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Ammonium-substitution for successfully activating the bulk of Keggin acid salts in 1-butanol dehydration

机译:Ammonium-substitution成功激活大部分在1-butanol Keggin酸盐脱水

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摘要

In 1-butanol dehydration (gas phase) on a Keggin heteropolyacid (HPA) catalyst, the large size of 1-butanol and its significant hydrophobicity make the bulk-type (also called pseudo liquid-type) catalytic mechanism impossible. This drastically limits the catalytic effect on the surface of the HPA, with an activity lower than what it could be. To overcome this limitation, partially substituted ammonium Keggin acid salts with the formula (NH4)(x)H(3-x)PW(12)O(40)were here synthesized. Still maintaining enough acidity for the dehydration reaction, the replacement of some protons of H(3)PW(12)O(40)with NH(4)(+)increases the hydrophobicity of the crystal matrix and allows 1-butanol to enter the bulk of the salt. This consequently makes the protons inside the solid able to catalyse the reaction. The penetration of 1-butanol in the bulk is demonstrated by a combination ofin situmethods (Raman, FTIR and XRD) applied during the pre-treatment of the catalyst and the catalytic reaction. When properly activated the pseudo liquid-type mechanism taking place in (NH4)(x)H(3-x)PW(12)O(40)leads to a markedly higher 1-butanol conversion in comparison to the surface-type mechanism which is the only one achieved with the non-modified pristine HPA.
机译:在1-butanol Keggin脱水(气相)heteropolyacid (HPA)催化剂,大尺寸的1-butanol及其重要的疏水性bulk-type(也称为伪种液态)催化机理是不可能的。限制了表面的催化作用下丘脑-垂体-肾上腺轴,一个活动低于它是。取代铵Keggin酸盐的公式(NH4) (x) H(法)PW (12) O (40)合成。脱水反应,更换一些质子的H (3) PW与NH (12) O(40)(4)(+)增加水晶矩阵和的疏水性允许1-butanol输入大量的盐。这个结果使得内部的质子固体催化反应。渗透的1-butanol散装证明了一个盒装situmethods组合(拉曼、红外光谱和x射线衍射)应用中预处理催化剂和催化的反应。发生在种液态机制(NH4) (x) H(法)PW (12) O(40)导致显著相比更高1-butanol转换这是唯一一个表面机制与非转基因原始HPA实现。

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