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生物油/植物油转换柴油发动机燃料的酯化反应

--酯交换反应过程分析仪,检控仪器

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由于石油供应越来越紧张,甲醇、乙醇来替代汽油燃烧，柴油车用菜籽油、葵花油等植物油做燃料可能在所难免。

甲醇和乙醇 取代汽油供发动机试用的技术已经进行20多年了,几乎是成熟的替代燃料.我相信各大汽车生产公司都准备好了甲醇或乙醇汽车的技术.然而植物油 取代柴油的研究工作方兴未艾。

澳大利亚,德国,意大利,美国已经制定了有关质量标准。柴油机植物油燃料主要成分是单烷基脂肪酸酯。

要保证发动机能很好地"消化"植物油, 必须对植物油进行加工。转换单,双,三甘油酰酯化合物为甲基酯油是最基本的过程，其中水分，游离脂肪酸，游离甘油和总甘油 （包括游离甘油和单,双,三甘油酰酯化合物） ,残留醇<LLA4812-OH>（影响闪点）等成分也需要控制 ，因为这些成分有可能使油品在储藏过程中变质，也会导致很多发动机工作问题，例如发动机中沉积物增加等。

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Biodiesel, defined as the monoalkyl esters of fatty acids from vegetable oils and animal fats (1), neat and blended with conventional diesel fuel has significant potential as alternative diesel fuel (2, 3). Initial stages of commercialization have been successful. Biodiesel is usually obtained from the neat vegetable oil by transesterification with an alcohol, usually methanol, in presence of a catalyst, usually a base such as KOH (Fig. 1). Glycerol is a by-product of the reaction. Other possible materials in biodiesel include residual alcohol, moisture, unreacted feedstock (triacylglycerides), incompletely reacted mono- and diglycerides, and free fatty acids.

Fuel standards have been developed in Austria (ÖNORM C 1190), Germany (DIN 51606) and Italy (UNI 10635:1997), and in the United States a provisional ASTM (American Society for Testing and Materials) standard has been completed. The fuel standards address quality issues of biodiesel by limiting materials such as free and total glycerol (total glycerol is the sum of free glycerol and glycerol bound as mono-, di-, and triacylglycerides), water (moisture), free fatty acid (by limiting the acid number), and residual alcohol (by limiting the flash point). These materials need to be limited in biodiesel because their presence can lead to fuel deterioration during storage as well as to significant operational problems such as engine deposits. The rationale for various quality test methods in biodiesel standards (United States, Austria) has been discussed (4, 5).

The analysis of biodiesel for various contaminants is usually conducted by gas chromatography (GC). Originally, a method for analyzing mono-, di-, and triacylglycerides together with methyl esters in one run was developed (6). This method was extended to include glycerol (7). Other papers also report on the GC analysis of biodiesel for determining contaminants such as methanol, glycerol, and glycerides (8-13). Biodiesel was also analyzed by GC for minor components such as sterols (14, 15). Preseparation of biodiesel and its contaminants by high-performance liquid chromatography (HPLC) prior to GC was reported (16). However, other methods have been utilized in the analysis of biodiesel, including HPLC with density detection (17) or pulsed amperometric detection for determining glycerol (18), and viscosity (19).

　

Fig. 1. Transesterification reaction.

On the other hand, spectroscopic methods are being increasingly utilized for quality control purposes. Near-infrared (NIR) spectroscopy is among the methods finding increased use. Operational ease, rapidity of measurement, and nondestructiveness are among the chief reasons for this development besides accuracy and reliability. NIR spectroscopy is now being used routinely for analyzing the fatty acid composition of oilseeds besides finding other applications in the field of fats and oils (20, 21). To the best of our knowledge, the NIR spectra of numerous fatty compounds were first reported more than 40 years ago (22). Several other papers discuss NIR spectra of long-chain compounds (23-25). Here we report differences in the NIR spectra of vegetable oils (soybean oil used as example here) and their methyl esters as well as initial results on the potential use of these spectral differences to monitor progress and endpoint of the transesterification. A model system consisting of defined concentrations of contaminants in biodiesel was used. By induction, biodiesel fuel quality can be assessed. NIR can be an alternative not only to GC but to other methods in biodiesel standards, for example flash point. Testing biodiesel for every such specification in the standard is a lengthy and extremely expensive process. A method such as NIR can shorten this process and render it considerably less expensive. Spectra were obtained with the aid of a fiber-optic probe, which makes the use of NIR spectroscopy particularly easy.