Catalytic synthesis of methanol, higher alcohols and ethers
Catalytic synthesis of methanol, higher alcohols and ethers
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DOI：
10.1016/s0920-5861(96)00190-3
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发表时间：
1997-04-25
期刊：
影响因子：
5.3
通讯作者：
Herman, RG
中科院分区：
文献类型：
--
作者：
Klier, K;Beretta, A;Herman, RG
具有特定功能的多相催化剂可以大规模合成甲醇、高级醇和醚。当铜是甲醇和高级醇催化剂的关键组分时，碱促进由于CO的非解离活化和促进羟醛偶联与氧保留的逆转而引起产率的显著提高。醚由醇在固体酸催化剂（有机磺酸树脂和无机化合物如沸石）上通过优先表面S（N）2途径形成。这是例证O-18保留在反应中的两种不同的醇，手性反转，其中涉及不对称碳，和动力学，反应物醇的表面酸位点的竞争。过渡态形状选择性的例子是2-戊醇和乙醇在H-ZSM-5中的反应，以及在H-丝光沸石中形成二甲醚时由于S（N）2途径与主通道方向的正交性而产生的选择性。
Methanol, higher alcohols and ethers are synthesized on a large scale over heterogeneous catalysts with specific functionalities. When copper is the key component of the methanol and higher alcohol catalysts, alkali promotion gives rise to dramatic enhancements of yields due to non-dissociative activation of CO and promotion of aldol coupling with reversal of oxygen retention. Ethers are formed from alcohols over solid acid catalysts, both organic sulfonic resins and inorganic compounds such as zeolites, by a preferential surface S(N)2 pathway. This is exemplified by O-18 retention in reactions of two different alcohols, chirality inversion where asymmetric carbon is involved, and kinetics that reflect competition of the reactant alcohols for surface acid sites. Transition state shape selectivity is exemplified in the reaction of 2-pentanol and ethanol in H-ZSM-5 and selectivity due to orthogonality of the S(N)2 pathway to main channel direction in the formation of dimethyl ether in H-mordenite.