透水NaA分子筛膜强化的CO_(2)加氢高效制甲醇  

Effective methanol production by CO_(2) hydrogenation using water-permeable NaA zeolite membrane

作　　者：李海鹏 吴桐 王琪 郜时旺[1,3] 王晓龙 李旭[1,4] 高新华 年佩 魏逸彬 LI Haipeng;WU Tong;WANG Qi;GAO Shiwang;WANG Xiaolong;LI Xu;GAO Xinhua;NIAN Pei;WEI Yibin(Institute of Clean Energy Technology,China Huaneng Group Co.,Ltd.,Beijing 102209,China;State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering,School of Chemistry and Chemical Engineering,Ningxia University,Yinchuan 750021,Ningxia,China;National Key Laboratory of Carbon Capture and Utilization Sequestration and Efficient and Flexible Coal Power Generation,Beijing 100031,China;Beijing Key Laboratory for Treatment and Capture of Carbon Dioxide,Beijing 102209,China)

机构地区：[1]中国华能集团清洁能源技术研究院有限公司,北京102209 [2]宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室,宁夏银川750021 [3]高效灵活煤电及碳捕集利用封存全国重点实验室,北京100031 [4]二氧化碳捕集与处理北京市重点实验室,北京102209

出　　处：《化工进展》2024年第5期2834-2842,共9页Chemical Industry and Engineering Progress

基　　金：宁夏重点研发计划(2023BDE03001);华能国际科技项目(HNKJ20-H58);宁夏自然科学基金(2023AAC05003)。

摘　　要：近年来,利用可再生能源产生的绿氢与CO_(2)反应制备甲醇备受关注。然而,由于CO_(2)催化加氢反应受热力学平衡限制,CO_(2)的转化率与甲醇选择性较低;另外,副产物水易导致催化剂失活。本研究采用母液晶种法在α-Al_(2)O_(3)膜管外制备了无缺陷的单通道NaA分子筛外膜,通过在膜管外填充Cu基催化剂,构建了一种分子筛膜-催化剂反应分离双功能反应体系,以同时实现CO_(2)加氢生成甲醇和在线选择性除水。通过XRD、SEM、N_(2)等温吸附-脱附、H_(2)-TPR表征技术对NaA分子筛膜和催化剂进行理化性质表征,并在膜反应器上对催化剂的CO_(2)催化加氢性能进行评价。结果表明,与传统固定床反应器对比,本反应体系可有效拉动反应平衡,大幅提高CO_(2)转化率。在250℃、3MPa条件下,CO_(2)转化率由3.34%提高至28.78%,甲醇收率由3.28%提高至27.62%。In recent years,the production of methanol by CO_(2) hydrogenation with green hydrogen produced from renewable energy sources has received a lot of attention.However,the CO_(2) conversion and methanol selectivity of the reaction are limited by the thermodynamic equilibrium of CO_(2) catalytic hydrogenation reaction.Moreover,the presence of water as a byproduct usually leads to catalyst deactivation.In this study,a mother liquid seeding method was used to prepare defect-free single-channel NaA zeolite membrane.Then Cu-based catalysts were filled on the membrane to create a zeolite membrane-catalyst bifunctional reaction system that allowed for the simultaneous hydrogenation of CO_(2) to produce methanol and the on-line selective removal of water.XRD,SEM,N_(2) isothermal adsorption desorption,and H_(2)-TPR were used to characterize the physical and chemical properties of the NaA zeolite membranes and the catalysts.The catalysts performance for CO_(2) hydrogenation were evaluated by the membrane reactor.The results showed that the reaction system can significantly increase the CO_(2) conversion and effectively drive the reaction equilibrium forward compared with the conventional fixed bed reactor.The CO_(2) conversion was increased from 3.34% to 28.78% and the methanol yield was promoted from 3.28% to 27.62% at 250℃ and 3MPa.

关 键 词：二氧化碳 加氢 甲醇 Cu基催化剂 膜 反应器 

分 类 号：O643[理学—物理化学]