ZSM-12制备、酸性调控及其烷烃异构化性能  

Review of synthesis and acidity regulation of ZSM-12 for alkane isomerization

作　　者：沈雨歌 于宏悦 李梦晨 胡达民 迟克彬 史得军 刘计省 刘坚[1,4] SHEN Yuge;YU Hongyue;LI Mengchen;HU Damin;CHI Kebin;SHI Dejun;LIU Jixing;LIU Jian(State Key Lab of Heavy Oil,China University of Petroleum(Beijing),Beijing 102249,China;Petrochina Petrochemical Research Institute,Beijing 102206,China;School of Chemistry and Chemical Engineering,Jiangsu University,Zhenjiang,Jiangsu 212013,China;State Key Lab of Heavy Oil,China University of Petroleum(Beijing),Karamay,Xinjiang 834000,China)

机构地区：[1]中国石油大学(北京)重质油国家重点实验室,北京102249 [2]中国石油天然气股份有限工公司石油化工研究院,北京102206 [3]江苏大学化学化工学院,江苏镇江212013 [4]中国石油大学(北京)克拉玛依校区重质油国家重点实验室,新疆克拉玛依834000

出　　处：《世界石油工业》2025年第2期137-152,共16页World Petroleum Industry

基　　金：江苏大学国家重点研发计划“烃转化用催化膜设计与制备技术”(2024YFA1510001);中国石油天然气股份有限公司“低成本一维纳米短轴分子筛材料开发及加氢异构性能研究”(2022DJ5602)。

摘　　要：为了优化ZSM-12分子筛的烷烃异构化性能并解决其高酸量、大晶粒尺寸及传质阻力等问题,系统研究了ZSM-12的合成规律、形貌/孔结构调控方法及酸性位点调控策略。通过对比不同拓扑结构分子筛的异构化反应机制,采用双模板剂复合法、原位矿化剂调控晶化时间、多级孔道设计及杂原子同晶置换等技术,探究了ZSM-12的酸强度、酸分布与金属-酸平衡的相互作用。研究结果表明:①通过甲基三乙基铵(MTEAOH)与四乙基铵(TEAOH)双模板剂复配,可将晶化时间缩短至72 h,并精准调控晶粒形貌为纳米片层结构(厚度22 nm),显著降低传质阻力;②以环状双季铵盐为介孔模板剂合成的多级孔ZSM-12(介孔体积0.24~0.30 cm^(3)/g)可优化产物扩散路径,使正十六烷异构化中多支链/单支链产物比提升至2.8;③铁同晶置换[Fe/(Al+Fe)=50%]显著降低Brønsted酸强度(NH3脱附温度从423℃降至385℃),同时维持异构化选择性达85%以上,抑制裂化副反应。结论认为,ZSM-12的酸性调控需结合酸中心空间定位与孔道限域效应,未来应聚焦长链烷烃(C_(18+))的异构化动力学机制,并开发低成本矿化剂与复合介孔-微孔材料以推进工业化应用。To enhance the alkane isomerization performance of ZSM-12 zeolite and address its limitations such as excessive medium-strong acidity,large particle size,and mass transfer resistance,this study systematically investigated the synthesis principles,morphology/pore structure modulation,and acidity regulation strategies of ZSM-12.By comparing isomerization mechanisms across zeolites with different topologies,dual-template synthesis,in-situ mineralization,hierarchical pore design,and isomorphous substitution were employed to optimize acid strength,spatial acid distribution,and metal-acid balance.Key findings include:(1)Co-using methyltriethylammonium(MTEAOH)and tetraethylammonium(TEAOH)as dual templates reduced crystallization time to 72 h and yielded nanosheet-like crystals(22 nm thickness),effectively mitigating diffusion limitations;(2)Hierarchical ZSM-12 synthesized with cyclic diquaternary ammonium templates(mesopore volume 0.24–0.30 cm^(3)/g)optimized product distribution,achieving a multi-/mono-branched isomer ratio of 2.8 for n-hexadecane;(3)Iron isomorphous substitution(Fe/(Al+Fe)=50%)lowered Brønsted acid strength(NH₃desorption peak shifted from 423℃to 385℃)while maintaining>85%isomer selectivity and suppressing cracking.The study concludes that precise spatial control of acid sites coupled with pore confinement is critical for ZSM-12 optimization.Future work should focus on isomerization kinetics of long-chain alkanes(C_(18+))and develop cost-effective mineralization agents and hierarchical materials for industrial applications.

关 键 词：ZSM-12分子筛 合成 结构 酸性 烷烃异构化 

分 类 号：TE624[石油与天然气工程—油气加工工程]