Research Papers: Fuel Combustion

Reactivity of Iron/Zirconia Powder in Fluidized Bed Thermochemical Hydrogen Production Reactors

[+] Author and Article Information
F. Al-Raqom

Department of Mechanical and
Aerospace Engineering,
University of Florida,
Gainesville, FL 32611
e-mail: fragom@ufl.edu

J. F. Klausner

Department of Mechanical and
Aerospace Engineering,
University of Florida,
Gainesville, FL 32611
e-mail: klaus@ufl.edu

1Corresponding author.

Contributed by the Advanced Energy Systems Division of ASME for publication in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received August 23, 2012; final manuscript received April 3, 2013; published online September 12, 2013. Assoc. Editor: Mansour Zenouzi.

J. Energy Resour. Technol 136(1), 012201 (Sep 12, 2013) (8 pages) Paper No: JERT-12-1192; doi: 10.1115/1.4024856 History: Received August 23, 2012; Revised April 03, 2013

A fluidized bed reactor has been developed which uses a two-step thermochemical water splitting process with a peak hydrogen production rate of 47 Ncm3/min.gFe at an oxidation temperature of 850 °C. Of particular interest, is that a mixture of iron and zirconia powder is fluidized during the oxidation reaction using a steam mass flux of 58 g/min-cm2. The zirconia powder serves to virtually eliminate iron powder sintering while maintaining a high reaction rate. The iron/zirconia powder is mixed in a ratio of 1:2 by apparent volume and has a mass ratio of 1:1. Both iron and zirconia particles are sieved to sizes ranging from 125 μm to 355 μm. The efficacy of zirconia as a sintering inhibitor was found to be dependent on the iron and zirconia mean particle size, particle size distribution and iron/zirconia apparent volume ratio. At 650 °C, the oxidation of iron powder with a mean particle size of 100 μm and a wide particle size distribution (40–250 μm) mixed with 44 μm zirconia powder with an iron/zirconia apparent volume ratio of 1:1 results in 75–90% sintering. In all cases, when iron is mixed with zirconia, the hydrogen production rate is not affected when compared with the pure iron case assuming an equivalent mass of iron is in the mixture. When iron powder is mixed with zirconia, both with a narrow particle size distribution (125–355 μm), the first oxidation step results in 3–7% sintering when the reactions are carried out at temperatures ranging between 840 and 895 °C. The hydrogen fractional yield is high (94–97%). For subsequent redox reactions, the macroscopic sintering is totally eliminated at 867 and 895 °C, although the hydrogen fractional yield decreases to 27 and 33%, respectively. It is demonstrated that mixing iron with zirconia in an equivalent mass ratio and similar particle size range can eliminate macroscopic sintering in a fluidized bed reactor at elevated temperatures up to 895 °C.

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Lubis, L. L., Dincer, I., and Rosen, M. A., 2010, “Life Cycle Assessment of Hydrogen Production Using Nuclear Energy: An Application Based on Thermochemical Water Splitting,” ASME J. Energy Resour. Technol., 132, p. 021004. [CrossRef]
Aceves, S. M., and Berry, G., 2005, “The Case for Hydrogen in a Carbon Constrained World,” ASME J. Energy Resour. Technol., 127, pp. 89–94. [CrossRef]
Shahid, M., Bidin, N., Mat, Y., and Inayatullah, M., 2012, “Production and Enhancement of Hydrogen From Water: A Review,” ASME J. Energy Resour. Technol., 134, p. 034002. [CrossRef]
Funk, J., 1976, “Thermochemical Process for the Production of Hydrogen From Water,” NASA-Lewis, Technical Report Grant No NGR 18-001-086.
Nakamura, T., 1976, “Hydrogen Production From Water Utilizing Solar Heat at High Temperatures,” Sol. Energy, 19, pp. 467–475. [CrossRef]
Hong, H., Liu, Q., and Jin, H., 2009, “Solar Hydrogen Production Integrating Low-Grade Solar Thermal Energy and Methanol Steam Reforming,” ASME J. Energy Resour. Technol., 131, p. 012601. [CrossRef]
Funk, J., and Reinstrom, R., 1966, “Energy Requirements in the Production of Hydrogen Water,” I&EC Process Des. Dev., 5, pp. 336–342. [CrossRef]
Vishnevetsky, I., Berman, A., and Epstein, M., 2011, “Features of Solar Thermochemical Redox Cycles for Hydrogen Production From Water as a Function of Reactants' Main Characteristics,” Int. J. Hydrogen Energy, 36, pp. 2817–2830. [CrossRef]
Charvin, P., Abanades, S., Flamant, G., and Lemort, F., 2007, “Two-Step Water Splitting Thermochemical Cycle Based on Iron Oxide Redox Pair for Solar Hydrogen Production,” Energy, 32, pp. 1124–1133. [CrossRef]
Steinfeld, A., Sanders, S., and Plumbo, 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, pp. 43–53. [CrossRef]
Aoki, H., Kaneko, H., Hasegawa, N., Ishihara, H., Suzuki, A., and Tamaura, Y., 2004, “The ZnFe2O4/(ZnO+Fe3O4) System for H2 Production Using Concentrated Solar Energy,” Solid State Ionics, 192, pp. 113–116. [CrossRef]
Steinfeld, A., 2002, “Solar Hydrogen Production via a Two-Step Water Splitting Thermochemical Cycle Based on Zn/Zno Redox Reaction,” Int. J. Hydrogen Energy, 27, pp. 611–619. [CrossRef]
Kodama, T., Kondoh, Y., Yamamoto, R., Andou, H., and Satou, N., 2005, “Thermochemical Hydrogen-Production by a Redox System of ZrO2-Supported Co(II)-Ferrite,” Sol. Energy, 78, pp. 623–631. [CrossRef]
Ehrensberger, K., Frei, A., Kuhn, P., Oswald, H. R., and Hug, P., 1995, “Comparative Experimental Investigations of the Water Splitting Reaction With Iron Oxide Fe1-yO and Iron Manganese Oxide (Fe1-xMnx)1-yO,” Solid State Ionics, 78, pp. 151–160. [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, pp. 4163–4173. [CrossRef]
Singh, A., Al-Raqom, F., Klausner, J., and Petrasch, J., 2011, “Hydrogen Production via the Iron/Iron Oxide Looping Cycle,” Proceedings of ASME 2011 5th International Conference on Energy Sustainability and 9th Fuel Cell Science, Engineering and Technology Conference ESFuelCell, Washington, DC, Aug. 7–10.
Kunii, D., and Levenspiel, O., 1968, Fluidization Engineering, Wiley, New York.
Clavenna, R., Davis, S. M., Fiato, R. A., and Say, G. R., 1995, “Particulate Solids for Catalyst Supports and Heat Transfer Materials,” U.S. Patent No. 5,476,877.
Reddy, K., Kannan, P., Al Shoaibi, A., and Srinivasakannan, C., 2012, “Thermal Pyrolysis of Polyethelene in Fluidized Beds: Review of the Influence on Product Distribution,” ASME J. Energy Resour. Technol., 134, p. 034001. [CrossRef]
Al-Raqom, F., Klausner, J. F., Hahn, D., Petrsach, J., and Sherif, S. A., 2011, “High Temperature Fluidized Bed Reactor Kinetics With Sintering Inhibitors for Iron Oxidation,” Proceedings of ASME 2011 International Mechanical Engineering Congress and Exposition (IMCE), Denver, CO, Nov. 11–17.
Gokon, N., Mizuno, T., Nakamuro, Y., and Kodama, T., 2008,“Iron-Containing Yttria-Stabilized Zirconia System for Two-Step Thermochemical Water Splitting,” ASME J. Solar Energy Eng., 130, p. 011018. [CrossRef]
Urasaki, K., Sekine, Y., Tanimoto, N., Tamura, E., Kikuchi, E., and Matsukata, M., 2005, “Effect of a Small Amount of Zirconia Additive on the Activity and Stability of Iron Oxide During Repeated Redox Cycles,” Chem. Lett., 34(2), pp. 230–231. [CrossRef]
“T Type Process Air Heater Manual,” Omega Engineering Inc., Last accessed Feb. 8, 2012, http://www.omega.com/Heaters/pdf/AHP_SERIES.pdf
“Ancor MH-100 Specification Sheet,” Hoeganaes Corporation, Last accessed: Feb. 8, 2012, http://www.hoeganaes.com/Product%20Datasheets/DataSheets%20Jan2001/ANCOR%20MH-100-1.pdf
“Product Data Sheet,” Z-TECH, Last accessed: Feb. 8, 2012, http://www.z-techzirconia.com/pdf/product_data_sheets/CF-Extra.pdf
German, R., 1996, Sintering Theory and Practice, John Wiley & Sons, New York.


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Fig. 1

Flow diagram of hydrogen production facility

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Fig. 2

Variation of hydrogen yield per mass of material (Fe) during the oxidation step

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Fig. 3

Hydrogen production rate per mass of reactive material (Fe) during the oxidation step

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Fig. 4

Variation of hydrogen yield per mass of material (Fe) for three successive oxidation steps

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Fig. 5

Hydrogen production rate per mass of reactive material (Fe) for three successive oxidation step

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Fig. 6

Powder sample after, (a) experiment 1, (b) experiment 2, (c) experiment 3-1, (d) experiment 3-2, (e)

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Fig. 7

SEM image for pure iron before reaction (125–355 μm)

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Fig. 8

SEM image for pure iron and ZrO2 before reaction (125–355 μm)

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Fig. 9

SEM image illustrating EDS points A and B for the single particle shown in Fig. 8 (right)

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Fig. 10

EDS for the single particle; (a) point A in Fig. 9 and (b) point B in Fig. 9

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Fig. 11

SEM image for the sample after first reduction step at different magnifications (850 °C reduction of the oxidized sample 3-Oxid-1)

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Fig. 12

SEM image for the sample after third oxidation step at different magnifications (867  °C reduction of the oxidized sample 3-Oxid-3)

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Fig. 13

SEM image for the fresh sample



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