CH4 dehydroaromatization on Mo/H-ZSM-5: 1. Effects of co-processing H2 and CH3COOH

Jeremy Bedard; Do Young Hong; Aditya Bhan

doi:10.1016/j.jcat.2013.06.003

CH₄ dehydroaromatization on Mo/H-ZSM-5: 1. Effects of co-processing H₂ and CH₃COOH

Jeremy Bedard, Do Young Hong, Aditya Bhan

Chemical Engineering and Materials Science

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

Abstract

The co-processing of acetic acid with methane (CH₃COOH/CH ₄ = 0.04-0.10) on Mo/ZSM-5 formulations at 950 K and atmospheric pressure in an effort to couple deoxygenation and dehydrogenation reaction sequences results instead in a stratified reactor bed with upstream CH ₄ reforming with acetic acid and downstream CH₄ pyrolysis. X-ray absorption spectroscopy and chemical transient experiments show that molybdenum carbide is formed inside zeolite micropores during CH₄ reactions. The introduction of acetic acid oxidizes a fraction of these carbide moieties upstream while producing H₂ and CO mixtures until completely consumed. Forward rates of CH₄ pyrolysis are unperturbed in the presence of an acetic acid or hydrogen co-feed after rigorously accounting for the reversibility of pyrolysis rates and the fraction of molybdenum carbide oxidized by CH₃COOH implying that all consequences of CH ₃COOH and H₂ co-feeds can be interpreted in terms of an approach to equilibrium.

Original language	English (US)
Pages (from-to)	58-67
Number of pages	10
Journal	Journal of Catalysis
Volume	306
DOIs	https://doi.org/10.1016/j.jcat.2013.06.003
State	Published - 2013

Bibliographical note

Funding Information:
Do-Young Hong was supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0001004. Jeremy Bedard was supported by the National Science Foundation Emerging Frontiers in Research and Innovation – Hydrocarbons from Biomass (NSF EFRI HyBi # 0937706). The authors also acknowledge financial support from the DOE Early Career Program under Award No. DE-SC0008418. We thank Prof. Jingguang Chen and Dr. Nebojsa Marinkovic for assistance with the X-ray absorption spectroscopy studies. We also thank Nancy Trejo for assistance with catalytic reactions.

Keywords

Acetic acid
Dehydroaromatization
Dehydrogenation
Deoxygenation
H-ZSM-5
Hydrogen transfer
Kinetic coupling
Methane
Molybdenum carbide
Oxygenates

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10.1016/j.jcat.2013.06.003

Cite this

@article{7c8d7a0b4c0c478184fb557c8663a3e4,

title = "CH4 dehydroaromatization on Mo/H-ZSM-5: 1. Effects of co-processing H2 and CH3COOH",

abstract = "The co-processing of acetic acid with methane (CH3COOH/CH 4 = 0.04-0.10) on Mo/ZSM-5 formulations at 950 K and atmospheric pressure in an effort to couple deoxygenation and dehydrogenation reaction sequences results instead in a stratified reactor bed with upstream CH 4 reforming with acetic acid and downstream CH4 pyrolysis. X-ray absorption spectroscopy and chemical transient experiments show that molybdenum carbide is formed inside zeolite micropores during CH4 reactions. The introduction of acetic acid oxidizes a fraction of these carbide moieties upstream while producing H2 and CO mixtures until completely consumed. Forward rates of CH4 pyrolysis are unperturbed in the presence of an acetic acid or hydrogen co-feed after rigorously accounting for the reversibility of pyrolysis rates and the fraction of molybdenum carbide oxidized by CH3COOH implying that all consequences of CH 3COOH and H2 co-feeds can be interpreted in terms of an approach to equilibrium.",

keywords = "Acetic acid, Dehydroaromatization, Dehydrogenation, Deoxygenation, H-ZSM-5, Hydrogen transfer, Kinetic coupling, Methane, Molybdenum carbide, Oxygenates",

author = "Jeremy Bedard and Hong, {Do Young} and Aditya Bhan",

note = "Funding Information: Do-Young Hong was supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0001004. Jeremy Bedard was supported by the National Science Foundation Emerging Frontiers in Research and Innovation – Hydrocarbons from Biomass (NSF EFRI HyBi # 0937706). The authors also acknowledge financial support from the DOE Early Career Program under Award No. DE-SC0008418. We thank Prof. Jingguang Chen and Dr. Nebojsa Marinkovic for assistance with the X-ray absorption spectroscopy studies. We also thank Nancy Trejo for assistance with catalytic reactions. ",

year = "2013",

doi = "10.1016/j.jcat.2013.06.003",

language = "English (US)",

volume = "306",

pages = "58--67",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

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T2 - 1. Effects of co-processing H2 and CH3COOH

AU - Bedard, Jeremy

AU - Hong, Do Young

AU - Bhan, Aditya

N1 - Funding Information: Do-Young Hong was supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0001004. Jeremy Bedard was supported by the National Science Foundation Emerging Frontiers in Research and Innovation – Hydrocarbons from Biomass (NSF EFRI HyBi # 0937706). The authors also acknowledge financial support from the DOE Early Career Program under Award No. DE-SC0008418. We thank Prof. Jingguang Chen and Dr. Nebojsa Marinkovic for assistance with the X-ray absorption spectroscopy studies. We also thank Nancy Trejo for assistance with catalytic reactions.

PY - 2013

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N2 - The co-processing of acetic acid with methane (CH3COOH/CH 4 = 0.04-0.10) on Mo/ZSM-5 formulations at 950 K and atmospheric pressure in an effort to couple deoxygenation and dehydrogenation reaction sequences results instead in a stratified reactor bed with upstream CH 4 reforming with acetic acid and downstream CH4 pyrolysis. X-ray absorption spectroscopy and chemical transient experiments show that molybdenum carbide is formed inside zeolite micropores during CH4 reactions. The introduction of acetic acid oxidizes a fraction of these carbide moieties upstream while producing H2 and CO mixtures until completely consumed. Forward rates of CH4 pyrolysis are unperturbed in the presence of an acetic acid or hydrogen co-feed after rigorously accounting for the reversibility of pyrolysis rates and the fraction of molybdenum carbide oxidized by CH3COOH implying that all consequences of CH 3COOH and H2 co-feeds can be interpreted in terms of an approach to equilibrium.

AB - The co-processing of acetic acid with methane (CH3COOH/CH 4 = 0.04-0.10) on Mo/ZSM-5 formulations at 950 K and atmospheric pressure in an effort to couple deoxygenation and dehydrogenation reaction sequences results instead in a stratified reactor bed with upstream CH 4 reforming with acetic acid and downstream CH4 pyrolysis. X-ray absorption spectroscopy and chemical transient experiments show that molybdenum carbide is formed inside zeolite micropores during CH4 reactions. The introduction of acetic acid oxidizes a fraction of these carbide moieties upstream while producing H2 and CO mixtures until completely consumed. Forward rates of CH4 pyrolysis are unperturbed in the presence of an acetic acid or hydrogen co-feed after rigorously accounting for the reversibility of pyrolysis rates and the fraction of molybdenum carbide oxidized by CH3COOH implying that all consequences of CH 3COOH and H2 co-feeds can be interpreted in terms of an approach to equilibrium.

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KW - Deoxygenation

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KW - Kinetic coupling

KW - Methane

KW - Molybdenum carbide

KW - Oxygenates

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