The Selectivity for Sulfur Removal from Oils: An Insight from Conceptual Density Functional Theory
The Selectivity for Sulfur Removal from Oils: An Insight from Conceptual Density Functional Theory
复制标题
从油中脱硫的选择性：概念密度泛函理论的见解
DOI：
10.1002/aic.15161
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发表时间：
2016-06-01
期刊：
影响因子：
3.7
通讯作者：
Li, Huaming
中科院分区：
文献类型：
--
作者：
Li, Hongping;Zhu, Wenshuai;Li, Huaming
从油中脱硫的选择性是一个重要的话题。在这项工作中，通过概念密度泛函理论（CDFT）在B3LYP/6-311++G(3df,2p)理论水平上研究了不同脱硫方法的选择性。原则上，选择性与脱硫机制直接相关。在完全了解其机制之前，无法对其进行精确阐明。然而，目前的工作表明，可以在 CDFT 和选择性之间构建关系。也就是说，对于加氢脱硫，好的描述符是 SC 的电离能、硬度和键长；对于吸附脱硫来说，硬度是一个很好的描述符；对于氧化脱硫，良好的描述符是电子密度和福井函数。对于萃取脱硫（非金属基离子液体），电子亲和力和亲电性可能是很好的描述符。此外，还讨论了各种硫化物的结构和前沿轨道。希望 CDFT 和选择性之间的这些关系能够提供有用的信息，以开发针对特定硫化物（如 4,6-二甲基二苯并噻吩和 4-甲基二苯并噻吩）的高效脱硫方法。 © 2016 美国化学工程师学会 AIChE J, 62: 2087–2100, 2016
The selectivity for sulfur removal from oils is an important topic. In this work, the selectivity for different sulfur removal methods has been studied by conceptual density functional theory (CDFT) at the B3LYP/6-311++G(3df,2p) level of theory. In principle, the selectivity is directly related to the mechanisms of sulfur removal. It cannot be precisely elucidated until the mechanisms are totally known. However, current work shows that relationships can be constructed between CDFT and the selectivity. That is, for hydrodesulfurization, good descriptors will be ionization energy, hardness, and bond lengths of SC; for adsorptive desulfurization, the hardness is a good descriptor; for oxidative desulfurization, good descriptors are electron density and Fukui function. And for extractive desulfurization (nonmetal-based ionic liquids), electron affinity and electrophilicity may be good descriptors. In addition, structures and frontier orbitals of various sulfides have also been discussed. It is hoped that these relationships between CDFT and selectivity can give useful information to develop highly efficient sulfur removal methods for specific sulfides, like 4,6-dimethyldibenzothiophene, and 4-methyldibenzothiophene. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2087–2100, 2016