铁系双亚胺基吡啶配合物MAO体系催化乙烯齐聚制备α烯烃中试研究
2019年2月
Feb．2019
润滑油LUBRICATING OIL 第34卷第1期Vo l．34，No．1添加剂ADDITIVE DOI ：10．19532/j．cnki．cn21-1265/tq．2019．01．008文章编号：1002-
3119（2019）01-0042-06铁系双亚胺基吡啶配合物/MAO 体系
催化乙烯齐聚制备α－烯烃中试研究
郑来昌1，王如文1，蒋斌波2，李化毅
3（1．中国石油兰州润滑油研究开发中心，甘肃兰州730060；
2．浙江大学化学工程联合国家重点实验室，浙江杭州310027；
3．中国科学院化学研究所北京分子科学国家实验室工程塑料重点实验室，北京100190）
摘要：以乙酰丙酮铁和双亚胺基吡啶类配体组成的配合物为催化剂，甲基铝氧烷（MAO ）为助催化剂，以混合己烷为溶剂，在0.3m 3高压反应釜中开展了乙烯齐聚制备α－烯烃的中试研究，考察了其放大效应，重点对釜内压力、温度、乙烯瞬时流量、累
积流量和催化剂活性的变化情况进行了考察，
通过对齐聚产物进行离心分离和精馏分离，确定出了合理的工艺路线和工艺条件。结果表明，该催化剂活性高达7.7?107 1.03?108g /mol ·h ·MPa ，合成的液相产品中，
C 6 C 24α－烯烃含量为77% 81%，α－烯烃选择性大于97%，与实验室水平基本相当。
关键词：双亚胺基吡啶；乙酰丙酮铁；MAO ；乙烯齐聚；α－烯烃；中试研究
中图分类号：TE624．82文献标识码：A
Pilot －scale Study on the Preparation of Alpha Olefins from Ethylene Oligomerization
Catalyzed by 2，6－Bis （imino ）－Pyridyl Iron Catalysts /MAO System
ZHENG Lai －chang 1，WANG Ru －wen 1，JIANG Bin －bo 2，LI Hua －yi 3
（1．PetroChina Lanzhou Lubricating Oil R＆D Institute ，Lanzhou 730060，China ；2．State Key Laboratory of Chemical
Engineering ，Zhejiang University ，Hangzhou 310027，China ；3．Beijing National Laboratory for Molecular Science ，Key
Laboratory of Engineering Plastics ，Institute of Chemistry ，Chinese Academy of Science ，Beijing 100190，China ）
Abstract ：Pilot －scale study on the preparation of α－olefins by iron －catalyzed oligomerization of ethylene in a 0．3m 3high －pressure re-actor was carried out．The catalytic system used in this study was a mixture of ferric acetylacetonate and the mono o －methyl －substituted bis （imino ）－pyridine ligand ，with methylaluminoxane （MAO ）as the co －catalyst and hexane as the solvent．The amplification effect of the reaction was investigated ，and the variation of pressure ，temperature ，ethylene instantaneous flow ，accumulative flow and catalytic activity during the oligomerization process was studied in details．In addition ，the product mixtures were kindly analyzed and divided into
different fractions by centrifugal and distillation separations．Based on these results ，
the reasonable process route and conditions were de-termined．It was showed that the catalyst activity is as high as 7．7?107 1．03?108g /mol －catalyst ·h ·MPa ，the content of C 6 C 24α－olefins is 77% 81%in the synthetic liquid products ，and the selectivity of linear α－olefins is greater than 97%，basically reaches the la-boratory level．
Key words ：2，6－bis （imino ）－pyridyl ；ferric acetylacetonate ；MAO ；ethylene oligomerization ；α－olefins ；pilot －scale study 0引言
线性α－烯烃用途广泛，依据碳数的长短不同，
在乙烯共聚单体、PAO 合成润滑油、增塑剂、合成洗
涤剂、润滑油添加剂和钻井液等领域都是重要和不可替代的原料，这些领域对线性α－烯烃的需求越来越大［1－3］。在我国，除了1－己烯具有自主的工业生产技术外，其他更高碳数的α－烯烃，目前仍采用国际上已经淘汰的蜡裂解法进行少量生产。