Real-time Analysis of a Working Triethylaluminium-Modified Cr/Ti/SiO2 Ethylene Polymerization Catalyst with In Situ Infrared Spectroscopy

利用原位红外光谱法实时分析三乙基铝改性 Cr/Ti/SiO2 乙烯聚合催化剂

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作者:Dimitrije Cicmil, Jurjen Meeuwissen, Aurélien Vantomme, Bert M Weckhuysen

Abstract

A diffuse reflectance infrared Fourier-transform (DRIFT) study has been conducted at 373 K and 1 bar on an industrial Cr/Ti/SiO2 Phillips-type catalyst modified with, and without, triethylaluminium (TEAl) as co-catalyst. The reaction rate of the polymerization of ethylene, as monitored by the increase in the methylene stretching band of the growing polyethylene (PE), has been investigated as a function of the titanium content. After an initial period of mixed kinetics, with the reaction rate significantly higher for the TEAl-modified catalysts compared with the non-modified catalysts, the polymerization proceeded as a pseudo-zero-order reaction with a reaction rate that increased as a function of titanium loading. Furthermore, it was found that the higher Ti loading caused the appearance of more acidic hydroxyl groups and modified the Cr sites by making them more Lewis acidic, ultimately shortening the induction time and increasing the initial polymerization rate.

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