燃料甲酯应用研究浅析

本阐述了分别使用燃料甲酯及柴油时由柴油机以加俐到的示功图，烟度及过量空气系统等的对比结果。经分析认为：当燃料甲酯取代柴油机时，用户可不必对柴油机另作调整，因而十分方便。     

Preparation of fatty acid methyl esters for gas-chromatographic analysis of lipids in biological materials

Theoretically, preparation of fatty acid methyl esters (FAMEs) deals with reversible chemical reactions in a complex system. Methodologically, there are numerous ways, generally characterized by the type of catalysts used and steps involved. Although there are more than a half dozen common catalysts, the majority fall into either acidic (HCl, H₂SO₄ and BF₃) or alkaline types (NaOCH₃, KOH and NaOH), with each having its own catalytic capability and application limitations. In terms of steps, many conventional methods, including those officially recognized, consist of drying, digestion, extraction, purification, alkaline hydrolysis, transmethylation/methylation and postreaction work-up. Although these methods are capable of providing reliable estimates if some precautions are taken, they are cumbersome, time-consuming and cost-inefficient. A new approach has been to transmethylate lipidsin situ. Due to its simplicity, high sensitivity, comparable reliability and capability to determine total fatty acids, the method of direct transmethylation is finding a unique place in lipid determination. Regardless of which method is used, quantitative methylation requires chemists to take precautions at every step involved, particularly during FAME formation and subsequent recovery steps. Evidently, there is an urgent need for more systematic studies, guided by the chemical principle of reactions involved and physicochemical properties of regents and end products, into factors affecting these steps. Hopefully, this will lead to an improved method, which measures lipid composition in biological materials not only with high accuracy but also with high efficiency and minimum costs.     

Process conditions for separating fatty acid esters by supercritical CO2

The solubilities of ethyl palmitate, ethyl oleate, ethyl eicosapentaenoate (EPA) and ethyl docosahexaenoate (DHA) in supercritical carbon dioxide were determined by a continuous flow method. The solubilities of fatty acid ethyl esters increased with pressure and decreased as the temperature was increased. An empirical equation, similar to Chrastil's equation, was used to describe the relationship between solute solubility and the density of carbon dioxide. The empirical equation was further used to qualitatively estimate the separation efficiency of isolating EPA and DHA ethyl esters from fatty acid esters. The operating conditions yielding high solubility gave fast extraction rate but resulted in low separation efficiency. Experiments were conducted to separate ethyl EPA and ethyl DHA from a model mixture containing four fatty acid ethyl esters and from esterified squid visceral oil. The experimental data compared closely with the calculated values.     

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.     

Synthesis and characterization of maltose fatty acid monoesters as biosurfactants

Maltose long-chain fatty acid esters (MFAE), esterified at the 6 and 6′ position, were synthesized with stearic, palmitic, myristic, and oleic groups. Synthesis yields were 15–20% based on initial maltose present, and structural confirmation was obtained using plasma desorption mass spectrometry and nuclear magnetic resonance spectroscopy. These surfactants have surface tensions in the range of 34–36 dyn/cm at their critical micelle concentrations (CMC) of approximately 10⁻⁵–10⁻⁶ mol/L. The increased chain lengths have a marked effect, reducing CMC values for MFAE by approximately three orders of magnitude over similar carbohydrate-based dodecyl chain sources. Within chain lengths between 14 and 18 carbons, the rate of change in CMC is significant and decreases with increasing chain length for MFAE. The melting points of MFAE are approximately 40°C, and the heat capacities range from 1.6 to 1.9 J/g·K. These numbers are comparable to those of sucrose esters, indicating their applicability in similar uses. However, because MFAE, unlike sucrose, possess an anomeric carbohydrate carbon position, these surfactants maintain their reducing nature and are susceptible to further derivatization. They are also synthesized from renewable, economical carbohydrates and lipids and may provide an excellent alternative to pertrochemical-derived products.     

甲基丙烯酸缩水甘油酯的合成

在季铵盐催化作用下 ,甲基丙烯酸与环氧氯丙烷反应生成甲基丙烯酸缩水甘油酯。实验结果表明 ,二步法可获得较高的产率     

Preparation of glycol derivatives of partially hydrogenated soybean oil fatty acids and their potential as lubricants

Glycol diesters and mixtures of mono- and diesters have been prepared from methyl esters of partially hydrogenated soybean oil fatty acids and diethylene, dipropylene, neopentyl and triethylene glycols. The catalyst used in these reactions was a mixture of calcium acetate/barium acetate (3∶1, w/w). The reactions were carried out under nitrogen with 0.5% catalyst at temperatures in the range of 190–275°C. Borated esters of mixed mono- and diesters were prepared with 0.33 equivalent of boric acid per 1.0 equivalent hydroxyl group on the ester. Refractive indices, viscosities, and flash and fire points were determined for diesters, mixed mono- and diesters, and mixed diesters and borated esters. The viscosities, flash points and fire points indicate that these esters can be used as a component of lubricating oils. Wear-prevention characteristics of mixed diesters and borated esters indicated that they can be used as antifriction additives in lubricating oils. Lecture presented at the joint meeting of the International Society for Fat Research and the American Oil Chemists' Society in Toronto, May 10, 1992.     

对羟基苯甲酸酯的催化剂研究

综述了固体超强酸TiO2/SO42-,磷钨、硅钨杂多酸及固载杂多酸盐TiSiW12O40/TiO2,浓硫酸(微波常压法),Lewis酸(FeCl3·6H2O,Fe2(SO4)3·xH2O)等几种不同催化剂催化合成对羟基苯甲酸酯的实验结果.分析各种固体催化剂对该酯化反应的催化活性、选择性、重复使用性能及使用范围.     

Phase diagrams for oil/methanol/ether mixtures

One-phase transmethylations of vegetable oils with methanol to form methyl esters occur considerably faster than conventional two-phase reactions. Addition of simple ethers is an efficient method for producing a single phase. Ternary phase diagrams have been determined at 23°C for oil/methanol/ether mixtures; these are useful when applying the one-phase method across a wide range of conditions. Soybean, canola, palm, and coconut oils were used in combination with five ethers, namely, tetrahydrofuran (THF), 1,4-dioxane (DO), diethyl ether (DE), diisopropyl ether (DI), andtert-butyl methyl ether (TBM). All five ethers can produce miscibility for all methanol/oil compositions. The ether/methanol volumetric ratios required for miscibility at a methanol/soybean or canola oil volumetric ratio of 0.20 (5.4 molar ratio) at 23°C are: THF, 1.15; DO, 1.60; DE, 1.38 DI, 1.57; and TBM, 1.57. For THF, this results in one-phase mixtures that contain 65 vol% oil. Soybean and canola oil form identical diagrams. Palm oil requires slightly less ether at the lower methanol concentrations, but coconut oil requires considerably less across the whole concentration range. Acid-catalyzed reactions, when performed at the boiling point of the most volatile component, require less ether than predicted from the diagrams.     

GMA接枝SEBS及其对PA 6的改性及增容

用双螺杆反应挤出法将甲基丙烯酸缩水甘油酯(GMA)接枝到氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)上(即SEBS-g-GMA)，研究引发剂过氧化二异丙苯用量、活性单体GMA用量对接枝率的影响；通过双螺杆挤出、共混，制备聚酰胺(PA)6／SEBS-g-GMA、PA 6／SEBS-g-GMA／SEBS合金，研究SEBS-g-GMA对合金体系的相容性影响及增韧作用，探讨了合金体系的形态结构和力学性能。