nMnO_x·HZSM-5催化正丁烷裂解增产乙烯丙烯性能研究  

Study on n-butane catalytic cracking for increasing production of ethylene and propylene over nMnO_x·HZSM-5

作　　者：李明航 迟姚玲 苗杰 谈冠希 靳广洲 Li Minghang;Chi Yaoling;Miao Jie;Tan Guanxi;Jin Guangzhou(Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology,School of Chemical Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China)

机构地区：[1]北京石油化工学院化学工程学院燃料清洁化及高效催化减排技术北京市重点实验室

出　　处：《工业催化》2019年第10期42-49,共8页Industrial Catalysis

基　　金：国家重点基础研究发展计划资助项目(“973”计划)(2012CB215002)

摘　　要：采用等体积浸渍法制备nMnO x·HZSM-5系列催化剂,用XRD、NH 3-TPD、Py-IR、BET和SEM等表征催化剂物相结构和表面性质。在固定床微型反应装置中,对nMnO x·HZSM-5催化剂进行正丁烷裂解性能评价。结果表明,活性组分Mn借助固相反应以MnO x簇形式定位于HZSM-5分子筛的直形和Z形孔道交叉处,并与其骨架氧结合形成nMnO x·HZSM-5单相复合体,引起分子筛骨架收缩,晶胞参数及晶胞体积减小;nMnO x·HZSM-5催化剂样品总酸量和强酸中心酸量随活性组分Mn用量的增大逐渐减小,B酸/L酸逐渐下降;在反应温度625℃和空速5 600 h-1条件下,Mn质量分数0.5%制备的nMnO x·HZSM-5-0.5催化剂催化正丁烷裂解反应,正丁烷转化率为76.26%,略低于HZSM-5分子筛,但乙烯和丙烯收率分别为13.68%和18.93%,分别提高0.76个百分点和1.09个百分点,表现出较好的增产乙烯和丙烯效果。A series of nMnO x·HZSM-5 catalysts were prepared by incipient-wetness impregnation,and tested in n-butane catalytic cracking using a continuous flowing micro reactor.Morphology and surface property of nMnO x·HZSM-5 catalyst were characterized by XRD,NH 3-TPD,Py-IR,BET and SEM techniques.The results indicated that part of Mn component located in the cross of Z-shaped and straight channels of HZSM-5 by solid-state reaction in forms of MnO x clusters,MnO x coordinated with the skeleton oxygen of HZSM-5 to generate nMnO x·HZSM-5 single-phase complexes,which made the crystal cell of HZSM-5 shrink and cell volume abate.With the increasing dosage of active component Mn,the acidity,mainly the strong acid sites of nMnO x·HZSM-5 decreased,and the ratio of BrΦnsted to Lewis acid sites reduced.Under the condition of gas hourly space velocity 5 600 h-1 and reaction temperature 625℃,the n-butane catalytic cracking conversion over nMnO x·HZSM-5-0.5 was 76.26%,slightly lower than that over HZSM-5.However,the yield of ethylene and propylene over nMnO x·HZSM-5-0.5 reached 13.68%,18.93%,which was 0.76 percent points and 1.09 percent points higher than that over HZSM-5,respectively.It exhibited better performance for increasing yield of ethylene and propylene.

关 键 词：石油化学工程 nMnO x·HZSM-5 正丁烷 乙烯 丙烯 单相复合体 

分 类 号：TE624.41[石油与天然气工程—油气加工工程] TQ426.95[化学工程]