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Title: Reducing Reaction Temperature, Steam Requirements, and Coke Formation During Methane Steam Reforming Using Electric Fields: A Microkinetic Modeling and Experimental Study

Abstract

In this study, we approach several common problems with the Ni-catalyzed methane steam reformation reaction (MSR) using a two-pronged approach combining density functional theory (DFT) calculations with experimental work. Specifically, we look at the deactivation of a Ni catalyst due to coke formation, its high operating temperature requirements, and the high steam-to-methane (H2O/CH4) ratio needed for proper MSR operation. A DFT-based microkinetic model was developed in the presence and absence of electric fields and the results were compared with experimental results. The microkinetic model shows that under various electric fields, the most favorable MSR mechanism changed slightly. It also shows that the presence of a positive electric field decreases the surface coverage of carbon, increases the water coverage, accelerates the rate-limiting step of the C-H bond cleavage in methane, and increases the desorption rates of the syngas product (CO + H2) during MSR. Consequently, for a given methane conversion, a positive electric field allows for significantly lower H2O/CH4 ratio and operating temperatures as compared to systems without an electric field. These findings correspond well with experimental tests under a variety of operating conditions. In addition, improvement in the catalytic activity due to the presence of a positive electric field remainedmore » significant even at industrially relevant applied pressures improving the hydrogen yield greatly. Overall, we find that an applied electric field can play a significant role in improving the catalytic activity of heterogeneous reactions. Here, this information can guide the design of heterogeneous reactions in the presence of an electric field. By utilizing the electric field generated by various renewable energy sources, electric field assisted heterogeneous reactions can open up a paradigm in future energy research.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [2]
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  1. Washington State Univ., Pullman, WA (United States)
  2. Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1773698
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 10; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
03 NATURAL GAS; 08 HYDROGEN; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 74 ATOMIC AND MOLECULAR PHYSICS; Electric field assisted catalysis; Low temperature methane activation; Methane steam reforming; Low steam-to-carbon ratio; Catalyst stability; First principles-based microkinetic modeling; Electric fields; Hydrocarbons; Catalysts; Chemical reactions; Water

Citation Formats

Che, Fanglin, Gray, Jake T., Ha, Su, and McEwen, Jean-Sabin. Reducing Reaction Temperature, Steam Requirements, and Coke Formation During Methane Steam Reforming Using Electric Fields: A Microkinetic Modeling and Experimental Study. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b01587.
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Che, Fanglin, Gray, Jake T., Ha, Su, & McEwen, Jean-Sabin. Reducing Reaction Temperature, Steam Requirements, and Coke Formation During Methane Steam Reforming Using Electric Fields: A Microkinetic Modeling and Experimental Study. United States. https://doi.org/10.1021/acscatal.7b01587
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Che, Fanglin, Gray, Jake T., Ha, Su, and McEwen, Jean-Sabin. Fri . "Reducing Reaction Temperature, Steam Requirements, and Coke Formation During Methane Steam Reforming Using Electric Fields: A Microkinetic Modeling and Experimental Study". United States. https://doi.org/10.1021/acscatal.7b01587. https://www.osti.gov/servlets/purl/1773698.
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@article{osti_1773698,
title = {Reducing Reaction Temperature, Steam Requirements, and Coke Formation During Methane Steam Reforming Using Electric Fields: A Microkinetic Modeling and Experimental Study},
author = {Che, Fanglin and Gray, Jake T. and Ha, Su and McEwen, Jean-Sabin},
abstractNote = {In this study, we approach several common problems with the Ni-catalyzed methane steam reformation reaction (MSR) using a two-pronged approach combining density functional theory (DFT) calculations with experimental work. Specifically, we look at the deactivation of a Ni catalyst due to coke formation, its high operating temperature requirements, and the high steam-to-methane (H2O/CH4) ratio needed for proper MSR operation. A DFT-based microkinetic model was developed in the presence and absence of electric fields and the results were compared with experimental results. The microkinetic model shows that under various electric fields, the most favorable MSR mechanism changed slightly. It also shows that the presence of a positive electric field decreases the surface coverage of carbon, increases the water coverage, accelerates the rate-limiting step of the C-H bond cleavage in methane, and increases the desorption rates of the syngas product (CO + H2) during MSR. Consequently, for a given methane conversion, a positive electric field allows for significantly lower H2O/CH4 ratio and operating temperatures as compared to systems without an electric field. These findings correspond well with experimental tests under a variety of operating conditions. In addition, improvement in the catalytic activity due to the presence of a positive electric field remained significant even at industrially relevant applied pressures improving the hydrogen yield greatly. Overall, we find that an applied electric field can play a significant role in improving the catalytic activity of heterogeneous reactions. Here, this information can guide the design of heterogeneous reactions in the presence of an electric field. By utilizing the electric field generated by various renewable energy sources, electric field assisted heterogeneous reactions can open up a paradigm in future energy research.},
doi = {10.1021/acscatal.7b01587},
journal = {ACS Catalysis},
number = 10,
volume = 7,
place = {United States},
year = {Fri Jul 21 00:00:00 EDT 2017},
month = {Fri Jul 21 00:00:00 EDT 2017}
}
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Works referenced in this record:

High Temperature Electrolysis of CO 2 for Fuel Production
journal, November 2015

  • Alioshin, Yury; Kohn, McKenzie; Rothschild, Avner
  • Journal of The Electrochemical Society, Vol. 163, Issue 2
  • DOI: 10.1149/2.0131602jes

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Chemisorption of Hydrogen on the (111) Plane of Nickel
journal, October 1972

  • Lapujoulade, J.; Neil, K. S.
  • The Journal of Chemical Physics, Vol. 57, Issue 8
  • DOI: 10.1063/1.1678790

Ru-doped Ni catalysts effective for the steam reforming of methane without the pre-reduction treatment with H2
journal, April 2006

Development of transition-state theory
journal, July 1983

  • Laidler, Keith J.; King, M. Christine
  • The Journal of Physical Chemistry, Vol. 87, Issue 15
  • DOI: 10.1021/j100238a002

Sn-doped Ni/YSZ anode catalysts with enhanced carbon deposition resistance for an intermediate temperature SOFC
journal, June 2010

Elucidating the Role of the Electric Field at the Ni/YSZ Electrode: A DFT Study
journal, June 2016

  • Che, Fanglin; Ha, Su; McEwen, Jean-Sabin
  • The Journal of Physical Chemistry C, Vol. 120, Issue 27
  • DOI: 10.1021/acs.jpcc.6b01292

CO oxidation on electrically charged gold nanotips
journal, December 2006

  • McEwen, J. -S.; Gaspard, P.
  • The Journal of Chemical Physics, Vol. 125, Issue 21
  • DOI: 10.1063/1.2400035

Low temperature hydrogen production by catalytic steam reforming of methane in an electric field
journal, March 2013

  • Oshima, Kazumasa; Shinagawa, Tatsuya; Haraguchi, Masayuki
  • International Journal of Hydrogen Energy, Vol. 38, Issue 7
  • DOI: 10.1016/j.ijhydene.2012.12.069

Extraction of kinetic parameters in temperature programmed desorption: A comparison of methods
journal, December 1987

  • Miller, J. B.; Siddiqui, H. R.; Gates, S. M.
  • The Journal of Chemical Physics, Vol. 87, Issue 11
  • DOI: 10.1063/1.453409

Reactions of hydrogen on silicon:  Kinetics and dynamics
journal, May 2003

Methane activation on Ni and Ru model catalysts
journal, December 2000

An Electric Field–Induced Change in the Selectivity of a Metal Oxide–Catalyzed Epoxide Rearrangement
journal, December 2011

  • Gorin, Craig F.; Beh, Eugene S.; Kanan, Matthew W.
  • Journal of the American Chemical Society, Vol. 134, Issue 1
  • DOI: 10.1021/ja210365j

The interaction of water with Ni(111) and H/Ni(111) studied by TPD and HREELS
journal, January 2008

  • Shan, Junjun; Aarts, Jacques F. M.; Kleyn, Aart W.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 16
  • DOI: 10.1039/b718266j

Low temperature steam reforming of methane over metal catalyst supported on CexZr1−xO2 in an electric field
journal, August 2011

Electric Field-Induced Isomerization of Azobenzene by STM
journal, November 2006

  • Alemani, Micol; Peters, Maike V.; Hecht, Stefan
  • Journal of the American Chemical Society, Vol. 128, Issue 45, p. 14446-14447
  • DOI: 10.1021/ja065449s

Catalytic water dehydrogenation and formation on nickel: Dual path mechanism in high electric fields
journal, December 2015

Catalytic Reaction Rates Controlled by Metal Oxidation State: C−H Bond Cleavage in Methane over Nickel-Based Catalysts
journal, February 2017

New design paradigm for heterogeneous catalysts
journal, April 2015

  • Vojvodic, Aleksandra; Nørskov, Jens K.
  • National Science Review, Vol. 2, Issue 2
  • DOI: 10.1093/nsr/nwv023

Ab initiomolecular dynamics for liquid metals
journal, January 1993

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 111, Issue 15
  • DOI: 10.1063/1.480097

Improving Ni Catalysts Using Electric Fields: A DFT and Experimental Study of the Methane Steam Reforming Reaction
journal, December 2016

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Density Functional Theory-Assisted Microkinetic Analysis of Methane Dry Reforming on Ni Catalyst
journal, May 2015

  • Fan, Chen; Zhu, Yi-An; Yang, Ming-Lei
  • Industrial & Engineering Chemistry Research, Vol. 54, Issue 22
  • DOI: 10.1021/acs.iecr.5b00563

Current Status of Transition-State Theory
journal, January 1996

  • Truhlar, Donald G.; Garrett, Bruce C.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp953748q

Simultaneous dry reforming and desulfurization of biomethane with non-equilibrium electric discharge at ambient temperature
journal, January 2010

  • Sekine, Yasushi; Yamadera, Junya; Matsukata, Masahiko
  • Chemical Engineering Science, Vol. 65, Issue 1
  • DOI: 10.1016/j.ces.2009.06.011

Oriented electric fields as future smart reagents in chemistry
journal, November 2016

  • Shaik, Sason; Mandal, Debasish; Ramanan, Rajeev
  • Nature Chemistry, Vol. 8, Issue 12
  • DOI: 10.1038/nchem.2651

Electric field induced oscillations in the catalytic water production on rhodium: A theoretical analysis
journal, August 2010

Effect of Ag on the control of Ni-catalyzed carbon formation: A density functional theory study
journal, June 2012

Challenges and errors: interpreting high resolution images in scanning tunneling microscopy
journal, June 2003

Enhanced Carbon-Resistant Dry Reforming Fe-Ni Catalyst: Role of Fe
journal, March 2015

  • Theofanidis, Stavros Alexandros; Galvita, Vladimir V.; Poelman, Hilde
  • ACS Catalysis, Vol. 5, Issue 5
  • DOI: 10.1021/acscatal.5b00357

Controlling Carbon Surface Chemistry by Alloying:  Carbon Tolerant Reforming Catalyst
journal, September 2006

  • Nikolla, Eranda; Holewinski, Adam; Schwank, Johannes
  • Journal of the American Chemical Society, Vol. 128, Issue 35
  • DOI: 10.1021/ja0638298

A molecular perspective of water at metal interfaces
journal, July 2012

  • Carrasco, Javier; Hodgson, Andrew; Michaelides, Angelos
  • Nature Materials, Vol. 11, Issue 8
  • DOI: 10.1038/nmat3354

Steam reforming of methane over nickel catalysts at low reaction temperature
journal, February 2004

Density functional theory studies of methyl dissociation on a Ni(111) surface in the presence of an external electric field
journal, January 2014

  • Che, Fanglin; Zhang, Renqin; Hensley, Alyssa J.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 6
  • DOI: 10.1039/C3CP54135E

Low-Temperature Hydrogen Production by Highly Efficient Catalytic System Assisted by an Electric Field †
journal, March 2010

  • Sekine, Yasushi; Haraguchi, Masayuki; Tomioka, Masahiko
  • The Journal of Physical Chemistry A, Vol. 114, Issue 11
  • DOI: 10.1021/jp906137h

The thermodynamics of electrochemical annealing
journal, December 2005

Electrolysis of water on oxide surfaces
journal, September 2007

Activity and stability enhancement of Ni-MCM-41 catalysts by Rh incorporation for hydrogen from dry reforming of methane
journal, March 2010

Vibrationally Promoted Dissociation of Water on Ni(111)
journal, May 2014

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Computational Investigation of Thermochemistry and Kinetics of Steam Methane Reforming on Ni(111) under Realistic Conditions
journal, February 2009

  • Blaylock, D. Wayne; Ogura, Teppei; Green, William H.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 12
  • DOI: 10.1021/jp806527q

To Wet or Not to Wet? Dispersion Forces Tip the Balance for Water Ice on Metals
journal, January 2011

Methane Decomposition into Hydrogen and Carbon Nanofibers over Supported Pd−Ni Catalysts:  Characterization of the Catalysts during the Reaction
journal, June 2004

  • Takenaka, Sakae; Shigeta, Yukio; Tanabe, Eishi
  • The Journal of Physical Chemistry B, Vol. 108, Issue 23
  • DOI: 10.1021/jp0377331

Ionization of water in interfacial electric fields: An electrochemical view
journal, January 2012

Electric Field Effects in Electrochemical CO 2 Reduction
journal, September 2016

Theory of dissociative and nondissociative adsorption and desorption
journal, April 1999

  • Kreuzer, H. J.; Payne, S. H.; Drozdowski, A.
  • The Journal of Chemical Physics, Vol. 110, Issue 14
  • DOI: 10.1063/1.478604

Physics and chemistry in high electric fields
journal, May 2004

  • Kreuzer, H. J.
  • Surface and Interface Analysis, Vol. 36, Issue 56
  • DOI: 10.1002/sia.1895

Progress and recent trends in biofuels
journal, February 2007

Production of hydrogen-rich syngas from methane reforming by steam microwave plasma
journal, February 2016

  • Choi, Dae Hyun; Chun, Se Min; Ma, Suk Hwal
  • Journal of Industrial and Engineering Chemistry, Vol. 34
  • DOI: 10.1016/j.jiec.2015.11.019

Surface Relaxations, Current Enhancements, and Absolute Distances in High Resolution Scanning Tunneling Microscopy
journal, November 2001

Complete oxidation of methane on Pd/YSZ and Pd/CeO2/YSZ by electrochemical promotion
journal, August 2009

  • Jiménez-Borja, Carmen; Dorado, Fernando; de Lucas-Consuegra, Antonio
  • Catalysis Today, Vol. 146, Issue 3-4
  • DOI: 10.1016/j.cattod.2009.04.011

Detailed Kinetic Models in the Context of Reactor Analysis:  Linking Mechanistic and Process Chemistry
journal, November 1999

  • Joshi, Prasanna V.; Kumar, Ankush; Mizan, Tahmid I.
  • Energy & Fuels, Vol. 13, Issue 6
  • DOI: 10.1021/ef990021i

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992

Methanol adsorption and decomposition on rhodium
journal, October 1989

Surface Protonics Promotes Catalysis
journal, December 2016

  • Manabe, R.; Okada, S.; Inagaki, R.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep38007

Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992

First-principles study of methane dehydrogenation on a bimetallic Cu/Ni(111) surface
journal, November 2009

  • An, Wei; Zeng, X. C.; Turner, C. Heath
  • The Journal of Chemical Physics, Vol. 131, Issue 17
  • DOI: 10.1063/1.3254383

Methane dehydrogenation on Au/Ni surface alloys – a first-principles study
journal, January 2013

  • Huang, Yucheng; Du, Jinyan; Ling, Chongyi
  • Catalysis Science & Technology, Vol. 3, Issue 5
  • DOI: 10.1039/c3cy20802h

Interfacial Electric Field Effects on a Carbene Reaction Catalyzed by Rh Porphyrins
journal, July 2013

  • Gorin, Craig F.; Beh, Eugene S.; Bui, Quan M.
  • Journal of the American Chemical Society, Vol. 135, Issue 30
  • DOI: 10.1021/ja404394z

Decomposition of methyl species on a Ni(211) surface: investigations of the electric field influence
journal, January 2014

  • Che, Fanglin; Hensley, Alyssa J.; Ha, Su
  • Catal. Sci. Technol., Vol. 4, Issue 11
  • DOI: 10.1039/C4CY00406J

Temperature programmed desorption: A statistical rate theory approach
journal, April 1997

  • Elliott, J. A. W.; Ward, C. A.
  • The Journal of Chemical Physics, Vol. 106, Issue 13
  • DOI: 10.1063/1.473588

Electrostatic catalysis of a Diels–Alder reaction
journal, March 2016

  • Aragonès, Albert C.; Haworth, Naomi L.; Darwish, Nadim
  • Nature, Vol. 531, Issue 7592
  • DOI: 10.1038/nature16989

Nanostructured Pt- and Ni-based catalysts for CO2-reforming of methane
journal, March 2010

Catalytic Reduction of NO 2 with Hydrogen on Pt Field Emitter Tips: Kinetic Instabilities on the Nanoscale †
journal, November 2010

  • McEwen, J. -S.; Gaspard, P.; De Decker, Y.
  • Langmuir, Vol. 26, Issue 21
  • DOI: 10.1021/la102003x

Elucidating the field influence on the energetics of the methane steam reforming reaction: A density functional theory study
journal, October 2016

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    Works referencing / citing this record:

    Production of Hydrogen by Methane Steam Reforming Coupled with Catalytic Combustion in Integrated Microchannel Reactors
    journal, August 2018

    • Chen, Junjie; Liu, Baofang; Gao, Xuhui
    • Energies, Vol. 11, Issue 8
    • DOI: 10.3390/en11082045

    Syngas production from methane steam reforming and dry reforming reactions over sintering-resistant Ni@SiO2 catalyst
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