化工进展

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磷化镍的制备、表征及其催化性能研究进展

李景锋,李学辉,柴永明,刘晨光   

  1. 中国石油大学重质油国家重点实验室,CNPC催化重点实验室,山东 青岛 266555
  • 出版日期:2013-11-05 发布日期:2013-11-05

Progress in the fabrication,characterization and catalytic reactivity of nickel phosphide

LI Jingfeng,LI Xuehui,CHAI Yongming,LIU Chenguang   

  1. State Key Laboratory of Heavy Oil Processing,Key Laboratory of Catalysis,CNPC,China University of Petroleum,Qingdao 266555,Shandong,China
  • Online:2013-11-05 Published:2013-11-05

摘要: 原油的劣质化和环保法规的日益严格使馏分油的加氢精制技术面临严峻挑战,近年来,磷化镍(Ni2P)由于具有优异的加氢脱硫和加氢脱氮性能已成为新型催化加氢材料研究的焦点。本文综述了Ni2P的制备、表征和催化性能方面的研究进展。磷化氢还原法、次磷酸盐还原法和氢气等离子体还原法可在较低温度下制备高活性Ni2P催化剂。扫描透射电镜表明Ni2P(0001)表面有Ni3P和Ni3P2两种可能的终端结构。Ni3P终端的Ni是四方锥型结构,有解离H吸附;而Ni3P2终端的Ni是四面体型结构,无解离H吸附,这表明四方锥型的Ni活性点具有高反应活性。从目前的研究看,Ni2P是具有潜在应用前景的一种新型加氢精制催化材料。

关键词: 磷化镍, 催化剂, 制备, 表征, 加氢脱硫

Abstract: The diminishing quality of petroleum feedstocks coupled with increasingly stringent environmental regulations have made the removal of sulfur and nitrogen an important problem in refining industry. Nickel phosphide (Ni2P) has recently received much attention because of its high activity for the hydrodesulfurization and hydrodenitrogenation of fuels. The present article intends to review recent progress in fabrication,characterization and catalytic performance of Ni2P. Reduction with phosphine,hypophosphite and the plasma reduction of phosphate can be carried out at lower temperatures,which leads to smaller articles and more active Ni2P catalyst. STM study has shown that Ni2P(0001) surface has two possible terminations in which the Ni∶P ratios are 3∶1 (Ni3P termination) and 3∶1 (Ni3P2 termination). On the Ni3P terminated surface the Ni atoms have a square pyramidal structure,and on the Ni3P2 terminated surface the Ni atoms have a tetrahedral structure. Evidence is found for dissociative hydrogen adsorbed on the Ni3P surface of Ni2P(0001),but not on the Ni3P2 surface,indicating that the square pyramidal sites on the Ni3P surface have high reactivity. It is proposed that Ni2P is a potentially promising catalyst for hyroprocessing process.

Key words: nickel phosphide, catalyst, fabrication, characterization, hydrodesulfurization

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