Competitive Hydrogenation between Linear Alkenes and Aromatics on Close-Packed Late Transition Metal Surfaces
Competitive Hydrogenation between Linear Alkenes and Aromatics on Close-Packed Late Transition Metal Surfaces
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DOI：
10.1021/acs.jpcc.8b09564
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发表时间：
2018-12
期刊：
影响因子：
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通讯作者：
Haoran He;Anish Dasgupta;R. Rioux;R. Meyer;M. Janik
中科院分区：
文献类型：
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作者：
Haoran He;Anish Dasgupta;R. Rioux;R. Meyer;M. Janik
在芳族化合物存在下选择性氢化直链烯烃以防止热解汽油（PYGAS）改质中的胶质形成是期望的。为了考察直链烯烃和芳烃之间的竞争加氢，我们考察了乙烯和苯在不同催化剂上的竞争加氢。通过密度泛函理论（DFT）计算，我们发现苯和乙烯的吸附能相关的monasterous紧密堆积的表面，与苯结合更强的相同的C表面金属原子比。DFT计算表明Bronsted-Evans-Polanyi和标度关系保持不变，并且这些被馈送到微动力学建模中，以仅用乙烯和氢结合能作为表面描述符来预测乙烯和苯氢化的速率。由于较强的结合，苯吸附将主导表面。苯加氢的势垒比乙烯加氢的势垒高，在乙烯加氢的温度下苯中毒。
Selective hydrogenation of linear alkenes in the presence of aromatics is desired to prevent gum formation in pyrolysis gasoline (PYGAS) upgrading. To examine the competitive hydrogenation between linear alkenes and aromatics, we investigate ethylene and benzene competitive hydrogenation on different catalysts. Through density functional theory (DFT) calculations, we show the adsorption energies of benzene and ethylene correlate on monometallic close-packed surfaces, with benzene binding stronger for the same C to surface metal atom ratio. DFT calculations demonstrate Bronsted–Evans–Polanyi and scaling relationships hold, and these are fed into microkinetic modeling to predict the rate of ethylene and benzene hydrogenation with only ethylene and hydrogen binding energies as the surface descriptors. Due to stronger binding, benzene adsorption will dominate the surface. Higher barriers for benzene hydrogenation versus ethylene hydrogenation lead to benzene poisoning at temperatures at which ethylene hydroge...