Fe_(2)O_(3)/MgAl_(2)O_(4)载氧体甲烷化学链制氢性能研究  

Research on the Performance of Fe_(2)O_(3)/MgAl_(2)O_(4)Oxygen Carriers for Methane Chemical-Looping Hydrogen Generation

作　　者：宋业恒 毛继平 任东伟 张国良 于琳浩 陈雅琪 向文国[1] 陈时熠[1] SONG Yeheng;MAO Jiping;REN Dongwei;ZHANG Guoliang;YU Linhao;CHEN Yaqi;XIANG Wenguo;CHEN Shiyi(School of Energy and Environment,Southeast University,Nanjing 210096,China;Luoyang R&D Center of Technology,SINOPEC Engineering(Group)Co.,Ltd.,Luoyang 471003,China;Qilu Division,SINOPEC catalyst Co.,Ltd.,Zibo 255336,China)

机构地区：[1]东南大学能源与环境学院,江苏南京210096 [2]中石化炼化工程(集团)股份有限公司洛阳技术研发中心,河南洛阳471003 [3]中国石化催化剂有限公司齐鲁分公司,山东淄博255336

出　　处：《石油学报(石油加工)》2025年第2期477-488,共12页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石油化工股份有限公司项目(123048)基金资助。

摘　　要：载氧体稳定性差是限制化学链制氢技术发展的主要因素之一,针对此问题,通过提高载体-活性组分之间的相互作用,抑制反应过程中的烧结团聚来增强载氧体稳定性。制备了Fe_(2)O_(3)/MgAl_(2)O_(4)载氧体,以甲烷为原料,在小型流化床反应器上模拟双床(甲烷还原/水蒸气氧化)化学链制氢过程,探究氧化铁含量和反应条件对载氧体甲烷化学链制氢反应性能的影响。结果表明,Fe_(2)O_(3)/MgAl_(2)O_(4)载氧体中氧化铁最佳质量分数为20%,最佳工艺条件为:CH_(4)体积分数5%,温度900℃,水蒸气体积分数20%。XRD、SEM等表征和实验结果表明,Fe离子融入了MgAl_(2)O_(4)尖晶石的体相内并增强了载氧体稳定性,当氧化铁质量分数高于20%时,载氧体会因烧结团聚迅速失活,高体积分数甲烷会因裂解速率高于载氧体释氧速率而产生大量积炭,升高温度可增强反应活性,但温度过高则会影响载氧体的稳定性。Poor stability of oxygen carrier is one of the main factors restricting the development of chemical looping hydrogen generation technique.In view of this,the stability of oxygen carrier was improved by enhancing the interaction between carrier and active component and inhibiting sintering agglomeration during reaction.Using the prepared Fe_(2)O_(3)/MgAl_(2)O_(4)oxygen carrier as oxygen carriers and CH_(4)as feedstock,the dual-bed(CH_(4)reduction/steam oxidation)hydrogen production process was simulated in a small fluidized bed reactor,so as to explore the effects of Fe_(2)O_(3)content and reaction conditions on the reaction performance of CH_(4)chemical looping hydrogen generation by oxygen carrier.The results indicate that the optimal mass fraction of Fe_(2)O_(3)in the oxygen carrier Fe_(2)O_(3)/MgAl_(2)O_(4)is 20%and the optimal processing conditions are 5%CH_(4)and 20%steam at 900℃.The XRD,SEM characterizations and experiment results show that Fe ion is integrated into MgAl_(2)O_(4)lattice and can enhance the stability of oxygen carrier.When Fe_(2)O_(3)mass fraction is higher than 20%,the oxygen carrier will be quickly deactivated due to sintering agglomeration.In addition,CH_(4)with a high volume fraction will lead to a large amount of carbon deposition due to the fact that pyrolysis rate is higher than the oxygen release rate of oxygen carrier;reaction activity can be boosted by increasing temperature,and the stability of oxygen carrier tends to decrease under overtemperature.

关 键 词：化学链制氢 载氧体 Fe_(2)O_(3) MgAlO_(4)载体 

分 类 号：TK91[动力工程及工程热物理]