Deactivation of Mo/H-ZSM-5 in Microwave-Assisted and Thermal-Driven Methane Dehydroaromatization

Kanitkar, Swarom; Abdelsayed, Victor; Bai, Xinwei; Dutta, Biswanath; Myshakin, Evgeniy; Haynes, Daniel

doi:10.1021/acs.energyfuels.5c00885

Deactivation of Mo/H-ZSM-5 in Microwave-Assisted and Thermal-Driven Methane Dehydroaromatization

Journal Article · Wed Jul 02 00:00:00 EDT 2025 · Energy & Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.5c00885· OSTI ID:2587586

^[1]; Abdelsayed, Victor ^[1]; ^[1]; Dutta, Biswanath ^[2]; ^[2]; Haynes, Daniel ^[1]

National Energy Technology Lab. (NETL), Morgantown, WV (United States)
National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)

A better understanding of catalyst deactivation is needed to improve catalyst design and performance in microwave-enhanced methane dehydroaromatization (MDA). Here, this study investigates the deactivation of a molybdenum supported H-ZSM-5 zeolite (Mo/H-ZSM-5) catalyst in MDA under microwave-heated conditions, comparing its performance to that of the same catalyst under conventional heating. While the microwave-assisted (MW) process achieved higher benzene yields, the catalyst experienced faster deactivation due to the selective and rapid deposition of coke within the pores of the zeolite, as confirmed through Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), ammonia-temperature programmed desorption (NH₃-TPD), thermal gravimetric analysis (TGA), temperature programmed oxidation (TPO), and X-ray photoelectron spectroscopy (XPS) analyses. The quantification of total coke content via TGA/TPO and surface carbon (XPS) revealed that nearly twice as much coke was deposited on the catalyst under MW conditions compared to that on the conventionally heated material, and the coke exhibited a more conductive and graphitic nature. The accelerated deactivation rates were attributed to the formation of hot spots in the MW system, leading to enhanced coupling with coke formed in situ during the reaction and resulting in increased Mo reduction. Observations indicated that the CO activation used to carburize the catalyst prior to the reaction is not advantageous in the MW heating environment. The presence of large amounts of Mo oxides at elevated temperatures (through hot spots) exposed to methane leads to instability under the reaction conditions. Optimizing the activation environment and improvement of the Mo dispersion within the pores are potential strategies to improve catalyst stability.

View Accepted Manuscript (DOE)

Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy and Carbon Management (FECM)

OSTI ID:: 2587586

Journal Information:: Energy & Fuels, Journal Name: Energy & Fuels Journal Issue: 28 Vol. 39; ISSN 1520-5029; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Reactivity, Selectivity, and Stability of Zeolite‐Based Catalysts for Methane Dehydroaromatization Kosinov, Nikolay; Hensen, Emiel J. M. Advanced Materials, Vol. 32, Issue 44 https://doi.org/10.1002/adma.202002565	journal	July 2020
Confined Carbon Mediating Dehydroaromatization of Methane over Mo/ZSM-5 Kosinov, Nikolay; Wijpkema, Alexandra S. G.; Uslamin, Evgeny Angewandte Chemie International Edition, Vol. 57, Issue 4 https://doi.org/10.1002/anie.201711098	journal	December 2017
Reversible Nature of Coke Formation on Mo/ZSM‐5 Methane Dehydroaromatization Catalysts Kosinov, Nikolay; Uslamin, Evgeny A.; Meng, Lingqian Angewandte Chemie International Edition, Vol. 58, Issue 21 https://doi.org/10.1002/anie.201902730	journal	May 2019
Dual Active Sites on Molybdenum/ZSM‐5 Catalyst for Methane Dehydroaromatization: Insights from Solid‐State NMR Spectroscopy Gao, Wei; Qi, Guodong; Wang, Qiang Angewandte Chemie International Edition, Vol. 60, Issue 19 https://doi.org/10.1002/anie.202017074	journal	April 2021
Determination of Molybdenum Species Evolution during Non‐Oxidative Dehydroaromatization of Methane and its Implications for Catalytic Performance Agote‐Arán, Miren; Kroner, Anna B.; Islam, Husn U. ChemCatChem, Vol. 11, Issue 1 https://doi.org/10.1002/cctc.201801299	journal	October 2018
Understanding the Preparation and Reactivity of Mo/ZSM‐5 Methane Dehydroaromatization Catalysts Liu, Yujie; Zhang, Hao; Wijpkema, Alexandra S. G. Chemistry – A European Journal, Vol. 28, Issue 5 https://doi.org/10.1002/chem.202103894	journal	December 2021
Dehydrogenation and aromatization of methane under non-oxidizing conditions Wang, Linsheng; Tao, Longxiang; Xie, Maosong Catalysis Letters, Vol. 21, Issue 1-2 https://doi.org/10.1007/BF00767368	journal	January 1993
Gas flaring: technicalities, challenges, and the economic potentials Omobolanle, Oluwasegun Cornelious; Ikiensikimama, Sunday Sunday Environmental Science and Pollution Research, Vol. 31, Issue 28 https://doi.org/10.1007/s11356-024-33784-y	journal	June 2024
Molybdenum Oxides Deposited by Modulated Pulse Power Magnetron Sputtering: Stoichiometry as a Function of Process Parameters Murphy, Neil R.; Sun, Lirong; Grant, John T. Journal of Electronic Materials, Vol. 44, Issue 10 https://doi.org/10.1007/s11664-015-3790-9	journal	May 2015
Studies on pore systems in catalysts I. The adsorption of nitrogen; apparatus and calculation Lippens, B. Journal of Catalysis, Vol. 3, Issue 1 https://doi.org/10.1016/0021-9517(64)90089-2	journal	February 1964
Measurement of the acidity of various zeolites by temperature-programmed desorption of ammonia Hidalgo, C. Journal of Catalysis, Vol. 85, Issue 2 https://doi.org/10.1016/0021-9517(84)90225-2	journal	February 1984
A TPD and IR study of the surface species formed from ammonia on zeolite H-ZSM-5, H-mordenite and H-beta Lónyi, F.; Valyon, J. Thermochimica Acta, Vol. 373, Issue 1 https://doi.org/10.1016/S0040-6031(01)00458-0	journal	June 2001
XPS study of potassium-promoted molybdenum carbides for mixed alcohols synthesis via CO hydrogenation Xiang, Minglin; Li, Debao; Zou, Juan Journal of Natural Gas Chemistry, Vol. 19, Issue 2 https://doi.org/10.1016/S1003-9953(09)60051-7	journal	March 2010
Characterization of MCM-41 mesoporous molecular sieves containing copper and zinc and their catalytic performance in the selective oxidation of alcohols to aldehydes Velu, S.; Wang, L.; Okazaki, M. Microporous and Mesoporous Materials, Vol. 54, Issue 1-2 https://doi.org/10.1016/S1387-1811(02)00358-X	journal	July 2002
Methane dehydro-aromatization on Mo/ZSM-5: About the hidden role of Brønsted acid sites Tessonnier, Jean-Philippe; Louis, Benoît; Rigolet, Séverinne Applied Catalysis A: General, Vol. 336, Issue 1-2 https://doi.org/10.1016/j.apcata.2007.08.026	journal	March 2008
A clue to exploration of the pathway of coke formation on Mo/HZSM-5 catalyst in the non-oxidative methane dehydroaromatization at 1073K Song, Yang; Xu, Yuebing; Suzuki, Yoshizo Applied Catalysis A: General, Vol. 482 https://doi.org/10.1016/j.apcata.2014.06.018	journal	July 2014
Impact of the presence of Mo carbide species prepared ex situ in Mo/HZSM-5 on the catalytic properties in methane aromatization Rahman, Mustafizur; Sridhar, Apoorva; Khatib, Sheima J. Applied Catalysis A: General, Vol. 558 https://doi.org/10.1016/j.apcata.2018.03.023	journal	May 2018
Bimetallic Mo-Co/ZSM-5 and Mo-Ni/ZSM-5 catalysts for methane dehydroaromatization: A study of the effect of pretreatment and metal loadings on the catalytic behavior Sridhar, Apoorva; Rahman, Mustafizur; Infantes-Molina, Antonia Applied Catalysis A: General, Vol. 589 https://doi.org/10.1016/j.apcata.2019.117247	journal	January 2020
A critical literature review of the advances in methane dehydroaromatization over multifunctional metal-promoted zeolite catalysts Menon, Unmesh; Rahman, Mustafizur; Khatib, Sheima J. Applied Catalysis A: General, Vol. 608 https://doi.org/10.1016/j.apcata.2020.117870	journal	November 2020
Deactivation mechanism and regeneration study of Zn/HZSM-5 catalyst in ethylene transformation Bonnin, Aurélien; Pouilloux, Yannick; Coupard, Vincent Applied Catalysis A: General, Vol. 611 https://doi.org/10.1016/j.apcata.2020.117976	journal	February 2021
Reaction regeneration cycle of Mo/HZSM-5 catalyst in methane dehydroaromatization with the addition of oxygen-containing components Gao, Ruiyao; Li, Xin; Wang, Zhiheng Applied Catalysis A: General, Vol. 647 https://doi.org/10.1016/j.apcata.2022.118916	journal	October 2022
On the deactivation of Mo/HZSM-5 in the methane dehydroaromatization reaction Tempelman, Christiaan H. L.; Hensen, Emiel J. M. Applied Catalysis B: Environmental, Vol. 176-177 https://doi.org/10.1016/j.apcatb.2015.04.052	journal	October 2015
Non-oxidative dehydroaromatization of methane over Mo/H-ZSM-5 catalysts: A detailed analysis of the reaction-regeneration cycle Han, Seung Ju; Kim, Seok Ki; Hwang, Ahron Applied Catalysis B: Environmental, Vol. 241 https://doi.org/10.1016/j.apcatb.2018.09.042	journal	February 2019
Supercritical solvothermal synthesis under reducing conditions to increase stability and durability of Mo/ZSM-5 catalysts in methane dehydroaromatization Julian, Ignacio; Roedern, Morten B.; Hueso, Jose L. Applied Catalysis B: Environmental, Vol. 263 https://doi.org/10.1016/j.apcatb.2019.118360	journal	April 2020
A DFT study of methane conversion on Mo-terminated Mo2C carbides: Carburization vs C–C coupling Zhang, Tianyu; Yang, Xiaofeng; Ge, Qingfeng Catalysis Today, Vol. 368 https://doi.org/10.1016/j.cattod.2020.02.001	journal	May 2021
Zeolites interactions with microwaves during methane non-oxidative coupling Abdelsayed, Victor; Shekhawat, Dushyant; Tempke, Robert S. Catalysis Today, Vol. 365 https://doi.org/10.1016/j.cattod.2020.06.022	journal	April 2021
From bench scale to pilot plant: A 150x scaled-up configuration of a microwave-driven structured reactor for methane dehydroaromatization Julian, I.; Pedersen, C. M.; Jensen, A. B. Catalysis Today, Vol. 383 https://doi.org/10.1016/j.cattod.2021.04.013	journal	January 2022
Non-oxidative methane conversion in microwave-assisted structured reactors Julian, Ignacio; Ramirez, Heidy; Hueso, Jose L. Chemical Engineering Journal, Vol. 377 https://doi.org/10.1016/j.cej.2018.08.150	journal	December 2019
Microwave-assisted conversion of methane over H-(Fe)-ZSM-5: Evidence for formation of hot metal sites Deng, Yifan; Bai, Xinwei; Abdelsayed, Victor Chemical Engineering Journal, Vol. 420 https://doi.org/10.1016/j.cej.2021.129670	journal	September 2021
A combined experimental and modeling study of Microwave-assisted methane dehydroaromatization process Bai, Xinwei; Muley, Pranjali D.; Musho, Terence Chemical Engineering Journal, Vol. 433 https://doi.org/10.1016/j.cej.2021.134445	journal	April 2022
Global gas flaring and energy justice: An empirical ethics analysis of stakeholder perspectives Aigbe, Godwin O.; Cotton, Matthew; Stringer, Lindsay C. Energy Research & Social Science, Vol. 99 https://doi.org/10.1016/j.erss.2023.103064	journal	May 2023
Effect of Si/Al ratio of ZSM-5 support on structure and activity of Mo species in methane dehydroaromatization Rahman, Mustafizur; Infantes-Molina, Antonia; Hoffman, Adam S. Fuel, Vol. 278 https://doi.org/10.1016/j.fuel.2020.118290	journal	October 2020
Non-oxidative direct conversion of methane: Improved reactivity via linkage with dehydroaromatization Lee, Jin-Ju; Lee, Sungwoo; Bae, Youn-Sang Fuel Processing Technology, Vol. 256 https://doi.org/10.1016/j.fuproc.2024.108067	journal	June 2024
The distribution of coke formed over a multilayer Mo/HZSM-5 fixed bed in H2 co-fed methane aromatization at 1073 K: Exploration of the coking pathway Song, Yang; Xu, Yuebing; Suzuki, Yoshizo Journal of Catalysis, Vol. 330 https://doi.org/10.1016/j.jcat.2015.07.017	journal	October 2015
Stable Mo/HZSM-5 methane dehydroaromatization catalysts optimized for high-temperature calcination-regeneration Kosinov, Nikolay; Coumans, Ferdy J. A. G.; Li, Guanna Journal of Catalysis, Vol. 346 https://doi.org/10.1016/j.jcat.2016.12.006	journal	February 2017
Identification of reversible and irreversible deactivation of MDA catalysts: A key to design a viable process Beuque, Antoine; Valtchev, Valentin; Mintova, Svetlana Journal of Catalysis, Vol. 426 https://doi.org/10.1016/j.jcat.2023.06.034	journal	October 2023
Structural changes to molybdenum and Brønsted acid sites in MFI zeolites during methane dehydroaromatization reaction-regeneration cycles Santiago-Colón, Ángel N.; Gounder, Rajamani Journal of Catalysis, Vol. 430 https://doi.org/10.1016/j.jcat.2024.115335	journal	February 2024
Enviro-economic investigation of various flare gas recovery and utilization technologies in upstream and downstream of oil and gas industries Khalili-Garakani, Amirhossein; Nezhadfard, Mahya; Iravaninia, Mona Journal of Cleaner Production, Vol. 346 https://doi.org/10.1016/j.jclepro.2022.131218	journal	April 2022
Taming of superacids: PVP-triflic acid as an effective solid triflic acid equivalent for Friedel–Crafts hydroxyalkylation and acylation Prakash, G. K. Surya; Paknia, Farzaneh; Kulkarni, Aditya Journal of Fluorine Chemistry, Vol. 171 https://doi.org/10.1016/j.jfluchem.2014.08.020	journal	March 2015
Overgrowth of lamellar silicalite-1 on MFI and BEA zeolites and its consequences on non-oxidative methane aromatization reaction Wu, Yiqing; Emdadi, Laleh; Schulman, Emily Microporous and Mesoporous Materials, Vol. 263 https://doi.org/10.1016/j.micromeso.2017.11.040	journal	June 2018
Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects Schwach, Pierre; Pan, Xiulian; Bao, Xinhe Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00715	journal	March 2017
Accessibility of Reactants and Neighborhood of Mo Species during Methane Aromatization Uncovered by Operando NAP-XPS and MAS NMR Peters, Stefan; Rieg, Carolin; Bartling, Stephan ACS Catalysis, Vol. 13, Issue 19 https://doi.org/10.1021/acscatal.3c02385	journal	September 2023
Brønsted Acid Site Catalytic Role in Methane Dehydroaromatization over Mo/HZSM-5 Zhang, Hongxiang; Wei, Lihong; Sun, Yuewen ACS Catalysis, Vol. 14, Issue 15 https://doi.org/10.1021/acscatal.4c02300	journal	July 2024
Methane Dehydroaromatization by Mo/HZSM-5: Mono- or Bifunctional Catalysis? Kosinov, Nikolay; Coumans, Ferdy J. A. G.; Uslamin, Evgeny A. ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b02497	journal	December 2016
A Straightforward Descriptor for the Deactivation of Zeolite Catalyst H-ZSM-5 Rojo-Gama, Daniel; Nielsen, Malte; Wragg, David S. ACS Catalysis, Vol. 7, Issue 12 https://doi.org/10.1021/acscatal.7b02193	journal	November 2017
Structure and Evolution of Confined Carbon Species during Methane Dehydroaromatization over Mo/ZSM-5 Kosinov, Nikolay; Uslamin, Evgeny A.; Coumans, Ferdy J. A. G. ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02491	journal	August 2018
In Situ Preparation of Mo₂C Nanoparticles Embedded in Ketjenblack Carbon as Highly Efficient Electrocatalysts for Hydrogen Evolution Wang, Dezhi; Wang, Junchao; Luo, Xiaonan ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 1 https://doi.org/10.1021/acssuschemeng.7b03317	journal	November 2017
Adsorption of Gases in Multimolecular Layers Brunauer, Stephen; Emmett, P. H.; Teller, Edward Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319 https://doi.org/10.1021/ja01269a023	journal	February 1938
Ordered Mesoporous Metallic MoO ₂ Materials with Highly Reversible Lithium Storage Capacity Shi, Yifeng; Guo, Bingkun; Corr, Serena A. Nano Letters, Vol. 9, Issue 12 https://doi.org/10.1021/nl902423a	journal	December 2009
MAS NMR, ESR and TPD studies of Mo/HZSM‐5 catalysts: evidence for the migration of molybdenum species into the zeolitic channels Ma, Ding; Zhang, Weiping; Shu, Yuying Catalysis Letters, Vol. 66, Issue 3, p. 155-160 https://doi.org/10.1023/A:1019099607029	journal	June 2000
Thermal and structural studies of carbon coated Mo2C synthesized via in-situ single step reduction-carburization Mir, Rameez Ahmad; Sharma, Piyush; Pandey, Om Prakash Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-03197-8	journal	June 2017
Enhancement of Fixed-bed Flow Reactions under Microwave Irradiation by Local Heating at the Vicinal Contact Points of Catalyst Particles Haneishi, Naoto; Tsubaki, Shuntaro; Abe, Eriko Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-018-35988-y	journal	January 2019
Catalytic aromatization of methane Spivey, James J.; Hutchings, Graham Chem. Soc. Rev., Vol. 43, Issue 3 https://doi.org/10.1039/C3CS60259A	journal	January 2014
Coke distribution determines the lifespan of a hollow Mo/HZSM-5 capsule catalyst in CH₄ dehydroaromatization Huang, Xin; Jiao, Xi; Lin, Minggui Catalysis Science & Technology, Vol. 8, Issue 22 https://doi.org/10.1039/C8CY01391H	journal	January 2018
On the dynamic nature of Mo sites for methane dehydroaromatization Vollmer, Ina; van der Linden, Bart; Ould-Chikh, Samy Chemical Science, Vol. 9, Issue 21 https://doi.org/10.1039/C8SC01263F	journal	January 2018
In situ UV-Raman spectroscopy of the coking-caused deactivation mechanism over an Mo/HMCM-22 catalyst in methane dehydroaromatization Jiao, Xi; Huang, Xin; Wang, Kai Catalysis Science & Technology, Vol. 9, Issue 23 https://doi.org/10.1039/C9CY01932D	journal	January 2019
Coke relocation and Mo immobilization in donut-shaped Mo/HZSM-5 catalysts for methane dehydroaromatization Cheng, Ming; Cruchade, Hugo; Pinard, Ludovic Journal of Materials Chemistry A, Vol. 11, Issue 45 https://doi.org/10.1039/D3TA05418G	journal	January 2023
Microwave-assisted, performance-advantaged electrification of propane dehydrogenation Kwak, Yeonsu; Wang, Cong; Kavale, Chaitanya A. Science Advances, Vol. 9, Issue 37 https://doi.org/10.1126/sciadv.adi8219	journal	September 2023
Insights into designing an efficient and reliable microwave-assisted methane dehydroaromatization process: effect of microwave absorber on catalyst performance Muley, Pranjali; Abedin, Ashraf; Bai, Xinwei International Journal of Energy for a Clean Environment, Vol. 25, Issue 8, p. 53-83 https://doi.org/10.1615/InterJEnerCleanEnv.2024051929	journal	January 2024
Overcoming Stability Problems in Microwave-Assisted Heterogeneous Catalytic Processes Affected by Catalyst Coking Julian, Ignacio; Pedersen, Christoffer M.; Achkasov, Kostiantyn Catalysts, Vol. 9, Issue 10 https://doi.org/10.3390/catal9100867	journal	October 2019
Molybdenum Oxide Thin Films Grown on Flexible ITO-Coated PET Substrates Marciel, Alice; Graça, Manuel; Bastos, Alexandre Materials, Vol. 14, Issue 4 https://doi.org/10.3390/ma14040821	journal	February 2021

Similar Records

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Journal Article · Thu Jun 20 00:00:00 EDT 2024 · Microporous and Mesoporous Materials · OSTI ID:2482303

Effect of Si/Al ratio of ZSM-5 support on structure and activity of Mo species in methane dehydroaromatization

Journal Article · Thu Oct 01 00:00:00 EDT 2020 · Fuel · OSTI ID:1769264

A critical literature review of the advances in methane dehydroaromatization over multifunctional metal-promoted zeolite catalysts

Journal Article · Sun Oct 18 00:00:00 EDT 2020 · Applied Catalysis. A, General · OSTI ID:1852802

Related Subjects

Mo/H-ZSM-5 zeolite
aromatic compounds
catalysts
coke
deactivation
hydrocarbons
methane dehydroaromatization
microwave-enhanced conversion

Deactivation of Mo/H-ZSM-5 in Microwave-Assisted and Thermal-Driven Methane Dehydroaromatization

Citation Formats

References (61)

Similar Records

Related Subjects