CAJ | 학술논문

采用Benson基团贡献法估算得到二甲醚（DME）和乙酸甲酯（MA）的标准生成焓和标准生成吉布斯自由能，在298～1000K时计算了DME与合成气制乙醇（DME羰基化反应、MA加氢反应以及二者组成的总反应）过程中的反应焓变、反应熵变、反应吉布斯自由能变和化学反应的平衡常数。在此基础上，分析了反应压力、反应温度和原料比对DME转化率的影响。在413K、1×105Pa、CO∶DME=1条件下考察了不同H2浓度情况下合成乙醇反应中两个反应的协同效应。分析结果表明，在低于493K、3MPa、n(CO)∶n(DME)=1的条件下有利于合成反应的进行，由于两反应的协同效应，使MA加氢反应的平衡转化率有大幅度提高。
채용Benson기단공헌법고산득도이갑미（DME）화을산갑지（MA）적표준생성함화표준생성길포사자유능，재298～1000K시계산료DME여합성기제을순（DME탄기화반응、MA가경반응이급이자조성적총반응）과정중적반응함변、반응적변、반응길포사자유능변화화학반응적평형상수。재차기출상，분석료반응압력、반응온도화원료비대DME전화솔적영향。재413K、1×105Pa、CO∶DME=1조건하고찰료불동H2농도정황하합성을순반응중량개반응적협동효응。분석결과표명，재저우493K、3MPa、n(CO)∶n(DME)=1적조건하유리우합성반응적진행，유우량반응적협동효응，사MA가경반응적평형전화솔유대폭도제고。
Both standard formation enthalpy and standard Gibbs free energy of dimethyl ether (DME) and methyl acetate were estimated with the Benson group contribution method. Reaction enthalpy change,reaction entropy change,reaction Gibbs free energy change and equilibrium constant of reactions of ethanol synthesis (DME carbonylation,MA hydrogenation,overall reactions) were calculated and analyzed. On this basis,effects of reaction temperature,reaction pressure,raw material ratio on DME conversion were investigated. The synergistic effect between the two reactions of ethanol synthesis were investigated at different concentrations of H2 under the conditions of 413K,normal pressure,CO∶DME=1. A moderate reaction temperature (lower than 493K),3MPa,n(CO)∶n(DME)=1 were beneficial to ethanol synthesis and the equilibrium conversion in MA hydrogenation increased greatly due to this synergistic effect.