甲烷裂解过程热力学分析.doc

甲烷热解过程热力学分析 克里斯托·古尔特，迈克尔·达罗克斯，弗朗西斯·比尔奥迪 (1996年5月15日接收，1996年12月17日接受） 摘要：依据烃类生成自由能变化与温度的函数可知，甲烷在530℃到1030℃环境中不稳定，但其依然是烃类在这一温度范围中最稳定的。利用甲烷分别生成乙炔和乙烯时，温度必须达到1200℃和1300℃。然而，升温至1230℃后，乙烯才是最稳定，在这一温度时乙炔含量占绝大多数。根据生成焓变换与温度的函数可得，甲烷热解生成乙炔需要吸收很高的能量，我们用最小吉布斯自由能法分析得出其合成物是CH4、C2H4、C2H2、C6H6和H2。最小吉布斯自由能法不需要对化学平衡反应有很深的认识，计算参量是初始氢碳比、温度、压强和各种物质的吉布斯自由能，对这个复杂化学平衡反应的分析有助于识别某一分子稳定时的温度域。温度低于1200℃时，甲烷含量几乎不变，最主要烃类生成物是苯，其次是乙烯，没有乙炔生成；温度高于1200℃时，有类乙炔结构（如乙炔）的烃类生成，同时还有C2H，C3H和一些像H和CH3的自由基生成。这意味着温度高于1200℃时C-C和C-H键断裂 ，出现的类乙炔结构烃类具有越来越小的H/C比，而且发现最初氢是以分子形式出现，反应介质中存在的氢具有提升富氢烃类（主要是CHI、C2H4和甲烷的转变减少）含量的影响。 关键字：甲烷；热力学；热解 ；高温；吉布斯自由能；化学平衡 Abstract-In accordance with the changes in the free energies of formation of hydrocarbons as a function of temperature, methane is unstable in terms of its elements from 530℃ , but remains the most stable of hydrocarbons up to 1030℃. Using methane, it is necessary to reach temperatures of 1200℃ and 1300℃ to produce, respectively, acetylene and ethylene. However, since acetylene becomes the most stable hydrocarbon from 1230℃, it is acetylene that predominates at this temperature. According to the variation in the enthalpies of formation as a function of temperature, the pyrolysis of methane demands a very high energy input to form primarily acetylene. We calculated the composition of a mixture CH4, CzH4, C2H2, C6H6 and H2 at thermodynamic equilibrium by minimizing the Gibbs energy of this system. This method does not require prior knowledge of the chemical reactions taking place at equilibrium. The calculation parameters are the initial H/C ratio, the temperature, the pressure and the Gibbs energies of each substance. The analysis of the complex chemical equilibria helps to identify temperature zones corresponding to stability domains of certain molecules. Below 1200℃, the disappearance of methane is slight, and the main hydrocarbon produced is benzene, followed by ethylene, without any significant formation of acetylene. Species with acetylenic structures (like C2H2) appear