用于甲烷无氧脱氢低聚与除氢过程耦合的复合催化剂研究  

Study on composite catalysts for methane anaerobic dehydrogenation oligomerization coupled with dehydrogenation process

作　　者：应永超 何冰清 杨一丁 韩树民[2] 於思瑜 刘社田 YING Yongchao;HE Bingqing;YANG Yiding;HAN Shumin;YU Siyu;LIU Shetian(School of Chemistry and Chemical Engineering,Southwest University,Chongqing 400715,China;School of Environment and Chemical Engineering,Yanshan University,Qinhuangdao,Qinhuangdao 066000,Hebei,China;School of Chemistry and Chemical Engineering,Northeast Petroleum University,Daqing 163318,Heilongjiang,China)

机构地区：[1]西南大学化学化工学院,重庆400715 [2]燕山大学环境与化学工程学院,河北秦皇岛066000 [3]东北石油大学化学化工学院,黑龙江大庆163318

出　　处：《工业催化》2025年第1期29-39,共11页Industrial Catalysis

基　　金：国家自然科学基金资助项目(22272129)。

摘　　要：甲烷无氧芳构化(MDA)因能将甲烷一步转化为苯、甲苯等高价值产物而被认为是富有前景的工业利用甲烷的途径。然而甲烷的C—H键能高,导致催化剂在低温下难以活化甲烷,高温MDA反应中催化剂易积碳失活。本文将Mo/HZSM-5与储氢合金CN-3混合制备的催化剂用于MDA,使甲烷脱氢与除氢过程耦合,加速低温下甲烷的活化和苯的生成。通过改变Mo/HZSM-5与CN-3的制备方法(机械研磨、球磨或浸渍)、Mo含量等,优化催化剂性能。结果表明,机械混合方式能较好地维持CN-3合金以及Mo/HZSM-5样品原有形貌和性能,制得催化剂的MDA催化活性最佳。该方法下,CN-3的加入使MDA反应中甲烷转化率从13.5%提升到22.9%,苯产速由28.7μmol·(min·g)^(-1)增加至52.3μmol·(min·g)^(-1)。Methane anaerobic aromatization(MDA)is considered as a promising industrial pathway for methane utilization,offering a single-step conversion of methane into high-value products like benzene and toluene.However,the formidable energy barrier posed by the methane C—H bond presents a challenge for catalysts to activate methane efficiently at low temperatures.Moreover,catalysts often suffer from deactivation due to carbon deposition during high-temperature MDA reactions,which hampers the widespread industrial adoption of MDA.To address these challenges,this study explored the preparation of catalysts by mixing Mo/HZSM-5 with a hydrogen storage alloy(CN-3)for MDA.This approach synergistically couples methane dehydrogenation with dehydrogenation process to facilitate methane activation and enhance benzene production even at low temperatures.The performance of the catalyst was optimized by varying the preparation methods of Mo/HZSM-5 and CN-3(e.g.,mechanical grinding,ball milling,or impregnation)along with adjusting Mo content.The results indicate that the mechanical mixing method proves superior in maintaining the original morphology and performance of CN-3 alloy and Mo/HZSM-5 samples,thereby resulting in optimal catalytic activity of prepared catalysts for MDA.With this method,the addition of CN-3 increased the methane conversion in the MDA reaction from 13.5%to 22.9%,and the benzene production rate increased from 28.7μmol·(min·g)^(-1) to 52.3μmol·(min·g)^(-1).

关 键 词：催化化学 甲烷芳构化 除氢耦合过程 储氢合金 

分 类 号：TQ426.6[化学工程] O643.36[理学—物理化学]