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Sulfonic Acid Functionalization of Different Zeolites and Their Use as Catalysts in the Microwave-Assisted Etherification of Glycerol with tert-Butyl Alcohol

机译:不同沸石的磺酸功能化及其在叔丁醇微波辅助甘油酯化反应中的应用

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摘要

The etherification of glycerol with tert-butyl alcohol in the liquid phase, over different sulfonic acid functionalized zeolites, has been studied. The reaction was carried out using microwaves as a way of heating, measured at autogenous pressure and without any solvent. Dealuminated HY and HZSM-5 zeolites by acid treatment were functionalized with two different organosilica precursors: 3-mercaptopropyltrimethoxysilane (>M), which incorporates thiol groups, and 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane (>C), which incorporates the sulfonic acid groups directly. The thiol groups were oxidized into sulfonic groups employing hydrogen peroxide. The textural and structural properties of the solids were studied by XRD and N2 adsorption–desorption isotherms, whereas the incorporation of the organosilica in the zeolites was studied by TGA and XPS. The novelty functionalization of >M gave rise to solids with the highest acidity, and exhibited the highest yields with more substituted ethers (Yh-GTBE = 13%), at 75 °C and 15 min of reaction time. In addition to the acidity, the textural properties of the zeolites played an important role in their activity; HY, with the largest size of the channels, were more active than the HZSM-5.
机译:研究了在不同的磺酸官能化沸石上,甘油与叔丁醇在液相中的醚化反应。使用微波作为加热方式进行反应,该反应在自生压力下且没有任何溶剂的条件下进行测量。经过酸处理的脱铝HY和HZSM-5沸石用两种不同的有机硅前体官能化:3-巯基丙基三甲氧基硅烷(> M ),其结合有硫醇基团;和2-(4-氯磺酰基苯基)乙基三甲氧基硅烷(> C ),它直接结合了磺酸基。使用过氧化氢将硫醇基氧化为磺酸基。通过XRD和N2吸附-解吸等温线研究了固体的结构和结构性质,而通过TGA和XPS研究了沸石中有机硅的掺入。在75°C和15分钟的反应时间下,> M 的新颖功能化产生了具有最高酸度的固体,并显示出最高收率,且带有更多的取代醚(Yh-GTBE = 13%)。除酸度外,沸石的质地特性在其活性中也起着重要作用。 HY频道最大,比HZSM-5更为活跃。

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