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废植物油直接烷基化中多相催化条件的优化

The optimization of heterogeneous catalytic conditions in the direct alkylation of waste vegetable oil.

作者信息

Gao Cheng-Long, Wang Xin, Gang Hong-Ze, Liu Jin-Feng, Mu Bo-Zhong, Yang Shi-Zhong

机构信息

State Key Laboratory of Bioreactor Engineering and Institute of Applied Chemistry, East China University of Science and Technology, Shanghai 200237, People's Republic of China.

出版信息

R Soc Open Sci. 2020 Jul 22;7(7):192254. doi: 10.1098/rsos.192254. eCollection 2020 Jul.

Abstract

Alkylated waste vegetable oil is a versatile intermediate product in the synthesis of bio-based materials. Heterogeneous catalytic condition with high conversion rate in the direct alkylation of waste vegetable oil was reported and the deactivation mechanism of catalyst was revealed. The total exchange capacity, elemental composition and pyrolysis product of catalyst before and after the alkylation reaction were analysed by back titration, elemental analysis, electrospray ionization mass spectrometry, gas chromatography mass spectrometry and pyrolysis-gas chromatography/mass spectrometry, respectively. The results indicated that the metallic and non-metallic (C, H) elements contents of the catalyst have very much increased with great changes in pyrolysis product and a slight decrease in the total exchange capacity. The formation of insoluble polymers through Diels-Alder cycloaddition between triglycerides was proved to be the major factor causing the dysfunction of the catalytic centre. The metal ions from corrosion of the reactor were the minor factor causing about 2.56% loss of the catalytic centre. Moreover, the catalyst was able to maintain high catalytic efficiency when replacing the raw materials with other waste vegetable oil having low concentration of polyunsaturated fatty acids, which is significant for producing not only the aryl fatty acids derivatives but also the bio-based surfactants.

摘要

烷基化废植物油是生物基材料合成中一种用途广泛的中间产物。报道了废植物油直接烷基化过程中具有高转化率的多相催化条件,并揭示了催化剂的失活机理。分别采用返滴定法、元素分析法、电喷雾电离质谱法、气相色谱 - 质谱法和热解 - 气相色谱/质谱法分析了烷基化反应前后催化剂的总交换容量、元素组成和热解产物。结果表明,催化剂的金属和非金属(C、H)元素含量大幅增加,热解产物变化很大,总交换容量略有下降。证明甘油三酯之间通过狄尔斯 - 阿尔德环加成形成不溶性聚合物是导致催化中心功能失调的主要因素。反应器腐蚀产生的金属离子是导致催化中心约2.56%损失的次要因素。此外,当用其他低浓度多不饱和脂肪酸的废植物油替代原料时,该催化剂能够保持较高的催化效率,这对于生产芳基脂肪酸衍生物和生物基表面活性剂都具有重要意义。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e57e/7428286/bc5bbd7289fd/rsos192254-g1.jpg

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