甲烷氧化偶联制烯烃的热力学平衡限度

选择适宜的热力学模型对甲烷氧化偶联制烯烃体系的热力学平衡进行分析，考察温度﹑压力﹑进料组成对体系组分的平衡限度影响。研究发现，在甲烷氧化偶联制烯烃体系中，H2、CO的生成相对容易，C2产物（C2H4、C2H6）不容易生成。通过计算，得到了该体系有利于烯烃生成的反应条件，500℃～800℃、1.5MPa、烷氧摩尔比为7。实验为甲烷氧化偶联反应器和催化剂的开发研究提供热力学依据。

Thermodynamic equilibrium limit of the methane oxidative coupling system

Thermodynamic equilibrium limit in the system of methane oxidative coupling was studied. The Van′t Hoff equation was used to study the influence of temperature. PR equation was used for calculating the fugacity of each compound. With thermodynamic model and related data, aimmimg at the minimum of Gibbs free energy in this system, the thermodynamic property of the methane oxidative coupling were calculated at ideal condition. The methane conversion, selectivity and yields of other compounds at equilibrium were studied. The influences to different compounds in the system caused by different temperatures， pressures， methane and oxygen molar ratio have been tested. It is found that in this system H2 and CO are easy to get while C2 products (C2H6 and C2H4) are difficult. Not only CO and H2 but CO2 and H2O have the same changing trend. The higher temperature, lower pressure and lower methane and oxygen molar ratio can help to improve the methane conversion. And it is advantageous for C2 products at the condition of higher temperature, pressure, methane and oxygen molar ratio.