钴基费托合成催化剂硫中毒热力学分析  

Thermodynamics analysis of sulfur poisoning over cobalt-based Fischer-Tropsch synthesis catalyst

作　　者：吴建民[1] 孙启文[1] 张宗森[1] 盛斌 WU Jian-min;SUN Qi-wen;ZHANG Zong-sen;SHENG Bin(State Key Laboratory of Coal Liquefaction and Coal Chemical Technology,Yankuang Energy R&D Co.,Ltd.,Shanghai 201203,China)

机构地区：[1]上海兖矿能源科技研发有限公司煤液化及煤化工国家重点实验室,上海201203

出　　处：《化学工程》2020年第7期48-52,共5页Chemical Engineering(China)

基　　金：国家高技术研究发展计划(863计划)(2011AA05A204)。

摘　　要：基于热力学基础数据和HSC Chemistry计算软件对473-623 K温度范围内钴基费托合成催化剂硫中毒反应的焓变、吉布斯自由能以及平衡常数等热力学数据进行了计算,分析了不同反应步骤的热力平衡与限度,对钴基催化剂硫中毒反应的热力学可能性与生成顺序进行了判断。结果表明:从热力学角度,钴基催化剂硫中毒均是放热反应,均能够自发进行;对于不同反应,其平衡常数差异很大,对应硫中毒反应发生时,所需H2S和COS的质量分数也不同,对COS的要求更为严格,并获得了H2S和COS的中毒极限,即原料气中的硫化物质量分数应低于10-9级;所获得的热力学基础数据可为抗硫性钴基费托合成催化剂的改性开发提供一定的数据依据和理论指导。According to some thermodynamic data and HSC Chemistry calculation software,the enthalpy change,Gibbs free energy change and equilibrium constant of sulfur poisoning on cobalt-based Fischer-Tropsch synthesis catalyst were calculated at 473 K to 623 K.The thermodynamic equilibrium and the limit of different reaction steps were analyzed.The thermodynamic possibility and formation sequences of sulfur poisoning reaction system on cobalt-based catalyst were also judged.The results show that sulfur poisoning reactions are exothermic reactions,which are spontaneous under the condition of Fischer-Tropsch synthesis reaction.Their equilibrium constants are much different for different reactions.The necessary mass fraction of H2S and COS are also different and more stringent requirements on the COS than H2S.The mass fractions limitations of H2S and COS are also obtained.The thermodynamic data obtained can provide useful data basis and theoretical guidance to the development of sulfur tolerant cobalt-based Fischer-Tropsch synthesis catalyst and desulfurization process study.

关 键 词：费托合成 钴基催化剂 硫中毒 热力学 

分 类 号：TQ529.2[化学工程—煤化学工程] TQ013.1