Transesterification of Palm-based Methyl Palmitate into Esteramine Catalyzed by Calcium Oxide Catalyst

The technology for transesterification reactions between methyl esters and alcohols is well established by using classical homogeneous alkaline catalysts, which provide high conversion of methyl esters to specialty or nonindigenous esters. However, in certain products where the purity of the esters is of concern, the removal of homogeneous catalysts after the completion of the reaction is a challenge in terms of production cost and water footprint. Therefore, a study to investigate the potential of heterogeneous catalysts was conducted on reactions between methyl palmitate and triethanolamine. The degree of basicity and active surface area of calcium oxide (CaO), zinc oxide (ZnO), and magnesium oxide (MgO) were first characterized by using temperature-programmed desorption (TPD-CO₂) and Brunauere–Emmett–Teller (BET), respectively. Among the metal oxides investigated, the CaO catalyst showed the best catalytic activity toward the transesterification process as it gave the highest conversion of methyl palmitate and yielded fatty esteramine compositions similar to the conventional homogeneous catalyst. The optimum transesterification condition by using the CaO catalyst utilized a lower vacuum system of approximately 200 mbar, which could minimize a considerable amount of energy consumption. Furthermore, low CaO dosage of 0.1% was able to give a conversion of 94.5% methyl ester and formed esteramine at 170 °C for 2 h. Therefore, the production of esterquats from esteramine may become more economically feasible through the methyl ester route by using the CaO catalyst, which can be recycled three times.     

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.     

酯交换法合成碳酸二苯酯研究进展

对碳酸二苯酯合成用催化剂、合成工艺、反应装置等进行了综述。认为国内应加强酯交换法合成碳酸二苯酯的基础研究 ,尽快实现其产业化     

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.     

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。     

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.     

Soybean oil transesterification over zinc oxide modified with alkali earth metals

Fatty acid methyl esters, derived from vegetable oils or animal fats and better known as biodiesel, have received considerable attention because of their environmental benefits and the limited resources of fossil fuels. Most biodiesel is usually produced by the transesterification of vegetable oils with methanol in the presence of a catalyst. This study reports on the preliminary results of using alkaline earth metal-doped zinc oxide as a heterogeneous catalyst for transesterification of soybean oil. The highest catalytic activity was obtained with ZnO loaded with 2.5 mmol Sr(NO₃)₂/g, followed by calcination at 873 K for 5 h. When the transesterification reaction was carried out at reflux of methanol (338 K), with a 12:1 molar ratio of methanol to soybean oil and a catalyst amount of 5 wt.%, the conversion of soybean oil was 94.7%. Besides, tetrahydrofuran (THF), when used as a co-solvent, could increase the conversion up to 96.8%. However, the recovered catalyst exhibited the lower catalytic activity with a conversion of soybean oil of 15.4%. Furthermore, DTA-TG, IR and the Hammett indicator method were employed for the catalyst characterizations.     

鸡蛋壳催化大豆油酯制备生物柴油

以废弃鸡蛋壳为原料制得固体碱催化剂,催化大豆油与甲醇的酯交换来制备生物柴油。利用热重分析仪、低温氮气吸附脱附仪等对制备的催化剂进行了表征。实验结果表明：950℃下焙烧3.0h制得的催化剂活性最佳。制备生物柴油的最佳工艺条件为：醇油物质的量比10∶1、催化剂质量分数为3.0%、反应时间3.0h。在最佳工艺条件下,生物柴油收率可达98.9%。对催化剂的稳定性做了进一步研究,实验结果表明：制备的催化剂在重复使用13次以上,仍保持了较高的催化活性,生物柴油收率可达到98%以上。