微波水热法制备含磷W/Al2O3催化剂及其加氢脱氮性能

doi:10.16085/j.issn.1000-6613.2015.06.024

化工进展 ›› 2015, Vol. 34 ›› Issue (06): 1646-1651.DOI: 10.16085/j.issn.1000-6613.2015.06.024

微波水热法制备含磷W/Al₂O₃催化剂及其加氢脱氮性能

王豪¹, 赵婉莹¹, 刘振伟^1,2, 尧振宇¹, 吴雁¹

1 西南石油大学化学化工学院, 四川成都 610500;
2 中国石油独山子石化公司炼油厂, 新疆克拉玛依 833699

收稿日期:2014-10-11 修回日期:2015-01-23 出版日期:2015-06-05 发布日期:2015-06-05
作者简介:王豪(1978—),男,博士,副教授,从事炼油催化研究。E-mail:swpuwanghao1216@sina.com。
基金资助:
国家自然科学基金项目(20906075)。

Preparation of phosphorous-containing W/Al₂O₃ catalysts via microwave hydrothermal method and their hydrodenitrogen activity

WANG Hao¹, ZHAO Wanying¹, LIU Zhenwei^1,2, YAO Zhenyu¹, WU Yan¹

1 School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China;
2 Dushanzi Refinery, China Petroleum, Karamay 833699, Xinjiang, China

Received:2014-10-11 Revised:2015-01-23 Online:2015-06-05 Published:2015-06-05

摘要/Abstract

摘要： 采用微波水热法(MWH)制备含磷W/Al₂O₃加氢精制催化剂, 分别以磷酸(PA)、磷酸三乙酯(TEP)和羟基乙叉二磷酸(HEDP)为磷源, 考察磷源、制备方法和磷含量对催化剂物化性质和加氢脱氮(HDN)性能的影响。结果表明, 使用HEDP为磷源不仅可减弱活性组分-载体间的相互作用, 其结构中的羟基还可与MWH产生的H₂WO₄形成氢键而吸附在H₂WO₄表面, 抑制H₂WO₄团聚, 从而实现WO₃的高分散。MWH快速均匀加热的特点可以有效抑制H₂WO₄的过度生长, 并促进其在Al₂O₃表面的均匀快速分散, 使得以HEDP为磷源制备的W/Al₂O₃中WO₃的分散度和HDN活性远高于浸渍法制备的相同磷源、磷含量和金属含量的催化剂。MWH法制备的磷质量分数为3%的催化剂兼具高的WO₃分散度和弱的WO₃-Al₂O₃相互作用, 有最佳的HDN活性。

关键词: 催化剂, 加氢, 微波, 水热, 磷

Abstract: Phosphorous-containing W/Al₂O₃hydrotreating catalysts were prepared via microwave hydrothermal (MWH) method, in which phosphoric acid (PA), triethyl phosphate (TEP) and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) were used as phosphorus sources, respectively. The effects of phosphorus sources, catalyst preparation methods and phosphorus contents on the physicochemical properties and hydrodenitrogenation (HDN) activity of catalysts were studied. The results show that the introduction of HEDP can weaken tungsten-alumina interaction and keep highly dispersed tungsten species by forming H-bonding between the hydroxyl groups of HEDP and H₂WO₄ to prevent tungsten species from aggregation. The MWH method, characterized by rapid and uniform heating, can greatly inhibit the excess growth of H₂WO₄ colloids and help to disperse tungsten oxide on alumina uniformly and quickly. When the HEDP is used as phosphorus resource, catalyst prepared via MWH method shows much higher WO₃ dispersion and HDN activity than that with the same phosphorus and metal contents prepared by impregnation method. The catalyst prepared via MWH method with 3% phosphorus combines high WO₃ dispersion with weak tungsten-alumina interaction, leading to the highest HDN activity.

Key words: catalyst, hydrogenation, microwave, hydrothermal, phosphorous

中图分类号:

TQ426

王豪, 赵婉莹, 刘振伟, 尧振宇, 吴雁. 微波水热法制备含磷W/Al₂O₃催化剂及其加氢脱氮性能[J]. 化工进展, 2015, 34(06): 1646-1651.

WANG Hao, ZHAO Wanying, LIU Zhenwei, YAO Zhenyu, WU Yan. Preparation of phosphorous-containing W/Al₂O₃ catalysts via microwave hydrothermal method and their hydrodenitrogen activity[J]. Chemical Industry and Engineering Progree, 2015, 34(06): 1646-1651.

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微波水热法制备含磷W/Al₂O₃催化剂及其加氢脱氮性能

Preparation of phosphorous-containing W/Al₂O₃ catalysts via microwave hydrothermal method and their hydrodenitrogen activity

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