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Cooperativity of Bronsted and Lewis Acid Sites on Zeolite for Glycerol Dehydration

机译:沸石上布朗斯台德和路易斯酸位点对甘油脱水的协同作用

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Selective dehydration of glycerol, a byproduct from the biodiesel industry, on solid acids is an important reaction in the production of the value-added chemical acrolein for economic-sustainable biorefinery. Most efforts have been made on the development of strong Brnsted acid sites (BAS) to improve the production of acrolein, because the Lewis acid sites (LAS) generally promote the generation of the byproduct acetol. However, exclusively tuning the properties of BAS or LAS did not well-promote the acrolein production from glycerol as indicated in this work. We provide a new route for efficient and selective glycerol transformation to acrolein via the cooperative dehydration between the BAS and LAS. The role of LAS (extra-framework aluminum species on zeolites) was altered from competition with BAS to generate the byproduct acetol to cooperation with the neighboring BAS. It is very beneficial for the sequential two-step dehydration of the internal and terminal hydroxyl groups of glycerol to value-added acrolein. This cooperativity of BAS and LAS significantly improved the yield of acrolein from the selective glycerol dehydration.
机译:生物柴油行业的副产品甘油在固体酸上的选择性脱水是增值化学丙烯醛生产中的重要反应,用于经济上可持续的生物炼油厂。由于强路易斯酸位点(LAS)通常促进副产物丙酮醇的产生,因此已经在开发强布朗斯台德酸位点(BAS)以改善丙烯醛生产方面做出了很多努力。但是,如本工作所示,仅调节BAS或LAS的性能并不能很好地促进甘油的丙烯醛生产。我们提供了一种新的途径,可通过BAS和LAS之间的协同脱水将甘油高效有效地转化为丙烯醛。 LAS(沸石上的超骨架铝物质)的作用已从与BAS竞争以生成副产物丙酮醇的方式转变为与邻近BAS的合作。对于甘油的内部和末端羟基连续两步脱水为增值丙烯醛非常有益。 BAS和LAS的这种协同作用显着提高了选择性甘油脱水的丙烯醛收率。

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