含氟改性剂对Cr(Ⅲ)/PNSiP/MMAO乙烯齐聚反应体系催化性能的影响  

Effect of Fluorine-Containing Modifiers on Catalytic Performance of Cr(Ⅲ)/PNSiP/MMAO Ethylene Oligomerization Catalytic System

作　　者：杨小蝶 邵会娟 蒿标标 范昊男 王亚婷 姜涛 YANG Xiaodie;SHAO Huijuan;HAO Biaobiao;FAN Haonan;WANG Yating;JIANG Tao(College of Chemical Engineering and Materials Science,Tianjin University of Science and Technology,Tianjin 300457,China;National Engineering Research Center of Distillation Technology,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China)

机构地区：[1]天津科技大学化工与材料学院,天津300457 [2]天津大学化工学院精馏技术国家工程研究中心,天津300072

出　　处：《石油学报(石油加工)》2025年第1期62-70,共9页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(22071178,22205160);中国博士后科学基金资助项目(2023M740348);中国石油科技创新基金项目(2020B-2512)资助。

摘　　要：在Cr(Ⅲ)/PNSiP/MMAO乙烯齐聚催化体系中分别加入不同种类的10种含氟改性剂,考察改性剂种类和加入量对乙烯齐聚反应活性和产物组成的影响规律,并提出改性剂与改性甲基铝氧烷(MMAO)的可能作用机理。结果表明:考察的不同种类含氟改性剂(直链烷烃类、环烷烃类、杂原子类和其他)中,杂原子类和其他含氟改性剂加入后使Cr(Ⅲ)/PNSiP/MMAO乙烯齐聚催化体系在高温(90℃)下的催化活性降低;而直链烷烃类和环烷烃类含氟改性剂的加入均能提升催化体系在高温(90℃)下的催化活性,全氟己烷和全氟萘烷对催化反应活性的提高最显著。在温度为90℃、压力为1.0 MPa的条件下,当全氟己烷和全氟萘烷与助催化剂MMAO中Al的摩尔比分别为0.5和0.3时,乙烯齐聚催化体系的反应活性最高,分别为1.82×10^(6)和1.65×10^(6) g/(mol·h),是催化体系中未加改性剂时反应活性的1.9倍和1.7倍。催化体系中全氟萘烷与MMAO反应可能会产生全氟萘基团修饰的MMAO,全氟萘基团不仅能增大MMAO的空间位阻,而且能改善MMAO和阳离子铬活性中心的电子效应。Ten fluorine-containing modifiers have been added to the Cr(Ⅲ)/PNSiP/MMAO ethylene oligomerization catalytic system,which aims to investigate the effect of the types and additions of modifiers on the activity and products composition of the system,and propose the possible reaction mechanism between modifiers and modified methylaluminoxane(MMAO).The results show that among the different types of fluorine-containing modifiers such as straight chain alkanes,cycloalkanes,heteroatoms and others,the addition of heteroatomic fluorine-containing modifiers will cause the catalytic activity of Cr(Ⅲ)/PNSiP/MMAO oligomerization catalytic system at high temperature(90℃)to decrease,both straight and cycloalkane fluorine-containing modifiers can improve the catalytic activity of the system,and the perfluorohexane(C 6F 14)and perfluorodecalin(C 10 F 18)can enhance the catalytic activity of the system at high temperature(90℃).At temperature of 90℃and pressure of 1.0 MPa,when the molar ratios of C 6F 14 and C 10 F 18 to Al in MMAO are 0.5 and 0.3,respectively,the Cr(Ⅲ)/PNSiP/MMAO oligomerization catalytic system exhibits the highest activity of 1.82×10^(6) and 1.65×10^(6) g/(mol·h),which is respectively 1.9 times and 1.7 times of that without adding any modifier.The reaction of perfluoronaphthalene with MMAO may produce MMAO modified by perfluoronaphthalene groups,which can not only increase the steric hindrance of MMAO,but also improve the electronic effects of MMAO and cationic chromium active centers.

关 键 词：乙烯齐聚 铬催化剂 1-己烯 1-辛烯 改性剂 氟代烃 

分 类 号：TQ426.94[化学工程]