Research Papers

Design of a Solar Reactor to Split CO2 Via Isothermal Redox Cycling of Ceria

[+] Author and Article Information
Roman Bader, Rohini Bala Chandran, Luke J. Venstrom, Stephen J. Sedler, Peter T. Krenzke, Robert M. De Smith

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

Aayan Banerjee

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

Thomas R. Chase

Department of Mechanical Engineering,
University of Minnesota,
Minneapolis, MN 55455
e-mail: trchase@umn.edu

Jane H. Davidson

Department of Mechanical Engineering,
University of Minnesota,
Minneapolis, MN 55455
e-mail: jhd@umn.edu

Wojciech Lipiński

Department of Mechanical Engineering,
University of Minnesota,
Minneapolis, MN 55455
e-mail: wojciech.lipinski@anu.edu.au

These assumptions are consistent with the experiments described in Section 3.2.

The higher heating value of CO is 283 kJ/mol.

1Present address: Research School of Engineering, The Australian National University, Canberra, ACT 2601, Australia.

2Present address: Mechanical Engineering Department, Valparaiso University, Valparaiso, IN 46383.

3Corresponding authors.

Contributed by the Solar Energy Division of ASME for publication in the JOURNAL OF SOLAR ENERGY ENGINEERING: INCLUDING WIND ENERGY AND BUILDING ENERGY CONSERVATION. Manuscript received April 23, 2014; final manuscript received October 20, 2014; published online December 23, 2014. Assoc. Editor: Prof. Nathan Siegel.

J. Sol. Energy Eng 137(3), 031007 (Jun 01, 2015) (10 pages) Paper No: SOL-14-1122; doi: 10.1115/1.4028917 History: Received April 23, 2014; Revised October 20, 2014; Online December 23, 2014

The design procedure for a 3 kWth prototype solar thermochemical reactor to implement isothermal redox cycling of ceria for CO2 splitting is presented. The reactor uses beds of mm-sized porous ceria particles contained in the annulus of concentric alumina tube assemblies that line the cylindrical wall of a solar cavity receiver. The porous particle beds provide high surface area for the heterogeneous reactions, rapid heat and mass transfer, and low pressure drop. Redox cycling is accomplished by alternating flows of inert sweep gas and CO2 through the bed. The gas flow rates and cycle step durations are selected by scaling the results from small-scale experiments. Thermal and thermo-mechanical models of the reactor and reactive element tubes are developed to predict the steady-state temperature and stress distributions for nominal operating conditions. The simulation results indicate that the target temperature of 1773 K will be reached in the prototype reactor and that the Mohr–Coulomb static factor of safety is above two everywhere in the tubes, indicating that thermo-mechanical stresses in the tubes remain acceptably low.

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Kodama, T., and Gokon, N., 2007, “Thermochemical Cycles for High-Temperature Solar Hydrogen Production,” Chem. Rev., 107(10), pp. 4048–4077. [CrossRef] [PubMed]
Romero, M., and Steinfeld, A., 2012, “Concentrating Solar Thermal Power and Thermochemical Fuels,” Energy Environ. Sci., 5(11), pp. 9234–9245. [CrossRef]
Nakamura, T., 1977, “Hydrogen Production From Water Utilizing Solar Heat at High Temperatures,” Sol. Energy, 19(5), pp. 467–475. [CrossRef]
Tamaura, Y., Kojima, M., Hasegawa, N., Tsuji, M., Ehrensberger, K., and Steinfeld, A., 1997, “Solar Energy Conversion Into H2 Energy Using Ferrites,” J. Phys. IV, 7(C1), pp. 673–674. [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]
Palumbo, R., Lédé, J., Boutin, O., Ricart, E. E., Steinfeld, A., Möller, S., Weidenkaff, A., Fletcher, E. A., and Bielicki, J., 1998, “The Production of Zn From ZnO in a High- Temperature Solar Decomposition Quench Process—I. The Scientific Framework for the Process,” Chem. Eng. Sci., 53(14), pp. 2503–2517. [CrossRef]
Hamed, T. A., Davidson, J. H., and Stolzenburg, M., 2008, “Hydrolysis of Evaporated Zn in a Hot Wall Flow Reactor,” ASME J. Sol. Energy Eng., 130(4), p. 041010. [CrossRef]
Hamed, T. A., Venstrom, L., Alshare, A., Brülhart, M., and Davidson, J. H., 2009, “Study of a Quench Device for the Synthesis and Hydrolysis of Zn Nanoparticles: Modeling and Experiments,” ASME J. Sol. Energy Eng., 131(3), p. 031018. [CrossRef]
Dombrovsky, L., Schunk, L., Lipiński, W., and Steinfeld, A., 2009, “An Ablation Model for the Thermal Decomposition of Porous Zinc Oxide Layer Heated by Concentrated Solar Radiation,” Int. J. Heat Mass Transf., 52(11–12), pp. 2444–2452. [CrossRef]
Schunk, L. O., Lipiński, W., and Steinfeld, A., 2009, “Heat Transfer Model of a Solar Receiver–Reactor for the Thermal Dissociation of ZnO—Experimental Validation at 10 kW and Scale-Up to 1 MW,” Chem. Eng. J., 150(2–3), pp. 502–508. [CrossRef]
Venstrom, L. J., and Davidson, J. H., 2013, “The Kinetics of the Heterogeneous Oxidation of Zinc Vapor by Carbon Dioxide,” Chem. Eng. Sci., 93, pp. 163–172. [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., 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]
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 Math. Phys. Eng. Sci., 368(1923), pp. 3269–3294. [CrossRef]
Venstrom, L. J., Petkovich, N., Rudisill, S., Stein, A., and Davidson, J. H., 2012, “The Effects of Morphology on the Oxidation of Ceria by Water and Carbon Dioxide,” ASME J. Sol. Energy Eng., 134(1), p. 011005. [CrossRef]
Rudisill, S. G., Venstrom, L. J., Petkovich, N. D., Quan, T., Hein, N., Boman, D. B., Davidson, J. H., and Stein, A., 2013, “Enhanced Oxidation Kinetics in Thermochemical Cycling of CeO2 Through Templated Porosity,” J. Phys. Chem. C, 117(4), pp. 1692–1700. [CrossRef]
Petkovich, N. D., Rudisill, S. G., Venstrom, L. J., Boman, D. B., Davidson, J. H., and Stein, A., 2011, “Control of Heterogeneity in Nanostructured Ce1–xZrxO2 Binary Oxides for Enhanced Thermal Stability and Water Splitting Activity,” J. Phys. Chem. C, 115(43), pp. 21022–21033. [CrossRef]
Scheffe, J. R., and Steinfeld, A., 2012, “Thermodynamic Analysis of Cerium-Based Oxides for Solar Thermochemical Fuel Production,” Energy Fuels, 26(3), pp. 1928–1936. [CrossRef]
Scheffe, J., Jacot, R., and Patzke, G., 2013, “Synthesis, Characterization and Thermochemical Redox Performance of Hf, Zr and Sc Doped Ceria for Splitting CO2,” J. Phys. Chem. C, 117(46), pp. 24104–24114. [CrossRef]
McDaniel, A. H., Miller, E. C., Arifin, D., Ambrosini, A., Coker, E. N., O'Hayre, R., Chueh, W. C., and Tong, J., 2013, “Sr- and Mn-Doped LaAlO3−δ for Solar Thermochemical H2 and CO Production,” Energy Environ. Sci., 6, pp. 2424–2428. [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]
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(3), 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]
Ermanoski, I., Siegel, N. P., and Stechel, E. B., 2013, “A New Reactor Concept for Efficient Solar-Thermochemical Fuel Production,” ASME J. Sol. Energy Eng., 135(3), p. 031002. [CrossRef]
Diver, R. B., Miller, J. E., Siegel, N. P., and Moss, T. A., 2010, “Testing of a CR5 Solar Thermochemical Heat Engine Prototype,” ASME Paper No. ES2010-90093. [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]
Bader, R., Venstrom, L. J., Davidson, J. H., and Lipiński, W., 2013, “Thermodynamic Analysis of Isothermal Redox Cycling of Ceria for Solar Fuel Production,” Energy Fuels, 27(9), pp. 5533–5544. [CrossRef]
Ermanoski, I., Miller, J. E., and Allendorf, M. D., 2014, “Efficiency Maximization in Solar-Thermochemical Fuel Production: Challenging the Concept of Isothermal Water Splitting,” Phys. Chem. Chem. Phys., pp. 8418–8427. [CrossRef]
Agrafiotis, C., Roeb, M., Konstandopoulos, A. G., Nalbandian, L., Zaspalis, V. T., Sattler, C., Stobbe, P., and Steele, A. M., 2005, “Solar Water Splitting for Hydrogen Production With Monolithic Reactors,” Sol. Energy, 79(4), pp. 409–421. [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. Sol. Energy Eng., 135(3), p. 031004. [CrossRef]
Lapp, J., and Lipiński, W., 2014, “Transient Three-Dimensional Heat Transfer Model of a Solar Thermochemical Reactor for H2O and CO2 Splitting via Non-Stoichiometric Ceria Redox Cycling,” ASME J. Sol. Energy Eng., 136(3), p. 031006. [CrossRef]
Lipiński, W., Davidson, J. H., and Chase, T. R., 2012, “Thermochemical Reactor Systems and Methods,” Patent No. WO2013119303 A2.
Lichty, P., Muhich, C., Arifin, D., Weimer, A. W., and Steinfeld, A., 2013, “Methods and Apparatus for Gas-Phase Reduction/Oxidation Processes,” U.S. patent application 20130266502 A1.
Banerjee, A., Bala Chandran, R., and Davidson, J. H., 2014, “Experimental Investigation of a Reticulated Porous Alumina Heat Exchanger for High Temperature Gas Heat Recovery,” Appl. Therm. Eng. (in press). [CrossRef]
Haussener, S., and Steinfeld, A., 2012, “Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation,” Materials (Basel), 5(1), pp. 192–209. [CrossRef]
Wade, A., 2010, “Natural Convection in Water-Saturated Metal Foam With a Superposed Fluid Layer,” M.S. thesis, University of Minnesota, Minneapolis, MN.
Ergun, S., and Orning, A. A., 1949, “Fluid Flow Through Randomly Packed Columns and Fluidized Beds,” Ind. Eng. Chem., 41(6), pp. 1179–1184. [CrossRef]
Chekhovskoy, V. Y., and Stavrovsky, G. I., 1969, “Thermal Conductivity of Cerium Dioxide,” Ninth Conference on Thermal Conductivity, Iowa State University, pp. 295–298.
Yaws, C., 2010, Transport Properties of Chemicals and Hydrocarbons, Knovel, New York.
Modest, M. F., 2003, “Approximate Solution Methods for One-Dimensional Media,” Radiative Heat Transfer, Academic Press, San Diego, CA, pp. 451–456. [CrossRef]
Oh, T.-S., Tokpanov, Y. S., Hao, Y., Jung, W., and Haile, S. M., 2012, “Determination of Optical and Microstructural Parameters of Ceria Films,” J. Appl. Phys., 112(10), p. 103535. [CrossRef]
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]
Petrasch, J., Wyss, P., and Steinfeld, A., 2007, “Tomography-Based Monte Carlo Determination of Radiative Properties of Reticulate Porous Ceramics,” J. Quant. Spectrosc. Radiat. Transf., 105(2), pp. 180–197. [CrossRef]
Van de Hulst, H. C., 2012, Light Scattering by Small Particles, Courier Dover Publications, New York.
Kamiuto, K., 1990, “Correlated Radiative Transfer in Packed-Sphere Systems,” J. Quant. Spectrosc. Radiat. Transf., 43(1), pp. 39–43. [CrossRef]
Venstrom, L. J., Smith, R. M. De, Hao, Y., Haile, S. M., and Davidson, J. H., 2014, “Efficient Splitting of CO2 in an Isothermal Redox Cycle Based on Ceria,” Energy Fuels, 28(4), pp. 2732–2742. [CrossRef]
Millot, F., and Mierry, P. D., 1985, “A New Method for the Study of Chemical Diffusion in Oxides With Application to Cerium Oxide CeO2−x,” J. Phys. Chem. Solids, 46(7), pp. 797–801. [CrossRef]
Hirsch, D., 2004, “Solar Hydrogen Production by Thermal Decomposition of Natural Gas Using a Vortex-Flow Reactor,” Int. J. Hydrogen Energy, 29(1), pp. 47–55. [CrossRef]
Charvin, P., Abanades, S., Neveu, P., Lemont, F., and Flamant, G., 2008, “Dynamic Modeling of a Volumetric Solar Reactor for Volatile Metal Oxide Reduction,” Chem. Eng. Res. Des., 86(11), pp. 1216–1222. [CrossRef]
Charvin, P., Abanades, S., Lemort, F., and Flamant, G., 2008, “Analysis of Solar Chemical Processes for Hydrogen Production From Water Splitting Thermochemical Cycles,” Energy Convers. Manag., 49(6), pp. 1547–1556. [CrossRef]
Bala Chandran, R., Banerjee, A., and Davidson, J. H., 2014, “Predicted Performance of a Ceramic Foam Gas Phase Heat Recuperator for a Solar Thermochemical Reactor,” ASME Paper No. ES2014-6413. [CrossRef]
Krueger, K. R., Davidson, J. H., and Lipiński, W., 2011, “Design of a New 45 kWe High-Flux Solar Simulator for High-Temperature Solar Thermal and Thermochemical Research,” ASME J. Sol. Energy Eng., 133(1), p. 011013. [CrossRef]
Krueger, K. R., Lipiński, W., and Davidson, J. H., 2013, “Operational Performance of the University of Minnesota 45 kWe High-Flux Solar Simulator,” ASME J. Sol. Energy Eng., 135(4), p. 044501. [CrossRef]
Alfano, G., 1972, “Apparent Thermal Emittance of Cylindrical Enclosures With and Without Diaphragms,” Int. J. Heat Mass Transf., 15(12), pp. 2671–2674. [CrossRef]
Häring, H. W., 2008, Industrial Gases Processing, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. [CrossRef]
Siegel, R., and Howell, J. R., 2002, Thermal Radiation Heat Transfer, Taylor & Francis, New York.
Kuehn, T. H., and Goldstein, R. J., 1976, “Correlating Equations for Natural Convection Heat Transfer Between Horizontal Circular Cylinders,” Int. J. Heat Mass Transf., 19(10), pp. 1127–1134. [CrossRef]
Leibfried, U., and Ortjohann, J., 1995, “Convective Heat Loss From Upward and Downward-Facing Cavity Solar Receivers: Measurements and Calculations,” ASME J. Sol. Energy Eng., 117(2), pp. 75–84. [CrossRef]
“Alumina Insulation Type ZAL-15 & ZAL-15AA.”
Churchill, S. W., and Chu, H. H. S., 1975, “Correlating Equations for Laminar and Turbulent Free Convection From a Horizontal Cylinder,” Int. J. Heat Mass Transf., 18(9), pp. 1049–1053. [CrossRef]
Churchill, S. W., and Chu, H. H. S., 1975, “Correlating Equations for Laminar and Turbulent Free Convection From a Vertical Plate,” Int. J. Heat Mass Transf., 18(11), pp. 1323–1329. [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]
Kaviany, M., 1995, Principles of Heat Transfer in Porous Media, Springer-Verlag, New York. [CrossRef]
Wakao, N., and Kaguei, S., 1982, Heat and Mass Transfer in Packed Beds, Gordon and Breach Science Publishers, New York.
Binnewies, M., and Milke, E., 2002, Thermochemical Data of Elements and Compounds, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. [CrossRef]
Lingart, Y. K., Petrov, V. A., and Tikhonova, N. A., 1983, “Optical Properties of Leucosapphire at High Temperatures. I. Translucent Region,” High Temp., 20(5), pp. 706–713.
Apetz, R., and Bruggen, M. P. B., 2003, “Transparent Alumina: A Light- Scattering Model,” J. Am. Ceram. Soc., 86(3), pp. 480–486. [CrossRef]
“AD-998 Alumina Material Properties.”
Patankar, S., 1980, Numerical Heat Transfer and Fluid Flow, Hemisphere Publishing Corporation, Washington.
ANSYS® Academic Research, 2011, Ansys Fluent Users Guide, Release 14.0, pp. 1715–1762.
ANSYS® Academic Research, 2011, Ansys Fluent User Defined Functions Guide, Release 14.0.
Juvinall, R. C., and Marshek, K. M., 2006, Fundamentals of Machine Component Design, John Wiley & Sons Inc., New York.
ANSYS® Academic Research, Release 14.0.
Munro, R. G., 1997, “Evaluated Material Properties for a Sintered α-Alumina,” J. Am. Ceram. Soc., 80(8), pp. 1919–1928. [CrossRef]


Grahic Jump Location
Fig. 1

Conceptual design of a solar reactor for isothermal redox cycling of ceria: (a) The reactor assembly consisting of the cavity, reactive elements, insulation and shell; and (b) an enlarged view of a single reactive element

Grahic Jump Location
Fig. 2

Comparison of pressure drop and heat transfer of the alternative ceria morphologies: (a) Pressure drop per unit length as a function of superficial mass flux and (b) overall thermal conductivity as a function of temperature

Grahic Jump Location
Fig. 3

Steady-state temperature distributions (in K) on the cavity wall and the outside surfaces of the reactive elements for the case with CO2 flowing through the reactive elements, as viewed from (a) aperture and (b) back (units of length: m)

Grahic Jump Location
Fig. 4

Steady-state temperature distributions (in K) in the reactive element, for the case of CO2 flowing through the reactive elements: (a) alumina tube walls and (b) gas phase

Grahic Jump Location
Fig. 5

Steady-state axial temperature distribution (in K) in the particle bed for CO2 flow through the reactive element (averaged radially and circumferentially)

Grahic Jump Location
Fig. 6

Cross section of the outer reactive element tube showing the distribution of the Mohr–Coulomb static factor of safety along the tube




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