摘要
基于Benson基团贡献法,计算了环己烯、乙烯、二氧化碳及氢气参与反应中可能涉及物质的热力学数据ΔfHm0、Sm0、Cp,m。对二氧化碳存在下的环己烯、乙烯与氢气可能存在的各种反应的ΔrGm、Kp进行估算,并对这些反应的可行性和反应程度进行了分析,讨论了温度和压力对反应的影响。研究表明低温高压对体系中各反应有利,二氧化碳氢化形成一氧化碳、甲酸,羧酸氢化形成醛是热力学不利的反应,烯烃氢化形成烷烃、醛氢化成醇、烯烃与二氧化碳、一氧化碳反应形成羧酸及醛在一定温度范围内是热力学有利的反应。烯烃的结构对反应热力学也有很大影响,乙烯比环己烯更易甲酰化。
The standard heat of formation △pHM^0, entropy Sm^0 and heat capacity Cpm of the possible compounds involved in the re- action system of cyclohexene, ethylene, carbon dioxide and hydrogen were calculated by Benson group contribution method. The Gibbs free energy and equilibrium constants of the possible reactions of above system were calculated and used to forecast the feasi- bility and the extent of reactions. The effects of temperature and pressure on the reactions were discussed. The results revealed that lower temperature and higher pressure are favorable to all reactions. The hydrogenation of carbon dioxide to carbon monoxide or formic acid, and hydrogenation of earboxylie acids to aldehydes were thermodynamically unfavorable. While hydrogenation of alkenes to alkanes, hydrogenation of aldehydes to alcohols, and formation of carboxylie acids or aldehydes from the reactions of alkenes with carbon dioxide or carbon monoxide were thermodynamically favorable within certain range of temperature. From the thermodynamic view, the structure of alkene had great effects on the above reactions and ethylene was more easily hydrofomylated than eyelohexene.
出处
《天然气化工—C1化学与化工》
CAS
CSCD
北大核心
2010年第4期45-50,共6页
Natural Gas Chemical Industry
基金
国家自然科学基金项目资
关键词
基团贡献法
热力学分析
环己烯
乙烯
二氧化碳
Benson group contribution method
thermodynamic analysis
eyelohexene
ethylene
carbon dioxide
