催化学报

催化学报 ›› 2009, Vol. 30 ›› Issue (10): 1017-1021.

• 研究论文 • 上一篇    下一篇

溶胶-凝胶法制备MoO3-CeO2-SiO2氧化脱硫催化剂

张健 1, 白秀梅 1, 李翔 1,2, 王安杰 1,2, 马学虎 2   

  1. 1大连理工大学精细化工国家重点实验室, 辽宁大连 116012 2大连理工大学辽宁省省级高校石油化工技术与装备重点实验室, 辽宁大连 116012
  • 收稿日期:2009-10-25 出版日期:2009-10-25 发布日期:2013-06-06

Preparation of MoO3-CeO2-SiO2 Oxidative Desulfurization Catalysts by a Sol-Gel Procedure

ZHANG Jian1, BAI Xiumei1, LI Xiang1,2, WANG Anjie1,2,*, MA Xuehu2   

  1. 1State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, Liaoning, China 2Liaoning Key Laboratory of Petrochemical Technology and Equipments, Dalian University of Technology, Dalian 116012, Liaoning, China
  • Received:2009-10-25 Online:2009-10-25 Published:2013-06-06

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摘要： 采用溶胶-凝胶法制备了 MoO3-CeO2-SiO2 复合氧化物催化剂, 通过 X 射线衍射、傅里叶变换红外光谱和 X 射线光电子能谱对催化剂进行了表征. 在温和条件 (40 oC, 常压) 下, 以过氧化羟基异丙苯 (CHP) 为氧化剂, 甲苯为溶剂, 二苯并噻吩 (DBT) 为模型硫化物, 在固定床流动反应器上考察了该复合氧化物催化剂的氧化脱硫反应性能, 并研究了催化剂中 Mo/Si 和 Ce/Si 摩尔比对反应活性的影响. 结果表明, Mo 物种主要以 MoO3 的形式存在, 最佳 Mo/Si 和 Ce/Si 摩尔比分别为 0.1 和 0.02. 适量 CeO2 的引入可以提高 SiO2 上 MoO3 的分散度. 不含 CeO2 的催化剂中钼主要以高价态的钼离子 (Mo6+) 存在, 添加 CeO2 后, 可能有一定量的低价态的钼离子 (Mo5+) 生成, MoO3-CeO2-SiO2 催化剂高的氧化脱硫活性可能与 Mo5+的存在有关.

关键词: 三氧化钼;二氧化铈;二氧化硅;溶胶–凝胶法, 二苯并噻吩, 氧化脱硫

Abstract: MoO3-CeO2-SiO2 mixed oxides were prepared by the sol-gel method. The catalysts were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The catalyst activity for the oxidative desulfurization of dibenzothiophene (DBT) with cumene hydroperoxide as the oxidant in toluene was investigated at 40 oC and atmospheric pressure. The optimum Mo/Si and Ce/Si molar ratios were 0.1 and 0.02, respectively. Crystalline MoO3 was observed in the MoO3-CeO2-SiO2 catalysts. The introduction of CeO2 promoted the high dispersion of MoO3 over SiO2. Mo6+ was the predominant species in MoO3/SiO2, and Mo5+ species appeared after the introduction of CeO2. The presence of Mo5+ may be responsible for the good performance of MoO3-CeO2-SiO2 in the oxidative desulfurization of DBT.

Key words: molybdenum oxide, cerium oxide, silica, sol-gel method, dibenzothiophene, oxidative desulfurization