Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study
Abstract
In this study, experimental studies using mass spectroscopy, thermogravimetric analysis, in situ X-ray diffraction (XRD), and theoretical density functional theory calculations were carried out to investigate the mechanism of methane partial oxidation over a CaFe2O4 oxygen carrier. The XRD analysis revealed the formation of the calcium ferrite phases during methane reduction occurred in the sequence CaFe2O4→CaFe3O5 + Ca2Fe2O5→FeO + Fe + CaO→Fe + CaO. Each of these phases was modeled using periodic density functional theory to study the activity of these phases for the reactivity with CH4, CO, and H2 along with the adsorbed surface species to help elucidate the effect that phase changes during reduction have on the chemical looping products CO and H2. Mass spectroscopic analysis revealed the formation of H2O and CO2 occurred prior to the formation of CO and H2, and these products may be due to the removal of lattice oxygen bound in the discrete primary phase, which contributes to a small portion (~16%) of the total transferable oxygen in the solid. The density functional theory (DFT) results suggest that the gaseous CO and H2 are not thermodynamically favorable to react with the Ca2Fe2O5 where the release of CO and H2 led to an increasemore »
- Authors:
-
- National Energy Technology Lab. (NETL), Morgantown, WV (United States); Leidos Research Support Team, Morgantown, WV (United States)
- National Energy Technology Lab. (NETL), Morgantown, WV (United States); Oak Ridge Inst. for Science and Education (ORISE), Oak Ridge, TN (United States)
- National Energy Technology Lab. (NETL), Morgantown, WV (United States)
- Publication Date:
- Research Org.:
- National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1635621
- Report Number(s):
- RSS257
Journal ID: ISSN 0887-0624
- Grant/Contract Number:
- 89243318CFE000003
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy and Fuels
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 2; Journal ID: ISSN 0887-0624
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Miller, Duane D., Riley, Jarrett, and Siriwardane, Ranjani. Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study. United States: N. p., 2019.
Web. doi:10.1021/acs.energyfuels.9b03623.
Miller, Duane D., Riley, Jarrett, & Siriwardane, Ranjani. Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study. United States. https://doi.org/10.1021/acs.energyfuels.9b03623
Miller, Duane D., Riley, Jarrett, and Siriwardane, Ranjani. Fri .
"Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study". United States. https://doi.org/10.1021/acs.energyfuels.9b03623. https://www.osti.gov/servlets/purl/1635621.
@article{osti_1635621,
title = {Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study},
author = {Miller, Duane D. and Riley, Jarrett and Siriwardane, Ranjani},
abstractNote = {In this study, experimental studies using mass spectroscopy, thermogravimetric analysis, in situ X-ray diffraction (XRD), and theoretical density functional theory calculations were carried out to investigate the mechanism of methane partial oxidation over a CaFe2O4 oxygen carrier. The XRD analysis revealed the formation of the calcium ferrite phases during methane reduction occurred in the sequence CaFe2O4→CaFe3O5 + Ca2Fe2O5→FeO + Fe + CaO→Fe + CaO. Each of these phases was modeled using periodic density functional theory to study the activity of these phases for the reactivity with CH4, CO, and H2 along with the adsorbed surface species to help elucidate the effect that phase changes during reduction have on the chemical looping products CO and H2. Mass spectroscopic analysis revealed the formation of H2O and CO2 occurred prior to the formation of CO and H2, and these products may be due to the removal of lattice oxygen bound in the discrete primary phase, which contributes to a small portion (~16%) of the total transferable oxygen in the solid. The density functional theory (DFT) results suggest that the gaseous CO and H2 are not thermodynamically favorable to react with the Ca2Fe2O5 where the release of CO and H2 led to an increase in selectivity for these products. The DFT results suggest that some of the adsorbed atomic hydrogen combined to form adsorbed H2 and then gaseous H2 on the CaFe2O4 surface, while the carbon deposition and some adsorbed atomic hydrogen react to form the CaFe3O5 and Ca2Fe2O5 phases simultaneously. DFT simulations suggest that both the gaseous H2 and adsorbed atomic H are less thermodynamically favorable to drive the deep reduction of Ca2Fe2O5 to CaO and Fe0. The deep reduction of the calcium ferrite therefore favors the generation of syngas products (CO and H2) through mechanisms of methane dehydrogenation and selective oxidation of carbon to CO. The significant difference in mechanisms for partial oxidation of methane to syngas with the CaFe2O4 carrier can be correlated to the differences in the oxide phases present during the reduction process, concentration of oxygen species, and bonding in the lattice structure.},
doi = {10.1021/acs.energyfuels.9b03623},
journal = {Energy and Fuels},
number = 2,
volume = 34,
place = {United States},
year = {Fri Dec 27 00:00:00 EST 2019},
month = {Fri Dec 27 00:00:00 EST 2019}
}
Web of Science
Works referenced in this record:
Enhanced Methane Reforming Activity of a Hydrothermally Synthesized Codoped Perovskite Catalyst
journal, October 2018
- Khazaal, Majida H.; Staniforth, John Z.; Alfatlawi, Zainab A.
- Energy & Fuels, Vol. 32, Issue 12
Experimental Design for Discrimination of Chemical Kinetic Models for Oxy-Methane Combustion
journal, April 2017
- Cai, Liming; Kruse, Stephan; Felsmann, Daniel
- Energy & Fuels, Vol. 31, Issue 5
Mechanism of the catalytic oxidation of methane on Pt(1 1 1) surfaces in moist environment: A density functional theory study
journal, March 2019
- Wang, Ruirui; Chen, Junjie; Zhao, Weilong
- Applied Surface Science, Vol. 471
Total Oxidation of Methane over Pt/Cr 2 O 3 Catalyst at Low Temperature: Effect of Pt 0 –Pt x + Dipoles at the Metal–Support Interface
journal, January 2019
- Corro, Grisel; Torralba, Rosalía; Pal, Umapada
- The Journal of Physical Chemistry C, Vol. 123, Issue 5
Kinetic mechanism of effects of hydrogen addition on methane catalytic combustion over Pt(1 1 1) surface: A DFT study with cluster modeling
journal, January 2016
- Qi, Wenjie; Ran, Jingyu; Wang, Ruirui
- Computational Materials Science, Vol. 111
Catalysts for combustion of methane and lower alkanes
journal, August 2002
- Choudhary, T. V.; Banerjee, S.; Choudhary, V. R.
- Applied Catalysis A: General, Vol. 234, Issue 1-2
Insight into Microscopic Reaction Pathways in Heterogeneous Catalysis
journal, October 2000
- Michaelides, A.; Hu, P.
- Journal of the American Chemical Society, Vol. 122, Issue 40
Identification of molybdenum oxide nanostructures on zeolites for natural gas conversion
journal, April 2015
- Gao, J.; Zheng, Y.; Jehng, J. -M.
- Science, Vol. 348, Issue 6235
Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen
journal, May 2014
- Guo, X.; Fang, G.; Li, G.
- Science, Vol. 344, Issue 6184
A review of catalytic partial oxidation of methane to synthesis gas with emphasis on reaction mechanisms over transition metal catalysts
journal, August 2008
- Christian Enger, Bjørn; Lødeng, Rune; Holmen, Anders
- Applied Catalysis A: General, Vol. 346, Issue 1-2
Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century
journal, December 2000
- Lunsford, Jack H.
- Catalysis Today, Vol. 63, Issue 2-4, p. 165-174
Chemical-looping technology platform
journal, December 2014
- Fan, Liang-Shih; Zeng, Liang; Luo, Siwei
- AIChE Journal, Vol. 61, Issue 1, p. 2-22
Stability and reactivity of copper oxo-clusters in ZSM-5 zeolite for selective methane oxidation to methanol
journal, June 2016
- Li, Guanna; Vassilev, Peter; Sanchez-Sanchez, Maricruz
- Journal of Catalysis, Vol. 338
Tuning metal cluster catalytic activity with morphology and composition: a DFT study of O 2 dissociation at the global minimum of Pt m Pd n (m + n = 5) clusters
journal, January 2016
- Lv, Peng; Lu, Zhansheng; Li, Shuo
- RSC Advances, Vol. 6, Issue 106
Tuning, via Counter Anions, the Morphology and Catalytic Activity of CeO2 Prepared under Mild Conditions
journal, May 2012
- Meher, Sumanta Kumar; Ranga Rao, Gangavarapu
- Journal of Colloid and Interface Science, Vol. 373, Issue 1
The relationship between catalyst morphology and performance in the oxidative coupling of methane
journal, June 1992
- Hargreaves, J.
- Journal of Catalysis, Vol. 135, Issue 2
Structure sensitivity of hydrocarbon synthesis from carbon monoxide and hydrogen
journal, May 1984
- Boudart, M.; McDonald, Mark A.
- The Journal of Physical Chemistry, Vol. 88, Issue 11
Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer
journal, September 2017
- Riley, Jarrett; Siriwardane, Ranjani; Tian, Hanjing
- Applied Energy, Vol. 201
Chemical looping coal gasification with calcium ferrite and barium ferrite via solid–solid reactions
journal, March 2016
- Siriwardane, Ranjani; Riley, Jarrett; Tian, Hanjing
- Applied Energy, Vol. 165
Activation of C−H Bonds by Metal Complexes
journal, December 1997
- Shilov, Alexander E.; Shul'pin, Georgiy B.
- Chemical Reviews, Vol. 97, Issue 8
Effects of oxide supports on the water-gas shift reaction over PtNi bimetallic catalysts: Activity and methanation inhibition
journal, September 2014
- Wang, Tiefeng; Porosoff, Marc D.; Chen, Jingguang G.
- Catalysis Today, Vol. 233
Methods for the catalytic activation of metallic structured substrates
journal, January 2014
- Montebelli, Andrea; Visconti, Carlo Giorgio; Groppi, Gianpiero
- Catalysis Science & Technology, Vol. 4, Issue 9, p. 2846-2870
Metallic structured catalysts: Influence of the substrate on the catalytic activity
journal, May 2014
- Domínguez, M. I.; Pérez, A.; Centeno, M. A.
- Applied Catalysis A: General, Vol. 478
Numerical evaluation of a microchannel methane reformer used for miniaturized GTL: Operating characteristics and greenhouse gases emission
journal, December 2017
- Cao, Chenxi; Zhang, Nian; Dang, Dan
- Fuel Processing Technology, Vol. 167
Reaction characteristics of methanol steam reforming inside mesh microchannel reactor
journal, January 2016
- Pan, Minqiang; Feng, Zhizhuo; Jiang, Lianbo
- International Journal of Hydrogen Energy, Vol. 41, Issue 3
Kinetic and mechanistic aspects for CO2 reforming of methane over Ni based catalysts
journal, October 2015
- Kathiraser, Yasotha; Oemar, Usman; Saw, Eng Toon
- Chemical Engineering Journal, Vol. 278
Methane catalytic combustion under pressure
journal, December 2012
- Di Benedetto, A.; Landi, G.; Di Sarli, V.
- Catalysis Today, Vol. 197, Issue 1
Enhancement of methane combustion in microchannels: Effects of catalyst segmentation and cavities
journal, June 2010
- Li, Yueh-Heng; Chen, Guan-Bang; Hsu, Hung-Wei
- Chemical Engineering Journal, Vol. 160, Issue 2
Influence of molar ratio on Pd–Pt catalysts for methane combustion
journal, October 2006
- Persson, K.; Ersson, A.; Jansson, K.
- Journal of Catalysis, Vol. 243, Issue 1
High‐Performance Ultrathin Co 3 O 4 Nanosheet Supported PdO/CeO 2 Catalysts for Methane Combustion
journal, March 2019
- Li, Wang; Liu, Dapeng; Feng, Xilan
- Advanced Energy Materials, Vol. 9, Issue 18
Heterogeneous reaction characteristics and its effects on homogeneous combustion of methane/air mixture in microchannels II. Chemical analysis
journal, January 2019
- Wang, Yefeng; Yang, Weijuan; Zhou, Junhu
- Fuel, Vol. 235
Performance assessment of catalytic combustion-driven thermophotovoltaic platinum tubular reactor
journal, February 2018
- Li, Yueh-Heng; Hong, Jing-Ru
- Applied Energy, Vol. 211
State-resolved probes of methane dissociation dynamics
journal, April 2009
- Juurlink, L. B. F.; Killelea, D. R.; Utz, A. L.
- Progress in Surface Science, Vol. 84, Issue 3-4
New insights into the two catalyst cycles of the Pt+-catalyzed oxidation of methane by oxygen: Spin–orbit coupling, spin-inversion probabilities, and kinetic information
journal, June 2012
- Xu, Xiang; Li, Yi; Qu, Baohan
- Computational and Theoretical Chemistry, Vol. 989
Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates
journal, June 2009
- Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T.
- Journal of the American Chemical Society, Vol. 131, Issue 23
Oxidation and reforming reactions of CH4 on a stepped Pt(557) single crystal
journal, May 2007
- Rioux, Robert M.; Marsh, Anderson L.; Gaughan, J. S.
- Catalysis Today, Vol. 123, Issue 1-4
Methane Oxidation Mechanism on Pt(111): A Cluster Model DFT Study
journal, November 2006
- Psofogiannakis, George; St-Amant, Alain; Ternan, Marten
- The Journal of Physical Chemistry B, Vol. 110, Issue 48
Ab initio molecular dynamics for liquid metals
journal, December 1995
- Kresse, G.
- Journal of Non-Crystalline Solids, Vol. 192-193
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
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
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
CaFe2O4 oxygen carrier characterization during the partial oxidation of coal in the chemical looping gasification application
journal, August 2018
- Miller, Duane D.; Siriwardane, Ranjani
- Applied Energy, Vol. 224
Oxygen-Induced Transformations of an FeO(111) Film on Pt(111): A Combined DFT and STM Study
journal, November 2010
- Giordano, L.; Lewandowski, M.; Groot, I. M. N.
- The Journal of Physical Chemistry C, Vol. 114, Issue 49
Nitrogen adsorption on Fe(111), (100), and (110) surfaces
journal, February 1999
- Mortensen, J. J.; Ganduglia-Pirovano, M. V.; Hansen, L. B.
- Surface Science, Vol. 422, Issue 1-3
Fabrication of p-type CaFe2O4 nanofilms for photoelectrochemical hydrogen generation
journal, March 2011
- Cao, Junyu; Kako, Tetsuya; Li, Peng
- Electrochemistry Communications, Vol. 13, Issue 3
Oxygen ionic conductivity, Mössbauer spectra and thermal expansion of CaFe2O4-δ
journal, October 2007
- Tsipis, E.; Pivak, Y.; Waerenborgh, J.
- Solid State Ionics, Vol. 178, Issue 25-26
Fabrication of a Au-loaded CaFe 2 O 4 /CoAl LDH p–n junction based architecture with stoichiometric H 2 & O 2 generation and Cr( vi ) reduction under visible light
journal, January 2019
- Das, Snehaprava; Patnaik, Sulagna; Parida, K. M.
- Inorganic Chemistry Frontiers, Vol. 6, Issue 1
Mapping of the range of operational conditions for Cu-, Fe-, and Ni-based oxygen carriers in chemical-looping combustion
journal, January 2007
- Abad, Alberto; Adánez, Juan; García-Labiano, Francisco
- Chemical Engineering Science, Vol. 62, Issue 1-2
Reduction Properties of Physically Mixed Metallic Oxide Oxygen Carriers in Chemical Looping Combustion
journal, October 2010
- Moghtaderi, B.; Song, H.
- Energy & Fuels, Vol. 24, Issue 10
Reaction kinetics of reduction and oxidation of metal oxides for hydrogen production
journal, November 2008
- Go, K.; Son, S.; Kim, S.
- International Journal of Hydrogen Energy, Vol. 33, Issue 21
Reduction kinetics of iron-based oxygen carriers using methane for chemical-looping combustion
journal, December 2014
- Luo, Ming; Wang, Shuzhong; Wang, Longfei
- Journal of Power Sources, Vol. 270
Reduction of ferric oxide pellets with methane.
journal, January 1986
- Ghosh, D.; Roy, A. K.; Ghosh, A.
- Transactions of the Iron and Steel Institute of Japan, Vol. 26, Issue 3
Kinetics of the reduction of hematite (Fe2O3) by methane (CH4) during chemical looping combustion: A global mechanism
journal, October 2013
- Monazam, Esmail R.; Breault, Ronald W.; Siriwardane, Ranjani
- Chemical Engineering Journal, Vol. 232
Reduction effect of α -Fe 2 O 3 on carbon deposition and CO oxidation during chemical-looping combustion
journal, October 2016
- Lin, Changfeng; Qin, Wu; Dong, Changqing
- Chemical Engineering Journal, Vol. 301
Density functional theory study on the reaction between hematite and methane during chemical looping process
journal, December 2015
- Huang, Liang; Tang, Mingchen; Fan, Maohong
- Applied Energy, Vol. 159
On the mechanism and energetics of Boudouard reaction at FeO(100) surface: 2CO→C+CO2
journal, May 1999
- Cheng, Hansong; Reiser, David B.; Dean, Sheldon
- Catalysis Today, Vol. 50, Issue 3-4
Reduction behavior of iron oxides in hydrogen and carbon monoxide atmospheres
journal, June 2007
- Jozwiak, W. K.; Kaczmarek, E.; Maniecki, T. P.
- Applied Catalysis A: General, Vol. 326, Issue 1
Oxygen Vacancy-Controlled Reactivity of Hydroxyls on an FeO(111) Monolayer Film
journal, March 2011
- Xu, Lingshun; Zhang, Wenhua; Zhang, Yulin
- The Journal of Physical Chemistry C, Vol. 115, Issue 14
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