乙醇辅助的化学沉积法制备硫化型Mo/γ-Al2O3加氢脱硫催化剂

doi:10.1016/S1872-2067(11)60516-0

催化学报 ›› 2013, Vol. 34 ›› Issue (4): 659-666.DOI: 10.1016/S1872-2067(11)60516-0

乙醇辅助的化学沉积法制备硫化型Mo/γ-Al₂O₃加氢脱硫催化剂

石冈^a, 韩伟^a,b, 袁珮^b, 范煜^b, 鲍晓军^a

a 中国石油大学(北京)重质油国家重点实验室, 北京102249;
b 中国石油大学(北京) CNPC催化重点实验室, 北京102249

收稿日期:2012-11-30 修回日期:2012-12-25 出版日期:2013-04-23 发布日期:2013-04-24
通讯作者: 袁珮,鲍晓军
基金资助:
国家重点基础研究发展计划(973计划, 2010CB226905); 国家自然科学基金(U1162116, 20825621).

Sulfided Mo/Al₂O₃ hydrodesulfurization catalyst prepared by ethanol-assisted chemical deposition method

SHI Gang^a, HAN Wei^a,b, YUAN Pei^b, FAN Yu^b, BAO Xiaojun^a

a State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China;
b The Key Laboratory of Catalysis, China University of Petroleum, Beijing 102249, China

Received:2012-11-30 Revised:2012-12-25 Online:2013-04-23 Published:2013-04-24
Supported by:
This work was supported by the National Basic Research Program of China (973 Program, 2010CB226905) and the National Natural Science Foundation of China (U1162116 and 20825621).

摘要/Abstract

摘要：

以硫代乙酰胺为硫源,钼酸钠为钼源,乙醇为分散剂,采用化学沉积法制备了MoS₃/Al₂O₃催化剂前驱体,再用H₂高温处理得到高分散硫化型MoS₂/γ-Al₂O₃催化剂,运用N₂吸附-脱附、X射线光电子能谱以及高分辨透射电子显微镜等技术对MoS₂/γ-Al₂O₃催化剂进行了表征,并以二苯并噻吩作为模型化合物评价了催化剂的加氢脱硫(HDS)活性.结果表明,与浸渍法相比,所制催化剂具有更大的比表面积和孔体积、更高的活性金属分散度、更佳的Mo物种硫化度以及更短的MoS₂片层长度和更高的堆积度,因而在二苯并噻吩HDS反应中表现出远优于浸渍法所制催化剂的活性.乙醇可通过S?H-O氢键吸附至MoS₃纳米粒子表面,可有效防止其生长和团聚,起到分散剂的作用.

关键词: 加氢脱硫催化剂, 水解, 乙醇辅助, 三硫化钼, 二硫化钼

Abstract:

In this communication, we report a novel strategy to prepare a MoS₂/Al₂O₃ hydrodesulfurization (HDS) catalyst by thermally treating a MoS₃/Al₂O₃ precursor in H₂ atmosphere. In our approach, the active phase precursor MoS₃ was first prepared using thioacetamide and sodium molybdate as sources of S and Mo, respectively, and ethanol as a dispersant. The precursor was deposited onto the surface of a γ-Al₂O₃ support and heat-treated to form the catalyst. The catalyst was characterized by N₂ adsorption-desorption, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The HDS activity of the catalyst was assessed using dibenzothiophene as a model reactant. The catalyst possessed larger specific surface area and pore volume, higher dispersion and degree of sulfidation of Mo species, and shorter and more suitable stacking of MoS₂ slabs, resulting in superior catalytic activity compared with a catalyst with the same metal content prepared by the conventional impregnation method. Ethanol could disperse the precursor MoS₃ particles via “S…H-O” H-bonding to lessen their aggregation.

Key words: Hydrodesulfurization catalyst, Hydrolysis, Ethanol-assisted preparation, Molybdenum trisulfide, Molybdenum disulfide

石冈, 韩伟, 袁珮, 范煜, 鲍晓军. 乙醇辅助的化学沉积法制备硫化型Mo/γ-Al₂O₃加氢脱硫催化剂[J]. 催化学报, 2013, 34(4): 659-666.

SHI Gang, HAN Wei, YUAN Pei, FAN Yu, BAO Xiaojun. Sulfided Mo/Al₂O₃ hydrodesulfurization catalyst prepared by ethanol-assisted chemical deposition method[J]. Chinese Journal of Catalysis, 2013, 34(4): 659-666.

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乙醇辅助的化学沉积法制备硫化型Mo/γ-Al₂O₃加氢脱硫催化剂

Sulfided Mo/Al₂O₃ hydrodesulfurization catalyst prepared by ethanol-assisted chemical deposition method

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