几种芳烃加氢反应的热力学分析  

Thermodynamic Analysis on the Hydrogenation Reaction of Several Aromatic Hydrocarbons

作　　者：胡意文[1] 达志坚[1] 王子军[1] 

机构地区：[1]中国石化石油化工科学研究院,北京100083

出　　处：《石油学报（石油加工）》2015年第1期7-17,共11页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点基础研究发展计划"973"项目(2012CB224801)基金资助

摘　　要：采用Benson基团贡献法计算得到萘、菲及芘加氢反应网络中各步反应在一定温度范围内的平衡常数,并系统分析了氢压、温度和物质结构对芳烃加氢平衡时的转化率、浓度分布和氢增量的影响。结果表明,加氢反应在低温下具有更好的热力学选择性,且氢压越高、温度越低时,那些芳环越少、环烷环越多及非取代芳香碳越多的芳烃具有越高的加氢平衡转化率。芳烃原料和其全加氢产物分别在高温低压、低温高压时热力学稳定,而部分氢化产物的热力学稳定区则位于两者之间,且对反应条件敏感。在芳烃各加氢产物中,全加氢产物具有较高的热力学选择性,部分氢化产物的热力学选择性较差。受热力学的限制,通过加氢来提高芳烃氢含量的效果有限。The equilibrium constants in a certain temperature range of every step conversion in the hydrogenation reaction networks of naphthalene,phenanthrene and pyrene were calculated with Benson group-contribution method.And the effects of hydrogen pressure,temperature and material structure to the equilibrium conversion,equilibrium concentration distribution and hydrogencontent increment of aromatic hydrogenation were systematically analyzed.The results showed that a significant thermodynamic selectivity of hydrogenation reaction seemed to be achieved only in low temperature zone,and when those aromatic hydrocarbons with less aromatic rings,more naphthenic rings and more non-substituted aromatic carbons were hydrogenated at higher hydrogen pressure and lower temperature,a higher equilibrium conversion could be obtained.The thermodynamic stabilization of reactant and perhydro-products was preserved at high temperature and low hydrogen pressure conditions,or low temperature and high hydrogen pressure conditions,respectively,while the thermodynamic stabilization of partial hydrogenation products was preserved at the middle conditions,which exhibited strong thermodynamic sensitivity to the reaction conditions.Among the hydrogenation products of aromatic hydrocarbons,perhydro-products held high thermodynamic selectivity compared with partial hydrogenation products.Also,the effect of hydrogen-content increase in aromatics by hydrogenation reaction was limited because of the thermodynamic restriction.

关 键 词：芳烃加氢 热力学 Benson基团贡献法 平衡常数 平衡转化率 平衡浓度分布 氢含量 

分 类 号：O625.15[理学—有机化学] O642.4[理学—化学]