Study on MWW-type zeolites prepared by seed-assisted method for methane dehydroaromatization

LI Weiqiang; DONG Xinfa; FAN Shuanshi; LANG Xuemei; WANG Yanhong; ZHONG Liuying; LI Gang

doi:10.12434/j.issn.2097-2547.20250277

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Study on MWW-type zeolites prepared by seed-assisted method for methane dehydroaromatization

更新时间：2026-02-02

- Study on MWW-type zeolites prepared by seed-assisted method for methane dehydroaromatization
- Vol. 51, Issue 1, Pages: 32-39(2026)
- 作者机构：
  
  1.华南理工大学化学与化工学院，广东广州 510641
  2.佛山灿石科技有限公司，广东佛山 528311
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250277
  CLC： TQ426;O643.3
- Received：17 June 2025，
  
  Revised：2025-07-23，
  
  Published：25 January 2026
- 稿件说明：
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李卫强,董新法,樊栓狮等.晶种法制备MWW型沸石分子筛用于甲烷脱氢芳构化反应研究[J].低碳化学与化工,2026,51(1):32-39.

LI Weiqiang,DONG Xinfa,FAN Shuanshi,et al.Study on MWW-type zeolites prepared by seed-assisted method for methane dehydroaromatization[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(1):32-39.
李卫强,董新法,樊栓狮等.晶种法制备MWW型沸石分子筛用于甲烷脱氢芳构化反应研究[J].低碳化学与化工,2026,51(1):32-39. DOI： 10.12434/j.issn.2097-2547.20250277.

LI Weiqiang,DONG Xinfa,FAN Shuanshi,et al.Study on MWW-type zeolites prepared by seed-assisted method for methane dehydroaromatization[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(1):32-39. DOI： 10.12434/j.issn.2097-2547.20250277.

摘要

甲烷脱氢芳构化（MDA）是非石油路线制备芳烃的重要途径，探讨催化剂的孔道结构对其MDA反应催化性能的影响，在指导高性能催化剂的制备上具有重要意义。通过晶种法合成了MWW型沸石分子筛（MCM-56和MCM-22），采用XRD、TEM、SEM和N

吸/脱附对Mo/MCM-56和Mo/MCM-22催化剂的物相、形貌和孔道结构进行了表征分析，并探究了MWW型沸石分子筛中不同孔道体系对Mo/MCM-56和Mo/MCM-22催化剂的MDA反应催化性能的影响。结果表明，晶种法大幅缩短了沸石分子筛的晶化时间，且MWW型沸石分子筛结构与晶种结构密切相关。在相同条件下（700 ℃、100 kPa）反应9.0 h后，Mo/MCM-22催化剂比Mo/MCM-56催化剂具有更高的芳烃选择性（95%左右）与芳烃产率（7.5%左右）以及更优异的催化稳定性，从而推测Mo/MCM-22催化剂中通过二维MWW沸石纳米片缩合形成的十二元环超笼是MDA反应的主要场所。本研究揭示了MWW型沸石分子筛中不同孔道体系对催化剂的MDA反应催化性能具有重要影响，以期为高产物选择性、高稳定性MDA催化剂的设计提供新思路。

Abstract

Methane dehydroaromatization (MDA) represents a promising non-petroleum route for aromatic production. Exploring the effects of the pore structures of catalysts on their MDA reaction catalytic performances is crucial for developing high-efficiency catalysts. MWW-type zeolites (MCM-56 and MCM-22) were synthesized by seed-assisted method. The phases

morphologies and pore structures of Mo/MCM-56 and Mo/MCM-22 catalysts were characterized by XRD

TEM

SEM

and N

adsorption/desorption. Furthermore

the effects of different pore channel systems of MWW-type zeolites on catalytic performances of Mo/MCM-56 and Mo/MCM-22 catalysts for MDA reaction were investigated. The results show that the seed-assisted method significantly reduces crystallization time of zeolites

and the structures of MWW zeolites are closely related to the structures of seeds. After reacting for 9.0 h under the same conditions (700 °C

100 kPa)

Mo/MCM-22 demonstrates higher aromatic selectivity (around 95%) and aromatic yield (around 7.5%)

and superior catalytic stability compared to Mo/MCM-56. Therefore

it is speculated that the 12-membered ring supercages

formed through condensation of adjacent two-dimensional MWW zeolite nanosheets in Mo/MCM-22 catalyst

serves as the primary sites for MDA reaction. The study reveals that different pore channe

l systems of MWW zeolites have significant effects on the catalytic performance of catalysts for MDA reaction

providing new ideas for designing highly selective and stable MDA catalysts.

关键词

Keywords

references

LIU H X , LI L W , QIN Y Y , et al . Synergetic C—H bond activation and C—O formation on CuO x facilities facile conversion of methane to methanol [J ] . Applied Surface Science , 2023 , 627 ( 1 ): 157283 .

PENG Y H , SONG Y F , XIAO W , et al . Electrochemical conversion of methane to bridge the gap in the artificial carbon cycle [J ] . Journal of Energy Chemistry , 2025 , 100 : 286 - 308 .

郑厚超 , 吴丽娟 , 熊烨 , 等 . 甲烷无氧芳构化技术研究进展 [J ] . 天然气化工—C1化学与化工 , 2020 , 45 ( 3 ): 108 - 114 .

ZHENG H C , WU L J , XIONG Y , et al . Progress in dehydroaromatization of methane under nonoxidative conditions [J ] . Natural Gas Chemical Industry , 2020 , 45 ( 3 ): 108 - 114 .

KOSINOV N , HENSEN E . Reactivity, selectivity, and stability of zeolite-based catalysts for methane dehydroaromatization [J ] . Advanced Materials . 2020 , 32 ( 44 ): 2002565 .

高睿遥 , 李鑫 , 孙炅 , 等 . 甲烷脱氢芳构化反应机理及Mo/HZSM-5催化剂研究进展 [J ] . 低碳化学与化工 , 2023 , 48 ( 1 ): 30 - 40 .

GAO R Y , LI X , SUN J , et al . Research progress on reaction mechanisms of methane dehydroaromatization and Mo/HZSM-5 catalysts [J ] . Low-Carbon Chemistry and Chemical Engineering , 2023 , 48 ( 1 ): 30 - 40 .

WANG L S , TAO L X , XIE M S , et al . Dehydrogenation and aromatization of methane under non-oxidizing conditions [J ] . Catalysis Letters , 1993 , 21 ( 1 ): 35 - 41 .

裴婷 , 张淑侠 , 张新庄 , 等 . Mo担载量对不同制备工艺甲烷无氧芳构化 Mo/HZSM-5催化剂性能的影响 [J ] . 天然气化工—C1化学与化工 , 2020 , 45 ( 4 ): 24 - 27 .

PEI T , ZHANG S X , ZHANG X Z , et al . Effect of Mo loading on the performance of Mo/ZSM-5 catalysts for methane non oxidative aromatization [J ] . Natural Gas Chemical Industry , 2020 , 45 ( 4 ): 24 - 27 .

GAO R Y , LI X , WANG Z H , et al . Reaction regeneration cycle of Mo/HZSM-5 catalyst in methane dehydroaromatization with the addition of oxygen-containing components [J ] . Applied Catalysis A: General , 2022 , 647 : 118916 .

WANG L , LEI X X , ZHANG W P . Insights into the coking and regeneration processes of methanol promoted methane dehydroaromatization reaction over Mo-ZSM-5/ZSM-11 intergrown zeolites [J ] . Applied Catalysis A: General , 2025 , 692 : 120097 .

HUANG M M , LI J P , LIU Q , et al . Enhanced catalytic performance of the hollow Mo/HZSM-5 nanocrystal for methane dehydroaromatization [J ] . Fuel , 2023 , 334 : 126765 .

XU Y B , CHEN M Y , LIU B , et al . CH 4 conversion over Ni/HZSM-5 catalyst in the absence of oxygen: Decomposition or dehydroaromatization [J ] . Chemical Communications , 2020 , 56 ( 32 ): 4396 - 4399 .

GU Y , CHEN P P , WANG X H , et al . Active sites and induction period of Fe/ZSM-5 catalyst in methane dehydroaromatization [J ] . ACS Catalysis , 2021 , 11 ( 12 ): 6771 - 6786 .

XU Y B , YUAN X , CHEN M Y , et al . Identification of atomically dispersed Fe-oxo species as new active sites in HZSM-5 for efficient non-oxidative methane dehydroaromatization [J ] . Journal of Catalysis , 2021 , 396 : 224 - 241 .

XU Y B , CHEN M Y , WANG T , et al . Probing cobalt localization on HZSM-5 for efficient methane dehydroaromatization catalysts [J ] . Journal of Catalysis , 2020 , 387 : 102 - 118 .

CHOI E J , LIM Y H , JEONG Y , et al . Effects of parameters in the preparation of Mo/MWW-type catalysts on the dehydroaromatization of shale gas [J ] . Catalysis Today , 2024 , 425 : 114348 .

GAN Y Y , XU Y Z , WANG W H , et al . Boron doped Mo/HMCM-22 catalyst for improving coke resistance in methane dehydroaromatization [J ] . Chemical Engineering Science , 2024 , 299 : 120485 .

WU Y Q , EMDADI L , LIU D X , et al . Textural and catalytic properties of Mo loaded hierarchical meso-/microporous lamellar MFI and MWW zeolites for direct methane conversion [J ] . Applied Catalysis A: General , 2014 , 470 : 344 - 354 .

YANG J H , CHU J , WANG J Q , et al . Synthesis and catalytic performance of hierarchical MCM-22 zeolite aggregates with the assistance of carbon particles and fluoride ions [J ] . Chinese Journal of Catalysis , 2014 , 35 ( 1 ): 49 - 57 .

XU C , GUAN J Q , WU S J , et al . Catalytic performance of zeolite ITQ-13 with 9- and 10-member rings for methane dehydroaromation [J ] . Reaction Kinetics, Mechanisms and Catalysis , 2010 , 99 : 193 - 199 .

SONG Y , ZHANG Q , XU Y B , et al . Coke accumulation and deactivation behavior of microzeolite-based Mo/HZSM-5 in the non-oxidative methane aromatization under cyclic CH 4 -H 2 feed switch mode [J ] . Applied Catalysis A: General , 2017 , 530 : 12 - 20 .

PETERS S , RIEG C , BARTLING S , et al . Accessibility of reactants and neighborhood of Mo species during methane aromatization uncovered by operando NAP-XPS and MAS NMR [J ] . ACS Catalysis , 2023 , 13 ( 19 ): 13056 - 13070 .

LIM T H , NAM K , KIM D H , et al . Effect of Si/Al 2 ratios in Mo/H-MCM-22 on methane dehydroaromatization [J ] . Applied Catalysis A: General , 2018 , 552 : 11 - 20 .

HASSAN A , SAYARI A . Oxygen-free dehydroaromatization of methane over Mo-based catalysts supported on MCM-41 and MCM-22 [J ] . Studies in Surface Science and Catalysis , 2005 , 156 : 761 - 768 .

LIU H M , SU L L , XU Y D , et al . The chemical nature of carbonaceous deposits and their role in methane dehydro-aromatization on Mo/MCM-22 catalysts [J ] . Applied Catalysis A: General , 2002 , 236 ( 1 ): 263 - 280 .

史建公 , 卢冠忠 , 曹钢 . MWW族分子筛的结构研究进展 [J ] . 中外能源 , 2010 , 15 ( 11 ): 66 - 74 .

SHI J G , LU G Z , CAO G . Advances in MWW zeolite structure research [J ] . Sino-Global Energy , 2010 , 15 ( 11 ): 66 - 74 .

LEONOWICZ M E , LAWTON J A , LAWTON S L , et al . MCM-22: A molecular sieve with two independent multidimensional channel systems [J ] . Science , 1994 , 264 ( 5167 ): 1910 - 1913 .

JUTTU G , LOBO R . Characterization and catalytic properties of MCM-56 and MCM-22 zeolites [J ] . Microporous and Mesoporous Materials , 2000 , 40 ( 1 ): 9 - 23 .

许宁 , 吴通好 , 王东阳 , 等 . 层状分子筛MCM-56的合成及表征 [J ] . 高等学校化学学报 , 2001 , 22 ( 11 ): 1898 - 1900 .

XU N , WU T H , WANG D Y , et al . Synthesis and characterization of a novel layered zeolite MCM-56 [J ] . Chemical Journal of Chinese Universities , 2001 , 22 ( 11 ): 1898 - 1900 .

甘海波 , 叶枫 , 吕义辉 , 等 . 无模板剂合成束状多级孔ZSM-5分子筛及其催化剂的甲烷无氧芳构化反应性能研究 [J ] . 天然气化工—C1化学与化工 , 2022 , 47 ( 4 ): 92 - 98 .

GAN H B , YE F , LV Y H , et al . Template-free synthesis of bundle-like hierarchical ZSM-5 zeolites and its catalytic performance for nonoxidative methane dehydroaromatization [J ] . Natural Gas Chemical Industry , 2022 , 47 ( 4 ): 92 - 98 .

OSTROUMOVA V A , MAKSIMOV A L . Synthesis of MCM-22, MCM-49 and MCM-56 zeolites [J ] . Petroleum Chemistry , 2019 , 59 : 788 - 801 .

ROTH W J . MCM-22 zeolite family and the delaminated zeolite MCM-56 obtained in one-step synthesis [J ] . Studies in Surface Science and Catalysis , 2005 , 158 : 19 - 26 .

KAMIMURA Y , ITABASHI K , KON Y , et al . Seed-assisted aynthesis of MWW-type zeolite with organic structure-directing agent-free Na-aluminosilicate gel system [J ] . Chemistry An Asian Journal , 2017 , 12 : 530 - 542 .

ROTH W J , ČEJKA J . Two-dimensional zeolites: Dream or reality? [J ] . Catalysis Science & Technology , 2011 , 1 : 43 - 53 .

ELREFAEI N , BASHA N , NOUNOU M , et al . Quantified database for methane dehydroaromatization reaction [J ] . ChemCatChem , 2022 , 14 ( 21 ): 1 - 17 .

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