文献类型：期刊文献

英文题名：Generation, transfer, and hydrogenation dynamics of active hydrogen in the CO-H2O system during lignite hydrogenation

作者：Li, Huan[1];Gu, Jiale[2];Gao, Xun[1];Huang, Sheng[2];Xiong, Zixiang[1];Ren, Changzai[3];Tang, Xiaoning[1];Wu, Shiyong[2]

机构：[1]Kunming Univ Sci & Technol, Sch Chem Engn, Kunming 650031, Yunnan, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Coal Liquiffcat Gasiffcat & Utilizat, Shanghai 200237, Peoples R China;[3]Qilu Univ Technol, Shandong Acad Sci, Dept Energy & Power Engn, Jinan 250014, Shandong, Peoples R China

年份：2026

卷号：126

外文期刊名：JOURNAL OF THE ENERGY INSTITUTE

收录：;EI(收录号：20261420430796);WOS:【SCI-EXPANDED(收录号:WOS:001736107300001)】；

基金：This work was supported by the National Natural Science Foundation of China (22378129) , Yunnan Provincial Natural Science Foundation General Project (202501AT070463) , the Natural Science Foundation of Shandong Province (ZR2024ME111) , the Fund of Central Government for Guiding Local Science and Technology Development (YDZX2025021) , and Kunming University of Science and Technology Analytical Testing Fund (2025T20230218) .

语种：英文

外文关键词：Lignite; WGSR; Active hydrogen; Hydrogenation conversion; Isotope tracing

摘要：This study establishes a lignite hydrogenation liquefaction process in the CO-H2O (or syngas) system. The key conversion laws of lignite are elucidated through systematic studies combined with isotope tracing and density functional theory calculations. Active hydrogen generated in situ by the water-gas shift reaction (WGSR) serves as the core hydrogen source for liquefaction reactions, and the catalyst synergistically promotes the WGSR and hydrogenation processes. Due to its low bond dissociation energy, the alpha-H of tetrahydronaphthalene (THN), used as a circulating solvent, is preferentially dehydrogenated to supply hydrogen. The dehydrogenated naphthalene is then hydrogenated by WGSR-derived the active hydrogen (H center dot), allowing THN to recirculate. Hydrogenation experiments with model compounds (1-naphthol, benzoic acid, and dibenzofuran) elucidated the hydrogenation conversion mechanism of WGSR on lignite's oxygen-containing structures. For 1-naphthol, H center dot attacked either the hydroxyl-adjacent carbon or the para carbon, generating naphthalene (subsequently hydrogenated to THN) or 1-tetrahydronaphthone (followed by THN formation), effectively inhibiting pyrolysis condensation and coking. For benzoic acid, pyrolysis generated benzene/biphenyl, and H center dot promoted hydrogenation deoxygenation to produce toluene as the main product. H center dot also attacked the oxygen atom of dibenzofuran, cleaving the C-O bond to form 2-hydroxybiphenyl, which further dehydroxylated to benzene. Addition of THN as a solvent considerably increased the conversion rate from 5.98 mol% to 11.62 mol%. The hydrogenation activity of lignite's oxygen-containing structures follows the order: carboxyl groups > ether/phenol > oxygen-containing heterocycles, with phenols undergoing condensation competition reactions. These studies reveal H center dot transfer pathway of WGSR and the hydrogenation conversion mechanism of oxygen-containing aromatic compounds in lignite, providing a theoretical basis and process optimization strategy for the efficient liquefaction of lignite.