Cr(acac)_3/Ph_2PN(~tBu)PPh_2/MAO催化乙烯高选择性齐聚的动力学研究  

Kinetics of ethylene selective oligomerization over Cr(acac)_3/Ph_2PN(~tBu)PPh_2/MAO catalyst system

作　　者：朱祥峰 程瑞华 孙任 刘霖 刘柏平[1] Zhu Xiangfeng;Cheng Ruihua;Sun Ren;Liu Lin;Liu Boping(State Key Laboratory of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化工学院化学工程国家重点实验室,上海市200237

出　　处：《合成树脂及塑料》2018年第5期5-9,28,共6页China Synthetic Resin and Plastics

基　　金：国家自然科学基金(21174037)

摘　　要：对乙酰丙酮铬[Cr(acac)_3]/二-(二苯基膦)叔丁胺[Ph_2PN(~tBu)PPh_2]/甲基铝氧烷(MAO)催化体系高选择性催化乙烯齐聚生成1-己烯/1-辛烯的动力学进行了研究。系统考察了催化剂浓度、乙烯压力和反应温度对反应活性及产物选择性的影响,并采用Aspen Plus软件建模计算乙烯在液相中的溶解度,对该体系进行了动力学模拟。结果表明:催化剂浓度对反应活性及选择性影响不大,最优的反应压力是3.5 MPa,最优的反应温度是45℃;该乙烯齐聚反应体系对催化剂浓度的反应级数是1.16,对乙烯浓度的反应级数是1.74;当温度为30~45℃,压力为2.0~3.5 MPa时,该反应的表观活化能为73.7 k J/mol。The experimental kinetics of ethylene oligomerization for 1-hexene/1-octylene over the Crbased catalyst system comprising chromium triacetylacetonate(Cr(acac)3),bis(diphenylphosphino)tertbutylamine(Ph2PN(tBu)PPh2)as ligand,and methylaluminoxane(MAO)as cocatalyst were investigated.The influence of catalyst concentration,ethylene pressure,and reaction temperature on the reaction activity and selectivity were systematically observed.The kinetic behavior of this catalyst system were simulated and the solubility of ethylene in liquid phase was established by Aspen Plus.The results show that the concentration of the catalyst contributes little to the reactivity and selectivity of the reaction,the optimal reaction pressure is 3.5 MPa and the reaction temperature is 45℃.The dependency of the reaction on catalyst concentration is the order of 1.16,and that on the ethylene concentration is the order of 1.74.The apparent activation energy of the reaction is 73.7 kJ/mol within 30-45℃and 2.0-3.5 MPa.

关 键 词：动力学 乙烯齐聚 乙烯四聚 1-己烯 1-辛烯 

分 类 号：TQ320.9[化学工程—合成树脂塑料工业] TQ027.1