由环戊二烯合成降冰片烯的动力学

Kinetics of Norbornene Synthesis from Cyclopentadiene

使用内循环式无梯度反应釜研究了环戊二烯与乙烯在气相条件下进行环加成反应生成降冰片烯的动力学参数。无梯度反应釜出口组成由气相 色谱仪进行在线分析。环戊二烯与乙 烯生成降冰片烯的反应属协同历程的环加成反应，是二级反应，反应速度 只与温度有关，普通的酸、碱催 化剂对此类反应没有作用。实验在５６２ ～６００ Ｋ 范围内进行，反应釜压力维持１ ．２ Ｍ Ｐａ 。测定了不同温度 下反应速率及速率常数，得出合成降冰片烯反应的表观活化能为１ ．５３５ ×１０５ Ｊ·ｍｏｌ － １ ，因此动 力学常数的表达式为 ｋ＝ ３ ．１９６ ×１０１２ ｅｘｐ（ － １ ．５３５ ×１０５／ Ｒ Ｔ）

Gaseous reaction for synthesis of norbornene from cyclopentadiene and ethylene was studied in a well mixing tank reactor and the kinetic parameters were estimated. The outlet products were analyzed with online chromatography. The studied reaction is a cycloaddition second order reaction and the rate depends only on the temperature, while common catalysts such as acids and alkalis do not play any role in this reaotion. Experiments were controlled under the temperature scale of 562～600 K and the pressure of 1.2 MPa. The reaction rate and rate constant were measured at different temperatures. In these conditions the apparent activiation energy was determined of the value of 1.535×10 5 J·mol -1 and the expression of kinetic parameter was: k =3.196×10 12 exp(-1.535×10 5/ RT )