Research Papers

Transient Three-Dimensional Heat Transfer Model of a Solar Thermochemical Reactor for H2O and CO2 Splitting Via Nonstoichiometric Ceria Redox Cycling

[+] Author and Article Information
Justin Lapp

Department of Mechanical Engineering,
University of Minnesota,
Minneapolis, MN 55455

Wojciech Lipiński

Research School of Engineering,
Australian National University,
Canberra, ACT 0200, Australia
e-mail: wojciech.lipinski@anu.edu.au

1Corresponding author.

Contributed by the Solar Energy Division of ASME for publication in the JOURNAL OF SOLAR ENERGY ENGINEERING. Manuscript received May 13, 2013; final manuscript received December 17, 2013; published online January 31, 2014. Assoc. Editor: Prof. Nesrin Ozalp.

J. Sol. Energy Eng 136(3), 031006 (Jan 31, 2014) (11 pages) Paper No: SOL-13-1133; doi: 10.1115/1.4026465 History: Received May 13, 2013; Revised December 17, 2013

A transient three-dimensional heat transfer model is developed for a 3 kWth solar thermochemical reactor for H2O and CO2 splitting via two-step nonstoichiometric ceria cycling. The reactor consists of a windowed solar receiver cavity, counter-rotating reactive and inert cylinders, and insulated reactor walls. The counter-rotating cylinders allow for continuous fuel production and heat recovery. The model is developed to solve energy conservation equations accounting for conduction, convection, and radiation heat transfer modes, and chemical reactions. Radiative heat transfer is analyzed using a combination of the Monte Carlo ray-tracing method, the net radiation method, and the Rosseland diffusion approximation. Steady-state temperatures, heat fluxes, and nonstoichiometry are reported. A temperature swing of up to 401 K, heat recovery effectiveness of up to 95%, and solar-to-fuel efficiency of up to 5% are predicted in parametric studies.

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Steinfeld, A., and Palumbo, R., 2001, “Solar Thermochemical Process Technology,” Encyclopedia of Physical Science & Technology, R. A.Meyers, ed., Academic, Burlington, VT, Vol. 15, pp. 237–256.
Kodama, T., 2003, “High-Temperature Solar Chemistry for Converting Solar Heat to Chemical Fuels,” Prog. Energy Combust. Sci., 29(6), pp. 567–597. [CrossRef]
Nakamura, T., 1977, “Hydrogen Production From Water Utilizing Solar Heat at High Temperatures,” Sol. Energy, 19(5), pp. 467–475. [CrossRef]
Diver, R. B., Miller, J. E., Allendorf, M. D., Siegel, N. P., and Hogan, R. E., 2008, “Solar Thermochemical Water-Splitting Ferrite-Cycle Heat Engines,” ASME J. Sol. Energy Eng., 130(4), p. 041001. [CrossRef]
Miller, J. E., Allendorf, M. D., Diver, R. B., Evans, L. R., Siegel, N. P., and StueckerJ. N., 2008, “Metal Oxide Composites and Structures for Ultra-High Temperature Solar Thermochemical Cycles,” J. Mater. Sci., 43(14), pp. 4714–4728. [CrossRef]
Kodama, T., Nakamuro, Y., and Mizuno, T., 2006, “A Two-Step Thermochemical Water Splitting by Iron-Oxide on Stabilized Zirconia,” ASME J. Sol. Energy Eng., 128(1), pp. 3–7. [CrossRef]
Abanades, S., and Flamant, G., 2006, “Thermochemical Hydrogen Production From a Two-Step Solar-Driven Water-Splitting Cycle Based on Cerium Oxides,” Sol. Energy, 80(12), pp. 1611–1623. [CrossRef]
Chueh, W. C., and Haile, S. M., 2010, “A Thermochemical Study of Ceria: Exploiting an Old Material for New Modes of Energy Conversion and CO2 Mitigation,” Philos. Trans. R. Soc., A, 368(1923), pp. 3269–3294. [CrossRef]
Abanades, S., Legal, A., Cordier, A., Peraudeau, G., Flamant, G., and Julbe, A., 2010, “Investigation of Reactive Cerium-Based Oxides for H2 Production by Thermochemical Two-Step Water-Splitting,” J. Mater. Sci., 45(15), pp. 4163–4173. [CrossRef]
Chueh, W. C., Falter, C., Abbott, M., Scipio, D., Furler, P., Haile, S. M., and Steinfeld, A., 2010, “High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria,” Science, 330(6012), pp. 1797–1801. [CrossRef] [PubMed]
Kaneko, H., Miura, T., Fuse, A., Ishihara, H., Taku, S., Fukuzumi, H., Naganuma, Y., and Tamaura, Y., 2007, “Rotary-Type Solar Reactor for Solar Hydrogen Production With Two-Step Water Splitting Process,” Energy Fuels, 21(4), pp. 2287–2293. [CrossRef]
Venstrom, L. J., Petkovich, N., Rudisill, S., Stein, A., and Davidson, J. H., 2011, “The Effect of Morphology on the Oxidation of Ceria by Water and Carbon Dioxide,” ASME J. Solar Energy Eng., 134(1), p. 011005. [CrossRef]
Chueh, W. C., and Haile, S. M., 2009, “Ceria as a Thermochemical Reaction Medium for Selectively Generating Syngas or Methane From H2O and CO2,” ChemSusChem, 2(8), pp. 735–739. [CrossRef] [PubMed]
Petkovich, N. D., Rudisill, S. G., Venstrom, L. J., Boman, D. B., Davidson, J. H., and Stein, A., 2011, “Control of Heterogeneity in Nanostructured Ce1xZrxO2 Binary Oxides for Enhanced Thermal Stability and Water Splitting Activity,” J. Phys. Chem. C, 115(43), pp. 21022–21033. [CrossRef]
Kaneko, H., Taku, S., and Tamaura, Y., 2011, “Reduction Reactivity of CeO2–ZrO2 Oxide Under High O2 Partial Pressure in Two-Step Water Splitting Process,” Sol. Energy, 85(9), pp. 2321–2330. [CrossRef]
Panlener, R. J., Blumenthal, R. N., and Garnier, J. E., 1975, “A Thermodynamic Study of Nonstoichiometric Cerium Dioxide,” J. Phys. Chem. Solids, 36(11), pp. 1213–1222. [CrossRef]
Furler, P., Scheffe, J. R., and Steinfeld, A., 2012, “Syngas Production by Simultaneous Splitting of H2O and CO2 Via Ceria Redox Reactions in a High-Temperature Solar Reactor,” Energy Environ. Sci., 5, pp. 6098–6103. [CrossRef]
Furler, P., Scheffe, J., Gorbar, M., Moes, L., Vogt, U., and Steinfeld, A., 2012, “Solar Thermochemical CO2 Splitting Utilizing a Reticulated Porous Ceria Redox System,” Energy Fuels, 26(11), pp. 7051–7059. [CrossRef]
Roeb, M., Säck, J.-P., Rietbrock, P., Prahl, C., Schreiber, H., Neises, M., de Oliveira, L., Graf, D., Ebert, M., Reinalter, W., Meyer-Grünefeldt, M., Sattler, C., Lopez, A., Vidal, A., Elsberg, A., Stobbe, P., Jones, D., Steele, A., Lorentzou, S., Pagkoura, C., Zygogianni, A., Agrafiotis, C., and Konstandopoulos, A. G., 2011, “Test Operation of a 100 kW Pilot Plant for Solar Hydrogen Production From Water on a Solar Tower,” Sol. Energy, 85(4), pp. 634–644. [CrossRef]
Chen, K. S., and Hogan, R. E., 2009, “A Two-Phase Model for Solar Thermochemical Water Splitting with FeO/Fe3O4,” ASME 2009 International Conference of Energy Sustainability (ES2009), San Francisco, CA, July 19–23, ASME Paper No. ES2009-90228. [CrossRef]
James, D. L., Siegel, N. P., Diver, R. B., Boughton, B. D., and Hogan, R. E., 2006, “Numerical Modeling of Solar Thermo-Chemical Water-Splitting Reactor,” ASME International Solar Energy Conference (ISEC2006), Denver, CO, July 8–13, ASME Paper No. ISEC2006-99141. [CrossRef]
Chen, K. S., and Hogan, R. E., “Modeling Solar Thermochemical Splitting of CO2 Using Metal Oxide and a CR5,” ASME 2010 International Conference of Energy Sustainability (ES2010), Phoenix, AZ, May 17–20, ASME Paper No. ES2010-90436. [CrossRef]
Hogan, R. E., Miller, J. E., James, D. L., Chen, K. S., and Diver, R. B., 2012, “Modeling Chemical and Thermal States of Reactive Metal Oxides in a CR5 Solar Thermochemical Heat Engine,” ASME 2012 International Conference on Energy Sustainability (ES2012), San Diego, CA, July 23–26, ASME Paper No. ES2012-91490. [CrossRef]
Lapp, J., Davidson, J. H., and Lipiński, W., 2012, “Efficiency of Two-Step Solar Thermochemical Non-Stoichiometric Redox Cycles With Heat Recovery,” Energy, 37(1), pp. 591–600. [CrossRef]
Lapp, J., Davidson, J. H., and Lipiński, W., 2013, “Heat Transfer Analysis of a Solid-Solid Heat Recuperation System for Solar-Driven Nonstoichiometric Redox Cycles,” ASME J. Solar Energy Eng., 135(3), p. 031004. [CrossRef]
Liang, Z., Chueh, W. C., Ganesan, K., Haile, S. M., and Lipiński, W., 2011, “Experimental Determination of Transmittance of Porous Cerium Dioxide Media in the Spectral Range of 300–1100 nm,” Exp. Heat Transfer, 24(4), pp. 285–299. [CrossRef]
Chekhovskoy, V., and Stavrovsky, G., 1970, “Thermal Conductivity of Cerium Dioxide,” 9th Conference on Thermal Conductivity, Ames, IA, October 6–8, 1969, pp. 295–298.
Binnewies, M., and Milke, E., 1999, Thermochemical Data of Elements and Compounds, Wiley, New York.
Touloukian, Y. S., 1967, Thermophysical Properties of High Temperature Solid Materials, Vol. 4, Macmillan, New York, pp. 8–47.
Chase, M. W., 1998, NIST-JANAF Thermochemical Tables, Parts 1 and 2, 4th ed., J. Phys. Chem. Ref. Data, Monograph No. 9, American Institute of Physics, Woodbury, NY.
Zircar Ceramics Inc., 2001, “Rigid Alumina Products,” from http://www.zircarceramics.com/pages/rigidmaterials/aluminaproducts.htm
Ganesan, K., and Lipiński, W., 2011, “Experimental Determination of Spectral Transmittance of Porous Cerium Dioxide in the Range 900–1700 nm,” ASME J. Heat Transfer, 133(10), p. 104501. [CrossRef]
Ganesan, K., Dombrovsky, L. A., and Lipiński, W., 2013, “Visible and Near-Infrared Optical Properties of Ceria Ceramics,” Infrared Phys. Technol., 57, pp. 101–109. [CrossRef]
Sarou-Kanian, V., Rifflet, J. C., and Millot, F., 2005, “IR Radiative Properties of Solid and Liquid Alumina: Effects of Temperature and Gaseous Environment,” Int. J. Thermophys., 26(4), pp. 1263–1275. [CrossRef]
Rosseland, S., 1936, Theoretical Astrophysics; Atomic Theory and the Analysis of Stellar Atmospheres and Envelopes, Clarendon, Oxford, UK.
Modest, M. F., 2013, Radiative Heat Transfer, 3rd ed., Academic, San Diego.
Dombrovsky, L. A., 2012, “The Use of Transport Approximation and Diffusion-Based Models in Radiative Transfer Calculations,” Comput. Therm. Sci., 4, pp. 297–315. [CrossRef]
Bohren, C. F., and Huffman, D. R., 1983, Absorption and Scattering of Light by Small Particles, John Wiley & Sons, New York.
Marabelli, F., and Wachter, P., 1987, “Covalent Insulator CeO2: Optical Reflectivity Measurements,” Phys. Rev. B, 36(2), pp. 1238–1243. [CrossRef]
Dombrovsky, L. A., Ganesan, K., and Lipiński, W., 2012, “Combined Two-Flux Approximation and Monte Carlo Model for Identification of Radiative Properties of Highly Scattering Dispersed Materials,” Comput. Therm. Sci., 4(4), pp. 365–378. [CrossRef]


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Fig. 2

Schematic of the computational domain: (a) horizontal cross section, and (b) vertical cross section. See the description of the subdomains AF in the text.

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Fig. 1

Schematic of solar thermochemical reactor realizing a nonstoichiometric ceria based redox cycle with solid–solid heat recovery [25]

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Fig. 3

A sample cell of the structured cylindrical grid for the ceria and inert cylinders: (a) r–θ and (b) r–z cross sections

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Fig. 8

Temperature profiles along the reactor cavity wall measured from the aperture plane (x = 0) at selected circumferential positions φ for the baseline simulation case. φ = 0 corresponds to the angular location nearest to where the ceria cylinder enters the cavity.

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Fig. 9

Outward net heat flux at the inner surface of the ceria cylinder as a function of the circumferential angle θ for the baseline simulation case: axially-averaged heat flux (solid line), heat flux at z = 0 (dashed line), and z = ± LD/2 (dotted line)

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Fig. 15

Effect of cylinder angular velocity on (a) heat recovery effectiveness and (b) maximum and minimum material-averaged temperatures

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Fig. 4

r–θ temperature distribution in the rotating cylinders at z = 0 for the baseline simulation case. The cavity-receiver is on the left-hand side of the plot, consistent with the arrangement shown in Fig. 2. The radial coordinate has been distorted by a ratio of 5:1.

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Fig. 5

Material-average temperatures of the ceria (dashed line) and inert (solid line) cylinders as a function of the circumferential angle θ for the baseline simulation case. The directions of rotation are indicated by the arrows.

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Fig. 6

Circumferential temperature variations of the ceria cylinder at selected radial (1: r = r3, 2: r = (r3 + r4)/2, and 3: r = r4) and axial (solid lines: z = 0, dashed lines: z = ± LD/2) locations for the baseline simulation case

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Fig. 7

Temperature distribution on the surface of the ceria cylinder as seen from the cavity aperture for the baseline simulation case

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Fig. 10

r–θ distribution of nonstoichiometry δ in the ceria cylinder at z = 0 for the baseline simulation case. The radial coordinate has been distorted by a ratio of 5.

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Fig. 11

Material-average value of δ as a function of the circumferential position for the baseline simulation case

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Fig. 12

r–θ distribution of temperature in the rotating cylinders at z = 0 for the case with increased thermal conductivity. The radial coordinate has been distorted by a ratio of 5.

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Fig. 13

r–θ distribution of nonstoichiometry δ in the ceria cylinder at z = 0 for the case of increased thermal conductivity. The radial coordinate has been distorted by a ratio of 5.

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Fig. 14

Effect of cylinder wall thickness on (a) heat recovery effectiveness and (b) maximum and minimum material-average temperatures



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