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Inert competitive adsorption for the inhibition of oligomerization of alkenes during alcohol dehydration†
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2018-07-05 00:00:00 , DOI: 10.1039/c8cy01222a Katherine P. Vinter 1, 2, 3, 4, 5 , Paul J. Dauenhauer 1, 2, 3, 4, 5
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2018-07-05 00:00:00 , DOI: 10.1039/c8cy01222a Katherine P. Vinter 1, 2, 3, 4, 5 , Paul J. Dauenhauer 1, 2, 3, 4, 5
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Inhibition of secondary chemistries in a linear series of reactions remains a catalytic challenge, particularly when targeting the selective synthesis of intermediate chemicals. In this work, the inhibition of cyclohexene oligomerization following cyclohexanol dehydration with H-BEA zeolite catalyst was achieved with the addition of 2,5-dimethylfuran (DMF). Suppression of undesired olefin oligomerization occurred with the competitive adsorption of the hydrolysis product of DMF, 2,5-hexanedione, thereby preventing cyclohexene adsorption onto Brønsted acid sites. Activation energies were measured for cyclohexanol dehydration both with and without DMF and were found to be the same within experimental error, suggesting that DMF does not alter the catalytic mechanism of cyclohexanol dehydration. Adsorption models were generated to investigate the general case of adding inert chemicals to inhibit product side reactions. Allowable differences in free energies of adsorption between reactant, product, and inert necessary to promote inhibition of product adsorption, while allowing for reactant surface saturation, were quantitatively determined. Reactions that might benefit from the addition of inert chemicals were proposed including linear alcohol dehydration and benzyl acylation and alkylation.
中文翻译：
惰性竞争性吸附可抑制酒精脱水过程中烯烃的低聚†
在线性系列反应中抑制次要化学物质仍然是一个催化挑战，特别是在针对中间化学品的选择性合成时。在这项工作中，通过添加2，5-二甲基呋喃（DMF），可以实现使用H-BEA沸石催化剂抑制环己醇脱水后对环己烯低聚的抑制作用。DMF水解产物2,5-己二酮的竞争性吸附会抑制不希望的烯烃低聚，从而防止环己烯吸附到布朗斯台德酸位上。在有和没有DMF的情况下，测量环己醇脱水的活化能，发现在实验误差范围内是相同的，这表明DMF不会改变环己醇脱水的催化机理。生成吸附模型以研究添加惰性化学物质以抑制产物副反应的一般情况。定量确定了反应物，产物和惰性物质之间的吸附自由能的差异，以促进抑制产物吸附，同时允许反应物表面饱和。提出了可能受益于添加惰性化学品的反应，包括线性醇脱水，苄基酰化和烷基化。
更新日期：2018-07-05
中文翻译：
惰性竞争性吸附可抑制酒精脱水过程中烯烃的低聚†
在线性系列反应中抑制次要化学物质仍然是一个催化挑战，特别是在针对中间化学品的选择性合成时。在这项工作中，通过添加2，5-二甲基呋喃（DMF），可以实现使用H-BEA沸石催化剂抑制环己醇脱水后对环己烯低聚的抑制作用。DMF水解产物2,5-己二酮的竞争性吸附会抑制不希望的烯烃低聚，从而防止环己烯吸附到布朗斯台德酸位上。在有和没有DMF的情况下，测量环己醇脱水的活化能，发现在实验误差范围内是相同的，这表明DMF不会改变环己醇脱水的催化机理。生成吸附模型以研究添加惰性化学物质以抑制产物副反应的一般情况。定量确定了反应物，产物和惰性物质之间的吸附自由能的差异，以促进抑制产物吸附，同时允许反应物表面饱和。提出了可能受益于添加惰性化学品的反应，包括线性醇脱水，苄基酰化和烷基化。
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