期刊
CHINESE JOURNAL OF CHEMICAL ENGINEERING
卷 35, 期 -, 页码 204-210出版社
CHEMICAL INDUSTRY PRESS CO LTD
DOI: 10.1016/j.cjche.2021.02.005
关键词
Oxygen-containing compound; Hydrogenation; Deoxygenation; Catalysis; Computational chemistry
资金
- National Key Research and Development Program of China [2016YFB0600305]
- National Natural Science Foundation of China [21808153, 22078220]
The study analyzed the hydrodeoxygenation process of dibenzofuran on Ni surface, revealing a stepwise hydrogenation to produce intermediate compounds such as 2-cyclohexylphenol. This mechanism provides insights for further optimization of nickel-based catalyst design.
The low-temperature coal tar contains a considerable number of oxygen-containing compounds, which results in poor quality. The catalytic hydrodeoxygenation of oxygen-containing compound to an added-value chemical compound is one of the most efficient methods to upgrade coal tar. In this study, density functional theory calculations are employed to assess and analyze in detail the hydrodeoxygenation of dibenzofuran, as a model compound of coal tar, on the Ni (1 1 1) surface. The obtained results indicate that dibenzofuran can be firstly hydrogenated to tetrahydrodiben zofuran and hexahydrodibenzofuran. The five-membered-ring opening reaction of tetrahydrodibenzofuran is more straightforward than that of hexahydrodibenzofuran (E-a = 0.71 eV vs. 1.66 eV). Then, both pathways generate an intermediate 2-cyclohexylphenoxy compound. One part of 2-cyclohexylphenoxy is hydrogenated to 2-cyclohexylphenol and consecutively hydrogenated to cyclohexylcyclohexanol, and another part is directly hydrogenated to cyclohexylcyclohexanone. The hydrogenated intermediates of 2-cyclohexylphenol have higher deoxygenation barriers than 2-cyclohexylphenol and cyclohexylcyclohexanol. During the hydrogenation process of cyclohexylcyclohexanone to cyclohexylcyclohexanol, the intermediate 26, formed by adding H to O atom of cyclohexylcyclohexa none, exhibits the lowest deoxygenation barrier of 1.08 eV. High hydrogen coverage may promote the hydrogenation of tetrahydrodibenzofuran, hexahydrodibenzofuran, and intermediate 26 to generate dodecahydrodiben zofuran and cyclohexylcyclohexanol. This dibenzofuran hydrodeoxygenation reaction mechanism corroborates well with previous experimental results and provides a theoretical basis for further optimization of the design of nickel-based catalysts. (C) 2021 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据