Ni_(3)CuSn_(0.3)/SiO_(2)催化剂上的裂解汽油C_(8)芳烃选择性加氢反应本征动力学与固定床反应器数学模型  

Intrinsic kinetics and fixed-bed reactor modeling of selective hydrogenation of C_(8) aromatics from pyrolysis gasoline on Ni_(3)CuSn_(0.3)/SiO_(2) catalysts

作　　者：王盈瑞 季国争 周志明[1] WANG Yingrui;JI Guozheng;ZHOU Zhiming(College 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,上海200237

出　　处：《高校化学工程学报》2024年第6期872-881,共10页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(21978093)。

摘　　要：苯乙烯是石化工业中的重要单体,可通过裂解汽油抽提法制备。为防止微量苯乙炔混入苯乙烯中,导致下游催化剂中毒和产品不达标,工业上普遍采用选择性加氢反应来去除苯乙炔。以裂解汽油C_(8)芳烃为原料,首先采用Ni_(3)CuSn_(0.3)/SiO_(2)催化剂粉末,在搅拌釜式反应器中,研究了60~90℃和0.2~1.0 MPa条件下苯乙炔和苯乙烯的浓度变化规律,得到了苯乙炔→苯乙烯和苯乙烯→乙苯的本征反应活化能分别为46.33 kJ·mol^(-1)和68.95 kJ·mol^(-1)。然后,在固定床反应器中,采用Ni_(3)CuSn_(0.3)/SiO_(2)颗粒,考察了反应温度、压力、进料H_(2)/苯乙炔的摩尔比和苯乙炔浓度对裂解汽油C_(8)芳烃选择性加氢反应的影响,并建立了反应器数学模型来描述该反应过程,分析了各组分效率因子沿反应器轴向的变化规律。实验结果验证了固定床反应器数学模型的准确性,苯乙炔、苯乙烯和乙苯的反应器出口浓度实验值与模型预测值之间的平均相对误差绝对值分别为9.8%、0.3%和0.3%。Styrene is an important monomer in the petrochemical industry and can be produced through the pyrolysis gasoline(PYGAS)extraction.To prevent contamination of styrene by trace amounts of phenylethylene,which leads to downstream catalyst poisoning and product non-compliance,selective hydrogenation technologies are commonly employed in industry to remove phenylethylene.The selective hydrogenation of C_(8) aromatic fraction of PYGAS over Ni_(3)CuSn_(0.3)/SiO_(2) catalysts was studied.The concentration variations of phenylethylene and styrene were first investigated under 60-90℃and 0.2-1.0 MPa in a stirred tank reactor using Ni_(3)CuSn_(0.3)/SiO_(2) catalyst powder.The intrinsic activation energies for phenylethylene→styrene and styrene→ethylbenzene were determined as 46.33 kJ×mol^(-1) and 68.95 kJ×mol^(-1),respectively.The effects of reaction temperature,pressure,molar ratio of H_(2) to phenylethylene,and phenylethylene concentration on the selective hydrogenation of C_(8) aromatic fraction of PYGAS were then examined in a fixed bed reactor using Ni_(3)CuSn_(0.3)/SiO_(2) catalyst pellets.A fixed-bed reactor mathematical model was established to describe the reaction process and the variation of effectiveness factors for each component along the reactor axis was analyzed.The experimental results validated the accuracy of the fixed-bed reactor mathematical model,with average absolute relative errors between experimental and predicted values of outlet concentrations for phenylethylene,styrene,and ethylbenzene of 9.8%,0.3%,and 0.3%,respectively.

关 键 词：Ni_(3)CuSn_(0.3)/SiO_(2) 反应动力学 反应器数学模型 苯乙炔 加氢 

分 类 号：TQ032[化学工程] TQ211