吴建民,孙启文,张宗森,庞利峰.乙烯齐聚制α-烯烃反应体系的热力学研究[J].分子催化,2013,(4):385-391
乙烯齐聚制α-烯烃反应体系的热力学研究
Thermodynamic Study for ethylene oligomerization to α-Olefins
投稿时间:2013-07-23  修订日期:2013-08-19
DOI:
中文关键词:  乙烯齐聚  α-烯烃  热力学  平衡常数
英文关键词:ethylene oligomerization  α-olefins  thermodynamics  equilibrium constant
基金项目:国家重点基础研究发展计划(973计划)
作者单位E-mail
吴建民* 上海兖矿能源科技研发有限公司煤液化及煤化工国家重点实验室 jminwu@163.com 
孙启文 上海兖矿能源科技研发有限公司煤液化及煤化工国家重点实验室 yetech@ye-tech.com 
张宗森 上海兖矿能源科技研发有限公司煤液化及煤化工国家重点实验室 yetech@ye-tech.com 
庞利峰 上海兖矿能源科技研发有限公司煤液化及煤化工国家重点实验室 yetech@ye-tech.com 
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中文摘要:
      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 %。
英文摘要:
      The standard molar enthalpy of formation, the standard molar entropy and isobaricmolar capacity of ethylene oligomerization products were estimated with Benson group contribution method. The reaction heat, Gibbs free energy change and equilibrium constant of ethylene oligomerization to α-olefins reantion system were calculated in detail as a function of the temperature from 298 K to 700 K. The thermodynamic equilibrium and the limit of different reaction steps wer analyzed. The thermodynamic possibility and formation sequences of ethylene oligomerization reaction system were also judged. The effects of temperature and pressure on the equilibrium conversion were investigated. The appropriate process conditions of ethylene oligomerization to α-olefins reactions were determined according to thermodynamic calculations. The results show that ethylene oligomerization to α-olefins reactions are exothermic reactions, which are spontaneous when the temperature is lower than 546 K. The ethylene oligomerization to linear α-olefins reactions are easier than α-olefins isomerization and olefins disproportionation. Low temperature and high pressure are favored to ethylene oligomerization to α-olefins reactions from a thermodynamic point of view. The appropriate process conditions of ethylene oligomerization to linear α-olefins are 323~473 K, 5~20 MPa. The equilibrium conversions of ethylene oligomerization to linear α-olefins reactions approach 100 % in the process conditions of 363 K, 10.3 MPa from SHOP method.
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