Claims
- 1. A continuous method for separating and purifying zirconium and hafnium comprising the steps of:
- (a) preparing an aqueous chloride feedstock solution of zirconium and hafnium ions while controlling the solution temperature to inhibit production of inseparable zirconium and hafnium copolymer complexes;
- (b) loading the aqueous chloride feedstock solution to a continuous ion exchange chromatographic column containing an ion exchange resin;
- (c) feeding an aqueous chloride eluant to the column to elute the feedstock solution from the ion exchange resin; and,
- (d) separately collecting a substantially pure zirconium fraction, a substantially pure hafnium fraction and at least one waste fraction.
- 2. The method of claim 1, in which step (a) further comprises:
- (i) chlorinating zircon sand in the presence of carbon to produce a crude ZrCl.sub.4 and HfCl.sub.4 fraction;
- (ii) partially hydrolyzing the crude ZrCl.sub.4 and HfCl.sub.4 fraction with water (H.sub.2 O.sub.(l)) to produce a ZrOCl.sub.2 and HfOCl.sub.2 fraction and HCl fraction;
- (iii) controlling the temperature during step (ii) at about 10.degree. to 25.degree. C.,
- (iv) removing the HCl fraction for reuse;
- (v) dissolving the ZrOCl.sub.2 and HfOCl.sub.2 fraction in water to form the feedstock solution of zirconium and hafnium ions.
- 3. The method of claim 1, in which step (a) further comprises:
- (i) chlorinating zircon sand in the presence of carbon to produce a crude ZrCl.sub.4 and HfCl.sub.4 fraction;
- (ii) concurrently hydrolyzing and dissolving the crude ZrCl.sub.4 and HfCl.sub.4 fraction with crushed ice (H.sub.2 O.sub.(s)) to form the feedstock solution of zirconium and hafnium ions; and,
- (iii) cooling as necessary to control the temperature during step (ii) to about 0.degree. to 5.degree. C.
- 4. The method of claim 1, in which step (a) further comprises:
- (i) chlorinating zircon sand in the presence of carbon to produce a crude ZrCl.sub.4 and HfCl.sub.4 fraction;
- (ii) subliming the ZrCl.sub.4 and HfCl.sub.4 fraction at a temperature of about 200.degree. C. to 450.degree. C. and a pressure of about 5 to 30 psi to form a ZrCl.sub.4 and HfCl.sub.4 vapor fraction;
- (iii) partially hydrolyzing the ZrCl.sub.4 and HfCl.sub.4 vapor fraction with steam (H.sub.2 O.sub.(g)) to form a ZrOCl.sub.2 and HfOCl.sub.2 vapor fraction and an HCl vapor fraction;
- (iv) removing the HCl vapor fraction for reuse; and,
- (v) condensing the ZrOCl.sub.2 and HfOCl.sub.2 vapor fraction to an anhydrous ZrOCl.sub.2 and HfOCl.sub.2 fraction;
- (vi) dissolving the ZrOCl.sub.2 and HfOCl.sub.2 anhydrous fraction in water to form the feedstock solution of zirconium and hafnium ions.
- 5. The method of claim 1, in which said continuous ion exchange chromatographic column of step (b) is a continuous annular chromatographic column.
- 6. The method of claim 1, which further comprises:
- (e) separately processing the zirconium fraction and the hafnium fraction to produce nuclear quality zirconium metal and hafnium metal;
- (f) volume reducing the at least one waste fraction for disposal; and,
- (h) recycling the eluant for reuse in step (c).
- 7. The method of claim 1, in which the ion exchange resin is cationic or anionic exchange resin.
- 8. The method of claim 1, in which the aqueous chloride eluant comprises HCl.
- 9. The method of claim 1, which further comprises:
- (e) separately processing the separated and purified zirconium fraction and hafnium fraction to produce isotopically enriched nuclear quality zirconium and hafnium by repeating steps (a) to (d) independently for each zirconium fraction and hafnium fraction.
- 10. The method of claim 1, which further comprises operating the column of step (b) at a temperature of about 0.degree. C. to 5.degree. C.
- 11. A continuous method for separating and purifying zirconium and hafnium comprising the steps of:
- (a) preparing an aqueous chloride feedstock solution of zirconium and hafnium ions while controlling the solution temperature to inhibit production of inseparable zirconium and hafnium copolymer complexes;
- (b) loading the aqueous chloride feedstock solution onto an ion exchange resin contained in a ion exchange chromatographic column of a continuous annular chromatograph;
- (c) feeding an aqueous chloride eluant onto the ion exchange resin to elute the feedstock solution along the ion exchange chromatographic column of the continuous annular chromatograph;
- (d) continuously rotating the continuous annular chromatograph during steps (b) and (c) while the aqueous chloride feedstock solution and the aqueous chloride eluant diffuse through the ion exchange resin;
- (e) separately collecting a substantially pure zirconium fraction, a substantially pure hafnium fraction, and at least two waste fractions at collection locations on the continuous annular chromatograph angularly displaced from each other;
- (f) separately processing the zirconium fraction and hafnium fraction to produce nuclear quality zirconium metal and hafnium metal; and,
- (g) recycling the aqueous chloride eluant for reuse in step (c).
- 12. The method of claim 11, which further comprises:
- (h) collecting a mixed zirconium and hafnium fraction, loading said mixed fraction onto the ion exchange resin of step (b) and repeating steps (c) to (g).
- 13. The method of claim 11, in which step (a) further comprises:
- (i) chlorinating zircon sand in the presence of carbon to produce a crude ZrCl.sub.4 and HfCl.sub.4 fraction;
- (ii) partially hydrolyzing the crude ZrCl.sub.4 and HfCl.sub.4 fraction with water (H.sub.2 O(1)) to produce a ZrCl.sub.2 and HfOCl.sub.2 fraction and HCl fraction;
- (iii) controlling the temperature during step (ii) to about 10.degree. to 25.degree. C.:
- (iv) removing the HCl fraction for reuse;
- (v) dissolving the ZrOCl.sub.2 and HfOCl.sub.2 fraction in water to form the feedstock solution of zirconium and hafnium ions.
- 14. The method of claim 11, in which step (a) further comprises:
- (i) chlorinating zircon sand in the presence of carbon to produce a crude ZrCl.sub.4 and HfCl.sub.4 fraction;
- (ii) concurrently hydrolyzing and dissolving the crude ZrCl.sub.4 and HfCl.sub.4 fraction with ice (H.sub.2 O.sub.(s)) while controlling a temperature of the fraction to about 0.degree. C. to 5.degree. C. to form the feedstock solution of zirconium and hafnium ions.
- 15. The method of claim 11, in which step (a) further comprises:
- (i) chlorinating zircon sand in the presence of carbon to produce a crude ZrCl.sub.4 and HfCl.sub.4 fraction;
- (ii) subliming the ZrCl.sub.4 and HfCl.sub.4 fraction at a temperature of about 200.degree. C. to 450.degree. C. and a pressure of about 5 to 30 psi to form a ZrCl and HfCl.sub.4 vapor fraction;
- (iii) partially hydrolyzing the ZrCl.sub.4 and HfCl.sub.4 vapor fraction with steam (H.sub.2 O.sub.(g)) to from a ZrOCl.sub.2 and HfOCl.sub.2 vapor fraction and an HCl vapor fraction;
- (iv) removing the HCl vapor fraction for reuse; and,
- (v) condensing the ZrOCl.sub.2 and HfOCl.sub.2 vapor fraction to an anhydrous ZrOCl.sub.2 and HfOCl.sub.2 fraction;
- (vi) dissolving the ZrOCl.sub.2 and HfOCl.sub.2 anhydrous fraction in water to form the feedstock solution of zirconium and hafnium ions.
- 16. The method of claim 11, which further comprises operating the continuous annular chromatograph of step (b) at a temperature of about 0.degree. C. to 5.degree. C.
- 17. The method of claim 11, in which the aqueous chloride eluant comprises HCl.
- 18. The method of claim 11, in which the zirconium fraction collected in step (e) has a concentration of greater than about 10 g/l, a purity of less than 100 ppm Hf in the zirconium product fraction, and a yield of greater than about 50%.
- 19. The method of claim 18, in which the method is performed in a single pass through the continuous annular chromatograph of step (c).
- 20. The method of claim 11, in which the zirconium fraction collected in step (e) has a concentration of greater than about 15 g/l, a purity of less than about 50 ppm Hf in the zirconium product fraction, and a yield of greater than about 90%.
Parent Case Info
This application is a continuation of application Ser. No. 08/502,994 filed Jul. 17, 1995, now abandoned.
US Referenced Citations (9)
Continuations (1)
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Number |
Date |
Country |
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502994 |
Jul 1995 |
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