Research Papers

A New Reactor Concept for Efficient Solar-Thermochemical Fuel Production

[+] Author and Article Information
Ivan Ermanoski

Sandia National Laboratories,
Albuquerque, NM 87185-1415
e-mail: iermano@sandia.gov

Nathan P. Siegel

Mechanical Engineering Department,
Bucknell University,
Lewisburg, PA 17837
e-mail: nate.siegel@bucknell.edu

Ellen B. Stechel

Arizona State University,
Tempe, AZ 85287
e-mail: Ellen.Stechel@asu.edu

Contributed by the Solar Energy Division of ASME for publication in the Journal of Solar Energy Engineering. Manuscript received March 16, 2012; final manuscript received December 23, 2012; published online February 8, 2013. Assoc. Editor: Wojciech Lipinski.

J. Sol. Energy Eng 135(3), 031002 (Feb 08, 2013) (10 pages) Paper No: SOL-12-1073; doi: 10.1115/1.4023356 History: Received March 16, 2012; Revised December 23, 2012

We describe and analyze the efficiency of a new solar-thermochemical reactor concept, which employs a moving packed bed of reactive particles produce of H2 or CO from solar energy and H2O or CO2. The packed bed reactor incorporates several features essential to achieving high efficiency: spatial separation of pressures, temperature, and reaction products in the reactor; solid–solid sensible heat recovery between reaction steps; continuous on-sun operation; and direct solar illumination of the working material. Our efficiency analysis includes material thermodynamics and a detailed accounting of energy losses, and demonstrates that vacuum pumping, made possible by the innovative pressure separation approach in our reactor, has a decisive efficiency advantage over inert gas sweeping. We show that in a fully developed system, using CeO2 as a reactive material, the conversion efficiency of solar energy into H2 and CO at the design point can exceed 30%. The reactor operational flexibility makes it suitable for a wide range of operating conditions, allowing for high efficiency on an annual average basis. The mixture of H2 and CO, known as synthesis gas, is not only usable as a fuel but is also a universal starting point for the production of synthetic fuels compatible with the existing energy infrastructure. This would make it possible to replace petroleum derivatives used in transportation in the U.S., by using less than 0.7% of the U.S. land area, a roughly two orders of magnitude improvement over mature biofuel approaches. In addition, the packed bed reactor design is flexible and can be adapted to new, better performing reactive materials.

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Repice, R., 2011, “Annual Energy Review 2010,” DOE/EIA-0384(2010), U.S. Energy Information Administration, Washington, DC.
Shapouri, H., Gallagher, P. W., Nefstead, W., Schwartz, R., Noe, S., and Conway, R., 2010, “2008 Energy Balance for the Corn-Ethanol Industry,” Agricultural Economic Report Number 846, United States Department of Agriculture, Washington, DC.
Fletcher, E. A., and Moen, R. L., 1977, “Hydrogen and Oxygen From Water,” Science, 197(4308), pp. 1050–1056. [CrossRef] [PubMed]
Nakamura, T., 1977, “Hydrogen Production From Water Utilizing Solar Heat at High Temperatures,” Sol. Energy, 19(5), pp. 467–475. [CrossRef]
Galvez, M. E., Loutzenhiser, P. G., Hischier, I., and Steinfeld, A., 2008, “CO2 Splitting via Two-Step Solar Thermochemical Cycles With Zn/ZnO and FeO/Fe3O4 Redox Reactions: Thermodynamic Analysis,” Energy Fuels, 22(5), pp. 3544–3550. [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]
Henao, C. A., Maravelias, C. T., Miller, J. E., and Kemp, R. A., 2010, “Foundations of Computer-Aided Process Design,” Synthetic Production of Methanol Using Solar Power, CRC Press, Boca Raton, FL.
Kim, J., Henao, C. A., Johnson, T. A., Dedrick, D. E., Miller, J. E., Stechel, E. B., and Maravelias, C. T., 2011, “Methanol Production From CO2 Using Solar-Thermal Energy: Process Development and Techno-Economic Analysis,” Energy Environ. Sci., 4(9), pp. 3122–3132. [CrossRef]
Pohl, P. I., Brown, L. C., Chen, Y., Diver, R. B., Besenbruch, G. E., Earl, B. L., Jones, S. A., and Perret, R. F., 2004, “Evaluation of Solar Thermo-Chemical Reactions for Hydrogen Production,” 12th International Symposium on Solar Power and Chemical Energy Systems, Oaxaca, Mexico, October 6–8.
Kolb, G. J., and Diver, R. B., 2008, “Screening Analysis of Solar Thermochemical Hydrogen Concepts,” Sandia Report No. SAND2008-1900, Sandia National Laboratories, Albuquerque, NM.
Funk, J. E., and Reinstrom, R. M., 1966, “Energy Requirements in the Production of Hydrogen From Water,” Ind. Eng. Chem. Process Des., 5(3), pp. 336–342. [CrossRef]
O'Keefe, D., Allen, C., Besenbruch, G., Brown, L. C., Norman, J., and Sharp, R., 1982, “Preliminary Results From Bench-Scale Testing of a Sulfur-Iodine Thermochemical Water-Splitting Cycle,” Int. J. Hydrogen Energy, 7(5), pp. 381–392. [CrossRef]
Steinfeld, A., 2002, “Solar Hydrogen Production Via a Two-Step Water-Splitting Thermochemical Cycle Based on Zn/ZnO Redox Reactions,” Int. J. Hydrogen Energy, 27(6), pp. 611–619. [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]
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]
Gokon, N., Takahashi, S., Yamamoto, H., and Kodama, T., 2008, “Thermochemical Two-Step Water-Splitting Reactor With Internally Circulating Fluidized Bed for Thermal Reduction of Ferrite Particles,” Int. J. Hydrogen Energy, 33(9), pp. 2189–2199. [CrossRef]
Chueh, W. C., Falter, C., Abbot, M., Scipio, D., Furler, P., Haile, S., and Steinfeld, A., 2010, “High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria,” Science, 330(6012), pp. 1797–1800. [CrossRef] [PubMed]
Wentorf, R. H., and Hanneman, R. E., 1974, “Thermochemical Hydrogen Generation,” Science, 185(4148), pp. 311–319. [CrossRef] [PubMed]
Abraham, B. M., and Schreiner, F., 1974, “General Principles Underlying Chemical Cycles Which Thermally Decompose Water into the Elements,” Ind. Eng. Chem. Fundam., 13(4), pp. 305–310. [CrossRef]
Fletcher, E. A., 2001, “Solarthermal Processing: A Review,” ASME J. Sol. Energy Eng., 123(2), pp. 63–74. [CrossRef]
Siegel, N. P., Diver, R. B., and Miller, J. E., 2009, “Reactive Structures for Two-Step Thermochemical Cycles Based on Non-Volatile Metal Oxides,” ASME 2009 3rd International Conference on Energy Sustainability, San Francisco, CA, June 19–23, Vol. 2, pp. 431–437. [CrossRef]
Diver, R. B., Miller, J. E., and Siegel, N. P., 2010, “Testing of a CR5 Solar Thermochemical Heat Engine Prototype,” ASME 2010 4th International Conference on Energy Sustainability, Phoenix, AZ, May 17–22, Vol. 2, pp. 97–104. [CrossRef]
Miller, J. E., Diver, R. B., Siegel, N. P., Coker, E. N., Ambrosini, A., Rodriguez, M. A., Garino, T. J., Dedrick, D. E., Johnson, T. A., Allendorf, M. D., McDaniel, A. H., Kellogg, G. L., Ermanoski, I., Hogan, R. E., Chen, K. S., and Stechel, E. B., 2011, “Energy Technology 2010: Conservation, Greenhouse Gas Reduction and Management, Alternative Energy Sources,” Sunshine to Petrol: Solar Thermochemistry for Liquid Fuels, Wiley, New York.
Miller, J. E., Allendorf, M. D., Ambrosini, A., Coker, E. N., Diver, R. B., Ermanoski, I., Evans, L. R., Hogan, R. E., and McDaniel, A., 2012, “Development and Assessment of Solar-Thermal-Activated Fuel Production: Phase 1 Summary,” Report No. SAND2012-5658, Sandia National Laboratories, Albuquerque, NM.
Olds Elevator, Nov. 18, 2011, http://www.oldselevator.com/
Miller, J. E., Allendorf, M. D., Diver, R. B., Evans, L. R., Siegel, N. P., and Stuecker, J. N., 2008, “Metal Oxide Composites and Structures for Ultra-High Temperature Solar Thermochemical Cycles,” J. Mater. Sci., 43(14), pp. 4714–4728. [CrossRef]
Steinfeld, A., Sanders, S., and Palumbo, R., 1999, “Design Aspects of Solar Thermochemical Engineering—A Case Study: Two-Step Water-Splitting Cycle Using the Fe3O4/FeO Redox System,” Sol. Energy, 65(1), pp. 43–53. [CrossRef]
Lapp, J., Davidson, J. H., and Lipinski, W., 2012, “Efficiency of Two-Step Solar Thermochemical Non-Stoichiometric Redox Cycles With Heat Recovery,” Energy, 37(1), pp. 591–600. [CrossRef]
Kodama, T., Enomoto, S.-I., Hatamachi, T., and Gokon, N., 2008, “Application of and Internally Circulating Fluidized Bed for Windowed Solar Chemical Reactor With Direct Irradiation of Reacting Particles,” ASME J. Sol. Energy Eng., 130(1), p. 014504. [CrossRef]
Darcy, H., 1856, Les Fontaines Publiques de la Ville de Dijon, Libraire des Corps Impériaux des Ponts et Chausées et des Mines, Paris.
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]
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]
McDaniel, A., and Chueh, W. C., 2011, personal communication.
Coker, E. N., Ambrosini, A., Rodriguez, M. A., and Miller, J. E., 2011, “Ferrite-YSZ Composites for Solar Thermochemical Production of Synthetic Fuels: In Operando Characterization of CO2 Reduction,” J. Mater. Chem., 21(29), pp. 10767–10776. [CrossRef]
Ricken, M., Nölting, J., and Riess, I., 1984, “Specific Heat and Phase Diagram of Nonstoichiometric Ceria (CeO2-x),” J. Solid State Chem., 54(1), pp. 89–99. [CrossRef]
Ivy, J., 2004, “Summary of Electrolytic Hydrogen Production,” NREL Report No. NREL/MP-560-36734, National Renewable Energy Laboratory, Golden, CO.
Dincer, I., 2002, “Technical, Environmental and Exergetic Aspects of Hydrogen Energy Systems,” Int. J. Hydrogen Energy, 27(3), pp. 265–285. [CrossRef]
Mancini, T., Heller, P., Butler, B., Osborn, B., Schiel, W., Goldberg, V., Buck, R., Diver, R. B., Andraka, C., and Moreno, J., 2003, “Dish-Stirling Systems: An Overview of Development and Status,” ASME J. Sol. Energy Eng., 125(2), pp. 135–151. [CrossRef]
Arifin, D., Aston, V. J., Liang, X., McDaniel, A., and Weimer, A. W., 2012, “CoFe2O4 on a Porous Al2O3 Nanostructure for Solar Thermochemical CO2 Splitting,” Energy Environ. Sci., 5, pp. 9438–9443. [CrossRef]
Häring, H.-W., and Ahner, C., 2008, Industrial Gas Processing, Wiley-VCH, New York.
Zinkevich, M., Djurovic, D., and Aldinger, F., 2006, “Thermodynamic Modelling of the Cerium-Oxygen System,” Solid State Ionics, 177(11–12), pp. 989–1001. [CrossRef]
Zhou, G., Sarah, P. R., kim, T., Fornasiero, P., and Gorte, R. J., 2007, “Oxidation Entropies and Enthalpies of Ceria-Zirconia Solid Solutions,” Catal. Today, 123(1–4), pp. 86–93. [CrossRef]
Stine, W. B., and Geyer, M., 2001, Power From the Sun, http://www.powerfromthesun.net/book.html
Schell, S., 2011, “Design and Evaluation of Esolar's Heliostat Fields,” Sol. Energy, 85(4), pp. 614–619. [CrossRef]


Grahic Jump Location
Fig. 1

Schematic drawing of the moving packed particle bed reactor. TR—thermal reduction chamber, FP—fuel production chamber. The packed bed of particles fills the entire reactor, but is only shown selectively, to preserve the clarity of the schematics.

Grahic Jump Location
Fig. 2

Isothermal log δ versus log pO2 plot for nonstoichiometric CeO2. Reprinted from Ref. [33] with permission from Elsevier.

Grahic Jump Location
Fig. 3

Solar efficiency (η) of the packed bed reactor based on the CeO2 water splitting cycle. The four solid curves represent solar efficiencies (left Y-axis) for four values of recuperator effectiveness. The dashed curve (right Y-axis) shows the reduction extent (δ) of CeO2-δ at the design temperature.

Grahic Jump Location
Fig. 4

Thermochemical efficiency (ηTC) of the packed bed reactor based on the CeO2 water splitting cycle. The legend is as in Fig. 3.

Grahic Jump Location
Fig. 5

Heat loads for the packed bed reactor for εR = 0. The largest heat loads, (a) and (b), require direct solar input, whereas (c) and (d) are met by use of waste heat. The HHV of the output H2 stream is also shown (H). Inset: normalized contributions to waste heat as function of pO2.

Grahic Jump Location
Fig. 6

Required O2 pumping speeds as a function of pO2 in the thermal reduction chamber of a vacuum-pumped packed bed reactor, for four values of recuperator effectiveness

Grahic Jump Location
Fig. 7

Thermochemical efficiency (ηTC) of a packed bed reactor based on the CeO2 water splitting cycle, with N2 sweeping of the thermal reduction chamber




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