Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study

Miller, Duane D.; Riley, Jarrett; Siriwardane, Ranjani

doi:10.1021/acs.energyfuels.9b03623

Title: Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study

Journal Article · Fri Dec 27 00:00:00 EST 2019 · Energy and Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.9b03623· OSTI ID:1635621

^[1]; Riley, Jarrett ^[2];

^[3]

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)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE

Grant/Contract Number:: 89243318CFE000003

OSTI ID:: 1635621

Report Number(s):: RSS257

Journal Information:: Energy and Fuels, Vol. 34, Issue 2; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 10 works

Citation information provided by
Web of Science

References (62)

Enhanced Methane Reforming Activity of a Hydrothermally Synthesized Codoped Perovskite Catalyst Khazaal, Majida H.; Staniforth, John Z.; Alfatlawi, Zainab A. Energy & Fuels, Vol. 32, Issue 12 https://doi.org/10.1021/acs.energyfuels.8b02848	journal	October 2018
Experimental Design for Discrimination of Chemical Kinetic Models for Oxy-Methane Combustion Cai, Liming; Kruse, Stephan; Felsmann, Daniel Energy & Fuels, Vol. 31, Issue 5 https://doi.org/10.1021/acs.energyfuels.6b03025	journal	April 2017
Mechanism of the catalytic oxidation of methane on Pt(1 1 1) surfaces in moist environment: A density functional theory study Wang, Ruirui; Chen, Junjie; Zhao, Weilong Applied Surface Science, Vol. 471 https://doi.org/10.1016/j.apsusc.2018.12.055	journal	March 2019
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 Corro, Grisel; Torralba, Rosalía; Pal, Umapada The Journal of Physical Chemistry C, Vol. 123, Issue 5 https://doi.org/10.1021/acs.jpcc.8b09748	journal	January 2019
Kinetic mechanism of effects of hydrogen addition on methane catalytic combustion over Pt(1 1 1) surface: A DFT study with cluster modeling Qi, Wenjie; Ran, Jingyu; Wang, Ruirui Computational Materials Science, Vol. 111 https://doi.org/10.1016/j.commatsci.2015.09.002	journal	January 2016
Catalysts for combustion of methane and lower alkanes Choudhary, T. V.; Banerjee, S.; Choudhary, V. R. Applied Catalysis A: General, Vol. 234, Issue 1-2 https://doi.org/10.1016/S0926-860X(02)00231-4	journal	August 2002
Insight into Microscopic Reaction Pathways in Heterogeneous Catalysis Michaelides, A.; Hu, P. Journal of the American Chemical Society, Vol. 122, Issue 40 https://doi.org/10.1021/ja0011919	journal	October 2000
Identification of molybdenum oxide nanostructures on zeolites for natural gas conversion Gao, J.; Zheng, Y.; Jehng, J. -M. Science, Vol. 348, Issue 6235 https://doi.org/10.1126/science.aaa7048	journal	April 2015
Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen Guo, X.; Fang, G.; Li, G. Science, Vol. 344, Issue 6184 https://doi.org/10.1126/science.1253150	journal	May 2014
A review of catalytic partial oxidation of methane to synthesis gas with emphasis on reaction mechanisms over transition metal catalysts Christian Enger, Bjørn; Lødeng, Rune; Holmen, Anders Applied Catalysis A: General, Vol. 346, Issue 1-2 https://doi.org/10.1016/j.apcata.2008.05.018	journal	August 2008
Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century Lunsford, Jack H. Catalysis Today, Vol. 63, Issue 2-4, p. 165-174 https://doi.org/10.1016/S0920-5861(00)00456-9	journal	December 2000
Chemical-looping technology platform Fan, Liang-Shih; Zeng, Liang; Luo, Siwei AIChE Journal, Vol. 61, Issue 1, p. 2-22 https://doi.org/10.1002/aic.14695	journal	December 2014
Stability and reactivity of copper oxo-clusters in ZSM-5 zeolite for selective methane oxidation to methanol Li, Guanna; Vassilev, Peter; Sanchez-Sanchez, Maricruz Journal of Catalysis, Vol. 338 https://doi.org/10.1016/j.jcat.2016.03.014	journal	June 2016
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 Lv, Peng; Lu, Zhansheng; Li, Shuo RSC Advances, Vol. 6, Issue 106 https://doi.org/10.1039/C6RA23266C	journal	January 2016
Tuning, via Counter Anions, the Morphology and Catalytic Activity of CeO2 Prepared under Mild Conditions Meher, Sumanta Kumar; Ranga Rao, Gangavarapu Journal of Colloid and Interface Science, Vol. 373, Issue 1 https://doi.org/10.1016/j.jcis.2011.09.050	journal	May 2012
The relationship between catalyst morphology and performance in the oxidative coupling of methane Hargreaves, J. Journal of Catalysis, Vol. 135, Issue 2 https://doi.org/10.1016/0021-9517(92)90055-M	journal	June 1992
Structure sensitivity of hydrocarbon synthesis from carbon monoxide and hydrogen Boudart, M.; McDonald, Mark A. The Journal of Physical Chemistry, Vol. 88, Issue 11 https://doi.org/10.1021/j150655a004	journal	May 1984
Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer Riley, Jarrett; Siriwardane, Ranjani; Tian, Hanjing Applied Energy, Vol. 201 https://doi.org/10.1016/j.apenergy.2017.05.101	journal	September 2017
Chemical looping coal gasification with calcium ferrite and barium ferrite via solid–solid reactions Siriwardane, Ranjani; Riley, Jarrett; Tian, Hanjing Applied Energy, Vol. 165 https://doi.org/10.1016/j.apenergy.2015.12.085	journal	March 2016
Activation of C−H Bonds by Metal Complexes Shilov, Alexander E.; Shul'pin, Georgiy B. Chemical Reviews, Vol. 97, Issue 8 https://doi.org/10.1021/cr9411886	journal	December 1997
Effects of oxide supports on the water-gas shift reaction over PtNi bimetallic catalysts: Activity and methanation inhibition Wang, Tiefeng; Porosoff, Marc D.; Chen, Jingguang G. Catalysis Today, Vol. 233 https://doi.org/10.1016/j.cattod.2013.09.037	journal	September 2014
Methods for the catalytic activation of metallic structured substrates Montebelli, Andrea; Visconti, Carlo Giorgio; Groppi, Gianpiero Catalysis Science & Technology, Vol. 4, Issue 9, p. 2846-2870 https://doi.org/10.1039/C4CY00179F	journal	January 2014
Metallic structured catalysts: Influence of the substrate on the catalytic activity Domínguez, M. I.; Pérez, A.; Centeno, M. A. Applied Catalysis A: General, Vol. 478 https://doi.org/10.1016/j.apcata.2014.03.028	journal	May 2014
Numerical evaluation of a microchannel methane reformer used for miniaturized GTL: Operating characteristics and greenhouse gases emission Cao, Chenxi; Zhang, Nian; Dang, Dan Fuel Processing Technology, Vol. 167 https://doi.org/10.1016/j.fuproc.2017.06.019	journal	December 2017
Reaction characteristics of methanol steam reforming inside mesh microchannel reactor Pan, Minqiang; Feng, Zhizhuo; Jiang, Lianbo International Journal of Hydrogen Energy, Vol. 41, Issue 3 https://doi.org/10.1016/j.ijhydene.2015.11.023	journal	January 2016
Kinetic and mechanistic aspects for CO2 reforming of methane over Ni based catalysts Kathiraser, Yasotha; Oemar, Usman; Saw, Eng Toon Chemical Engineering Journal, Vol. 278 https://doi.org/10.1016/j.cej.2014.11.143	journal	October 2015
Methane catalytic combustion under pressure Di Benedetto, A.; Landi, G.; Di Sarli, V. Catalysis Today, Vol. 197, Issue 1 https://doi.org/10.1016/j.cattod.2012.08.032	journal	December 2012
Enhancement of methane combustion in microchannels: Effects of catalyst segmentation and cavities Li, Yueh-Heng; Chen, Guan-Bang; Hsu, Hung-Wei Chemical Engineering Journal, Vol. 160, Issue 2 https://doi.org/10.1016/j.cej.2010.03.057	journal	June 2010
Influence of molar ratio on Pd–Pt catalysts for methane combustion Persson, K.; Ersson, A.; Jansson, K. Journal of Catalysis, Vol. 243, Issue 1 https://doi.org/10.1016/j.jcat.2006.06.019	journal	October 2006
High‐Performance Ultrathin Co ₃ O ₄ Nanosheet Supported PdO/CeO ₂ Catalysts for Methane Combustion Li, Wang; Liu, Dapeng; Feng, Xilan Advanced Energy Materials, Vol. 9, Issue 18 https://doi.org/10.1002/aenm.201803583	journal	March 2019
Heterogeneous reaction characteristics and its effects on homogeneous combustion of methane/air mixture in microchannels II. Chemical analysis Wang, Yefeng; Yang, Weijuan; Zhou, Junhu Fuel, Vol. 235 https://doi.org/10.1016/j.fuel.2018.08.097	journal	January 2019
Performance assessment of catalytic combustion-driven thermophotovoltaic platinum tubular reactor Li, Yueh-Heng; Hong, Jing-Ru Applied Energy, Vol. 211 https://doi.org/10.1016/j.apenergy.2017.11.095	journal	February 2018
State-resolved probes of methane dissociation dynamics Juurlink, L. B. F.; Killelea, D. R.; Utz, A. L. Progress in Surface Science, Vol. 84, Issue 3-4 https://doi.org/10.1016/j.progsurf.2009.01.001	journal	April 2009
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 Xu, Xiang; Li, Yi; Qu, Baohan Computational and Theoretical Chemistry, Vol. 989 https://doi.org/10.1016/j.comptc.2012.03.013	journal	June 2012
Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T. Journal of the American Chemical Society, Vol. 131, Issue 23 https://doi.org/10.1021/ja9000097	journal	June 2009
Oxidation and reforming reactions of CH4 on a stepped Pt(557) single crystal Rioux, Robert M.; Marsh, Anderson L.; Gaughan, J. S. Catalysis Today, Vol. 123, Issue 1-4 https://doi.org/10.1016/j.cattod.2007.02.018	journal	May 2007
Methane Oxidation Mechanism on Pt(111): A Cluster Model DFT Study Psofogiannakis, George; St-Amant, Alain; Ternan, Marten The Journal of Physical Chemistry B, Vol. 110, Issue 48 https://doi.org/10.1021/jp061559+	journal	November 2006
Ab initio molecular dynamics for liquid metals Kresse, G. Journal of Non-Crystalline Solids, Vol. 192-193 https://doi.org/10.1016/0022-3093(95)00355-X	journal	December 1995
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
CaFe2O4 oxygen carrier characterization during the partial oxidation of coal in the chemical looping gasification application Miller, Duane D.; Siriwardane, Ranjani Applied Energy, Vol. 224 https://doi.org/10.1016/j.apenergy.2018.05.035	journal	August 2018
Oxygen-Induced Transformations of an FeO(111) Film on Pt(111): A Combined DFT and STM Study Giordano, L.; Lewandowski, M.; Groot, I. M. N. The Journal of Physical Chemistry C, Vol. 114, Issue 49 https://doi.org/10.1021/jp1070105	journal	November 2010
Nitrogen adsorption on Fe(111), (100), and (110) surfaces Mortensen, J. J.; Ganduglia-Pirovano, M. V.; Hansen, L. B. Surface Science, Vol. 422, Issue 1-3 https://doi.org/10.1016/S0039-6028(98)00802-4	journal	February 1999
Fabrication of p-type CaFe2O4 nanofilms for photoelectrochemical hydrogen generation Cao, Junyu; Kako, Tetsuya; Li, Peng Electrochemistry Communications, Vol. 13, Issue 3 https://doi.org/10.1016/j.elecom.2011.01.002	journal	March 2011
Oxygen ionic conductivity, Mössbauer spectra and thermal expansion of CaFe2O4-δ Tsipis, E.; Pivak, Y.; Waerenborgh, J. Solid State Ionics, Vol. 178, Issue 25-26 https://doi.org/10.1016/j.ssi.2007.09.003	journal	October 2007
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 Das, Snehaprava; Patnaik, Sulagna; Parida, K. M. Inorganic Chemistry Frontiers, Vol. 6, Issue 1 https://doi.org/10.1039/C8QI00952J	journal	January 2019
Mapping of the range of operational conditions for Cu-, Fe-, and Ni-based oxygen carriers in chemical-looping combustion Abad, Alberto; Adánez, Juan; García-Labiano, Francisco Chemical Engineering Science, Vol. 62, Issue 1-2 https://doi.org/10.1016/j.ces.2006.09.019	journal	January 2007
Reduction Properties of Physically Mixed Metallic Oxide Oxygen Carriers in Chemical Looping Combustion Moghtaderi, B.; Song, H. Energy & Fuels, Vol. 24, Issue 10 https://doi.org/10.1021/ef1006963	journal	October 2010
Reaction kinetics of reduction and oxidation of metal oxides for hydrogen production Go, K.; Son, S.; Kim, S. International Journal of Hydrogen Energy, Vol. 33, Issue 21 https://doi.org/10.1016/j.ijhydene.2008.05.039	journal	November 2008
Reduction kinetics of iron-based oxygen carriers using methane for chemical-looping combustion Luo, Ming; Wang, Shuzhong; Wang, Longfei Journal of Power Sources, Vol. 270 https://doi.org/10.1016/j.jpowsour.2014.07.100	journal	December 2014
Reduction of ferric oxide pellets with methane. Ghosh, D.; Roy, A. K.; Ghosh, A. Transactions of the Iron and Steel Institute of Japan, Vol. 26, Issue 3 https://doi.org/10.2355/isijinternational1966.26.186	journal	January 1986
Kinetics of the reduction of hematite (Fe2O3) by methane (CH4) during chemical looping combustion: A global mechanism Monazam, Esmail R.; Breault, Ronald W.; Siriwardane, Ranjani Chemical Engineering Journal, Vol. 232 https://doi.org/10.1016/j.cej.2013.07.091	journal	October 2013
Reduction effect of α -Fe 2 O 3 on carbon deposition and CO oxidation during chemical-looping combustion Lin, Changfeng; Qin, Wu; Dong, Changqing Chemical Engineering Journal, Vol. 301 https://doi.org/10.1016/j.cej.2016.04.136	journal	October 2016
Density functional theory study on the reaction between hematite and methane during chemical looping process Huang, Liang; Tang, Mingchen; Fan, Maohong Applied Energy, Vol. 159 https://doi.org/10.1016/j.apenergy.2015.08.118	journal	December 2015
On the mechanism and energetics of Boudouard reaction at FeO(100) surface: 2CO→C+CO2 Cheng, Hansong; Reiser, David B.; Dean, Sheldon Catalysis Today, Vol. 50, Issue 3-4 https://doi.org/10.1016/S0920-5861(98)00492-1	journal	May 1999
Reduction behavior of iron oxides in hydrogen and carbon monoxide atmospheres Jozwiak, W. K.; Kaczmarek, E.; Maniecki, T. P. Applied Catalysis A: General, Vol. 326, Issue 1 https://doi.org/10.1016/j.apcata.2007.03.021	journal	June 2007
Oxygen Vacancy-Controlled Reactivity of Hydroxyls on an FeO(111) Monolayer Film Xu, Lingshun; Zhang, Wenhua; Zhang, Yulin The Journal of Physical Chemistry C, Vol. 115, Issue 14 https://doi.org/10.1021/jp200423j	journal	March 2011
Enhanced Carbon-Resistant Dry Reforming Fe-Ni Catalyst: Role of Fe Theofanidis, Stavros Alexandros; Galvita, Vladimir V.; Poelman, Hilde ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/acscatal.5b00357	journal	March 2015

Similar Records

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 Article · Sat May 20 00:00:00 EDT 2017 · Applied Energy · OSTI ID:1635621

Riley, Jarrett; Siriwardane, Ranjani; Tian, Hanjing; +2 more

CaFe₂O₄ oxygen carrier characterization during the partial oxidation of coal in the chemical looping gasification application

Journal Article · Thu May 17 00:00:00 EDT 2018 · Applied Energy · OSTI ID:1635621

Miller, Duane D.; Siriwardane, Ranjani

CO₂ utilization potential of a novel calcium ferrite based looping process fueled with coal: Experimental evaluation of various coal feedstocks and thermodynamic integrated process analysis

Journal Article · Thu Jul 14 00:00:00 EDT 2022 · Applied Energy · OSTI ID:1635621

Siriwardane, Ranjani; Riley, Jarrett; Atallah, Chris

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study

Citation Formats

References (62)

Similar Records

Related Subjects