甲烷直接部分氧化制甲醇的热力学分析  

Thermodynamic analysis of direct partial oxidation of methane to methanol

作　　者：易天立 YI Tianli(School of Environment and Energy,South China University of Technology,Guangzhou 510006,China)

机构地区：[1]华南理工大学环境与能源学院,广东广州510006

出　　处：《精细石油化工进展》2025年第1期38-41,共4页Advances in Fine Petrochemicals

摘　　要：为了给甲烷直接部分氧化制甲醇反应的催化剂研制、反应器开发和工艺条件优化提供热力学理论指导,重点计算甲烷直接部分氧化制甲醇反应体系各反应的标准摩尔反应焓(Δ_(r)H_(T)^(θ))、标准摩尔反应吉布斯自由能(Δ_(r)G_(T)^(θ))和标准平衡常数,并进行热力学分析。结果表明:甲烷直接部分氧化制甲醇反应体系各反应的Δ_(r)H_(T)^(θ)均小于0,都是放热反应,但是放热程度有所差别,升高反应温度对各反应均不利;甲烷直接部分氧化制甲醇反应体系各反应的Δ_(r)G_(T)^(θ)均小于0,热力学上都可以自发进行,但相同反应温度下反应的发生倾向各不相同;甲烷直接部分氧化制甲醇反应体系各反应的标准平衡常数的数量级均较大,都属于不可逆反应,相同反应温度下,热力学上更有利于生成CO_(2)和CO。因此,甲烷直接部分氧化制甲醇反应需要控制通入反应器的O_(2)流量,进而有效调控CH_(4)与O_(2)摩尔比,实现甲醇的高度选择性。To provide thermodynamic theoretical guidance for catalyst development,reactor design,and process optimization,the standard molar reaction enthalpy(Δ_(r)H_(T)^(θ)),standard molar reaction Gibbs free energy(Δ_(r)G_(T)^(θ)),and standard equilibrium constant of each reaction system of direct partial oxidation of methane to methanol were calculated,and thermodynamic analysis was carried out.The results showed thatΔ_(r)H_(T)^(θ)of each reaction was less than 0 and all reactions are exothermic reactions.Still,the degree of an exothermic reaction differed,and increasing reaction temperature was unfavorable to all reactions.TheΔ_(r)G_(T)^(θ)of each reaction was less than 0,and all reactions can be spontaneous thermodynamically,but the tendency was different at the same reaction temperature.The standard equilibrium constants of each reaction system of direct partial oxidation of methane to methanol were large,and all reactions belonged to irreversible reactions.At the same reaction temperature,the thermodynamics was more conducive to the generation of CO_(2)and CO.Direct partial oxidation of methane to methanol required effective regulation of the CH_(4)to O_(2)ratio to achieve high selectivity of methanol.

关 键 词：甲烷 部分氧化 甲醇 热力学分析 平衡常数 

分 类 号：TQ223.121[化学工程—有机化工]