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利用Benson基团贡献法计算了乙烯齐聚制α-烯烃反应各物质的标准摩尔生成焓、标准摩尔熵和摩尔定压热容,在298～700 K温度范围内对乙烯齐聚制α-烯烃反应体系的反应热、吉布斯自由能以及反应平衡常数进行了详尽的计算,分析了不同反应步骤的热力学平衡与限度,对不同反应发生的热力学可能性与顺序进行了判断,考察了反应温度和压力对乙烯齐聚制α-烯烃反应化学平衡的影响,确定了乙烯齐聚制α-烯烃反应体系适宜的工艺条件.结果表明:乙烯齐聚制α-烯烃反应为放热反应;从热力学上看,温度低于546 K时,乙烯齐聚生成直链α-烯烃反应为自发过程,且比α-烯烃异构化和烯烃歧化反应更容易进行;低温、高压有利于乙烯齐聚制α-烯烃反应的进行;乙烯齐聚制α-烯烃反应体系适宜的工艺条件为温度323～473 K,压力5～20 MPa,且在SHOP法的工艺条件下(温度363 K,压力10.3 MPa),乙烯齐聚生成直链α-烯烃反应的热力学平衡转化率接近于100%.
The standard molar enthalpy of formation, standard molar enthalpy and molar constant pressure heat capacity of the oligomerization of ethylene to oligomerization of ethylene were calculated by the Benson group contribution method. The oligomerization of ethene to α-olefin in the temperature range of 298 ~ 700 K The reaction heat, Gibbs free energy and reaction equilibrium constant of the reaction system were calculated in detail. The thermodynamic equilibrium and limit of different reaction steps were analyzed. The thermodynamic possibility and sequence of different reactions were also evaluated. The effects of reaction temperature And the influence of pressure on the chemical equilibrium of oligomerization of ethylene to α-olefin, the suitable process conditions for the oligomerization of ethylene to α-olefin were determined.The results show that the oligomerization of ethylene to α-olefin is an exothermic reaction, In conclusion, oligomerization of ethylene into linear α-olefins at temperatures below 546 K is a spontaneous process and is easier to carry out than isomerization of α-olefins and disproportionation of olefins; low temperature and high pressures favor oligomerization of α - olefins. The suitable process conditions for the oligomerization of ethylene to α-olefin system are temperature 323 ~ 473 K, pressure 5 ~ 20 MPa, and under the process conditions of SHOP (temperature 363 K, pressure 10.3 MPa) B The thermodynamic equilibrium conversion of olefin oligomerization to linear α-olefin reaction is close to 100%.