中国炼油与石油化工 ›› 2012, Vol. 14 ›› Issue (3): 10-16.

• Scientific Research • 上一篇    下一篇

磷钨酸催化丙烯齐聚的研究

刘依农   

  1. 石油化工科学研究院七室
  • 收稿日期:2012-03-31 修回日期:2012-05-23 出版日期:2012-09-30 发布日期:2012-10-22
  • 通讯作者: 刘依农 E-mail:liuyinong.ripp@sinopec.com

Investigation of Propene Oligomerization Catalyzed by Phosphootungstic Acid Catalysts

  • Received:2012-03-31 Revised:2012-05-23 Online:2012-09-30 Published:2012-10-22

摘要: 本文介绍了以磷钨酸负载硅胶为催化剂,在固定床微型反应装置进行丙烯齐聚的反应研究。结果发现;A型硅胶负载磷钨酸催化剂催化的丙烯转化率只有3.38%,而B型硅胶负载磷钨酸催化剂催化的丙烯转化率达到90.1%,产物中壬烯的选择性为42.33%,四聚丙烯的选择性为31.79%。考察了B型硅胶负载磷钨酸催化丙烯齐聚时的反应温度、压力、液时空速等因素对于产物选择性和收率的影响。考察反应温度时发现;随着反应温度从170℃升高到190℃时,丙烯的转化率逐渐上升,壬烯和四聚丙烯的选择性逐渐下降。考察反应压力时发现;当压力从3.5MPa升高到4.5MPa时,随着压力的升高,丙烯的转化率也在增加,壬烯和四聚丙烯的选择性变化非常小。考察反应空速时发现;丙烯空速在0.5h-1和1.0 h-1时的丙烯转化率要高于2.0 h-1时的转化率。壬烯和四聚丙烯的选择性变化没有明显的规律。最后得到的较优的反应条件是;反应温度170℃,反应压力4.5MPa,液时空速1.0 h-1,此时丙烯的转化率是91.05%,壬烯和四聚丙烯的选择性之和是89.51%。研究发现;催化剂活性只有25小时,必须活化后才能使用。

关键词: 磷钨酸, 担体, 丙烯齐聚, 产率, 选择性, 壬烯, 四聚丙烯

Abstract: In this paper, the propene oligomerization catalyzed by phosphotungstic acid which was fixed on two types of silica gel was studied, it has been found that the conversion rate of propene catalyzed by A type silica gel-phosphotungstic acid catalyst is 3.38%, while the conversion rate of propene catalyzed by B type silica gel-phosphotungstic acid catalyst is 90.1%, and its selectivity to nonene is 42.33%, selectivity to dodecene is 31.79%. Influence of reaction temperature, pressure and liquid hour space velocity (LHSV)catalyzed by B type silica gel-phosphotungstic acid catalyst are investigated. It has been found that when the reacting temperature increases from 170℃ to 190 ℃,the conversion rate of propene increases while the selectivity to nonene and dodecene decrease, when the reactive pressure increases from 3.5MPa to 4.5MPa,the conversion rate of propene increases also, the selectivity to nonene and dodecene changes very little.The conversion rate of propene in 0.5 h-1 LHSV, 1.0 h-1 LHSV is high than that of 2.0 h-1 LHSV, but the selectivity to nonene and dodecene does not show regular fluctuation. The optimized conversion rate, 91.05%,and optimized selectivity to nonene and dodecene, 89.51% could be achieved when the reaction temperature is 170℃, pressure is 4.5MPa and LHSV is 1.0h-1.The catalyst life experiments show that catalyst keeps activity only about 25 hours, and it had to be regenerated after that.

Key words: phosphotungstic acid, support, propene oligomerization, yield, selectivity, nonene, dodecene