无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ

无机盐工业 ›› 2015, Vol. 47 ›› Issue (7): 66-.

• 论文 • 上一篇    下一篇

氯化亚铜催化四氯化硅和硅耦合加氢的机理研究

王志博,丁伟杰,阎建民,肖文德   

  1. 上海交通大学化学化工学院,上海 200240
  • 出版日期:2015-07-10 发布日期:2015-09-24

Mechanism of CuCl-catalyzed co-hydrogenation of silicon tetrachloride and silicon

 WANG  Zhi-Bo, DING  Wei-Jie, YAN  Jian-Min, XIAO  Wen-De   

  1. School of Chemistry and Chemical Engineering,Shanghai Jiaotong University,Shanghai 200240,China
  • Published:2015-07-10 Online:2015-09-24

摘要: 以氯化亚铜为催化剂、使用固定床反应器,对四氯化硅和硅耦合加氢反应进行反应历程中固体催化物种活性变化的机理研究。利用程序升温策略使Cu3Si在反应前完全生成,开启反应后观察到包含诱导期、稳定期、失活期的反应活性曲线,对诱导期的成因进行了讨论,认为Cu3Si在反应气氛下的氯化是形成活性中心的必要条件。使用惰性气体吹扫降温法制备了不同反应阶段的颗粒样品。利用SEM-EDS、XRD、XRF等研究了反应历程中表面形貌、晶型及体相组成的演化规律,提出了反应失活模型,认为颗粒表面形貌组成的变化导致扩散速率下降是失活的原因。

关键词: 冷氢化, 活性, 扩散, 四氯化硅, 氯化亚铜

Abstract: The co-hydrogenation of silicon tetrachloride and silicon with CuCl as catalyst was studied in a fixed bed reactor for the purpose of studying mechanism of activity changes of solid active species.Heating strategy was designed to ensure Cu3Si formed completely before co-hydrogenation.Typical activity curves including induction period,steady period,and deactivation period were observed after reaction started.The causes of induction period were discussed and the chlorination of Cu3Si sites was indicated to be a necessary step to form catalytic active site.The particle samples were prepared by utilizing inert gas sweeping cooling technology to discontinue the reaction.Changes in particle surface morphology,crystalline structure,and elemental composition of the particles were measured by SEM-EDS,XRD,and XRF,respectively,in reaction process.A deactivation model was proposed and the decrease of diffusion rate due to the changes of surface morphology and composition was indicated to be the main reason of deactivation.

Key words: hydrogenation, activity, diffusion, SiCl4, CuCl

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