过渡金属掺杂MnOx/ZSM-5对甲苯吸附和催化氧化的影响  

Effect of transition metal oxide doping MnOx/ZSM-5 on the adsorption and catalytic oxidation of toluene

作　　者：刘晗 周媛媛 邓琳 万杰 刘雁军 王晓丽[2] 于先坤 杨晓军 胡纯政 吴功德[2] LIU Han;ZHOU Yuanyuan;DENG Lin;WAN Jie;LIU Yanjun;WANG Xiaoli;YU Xiankun;YANG Xiaojun;HU Chunzheng;WU Gongde(Department of Municipal Engineering,Southeast University,Nanjing,211189,China;Energy Research Institute,Nanjing Institute of Technology,Nanjing,211167,China;Sinosteel Maanshan Mining Research Institute Co.,Ltd,Maanshan,243000;Jiangsu Subei Environmental Protection Group Co.,Ltd,Shuyang,223624,China)

机构地区：[1]东南大学市政工程系,南京211189 [2]南京工程学院能源研究院,南京211167 [3]中钢集团马鞍山矿山研究总院股份有限公司,马鞍山243000 [4]江苏苏北环保集团有限公司,沭阳223624

出　　处：《环境化学》2023年第4期1209-1221,共13页Environmental Chemistry

基　　金：国家自然科学基金(22076023);安徽省重点研发计划项目(202104g01020006);江苏省创新支撑计划项目(BZ2022053);江苏省基础研究计划(自然科学基金)(BK20201037);江苏省产学研合作项目(BY2022101);南京工程学院引进人才科研启动基金(YKJ2019111,YJK2019110)资助。

摘　　要：实验采用柠檬酸络合法制备了一系列过渡金属掺杂MnO_(x)/ZSM-5的吸附/催化双功能材料,以甲苯为处理对象,探讨了过渡金属Cu、Co和Ni掺杂对MnO_(x)/ZSM-5吸附和催化氧化性能的影响.通过BET、XRD、SEM、H2-TPR和XPS对所制备催化剂进行了表征,并进一步评估了CuMnO_(x)/ZSM-5的工业适用性.结果显示,CuMnO_(x)/ZSM-5在所有催化剂中表现出最好的吸附和催化氧化性能,对甲苯的平衡吸附量为25.90 mg·g^(−1),与MnO_(x)/ZSM-5和CuO_(x)/ZSM-5相比,其催化氧化甲苯的T50和T90均降低了30℃左右.由表征结果可知,CuMnOx/ZSM-5中的Cu和Mn在甲苯吸附和催化氧化过程中产生强相互作用,使催化剂中Mn^(4+)以及表面吸附氧(O_(β))物种量增多,提供了大量的活性位点,增强了其吸附和催化氧化性能.此外,CuMnOx/ZSM-5在不同空速下均表现出良好的吸附和催化氧化性能,在高湿环境中吸附性能下降,但仍能对甲苯表现出良好的催化氧化性能,同时还具有良好的再生性和稳定性,可在吸附-催化氧化一体化技术处理工业VOCs中发挥重要作用.A series of transitional metal oxide doping MnOx/ZSM-5 were prepared via conventional citric acid complex method,and evaluated as adsorbent/catalyst bifunctional materials for VOCs elimination.The effects of transition metal Cu,Co and Ni doping on the adsorption and catalytic oxidation properties of MnOx/ZSM-5 were examined using toluene as representative molecules.Systematic structural/physicochemical characterizations such as BET,XRD,SEM,H2-TPR,XPS were also performed along with practical application tests under simulated industrial conditions.Results showed that the CuMnOx/ZSM-5 exhibited the best adsorption and catalytic oxidation performance among all the prepared catalysts.Compared with MnOx/ZSM-5 and CuOx/ZSM-5,the T50 and T90 of CuMnOx/ZSM-5 by toluene combustion were reduced by about 30°C with its equilibrium adsorption capacity of toluene above 25.90 mg·g−1.Characterization results suggested that strong interaction existed between Cu and Mn of CuMnOx/ZSM-5,which resulted in the formation of more Mn4+and surface adsorbed oxygen(Oβ)species,providing more reactive sites and enhancing the adsorption and catalytic oxidation performance.In addition,practical application tests demonstrated that CuMnOx/ZSM-5 presented excellent tolerance to different space velocities turbulence,as well as good regeneration ability and long-term stability,although the high humidity environment could cause certain deterioration in adsorption performance.All the results suggested that CuMnOx/ZSM-5 could be promising candidates with practical potentials for the treatment of industrial VOCs by the integrated adsorption-catalytic oxidation technology.

关 键 词：甲苯 过渡金属 ZSM-5 沸石分子筛 吸附 催化氧化. 

分 类 号：O647.33[理学—物理化学] O643.36[理学—化学] X701[环境科学与工程—环境工程]