催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (4): 317-320.

• 研究论文 • 上一篇    下一篇

用于乙烯齐聚高选择性制 1-辛烯反应的Cr(Ⅲ)基催化剂体系

张宝军1,2,王刚2,王斯晗2,张德顺2,王延吉1   

  1. 1 河北工业大学化工学院, 天津 300130; 2 中国石油天然气股份有限公司大庆化工研究中心, 黑龙江大庆 163714
  • 收稿日期:2007-04-25 出版日期:2007-04-25 发布日期:2011-03-28

Cr(Ⅲ)-Based Catalyst System for Oligomerization of Ethylene to 1-Octene with High Selectivity

ZHANG Baojun1,2, WANG Gang2, WANG Sihan2, ZHANG Deshun2, WANG Yanji1*   

  1. 1 School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China; 2 Daqing Petrochemical Research Center, PetroChina Company Limited, Daqing 163714, Heilongjiang, China
  • Received:2007-04-25 Online:2007-04-25 Published:2011-03-28

PDF

780

被引次数

15

摘要： 将四元催化剂体系(乙酰丙酮铬-膦胺型配体-助催化剂甲基铝氧烷-促进剂六氯乙烷)用于乙烯齐聚制 1-辛烯反应,考察了促进剂、助催化剂、 Al/Cr摩尔比、反应温度和反应压力等对催化剂的活性和 1-辛烯的选择性的影响. 结果表明,该四元催化剂体系比三元催化剂体系(铬化合物-膦胺型配体-甲基铝氧烷)对乙烯齐聚反应具有更高的 1-辛烯选择性. 产物除有 1-辛烯外,还有较大量的 1-己烯、甲基环戊烷和亚甲基环戊烷. 甲基铝氧烷是高选择性生成 1-辛烯必不可少的助催化剂. 作为促进剂的六氯乙烷可以使乙酰丙酮铬更有利于催化乙烯齐聚反应生成 1-辛烯.

关键词: 乙酰丙酮铬, 二苯基膦胺, 甲基铝氧烷, 六氯乙烷, 乙烯, 齐聚, 辛烯

Abstract: A four-membered catalyst system (chromium acetyl acetonate (Cr(acac)3)-diphosphinoamine-methylaluminoxane-hexachloroethane) was used in ethylene oligomerization. The effects of promoters, cocatalysts, and reaction conditions such as Al/Cr molar ratio, reaction temperature, and reaction pressure on its catalytic activity and selectivity for 1-octene were studied. The results showed that the four-membered catalyst system for ethylene oligomerization improved the selectivity for 1-octene evidently. Besides the target product 1-octene, main side-products such as 1-hexene, methylcyclopentane, and methylenecyclopentane were also valuable. Methylaluminoxane was an indispensable cocatalyst for producing 1-octene with high selectivity. Hexachloroethane showed a significant promotion effect on improving selectivity towards 1-octene over chromium centers.

Key words: chromium acetyl acetonate, diphosphinoamine, methylaluminoxane, hexachloroethane, ethylene, oligomerization, octene