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Mixed-Conducting Membranes for Hydrogen Production and Separation

  • U. Balachandran (a1), Beihai Ma (a2), Tae H Lee (a3), Sun-Ju Song (a4), Ling Chen (a5) and Stephen E Dorris (a6)...

Abstract

Mixed-conducting oxides, possessing both ionic and electronic charge carriers, have found wide application in recent years in solid-state electrochemical devices that operate at high temperatures, e.g., solid-oxide fuel cells, batteries, and sensors. These materials also hold promise as dense ceramic membranes that separate gases such as oxygen and hydrogen from mixed-gas streams. We are developing Sr-Fe-Co oxide (SFC) as a membrane that selectively transports oxygen during partial oxidation of methane to syngas (mixture of CO and H2) because of SFC's high combined electronic and ionic conductivities. We have evaluated extruded tubes of SFC for conversion of methane to syngas in a reactor that was operated at ≈900°C. Methane conversion efficiencies were >90%, and some of the reactor tubes were operated for >1000 h. We are also developing dense proton-conducting oxides to separate pure hydrogen from product streams that are generated during methane reforming and coal gasification. Hydrogen selectivity in these membranes is nearly 100%, because they are free of interconnected porosity. Although most studies of hydrogen separation membranes have focused on proton-conducting oxides by themselves, we have developed cermet (i.e., ceramic-metal composite) membranes in which metal powder is mixed with these oxides in order to increase their hydrogen permeability. Using several feed gas mixtures, we measured the nongalvanic hydrogen permeation rate, or flux, for the cermet membranes in the temperature range of 500-900°C. This rate varied linearly with the inverse of membrane thickness. The highest rate, ≈32 cm3(STP)/min-cm2, was measured at 900°C for an ≈15-μm-thick membrane on a porous support structure when 100% H2 at ambient pressure was used as the feed gas.

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1. Teraoka, Y., Nobunaga, T., and Yamazoe, N.: Effect of cation substitution on the oxygen semipermeability of perovskite-type oxides. Chem. Lett., 503, 1988.
2. Mazanec, T. J., Cable, T. L., and Frye, J. G. Jr.: Electrocatalytic cells for chemical reaction. Solid State Ionics, 53–56, 111, 1992.
3. Wiley, J. B. and Poeppelmeier, K. R.: LaSrO5 – A new oxygen deficient perovskite. J. Solid State Chem., 88, 250, 1990.
4. Balachandran, U., Morissette, S. L., Dusek, J. T., Mieville, R. L., Poeppel, R. B., Kleefisch, M. S., Pei, S., Kobylinski, T. P., and Udovich, C. A.: Development of ceramic membranes for partial oxygenation of hydrocarbon fuels to high-value-added products. Proc. of coal liquefaction and gas conversion contractors' review conference, Eds. Rogers, S., Zhou, P., Lockhart, K., and Maceil, N., U. S. Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, PA, September 2729, 1993.
5. Ma, B., Park, J. H., Segre, C. U., and Balachandran, U.: Electronic/ionic conductivity and oxygen diffusion coefficient of the Sr-Fe-Co-O system. Mater. Res. Soc. Symp. Proc., 393, 49, 1995.
6. Balachandran, U., Dusek, J. T., Mieville, R. L., Poeppel, R. B., Kleefisch, M. S., Pei, S., Kobylinski, T. P., Udovich, C. A., and Bose, A. C.: Dense ceramic membranes for partial oxidation of methane to syngas. Applied Catalysis A: General, 133, 19, 1995.
7. Balachandran, U., Kleefisch, M. S., Kobylinski, T. P., Morissette, S. L., and Pei, S.: Oxygen ion conducting dense ceramic. U. S. Patent 5,580,497, Dec. 3, 1996.
8. Ma, B., Balachandran, U., Park, J. H., and Segre, C. U.: Electrical transport properties and defect structure of SrFeCo0.5Ox. J. Electrochem. Soc., 143, 1736, 1996.
9. Iwahara, H., Yajima, T., and Uchida, H.: Effect of ionic radii of dopants on mixed ionic conduction (H++O2-) in BaCeO3-based electrolytes. Solid State Ionics, 70–71, 267, 1994.
10. Iwahara, H.: Technological challenges in the application of proton conducting ceramics. Solid State Ionics, 77, 289, 1995.
11. Guan, J., Dorris, S. E., Balachandran, U., and Liu, M.: Transport properties of BaCe0.95Y0.05O3-δ mixed conductors for hydrogen separation. Solid State Ionics, 100, 45, 1997.
12. Guan, J., Dorris, S. E., Balachandran, U., and Liu, M.: The effects of dopants and A:B site nonstoichiometry on properties of perovskite-type proton conductors. J. Electrochem. Soc., 145, 1780, 1998.
13. Guan, J., Dorris, S. E., Balachandran, U., and Liu, M.: Development of mixed-conducting ceramic membranes for hydrogen separation. Ceram. Trans., 92, 1, 1998.
14. Ma, B., Balachandran, U., Chao, C. C., and Park, J. H.: Oxygen permeation in Sr-Fe-Co-O dense ceramic membranes. Ceram. Trans., 73, 169, 1997.
15. Balachandran, U. and Ma, B.: Mixed conducting dense ceramic membranes for air separation and natural gas conversion. J. Solid State Electrochem., 10, 617, 2006.
16. Balachandran, U., Ma, B., Maiya, P. S., Mieville, R. L., Dusek, J. T., Picciolo, J. J., Guan, J., Dorris, S. E., and Liu, M.: Development of mixed-conducting oxides for gas separation. Solid State Ionics, 108, 363, 1998.
17. Balachandran, U., Lee, T. H., Chen, L., Song, S. J., Picciolo, J. J., and Dorris, S. E.: Current status of dense cermet membranes for hydrogen separation. Proc. 22nd Annual International Pittsburgh Coal Conf., Pittsburgh, PA, Sept. 1215, 2005.
18. Buxbaum, R. E. and Marker, T. L.: Hydrogen transport through non-porous membranes of palladium-coated niobium, tantalum, and vanadium. J. Memb. Sci., 85, 29 (1993).

Keywords

Mixed-Conducting Membranes for Hydrogen Production and Separation

  • U. Balachandran (a1), Beihai Ma (a2), Tae H Lee (a3), Sun-Ju Song (a4), Ling Chen (a5) and Stephen E Dorris (a6)...

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