CM samples were characterized by XRD and SEM and an in sit growth mechanismof HT on CMwas proposed. KF/HT/CMobtained by loading potassium fluoride (KF) on the HT layer by impregnation and calcination method was used as catalyst for transesterification between palm oil and methanol. The comparison of KF/HT/CMand pure KF/HT powder under identical reaction conditions shows that the production of fatty acid methyl ester is equivalent, which means that the use of inorganic catalytic membrane in the transesterification is a viable alternative.