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.     

Low-temperature properties of triglyceride-based diesel fuels: Transesterified methyl esters and petroleum middle distillate/ester blends

This work examines low-temperature properties of triglyceride-based alternate fuels for direct-injection compression-ignition engines. Methyl esters from transesterified soybean oil were studied as neat fuels and in blends with petroleum middle distillates (No. 1 or No. 2 diesel fuel). Admixed methyl esters composed of 5–30 vol% tallowate methyl esters in soyate methyl esters were also examined. Pour points, cloud points, and kinematic viscosities were measured; viscosities at cooler temperatures were studied to evaluate effects of sustained exposure. Low-temperature filterability studies were conducted in accordance with two standard methodologies. The North American standard was the low-temperature flow test (LTFT), and its European equivalent was the cold-filter plugging point (CFPP). With respect to cold-flow properties, blending methyl esters with middle distillates is limited to relatively low ester contents before the properties become preclusive. Under most conditions, cold-flow properties were not greatly affected by admixing the methyl esters with up to 30 vol% tallowate (before blending). Least squares analysis showed that both LTFT and CFPP of formulations containing at least 10 vol% methyl esters are linear functions of cloud point. In addition, statistical analysis of the LTFT data showed a strong 1:1 correlation between LTFT and CP. This result may prove crucial in efforts to improve low-temperature flow properties of alternate diesel fuels that contain methyl esters derived from triglycerides.     

脂肪酸甲酯处理含苯胺工业废水

采用正交实验设计研究了用脂肪酸甲酯处理工业苯胺废水的条件。实验表明:在影响苯胺废水萃取效果的诸因素中,影响大小的顺序为pH值、油水相比、溶液初始浓度和温度。在pH值=7,油水相比为2∶1,20℃的最佳萃取条件下,高浓度苯胺废水经萃取剂脂肪酸甲酯三级萃取后,苯胺去除率达99.98%。     

Synthesis of Biodiesel from Soybean Oil using Heterogeneous KF/ZnO Catalyst

Biodiesel was produced by transesterification of soybean oil with methanol using ZnO loaded with KF as a solid base catalyst. It was found that the catalyst with 15 wt.% KF loading and calcined at 873 K showed the optimum activity. XRD, IR and Hammett indicator method were employed for the catalyst characterization. The results showed the activity of the catalysts was correlated with their basicity. The influence of various reaction variables on the conversion was also discussed.     

羰基化法合成氨基甲酸酯催化剂的研究进展

对氧化羰基化法、还原羰基化法及氧化还原羰基化法3种羰基化合成氨基甲酸酯方法中催化剂的研究进展进行了综述,其中着重讨论了各种配体及助剂对催化剂活性的影响。指出今后的研究应集中在寻找高效、价廉及可重复使用的催化体系或对高效的均相催化体系进行负载化以及研究多相催化体系的催化机理。     

Self-emulsifiable soybean oil phosphate ester polyols for low-VOC corrosion resistant coatings

A series of soybean oil phosphate ester polyols (SOPEP) was prepared by reaction of fully epoxidized soybean oil with phosphoric acid and simultanoeous hydrolysis in the presence of a polar solvent. The polyols were characterized by determination of acid value, oxirane number, hydroxyl value, molecular weight (GPC), and FTIR spectra. These polyols with varying amounts of acid phosphate groups could be self-emulsified to form aqueous dispersions after neutralization with organic base. These aqueous dispersion showed varying degrees of stability and their appearance ranged from opaque dispersions to translucent to clear solutions. Waterborne coating compositions were prepared using these aqueous dispersions as principal components and their thermally cured film properties were studied. it was found that by careful selection and formulation, SOPEPs can be successfully used for low-VOC waterborne coating formulations. SOPEPs with 3.5% phosphate ester content showed visibly superior corrosion resistance properties.     

Transient testing of soy methyl ester fuels in an indirect injection,compression ignition engine

An evaluation of the exhaust emissions from a compression ignition engine for fuels composed of 100 and 30% methyl esters of soy oil (SME) is described. These fuels were compared with a low-sulfur, petroleum #2 diesel fuel in a Caterpillar 3304, prechamber, 75 kW diesel engine, operated over heavy- and light-duty transient test cycles developed by the United States Bureau of Mines. More than 60 h of testing was performed on each fuel. The objective was to determine the influence of the fuels upon diesel particulate matter (DPM) and gaseous emissions. The effect of a modern diesel oxidation catalyst (DOC) also was determined in an effort to minimize emissions. Neat SME produced a higher volatile fraction of the DPM, but much less carbon soot fraction, leading to overall DPM reductions of 23 to 30% for the light- and heavy-duty transients. The DOC further reduced the volatile fraction and the total DPM. The SME fuel reduced gaseous emissions of CO by 23% and hydrocarbons by over 30% without increasing NO_x. The DOC further reduced CO and hydrocarbon levels. Mutagenicity of the SME exhaust was low. Results indicate that SME fuel, used with a proper DOC, may be a feasible emission reduction technology for underground mines. References to specific products do not imply endorsement by the U.S. Bureau of Mines, a now defunct agency.     

Enzymatic production of alkyl esters through alcoholysis: A critical evaluation of lipases and alcohols

This paper focuses on a detailed evaluation of commercially available immobilized lipases and simple monohydric alcohols for the production of alkyl esters from sunflower oil by enzymatic alcoholysis. Six lipases were tested with seven alcohols, including straight and branched-chain primary and secondary alcohols. The reactions were conducted in a batch stirred reaction vessel using stoichiometric amounts of substrates under solvent-free conditions. Dramatic differences in alcoholysis performance were observed among the different lipases. For most of the alcohols, Novozym 435 produced the highest yield of FA alkyl esters, with yields well over 90% for methanol, absolute ethanol, and 1-propanol. Overall, 96% ethanol was the preferred alcohol for all lipases except Novozym 435, and ethanolysis reactions reached the maximal conversion efficiency. Increasing the water content in the system resulted in an increased degree of conversion for all lipases except Novozym 435. The secondary alcohol 2-propanol significantly reduced the alcoholysis reaction with all lipases; however, the branch-chain isobutanol was more advantageous than linear 1-butanol for Novozym 435, Lipozyme RMIM, and Lipase PS-C. Many commercial immobilized lipases are highly efficient and promising for the production of alkyl esters, offering high reaction yields and a simple operation process.