NES结构分子筛的合成及其催化性能研究

石油炼制与化工 ›› 2026, Vol. 57 ›› Issue (11): 83-90.

NES结构分子筛的合成及其催化性能研究

龚郁丹,刘闯,马多征,王振东

中石化（上海）石油化工研究院有限公司绿色化工与工业催化全国重点实验室

收稿日期:2026-05-22 修回日期:2026-07-24 出版日期:2026-11-12 发布日期:2026-10-19
通讯作者: 王振东 E-mail:wangzd.sshy@sinopec.com
基金资助:
面向烯烃及衍生物低碳制备的新型分子筛材料;拓扑适配晶种导向IM-5分子筛及其甲苯歧化催化应用

SYNTHESES AND CATALYTIC PERFORMANCEOF NES-TYPE ZEOLITE

Received:2026-05-22 Revised:2026-07-24 Online:2026-11-12 Published:2026-10-19

摘要/Abstract

摘要： NES结构分子筛因其独特的十元环孔道与十二元环空腔结构，在歧化、烷基转移等反应中表现出广阔的应用前景。然而，其合成存在晶化时间长、重复性差以及依赖昂贵有机结构导向剂的问题。采用EUO结构分子筛晶种，缩短了NES结构分子筛的晶化时间，所得分子筛（NES-E）晶体呈现长方形片状（0.2 μm×1 μm），酸量大（总酸量为1094 μmol/g，其中中强酸酸量为438 μmol/g）。进一步系统研究了不同晶种导向与无晶种合成的差异，并考察了3条路线所得NES结构分子筛对甲苯歧化反应的催化性能，结果表明：EUO分子筛晶种导向具有合成相区宽、晶化时间短、晶相可控等优势，并且所得NES-E分子筛上甲苯转化率高（34.3%）。

关键词: 分子筛, NES结构, EUO结构, 晶种导向法, 甲苯歧化

Abstract: NES-type zeolite exhibits promising application prospects in reactions such as disproportionation and transalkylation, owing to its unique structure comprising 10-membered ring channels and 12-membered ring cavities. However, its synthesis suffers from long crystallization time, poor reproducibility, and the reliance on expensive organic structure-directing agents. In this work, EUO-type zeolite was used as seed shorten the crystallization time of NES zeolite. The resulting zeolite crystals exhibit a rectangular platelet-like morphology (0.2 μm × 1 μm) and a high acid amount (total acid amount: 1094 μmol/g, with a medium strong acid amount of 438 μmol/g). The influences of seeds were systematically investigated, and the catalytic performance of the NES zeolites in disproportionation of toluene were examined. The use of EUO-type zeolite as seed showed advantages including a wide synthesis phase region, shortened crystallization time, and controllable crystal phase. The obtained NES-E zeolite exhibits a high toluene conversion (34.3%).

Key words: zeolite, NES structure, EUO structure, seed-directed method, toluene disproportionation

龚郁丹刘闯马多征王振东. NES结构分子筛的合成及其催化性能研究[J]. 石油炼制与化工, 2026, 57(11): 83-90.

参考文献

[1]Dai, H.Shen,YF.,Yang,T. M.,et al,Finned zeolite catalysts[J].Nat Mater, 2020, 19,(10):1074-1080
[2]Devos, J.S.,A,Aelbers,C.,et al,Parallel-consecutive CO formation during CO2 hydrogenation to olefins in a tandem ZnZrOxSSZ-13[J].Acs Sustain Chem Eng, 2025, 13,(26):9964-9973
[3]Yu, L. F., S. Grahn, M. Grahn, et al.Ultra-thin MFI membranes with different Si/Al ratios for CO2/CH4 separation[J].Micropor Mesopor Mat, 2019, 284:258-264
[4]Xu, C.C., Lu, X. F., Wang, Z. B., Effects of sodium ions on the separation performance of pure-silica MFI zeolite membranes[J]. J Membrane Sci, 2017, 524: 124-131.
[5]Li, Y.Q., Zhu, M. H., Hu, N., et al, Scale-up of high performance mordenite membranes for dehydration of water-acetic acid mixtures[J]. J Membrane Sci, 2018, 564: 174-183.
[6]Wu, X.W., Li, Y. Q., Yang, Z. Q., et al, Intensified esterification of oleic acid and n-butanol using a beta zeolite membrane reactor at low temperature[J]. Fuel, 2025, 388.
[7]Park, S.H.,Rhee,HK.,Shape selective conversion of 1,2,4-trimethylbenzene over zeolite NU-87[J].Catal Today, 2000, 63,(2-4):267-273
[8]Toda, J.Corma,A,Sastre,G.,Diffusion of trimethylbenzenes and xylenes in zeolites with 12-and 10-ring channels as catalyst for toluene-trimethylbenzene transalkylation[J].J Phys Chem C, 2016, 120,(30):16668-16680
[9]Toda, J.S.,G,Diffusion of Trimethylbenzenes,Toluene,and Xylenes in UWY Zeolite as a Catalyst for Transalkylation of Trimethylbenzenes with Toluene[J].J Phys Chem C, 2018, 122,(14):7885-7897
[10]Shannon, M.D., Casci, J. L., Andrews, S. J., Structure of the two-dimensional medium-pore high-silica zeolite NU-87[J]. Nature, 1991, 353: 417-420.
[11]王丽丽，李晓峰，张成涛, 一种新型的高硅沸石NU-87的合成与表征[J].分子催化, 2007, 21, (增刊): 617-618.
[12]Byun, Y.Jo,D,Shin,D. N.,et al,Theoretical investigation of the isomerization and disproportionation of xylene over medium-pore zeolites with different framework topologies[J].Acs Catal, 2014, 4,(6):1764-1776
[13]Park, S.H.,Rhee,HK.,Catalytic properties of zeolites MCM-22 and NU-87 in disproportionation of toluene[J].React Kinet Catal L, 2003, 78,(1):81-89
[14]Corma, A.Sorption,diffusion and catalytic properties of zeolites containing 10- and 12-member ring pores in the same structure[J].Micropor Mesopor Mat, 1998, 21,(4-6):487-495
[15]Llopis, F.J.,Sastre,G,Corma,A.,Xylene isomerization and aromatic alkylation in zeolites NU-87,SSZ-33,β,and ZSM-5: molecular dynamics and catalytic studies[J].J Catal, 2004, 227,(1):227-241
[16]Chen, H.Y.,Liu,L,Xu,L. Y.,et al,Catalytic performance of zeolite NU-87 with 10-and 12-member rings for methane dehydroaromatization[J].Chinese J Catal, 2004, 25,(11):845-846
[17]Almulla, F.M.,Zholobenko,VI.,Hi,P. I.,et al,Transalkylation of toluene with 1,2,4-trimethylbenzene over large pore zeolites[J].Ind Eng Chem Res, 2017, 56,(35):9799-9808
[18]Glaser, R.Li,RF.,Hunger,M.,Ernst,S.,et al,Zeolite HNU-87: synthesis,characterization and catalytic properties in the shape-selective conversion of methylnaphthalenes[J].Catal Lett, 1998, 50,(3-4):141-148
[19]Zhang, Z.Z.,Qin,B,Zhang,X. W.,et al,The seeds effect on zeolite NU-87: synthesis parameters and structural properties[J].J Porous Mat, 2013, 20,(3):515-521
[20]Iyoki, K., Takase, M., Itabashi, K., et al, Organic structure-directing agent-free synthesis of NES-type zeolites using EU-1 seed crystals[J]. Micropor Mesopor Mat, 2015, 215: 191-198.
[21]Shang, W.X.,Li,PL.,Dai,W. L.,et al,Synthesis of NU-87 zeolite via aging and dual-templating methods[J].Chemistryselect, 2021, 6,(16):3952-3957
[22]Marler, B.Daniels,P,Muné,J. S. I.,Synthesis and structure of RUB-35,a disordered material of the EUO-NES-NON family[J].Micropor Mesopor Mat, 2003, 64,(1-3):185-201
[23]陈媛媛，马波，张志智, 等, NU-87分子筛的合成与表征[J].工业催化, 2010, 18, (10): 28-32.