化工进展 ›› 2019, Vol. 38 ›› Issue (08): 3658-3669.DOI: 10.16085/j.issn.1000-6613.2018-1987

• 工业催化 • 上一篇    下一篇

酚类加氢脱氧催化剂研究进展

邱泽刚(),尹婵娟,李志勤(),冯跃阔   

  1. 西安石油大学化学化工学院,陕西 西安 710065
  • 收稿日期:2018-10-08 出版日期:2019-08-05 发布日期:2019-08-05
  • 通讯作者: 李志勤
  • 作者简介:邱泽刚(1981—),男,博士,副教授,研究方向为能源化工。E-mail:qiuzegang@xsyu.edu.cn
  • 基金资助:
    国家自然科学基金(21606177);大学生创新创业训练计划(201819059)

Recent advances in hydrodeoxygenation catalysts for phenols

Zegang QIU(),Chanjuan YIN,Zhiqin LI(),Yuekuo FENG   

  1. College of Chemistry and Chemical Engineering,Xi’an Shiyou University,Xi’an 710065,Shaanxi,China
  • Received:2018-10-08 Online:2019-08-05 Published:2019-08-05
  • Contact: Zhiqin LI

摘要:

酚类加氢脱氧(HDO)是石油、煤基液体燃料和生物质油转化利用中的重要过程,催化剂在其中起关键作用。酚类加氢脱氧催化剂包括过渡金属硫化物、还原态金属催化剂、磷化物、碳化物和氮化物等。本文从活性、选择性、稳定性和催化机理等方面介绍了各类催化剂的研究进展。过渡金属硫化物重点介绍了负载的CoMoS催化剂和非负载的MoS2,其中晶态MoS2具有优异的活性和选择性。还原态金属介绍了负载的非贵金属(Ni、Mo和Co)、贵金属(Rh、Ru、Pd和Pt)和双金属(NiRu、Ni-Fe、Mo-Pt和Pd-X)等催化剂,并对不同的金属催化剂进行了比较。磷化物重点介绍了SiO2负载的Ni2P、MoP和CoP,Ni2P/SiO2具有很高的催化活性和选择性。碳化物主要是Mo2C催化剂,其具有较高的芳环类产物选择性。氮化物主要是Mo2N催化剂,其加氢脱氧活性仍有待提高。各类催化剂大多存在稳定性欠缺的问题,过渡金属硫化物主要是提高催化剂对水的稳定性,还原态金属必须重视杂质尤其是硫引起的中毒问题,可考虑与脱硫催化剂组合使用,磷化物应关注积炭和颗粒团聚。

关键词: 酚类, 加氢, 加氢脱氧, 催化剂, 生物质, 煤焦油

Abstract:

Hydrodeoxygenation (HDO) of phenols is an essential process in the conversion of crude oil, coal-based liquid fuel and bio-oil. Catalysts play a key role in this process. The HDO catalysts for phenols include the transition metal sulfides, the reduced metal catalysts, the metal phosphides, carbides and nitrides. Recent research on these catalysts was summarized in terms of the activity, selectivity, stability and catalytic mechanism. The supported CoMoS catalysts and unsupported MoS2 were introduced emphatically as the transition metal sulfides. The crystalline MoS2 had excellent activity and selectivity. The catalysts of the supported non-noble metals (Ni, Mo and Co), noble metals (Rh, Ru, Pd and Pt) and bimetals (NiRu,Ni-Fe,Mo-Pt and Pd-X) were introduced. The performance of different metal catalysts was compared. The catalysts of Ni2P,MoP and CoP supported on SiO2 were introduced as the metal phosphides, among which the Ni2P/SiO2 exhibited the highest catalytic activity and selectivity. In the metal carbides, Mo2C had a high selectivity to the aromatics, while the HDO activity of the Mo2N should be improved. The stability of all catalysts is not good enough. As to the transition metal sulfides, the stability to water should be strengthened. For the reduced metal catalysts, the impurities, especially sulfur, should be considered. The reduced metal catalysts were suggested to be used together with the desulfurization catalysts. In the case of the metal phosphides, more attention should be paid to the carbon deposition and particle agglomeration.

Key words: phenols, hydrogenation, hydrodeoxygenation, catalysts, biomass, coal tar

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