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Alternative reagent to mercuric nitrate catalyst for dissolution of aluminum-clad nuclear fuels in nitric acid

Published online by Cambridge University Press:  31 January 2011

Philip A. Anderson  and
Jerry D. Christian
Philip A. Anderson
Affiliation:
Lockheed Martin Idaho Technologies Company, Idaho National Engineering and Environmental Laboratory, Idaho Falls, Idaho 83415
Jerry D. Christian
Affiliation:
Lockheed Martin Idaho Technologies Company, Idaho National Engineering and Environmental Laboratory, Idaho Falls, Idaho 83415
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Extract

A substitute additive, HBF4, has been discovered that will replace Hg(NO3)2 catalyst for dissolving aluminum spent nuclear fuels in nitric acid for recovery of usable materials. The catalyst or substitute is necessary to penetrate a protective oxide film that continuously forms on the Al surface in the oxidizing acid. A penetration rate of alloy Al-6061 T6 of 40 mg/cm2-h can be achieved in a continuous dissolution process at 100 °C using a dissolvent of 0.15 M HBF4 in 7 M HNO3 that achieves a steady-state composition of 1.0 M Al3+ and 3.3 M HNO3, while maintaining a corrosion rate of a type 304L stainless steel dissolver vessel of 0.015 mm/mo. The penetration rate of aluminum is correlated with the equilibrium concentration of HF in the system. The postulated mechanism involves dissolution of the alumina film by approximately 0.006 M HF in equilibrium with the HBF4 and complexed aluminum fluoride species in nitric acid, which provide a large semi-buffered supply of HF. This allows the HNO3 to attack the aluminum metal. The small concentration of HF does not compete favorably with HNO3 for reaction with and consumption by Al.

Type
Articles
Information
Journal of Materials Research , Volume 13 , Issue 1 , January 1998 , pp. 68 - 76
Copyright
Copyright © Materials Research Society 1998

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References

1.Bruce, F. R., The Laboratory Development of a Continuous Solvent Extraction Process for the Recovery of U235, U.S. Atomic Energy Commission (USAEC) Report ORNL-343 (March 21, 1950).Google Scholar
2.Rom, A. M., Terminal Report of ORNL Pilot Plant Development of the Materials Testing Reactor 25 Recovery Process, USAEC Report ORNL 676 (May 23, 1950).Google Scholar
3.Foster, D. L. and Nurmi, E. O., Dissolution of Uranium-Aluminum Alloy Slugs, USAEC Report ORNL-1195 (July 7, 1952).Google Scholar
4.Burns, R. E. and Holm, C. H., Nitric Acid Dissolution of Uranium-Aluminum Alloy, USAEC Report HW-18414 (August 12, 1952).CrossRefGoogle Scholar
5.Blanco, R. E., “Dissolution and Feed Adjustment,” in Symposium on the Reprocessing of Irradiated Fuels, held at Brussels, Belgium May 20–25, 1957, USAEC Report TID-7534 (Bk. 1), pp. 22–44.Google Scholar
6.Wymer, R. G. and Blanco, R. E., Industrial Eng. Chem. 49, 59–61 (1957).CrossRefGoogle Scholar
7.Boeglin, A. F., Buckham, J. A., Chajson, L., Lemon, R. B., Paige, B. M., and Stoops, C. E., A.I.Ch.E.J. 2 (2), 190–194 (1956).CrossRefGoogle Scholar
8.Long, J. T., Engineering for Nuclear Fuel Processing (American Nuclear Society, La Grange Park, IL, 1978).Google Scholar
9.Hammer, R. R., A Determination of the Stability Constants of a Number of Metal Fluoride Complexes and Their Rates of Formation, U.S. Department of Energy (USDOE) Report ENICO-1004 (August 1979).CrossRefGoogle Scholar
10.Murphy, J. A., Determination of the Zirconium Fluoride Stability Constants by Direct Measurement of Equilibrium Hydrofluoric Acid Using the Amperometric Response of Titanium and Hafnium Electrodes, USDOE Report WINCO-1098 (May 1992).Google Scholar
11.Frost, A. A. and Pearson, R. G., Kinetics and Mechanism (John Wiley & Sons, Inc., New York, 1953), p. 191. See, also, Moore, J. W. and Pearson, R. G., Kinetics and Mechanism, 3rd ed. (John Wiley & Sons, Inc., New York, 1981), p. 334, which retains this original description.Google Scholar
12.Bell, R. P., Acid-Base Catalysis (Oxford University Press, Oxford, 1941).Google Scholar
13.Christian, J. D., Illum, D. B., and Murphy, J. A., Talanta, 37, 651–654 (1990).CrossRefGoogle Scholar