La＿2O＿3／SiO＿2上丁烯－1异构化水分压的影响及稳态和脉冲动力学研究

用外循环流动无梯度反应器研究了Ｌａ＿２Ｏ＿３／ＳｉＯ＿２上丁烯－１异构化稳态及脉冲色谱动力学。随水分压ＰＨ＿２Ｏ的增加，丁烯－１异构化活性随之下降。丁烯－１异构化稳态动力学服从Ｌ－Ｈ机理动力学方程，可近似表示为一级速度方程。用脉冲法测得丁烯－１、２－丁烯及水的吸附热，实验值与正交设计法估计值一致。丁烯－１异构化脉冲色谱动力学服从一级反应的Ｂａｓｓｅｔｔ方程。用稳态法与脉冲法测定的丁烯－１异构成ｔ－２－丁烯和ｃ－２－丁烯相对活性及真反应活化能一致。

The Effect of Partial Pressure of Water and Studies on Kinetics of Isomerization for Butene over La_2O_3/SiO_2 Catalyst by the Steady-State and Pulse Methods

The kinetics of isomerization of 1-butene over La_2O_3/SiO_2 catalyst has been investigated by the flow-reciculation glass reactor by the steady-state and pulse methods. The activity of isomerization for butene decreased with increasing the partial pressure of water. The steady-state kinetics of isomerization for butene obeyed the L-H mechanizm kinetic equation, which represented the rate equation offirst order approximately. The heats of adsorption for 1-butene,2-butene and water were determined by the pulse method. The values of adsorption heats for 1-butene,2-butene and water were coincided with the values estimated by the method of orthoganol design. The pulse kinetics of isomerization for 1-butene obeyed the Bassett equation of first order. The relative activity of isomerization for 1-butene to t-2-butene and c-2-butene by the steady-state method were coincided with the values by the pulse method. The intrinsical activation energy of isomerization for 1-butene to t-2-batene and c-2-butene were coincided with the values by the pulse method.