Hydrodeoxygenation of biodiesel-related fatty acid methyl esters to diesel-range alkanes over zeolite-supported ruthenium catalysts
Hydrodeoxygenation of biodiesel-related fatty acid methyl esters to diesel-range alkanes over zeolite-supported ruthenium catalysts
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在沸石负载的钌催化剂上，生物柴油相关的脂肪酸甲酯加氢脱氧为柴油范围的烷烃。
DOI：
10.1039/c6cy01242f
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发表时间：
2016-01-01
影响因子：
5
通讯作者：
Xu, Qiyong
中科院分区：
文献类型：
--
作者：
Chen, Jinzhu;Xu, Qiyong
在双功能催化剂上，反应介质对脂肪酸甲酯(FAME)加氢脱氧反应产物的分布有显著影响。在Ru/HZSM-5催化剂上，生物柴油相关硬脂酸甲酯加氢脱氧为正十七烷和正十八烷。在水介质中，由于水对十八醇脱水过程的抑制作用，正十七烷是主要产物。在环己烷介质中，由于反应温度对十八醇加氢脱氧过程的促进作用，C-17/(C-17+C-18)比随着反应温度的升高而显著降低。我们的研究结果进一步揭示了在硬脂酸甲酯的加氢脱氧网络中，溶剂水能显著促进硬脂酸甲酯通过水解和氢解步骤转化为硬脂酸。硬脂酸甲酯在水中的加氢脱氧温度比在环己烷中低约40度。反应途径包括硬脂酸甲酯在Ru/HZSM-5上的氢解(在水或有机相中)和硬脂酸甲酯在HZSM-5上的水解(在水中)，生成硬脂酸。十八醛是硬脂酸转化为十八醇的关键中间体，负责在Ru/HZSM-5催化剂上通过脱碳途径生成十八烷，而十八醇的加氢脱氧则导致十八烷的生成。
The reaction medium shows a significant effect on the distribution of alkane products for the hydro-deoxygenation of fatty acid methyl esters (FAMEs) over a bifunctional catalyst. Biodiesel-related methyl stearate was hydrodeoxygenated to heptadecane and octadecane over Ru/HZSM-5. In aqueous medium, heptadecane is a predominant product owing to a suppression effect of water on the octadecanol dehydration process. In the case of cyclohexane medium, the C-17/(C-17 + C-18) ratio significantly decreases with the temperature due to a promotion effect of reaction temperature on the octadecanol hydro-deoxygenation process. Our research results further reveal that solvent water can remarkably promote the methyl stearate-to-stearic acid transformation in the network of hydrodeoxygenation of methyl stearate via hydrolysis and hydrogenolysis steps. The hydrodeoxygenation temperature required for methyl stearate is approximately 40 degrees lower in water than in cyclohexane. The reaction pathway involves methyl stearate hydrogenolysis over Ru/HZSM-5 (in water or organic phase) and methyl stearate hydrolysis over HZSM-5 (in water) to generate stearic acid. Octadecanal is a key "intermediate" for subsequent stearic acid-to-octadecanol transformation and is responsible for heptadecane production via the decarbonylation pathway over Ru/HZSM-5, while hydrodeoxygenation of octadecanol leads to the formation of octadecane.