Kinetic studies on the pyrrole–Cr-based Chevron-Phillips ethylene trimerization catalyst system
Kinetic studies on the pyrrole–Cr-based Chevron-Phillips ethylene trimerization catalyst system
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吡咯-Cr基Chevron-Phillips乙烯三聚催化剂体系的动力学研究
DOI：
10.1016/j.apcata.2014.04.006
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发表时间：
2014-07
期刊：
影响因子：
--
通讯作者：
Boping Liu
中科院分区：
文献类型：
--
作者：
Ning Li;Ruihua Cheng;Xuelian He;Boping Liu
在Chevron-Phillips均相催化体系[Cr(2-乙基己酸酯)3(Cr(2-EH)3)/2，5-二甲基吡咯(DMP)/助催化剂/卤化物]上，考察了有机卤化物添加剂、助催化剂类型、温度、乙烯压力、铬浓度、配体/铬摩尔比等因素对乙烯三聚反应的影响，考察了10种有机卤化物和4种有机金属助催化剂的催化性能。发现1，1，2，2-四氯乙烷(TCE)和三乙基铝(TEA)是该催化体系的最佳候选者。DMP/Cr、TCE/Cr和TEA/Cr的摩尔比对乙烯三聚的催化性能有很大影响。首次对该催化体系进行了详细的催化动力学行为和动力学模拟。可以推断，三聚反应速率与乙烯浓度和催化剂浓度的关系分别为二级和一级。在65~95℃温度范围内，该反应的表观活化能为99.1kJ/mol，表观反应速率方程为：R=5.23×1018EXP−99.1R T C ca 1.12C e 1.95.
An extensive experimental kinetic study of ethylene trimerization was carried out over the Chevron-Phillips homogeneous catalyst system [Cr (2-ethylhexanoate) 3 (Cr (2-EH) 3)/2, 5-dimethylpyrrole (DMP)/co-catalyst/halide] in terms of the effects from organic halide additives, type of co-catalysts, temperature, ethylene pressure, Cr concentration, and ligand/Cr molar ratio, etc. Ten kinds of organic halides and four kinds of organometallic co-catalysts were tested in this work. The 1, 1, 2, 2-tetrachloroethane (TCE) and triethylaluminum (TEA) were found to be the best candidates for this catalyst system. The molar ratios of DMP/Cr, TCE/Cr and TEA/Cr showed a strong impact on the catalytic performance of ethylene trimerization. A detailed catalytic kinetic behavior and the kinetic simulation were also performed for the first time over this catalyst system. It could be extrapolated that the dependency of the trimerization reaction rate on ethylene concentration and catalyst concentration is second-order and first-order, respectively. The apparent activation energy of this reaction is 99.1 kJ/mol at the temperature range from 65° C to 95° C. And the apparent reaction rate equation is achieved as follows:. R= 5.23× 10 18 exp− 99.1 R T C ca 1.12 C e 1.95.
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影响因子：
5.4
作者：
T. Jiang;R. Ji;Hong-xia Chen;Chengang Cao;Guoliang Mao;Ying-Jie Ning
通讯作者：
T. Jiang;R. Ji;Hong-xia Chen;Chengang Cao;Guoliang Mao;Ying-Jie Ning
影响因子：
--
作者：
A. Wöhl;W. Müller;Stephan Peitz;N. Peulecke;B. Aluri;Bernd H. Müller;D. Heller;U. Rosenthal;Mohammed H. Al-Hazmi;Fuad M Mosa
通讯作者：
A. Wöhl;W. Müller;Stephan Peitz;N. Peulecke;B. Aluri;Bernd H. Müller;D. Heller;U. Rosenthal;Mohammed H. Al-Hazmi;Fuad M Mosa
影响因子：
4.9
作者：
Carter, A;Cohen, SA;Wass, DF
通讯作者：
Wass, DF
DOI：
10.1039/c39890000674
发表时间：
1989-06-01
影响因子：
--
作者：
BRIGGS, JR
通讯作者：
BRIGGS, JR
影响因子：
--
作者：
M. Camargo;P. Dani;J. Dupont;R. F. Souza;M. Pfeffer;I. Tkatchenko
通讯作者：
M. Camargo;P. Dani;J. Dupont;R. F. Souza;M. Pfeffer;I. Tkatchenko