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Title: Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer

Abstract

Chemical Looping Gasification (CLG) is an emerging technology that shows promise for efficient coal gasification by eliminating the need for energy intensive gas separations to achieve a non-nitrogen diluted syngas stream. Oxygen from oxygen carriers, such as CaFe2O4, are used for coal gasification in place of conventionally produced gaseous oxygen from cryogenic separation of air. These oxygen carriers are unique for their ability to selectively oxidize coal to form syngas and show limited reactivity with syngas components (H2, CO). To gain a deeper understanding of how these unique oxygen carriers perform and to offer a first attempt at the reaction modeling of solid mediated interactions of this nature, this study was carried out to determine the kinetic parameters associated with the selective oxidation of coal derived char (Wyodak and Illinois #6) with a metal ferrite, CaFe2O4. Using thermogravimetric analysis (TGA) coupled with mass spectrometry, the selective oxygen release of metal ferrite in the presence of char by proximal contact was examined. The application of combinatory model fitting approaches was used to describe controlling resistances during oxygen release. A combination of the modified shrinking core model (SCM) with planar oxygen ion diffusion control and reaction order based models was used formore » kinetic parameter determination. CaFe2O4 particle size plays a major role in the prevailing mode of oxygen release. Particle sizes on the order of 40–50 μm tend to favor first order kinetically controlled regimes independent of geometric and diffusion controls. The probability for oxygen ion diffusion controlling regimes increased when the particle size range of the oxygen carrier was increased up to 350 μm. Char type also impacted the prevalence of the controlling regime. Higher ranked chars react in a slower manner, limiting the gradient for oxygen ion release from the oxygen carrier. Activation energies determined for this process range from 120–200kJ/mol and oxygen ion diffusion coefficients are on the order of 10-8 cm2/s. It is suggested that oxygen ion movement is regulated by lattice diffusion out of partially reduced phases (Ca2Fe2O5) and through reduced outer layers composed of CaO and Fe. The controlled movement of oxygen ions influences the rate of carbon oxidation in the char and therefore the selectivity towards partial oxidation products, which are desirable in CLG applications.« less

Authors:
 [1];  [2];  [1];  [1];  [2]
  1. National Energy Technology Lab. (NETL), Morgantown, WV (United States); West Virginia Univ., Morgantown, WV (United States)
  2. National Energy Technology Lab. (NETL), Morgantown, WV (United States)
Publication Date:
Research Org.:
National Energy Technology Lab. (NETL), Morgantown, WV (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1433638
Report Number(s):
NETL-PUB-21035
Journal ID: ISSN 0306-2619; PII: S0306261917306086
Resource Type:
Accepted Manuscript
Journal Name:
Applied Energy
Additional Journal Information:
Journal Volume: 201; Journal Issue: C; Journal ID: ISSN 0306-2619
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Riley, Jarrett, Siriwardane, Ranjani, Tian, Hanjing, Benincosa, William, and Poston, James. Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer. United States: N. p., 2017. Web. https://doi.org/10.1016/j.apenergy.2017.05.101.
Riley, Jarrett, Siriwardane, Ranjani, Tian, Hanjing, Benincosa, William, & Poston, James. Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer. United States. https://doi.org/10.1016/j.apenergy.2017.05.101
Riley, Jarrett, Siriwardane, Ranjani, Tian, Hanjing, Benincosa, William, and Poston, James. Sat . "Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer". United States. https://doi.org/10.1016/j.apenergy.2017.05.101. https://www.osti.gov/servlets/purl/1433638.
@article{osti_1433638,
title = {Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer},
author = {Riley, Jarrett and Siriwardane, Ranjani and Tian, Hanjing and Benincosa, William and Poston, James},
abstractNote = {Chemical Looping Gasification (CLG) is an emerging technology that shows promise for efficient coal gasification by eliminating the need for energy intensive gas separations to achieve a non-nitrogen diluted syngas stream. Oxygen from oxygen carriers, such as CaFe2O4, are used for coal gasification in place of conventionally produced gaseous oxygen from cryogenic separation of air. These oxygen carriers are unique for their ability to selectively oxidize coal to form syngas and show limited reactivity with syngas components (H2, CO). To gain a deeper understanding of how these unique oxygen carriers perform and to offer a first attempt at the reaction modeling of solid mediated interactions of this nature, this study was carried out to determine the kinetic parameters associated with the selective oxidation of coal derived char (Wyodak and Illinois #6) with a metal ferrite, CaFe2O4. Using thermogravimetric analysis (TGA) coupled with mass spectrometry, the selective oxygen release of metal ferrite in the presence of char by proximal contact was examined. The application of combinatory model fitting approaches was used to describe controlling resistances during oxygen release. A combination of the modified shrinking core model (SCM) with planar oxygen ion diffusion control and reaction order based models was used for kinetic parameter determination. CaFe2O4 particle size plays a major role in the prevailing mode of oxygen release. Particle sizes on the order of 40–50 μm tend to favor first order kinetically controlled regimes independent of geometric and diffusion controls. The probability for oxygen ion diffusion controlling regimes increased when the particle size range of the oxygen carrier was increased up to 350 μm. Char type also impacted the prevalence of the controlling regime. Higher ranked chars react in a slower manner, limiting the gradient for oxygen ion release from the oxygen carrier. Activation energies determined for this process range from 120–200kJ/mol and oxygen ion diffusion coefficients are on the order of 10-8 cm2/s. It is suggested that oxygen ion movement is regulated by lattice diffusion out of partially reduced phases (Ca2Fe2O5) and through reduced outer layers composed of CaO and Fe. The controlled movement of oxygen ions influences the rate of carbon oxidation in the char and therefore the selectivity towards partial oxidation products, which are desirable in CLG applications.},
doi = {10.1016/j.apenergy.2017.05.101},
journal = {Applied Energy},
number = C,
volume = 201,
place = {United States},
year = {2017},
month = {5}
}

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    Chemical looping gasification of pyrolyzed biomass and coal char with copper ferrite as an oxygen carrier
    journal, November 2018

    • Liu, Chenlong; Wang, Wenju
    • Journal of Renewable and Sustainable Energy, Vol. 10, Issue 6
    • DOI: 10.1063/1.5040379

    Catalysts for gasification: a review
    journal, January 2019

    • Arnold, R. A.; Hill, J. M.
    • Sustainable Energy & Fuels, Vol. 3, Issue 3
    • DOI: 10.1039/c8se00614h

    A Kinetic Study on Combustible Coastal Debris Pyrolysis via Thermogravimetric Analysis
    journal, March 2019

    • Song, Eunhye; Kim, Daegi; Jeong, Cheol-Jin
    • Energies, Vol. 12, Issue 5
    • DOI: 10.3390/en12050836

    Performance Evaluation of a Chinese Lean Iron Ore as the Oxygen Carrier in Multi and Short-Time Redox Cycles
    journal, April 2018

    • Wang, Xudong; Wang, Xiaojia; Hu, Xiaoyu
    • Applied Sciences, Vol. 8, Issue 5
    • DOI: 10.3390/app8050682