Hostname: page-component-586b7cd67f-dsjbd Total loading time: 0 Render date: 2024-11-28T06:51:42.362Z Has data issue: false hasContentIssue false

Mixed-Conducting Membranes for Hydrogen Production and Separation

Published online by Cambridge University Press:  26 February 2011

U. Balachandran
Affiliation:
[email protected], Argonne National Laboratory, Energy Systems Division, Building 212, 9700S. Cass avenue, Argonne, IL, 60439, United States
Beihai Ma
Affiliation:
[email protected], Argonne National Laboratory, Energy Systems Division, Argonne, IL, 60439, United States
Tae H Lee
Affiliation:
[email protected], Argonne National Laboratory, Energy Systems Division, Argonne, IL, 60439, United States
Sun-Ju Song
Affiliation:
[email protected], Argonne National Laboratory, Energy Systems Division, Argonne, IL, 60439, United States
Ling Chen
Affiliation:
[email protected], Argonne National Laboratory, Energy Systems Division, Argonne, IL, 60439, United States
Stephen E Dorris
Affiliation:
[email protected], Argonne National Laboratory, Energy Systems Division, Argonne, IL, 60439, United States
Get access

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.

Type
Research Article
Copyright
Copyright © Materials Research Society 2007

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Teraoka, Y., Nobunaga, T., and Yamazoe, N.: Effect of cation substitution on the oxygen semipermeability of perovskite-type oxides. Chem. Lett., 503, 1988.Google Scholar
2. Mazanec, T. J., Cable, T. L., and Frye, J. G. Jr.: Electrocatalytic cells for chemical reaction. Solid State Ionics, 53–56, 111, 1992.Google Scholar
3. Wiley, J. B. and Poeppelmeier, K. R.: LaSrO5 – A new oxygen deficient perovskite. J. Solid State Chem., 88, 250, 1990.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
10. Iwahara, H.: Technological challenges in the application of proton conducting ceramics. Solid State Ionics, 77, 289, 1995.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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).Google Scholar