低碳化学与化工2025，Vol.50Issue(7)：51-57,7.DOI:10.12434/j.issn.2097-2547.20250071
H2S对Pd/α-Al2O3催化剂催化草酸二甲酯合成反应性能的影响
Effect of H2S on catalytic performance of Pd/α-Al2O3 catalyst for synthesis of dimethyl oxalate
赵立红 1梁旭 1蒋元力 1刘振峰 2谢肥东 3蔡教民 4谢进军5
作者信息
- 1. 河南能源集团研究总院有限公司,河南 郑州 450046||郑州市绿色低碳化工能源材料工程技术研究中心,河南 郑州 450046
- 2. 贵州黔希化工有限责任公司,贵州 毕节 551500
- 3. 河南龙宇煤化工有限公司,河南 永城 476600
- 4. 河南省中原大化集团有限责任公司,河南 濮阳 457000
- 5. 山西沃能化工科技有限公司,山西 临汾 041000
- 折叠
摘要
Abstract
Dimethyl oxalate(DMO)is an intermediate product of syngas to ethylene glycol.In industry,DMO is typically produced via the reaction of CO and methyl nitrite(MN)over Pd/α-Al2O3 catalyst.However,during the production of DMO using industrial tail gas,significant load fluctuations are unavoidable,and the concentration of toxic substances such as H2S may exceed permissible limits.Therefore,investigating the toxic effects of H2S on the catalyst is of critical importance.The impact of H2S on catalytic performance of the Pd/α-Al2O3 catalyst for synthesis of DMO from CO and MN was examined using a fixed-bed microreactor.Under the temperature of 120℃,normal pressure,n(CO)/n(MN)of 2.0,and the space velocity of 3000 h-1,after exposure to H2S poisoning,the conversion rate of MN decreases from 83%to about 64%.After H2 reduction treatment on the poisoned catalyst,the MN conversion rate further decreases to about 51%.The structures of catalysts were characterized by XRD,FT-IR,HRTEM and XPS,etc.The results indicate that H2S preferentially reacts with palladium active species on the catalyst surface to form inert compounds such as PdSO4,PdOx-S,and PdOx-SOx,while the palladium particles retain Pd0 state internally.H2 reduction treatment removes some surface sulfur species and some oxidized Pd species are reduced back to Pd0.However,this reduction process induces the aggregation of Pd0 particles.The occupation and coverage of active sites by inert species such as PdSO4,PdOx-S,and PdOx-SOx,along with the aggregation of Pd0 are the main reasons for the decrease of cataltic activity of catalyst.关键词
草酸二甲酯/Pd/α-Al2O3催化剂/H2S预处理/再生处理Key words
dimethyl oxalate/Pd/α-Al2O3 catalyst/H2S pretreatment/regenerative treatment分类
化学化工引用本文复制引用
赵立红,梁旭,蒋元力,刘振峰,谢肥东,蔡教民,谢进军..H2S对Pd/α-Al2O3催化剂催化草酸二甲酯合成反应性能的影响[J].低碳化学与化工,2025,50(7):51-57,7.
