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Title: 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 » 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.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]
  1. National Energy Technology Lab. (NETL), Morgantown, WV (United States); Leidos Research Support Team, Morgantown, WV (United States)
  2. National Energy Technology Lab. (NETL), Morgantown, WV (United States); Oak Ridge Inst. for Science and Education (ORISE), Oak Ridge, TN (United States)
  3. 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. https://doi.org/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 = {2019},
month = {12}
}

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