化学链甲醇氧化蒸汽重整过程的性能研究  

Performance Study on Chemical Looping Oxidative Steam Reforming of Methanol

作　　者：刘雷阳 刘日新 刘振江 刘晓旭 郑浩 曾亮 辛峰[1] LIU Leiyang;LIU Rixin;LIU Zhenjiang;LIU Xiaoxu;ZHENG Hao;ZENG Liang;XIN Feng(School of Chemical Engineering and Technology,Tianjin University,Tianjin 300354,China;Goldwind Green Energy Chemicals Technology(Jiangsu)Company Limited,Wuxi 214131,China)

机构地区：[1]天津大学化工学院,天津300354 [2]金风绿色能源化工科技(江苏)有限公司,江苏无锡214131

出　　处：《化学反应工程与工艺》2025年第1期238-245,共8页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金(22211540711)。

摘　　要：化学链甲醇氧化蒸汽重整(CL-OSRM)可以在自热重整的同时实现气体分离,是新型分布式高效制氢途径。本工作以CuO/ZnO/Al_(2)O_(3)催化剂为载氧体,通过CL-OSRM过程实现载氧体在还原阶段提供晶格氧并催化甲醇重整,氧化阶段再利用空气再生载氧体。通过固定床反应器评价载氧体的反应性能,对反应温度、进料流量及水醇比进行优化,在反应温度为220℃、进料流量为0.04mL/min、水醇比(物质的量之比)为1的条件下,实现甲醇转化率超90%且氢气中CO浓度低于1%。氧化-还原循环实验表明,载氧体在CL-OSRM过程中保持良好的活性和结构稳定性。高分辨透射电子显微镜及X射线衍射分析表明,载氧体与甲醇反应过程中,铜物种由CuO经过Cu^(+)的中间态逐步被还原为Cu^(0),其分别对应甲醇完全氧化、部分氧化与催化重整阶段。本工作为CL-OSRM工艺的进一步优化及在清洁制氢领域的应用提供了重要理论基础。The chemical looping oxidative steam reforming of methanol(CL-OSRM)enables gas separation while achieving autothermal reforming,representing a novel and efficient distributed hydrogen production method.In this study,CuO/ZnO/Al₂O₃catalyst was used as the oxygen carrier.During the CL-OSRM process,the oxygen carrier provided lattice oxygen and catalyzed methanol reforming in the reduction stage,while its regeneration was achieved in the oxidation stage using air.The reaction performance of the oxygen carrier was evaluated using a fixed-bed reactor,with optimization of reaction temperature,feed flow rate,and water methanol ratio.Under optimized conditions of 220℃,a feed flow rate of 0.04 mL/min,and a water methanol ratio of 1,methanol conversion rates exceeded 90%,with CO concentration in the hydrogen product remaining below 1%.Redox cycling experiments demonstrated that the oxygen carrier maintained good activity and structural stability during the CL-OSRM process.Characterization techniques such as high resolution transmission electron microscopy(HRTEM)and X-ray diffraction(XRD)confirmed that during the reaction with methanol,copper species in the oxygen carrier were gradually reduced from CuO to Cu^(+)and further to Cu^(0),corresponding to the stages of complete methanol oxidation,partial oxidation,and catalytic reforming,respectively.This work provided an important theoretical foundation for the further optimization of the CL-OSRM process and its application in clean hydrogen production.

关 键 词：甲醇重整 化学链制氢 载氧体 

分 类 号：TQ116.2[化学工程—无机化工]