CO2氧化1-丁烯脱氢制1,3-丁二烯反应热力学分析

通过热力学分析了CO2氧化1-丁烯脱氢制1,3-丁二烯反应及反应限度.计算结果表明:目标反应在常温下不能发生,而在实验室最佳反应温度873.15 K下可逆进行;CO2的引入促进了1-丁烯脱氢反应的进行;反应可以通过氧化脱氢反应的一步路径和直接脱氢与逆水煤气变换耦合的二步路径进行.并且,在热力学上异构化反应比氧化脱氢反应...

Thermodynamic Analysis on the Reaction of Oxidative Dehydrogenation of 1-Butene to 1, 3-Butadiene With CO2 as the Soft Oxidant

A thermodynamic study was conducted to analyze thereaction of oxidative dehydrogenation of 1-butene to 1,3-butadiene with CO₂ as the soft oxidant. The results show that the target reaction cannot occur atroom temperature, but the reaction is reversible at 873.15 K (the optimum-laboratoryreaction temperature). The introduction of CO₂ promotes the dehydrogenationof 1-butene, and the reaction can proceed through both the one-step pathway(through oxidative dehydrogenation) and the two-step pathway (directdehydrogenation coupled with inverse water gas transformation). Moreover, it isfound that the isomerization reactions are more likely to occur than theoxidative dehydrogenation reaction thermodynamically. Under the condition offree competitive reaction without catalyst, the conversion of 1-butene couldreach up to 93.68%, while the 1,3-butadiene yield could only reach to 54.64%.These findings demonstrate that the occurrence of the isomerization reactionsis the cause of the low selectivity of the target reaction. Therefore, thedesign and development of the catalyst which inhibit the isomerization reactionswill effectively improve the catalytic performance of the catalyst.