脂肪酸异丙酯的碱性合成

S. Zubenko, S. Konovalov, B.A. Denysiuk, L. Patrylak
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摘要

脂肪酸烷基酯是应用广泛的产品。其中大部分被用作可再生运输燃料,称为“生物柴油”。脂肪酸异丙酯的生产主要以酸法为主,但使用碱性催化剂也可获得较好的收率。碱性催化剂具有腐蚀性低、反应速度快等优点。目前的研究比较了氢氧化钾和处理过的氢氧化钾溶液作为酯交换反应催化剂的效果。结果表明,在特殊处理后的异丙醇中使用KOH溶液,精制葵花籽油甘油三酯的收率(95- 96%)几乎是相同条件下使用KOH溶液的两倍。废煎炸油在两种催化剂上反应1-1.5小时后,脂肪酸异丙酯的产率稳定。在90℃下使用1.8和2.0%处理过的催化剂,在9:1醇油比下,产率约为86- 88%。反应温度对产率有显著影响,在30 ~ 90℃范围内,产率随温度的降低而降低。在反应过程中碱皂化导致催化活性丧失,抑制了产率的提高。废油中酯的产率较成品油低,可能是由于在油炸过程中形成的重聚合甘油三酯成分的存在。这些成分不能完全转化为单烷基酯,也会产生低聚酯,这在生物柴油的标准气相色谱分析中是不可见的。在废弃的煎炸油样品中间接证实这类化合物的存在是真空蒸馏中立方体残渣的足够大的质量。成品油的残渣率仅为5.4%,而废油的残渣率为14.9%,是废油的3倍。以废弃的煎炸油为原料,即使经过充分转化和有效的自分离,传统的净化方法(如水洗或用吸附剂干洗)也可能无法提供所得到的生物柴油的必要纯度,因为存在重的低聚外加剂。在这种情况下,真空蒸馏应作为必要的最后净化阶段。
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Alkaline synthesis of fatty acids iso-propyl esters
Fatty acid alkyl esters are widely used products. Most of them are used as renewable transport fuel named “biodiesel”. Production of fatty acid iso-propyl esters mainly based on acid process, but using of alkaline catalysts may give good yields also. Alkaline catalysts have some advantageous such as low corrosivity and higher reaction rate. In current work the effectivity of potassium hydroxide and treated potassium hydroxide solution as catalyst for transesterification was compared. It was shown that using of KOH solution in iso-propyl alcohol after special treatment gives almost twice higher yields (95-96 %) from refined sunflower oil triglycerides than over KOH under the same conditions. Yield of fatty acids iso-propyl esters from wasted frying oil stabilized after 1-1.5 hours of reaction over both catalysts. Using 1.8 and 2.0 % treated catalyst at 90 °C leads to yield of about 86-88 % at 9:1 alcohol-to-oil ratio. Reaction temperature has significant impact on a yield wich decreases with temperature reduce in the range from 30 to 90 °C. During reaction proceeding the alkali saponification and thus loss the catalytic activity, which displayed in stopping the yield rising. The lower yield of esters from wasted oil comparing to the refined oil may be caused by presence of heavy polymerized triglycerides components formed during frying. Such components cannot be fully converted into monoalkylesters and gives also the oligomerized esters, which is not visible in standard gas chromatographic analysis of biodiesel. Indirect confirmation of the presence of such compounds in wasted frying oil sample is the sufficiently larger mass of the cube residue in vacuum distillation. For refined oil amount of such residue was only 5.4 %, while for wasted oil it was three time higher (14.9 %). In case of wasted frying oil as raw stuff, even after full conversion and effective self-separation conventional purification methods (like water washing or dry washing with adsorbents) may not provide the necessary purity of resulted biodiesel due to the presence of heavy oligomeric admixtures. In such cases vacuum distillation should be included as necessary final purification stage.
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