Recovery of scandium, yttrium and lanthanides from zircon sand

• US 5,039,336 A
• Filed: 12/30/1988
• Issued: 08/13/1991
• Est. Priority Date: 12/30/1988
• Status: Expired due to Term

• Current Assignee: Westinghouse Electric Company LLC (Brookfield Asset Management Incorporated)
• Original Assignee: Westinghouse Electric Corporation (Paramount Global (f/k/a ViacomCBS Inc.))
• Inventors: Feuling, Robert J.
• Primary Examiner(s): Andrews, Melvyn J.
• Application Number:
  US07/292,035
• Time in Patent Office: 956 Days
• Field of Search: 75/419, 75/618, 423/21.1, 423/79
• US Class Current: 75/419
• CPC Class Codes: C01F 17/17 involving a liquid-liquid extraction
• CPC Class Codes: C01F 17/212 Scandium oxides or hydroxides
• CPC Class Codes: C01F 17/218 Yttrium oxides or hydroxides
• CPC Class Codes: C01F 17/224 Oxides or hydroxides of lanthanides
• CPC Class Codes: C22B 1/08 Chloridising roasting
• CPC Class Codes: C22B 1/10 in fluidised form
• CPC Class Codes: C22B 3/1616 Leaching with acyclic or carbocyclic agents of a single type
• CPC Class Codes: C22B 3/322 Oxalic acids
• CPC Class Codes: C22B 3/3846 Phosphoric acid, e.g. (O)P(OH)3
• CPC Class Codes: C22B 34/14 Obtaining zirconium or hafnium treatment or purification of solutions by liquid-liquid extraction, by ion exchange or by adsorption C22B3/00, C01G25/003, C01G27/003
• CPC Class Codes: C22B 59/00 Obtaining rare earth metals
• CPC Class Codes: C22B 60/0291 obtaining thorium
• CPC Class Codes: Y02P 10/20 Recycling

Abstract

This is a process for extracting scandium from zircon ore. It utilizes feeding zircon sand to a fluidized bed chlorinator at about 1000° C. to produce a vaporous (principally zirconium and silicon chlorides) phase and a solid residue and recovering scandium from the solid residue. Surprisingly, despite the relatively low sublimation temperature of scandium chloride the very low level of scandium present in zircon ore is concentrated in the residue (rather than going with the vapor phase, where it would not be concentrated), making recovery of scandium from the zircon ore economically feasible. Generally, the process can be part of the production of zirconium metal, whereby scandium is a byproduct of zirconium production. Preferably, the recovery is performed by leaching the residue with aqueous acid (e.g. HCl) to produce a scandium-containing aqueous solution, followed by contacting the aqueous solution with a polyalkyl phosphate-containing organic phase, the polyalkyl phosphate (e.g. tributyl phosphate) extracting scandium into the organic phase, followed by scandium precipitation by an ammonium addition to produce a scandium hydroxide precipitate and the scandium hydroxide is calcined, whereby scandium is recovered as an oxide. The residue generally also contains yttrium and lanthanides, and the yttrium and lanthanides can also be recovered from the residue as a part of the scandium recovery process. The recovering of the scandium chloride from the residue can also be performed by leaching the residue with alcohol (preferably methanol) to produce a scandium-containing alcohol solution (the remaining residue can then be recycled to the chlorinator). The leaching with alcohol can be followed by contacting the alcohol solution with oxalic acid to precipitate oxalates of scandium, thorium, and lanthanides.

Claims

1. A process for extracting scandium from ore comprising zirconium silicate;

said process comprising;

a. feeding scandium-containing zircon ore to a fluidized bed chlorinator at 800°

-1250°

C. to produce a vaporous phase, said vaporous phase principally comprising zirconium and silicon chlorides, and to produce a solid scandium-containing residue; and

b. recovering the scandium as a compound from said solid residue, whereby the very low level of scandium present in zircon ore is concentrated in the residue, making recovery of scandium from the zircon ore economically feasible.

2. The process of claim 1, wherein said zirconium chloride in said vaporous phase is separated from said silicon chloride in said vaporous phase after said vaporous phase is separated from said scandium-containing residue, and is then processed into zirconium metal.

3. The process of claim 1, wherein said scandium is present in said residue principally as scandium chloride and said recovering of said scandium chloride from said residue is performed by leaching said residue with aqueous acid to produce a scandium-containing aqueous solution.

4. The process of claim 3, wherein said acid is HCl.

5. The process of claim 3, wherein said leaching with acid is followed by contacting said aqueous solution with a polyalkyl phosphate-containing organic phase, said polyalkyl phosphate extracting scandium ions into said organic phase.

6. The process of claim 5, wherein said acid is HCl and said polyalkyl phosphate in said organic phase is tributyl phosphate.

7. The process of claim 5, wherein after said extracting of scandium into said organic phase, scandium is precipitated by an ammonium addition to produce a scandium hydroxide precipitate and said scandium hydroxide is calcined, whereby scandium is recovered as an oxide.

8. A process for extracting zirconium and scandium from zircon sand;

comprising silica said process comprising;

a. feeding scandium-containing zircon sand to a fluidized bed chlorinator at 800°

-1250°

C. to volatilize zirconium and silicon chlorides from said sand and to produce a residue containing a scandium compound and other solids;

b. separating said scandium-compound from the other solids of said residue;

c. separating said zirconium chloride from said silicon chloride; and

d. reducing said zirconium chloride to produce zirconium metal.

9. The process of claim 8, wherein said scandium compound is present in said residue as scandium chloride and said separating of said scandium chloride from said other solids is performed by leaching said residue with acid to produce an aqueous solution followed by contacting said solution with an organic phase to extract scandium into said organic phase, and by calcining said extracted scandium, whereby scandium is recovered as an oxide.

10. The process of claim 9, wherein said zircon sand contains yttrium and lanthanide which accumulate in said residue, and said yttrium and lanthanides are also recovered from said residue.

11. The process of claim 10, wherein said yttrium and lanthanides are leached by said acid with said scandium into said scandium-containing aqueous solution, said yttrium and lanthanides are precipitated as mixed hydroxides by an ammonium addition along with said scandium and said yttrium and said lanthanide mixed hydroxides are calcined and recovered with said scandium.

12. The process of claim 10, wherein said yttrium and lanthanides are leached by said acid with said scandium into said scandium-containing aqueous solution, which leaching is followed by contacting said aqueous solution with a polyalkyl phosphate-containing organic phase, to produce a scandium-containing organic phase and a yttrium and lanthanide-containing aqueous phase, and then by calcining said extracted scandium, whereby scandium is recovered as an oxide, and by calcining said aqueous phase, whereby yttrium and lanthanides are recovered as oxides.

13. The process of claim 12, wherein said scandium is present in said residue principally as scandium chloride and said recovering of said scandium chloride from said residue is performed by leaching said residue with alcohol to produce a scandium-containing alcohol solution.

14. The process of claim 13, wherein said alcohol is methanol and the remaining residue is recycled to said chlorinator.

15. The process of claim 13, wherein said zircon sand contains thorium and iron which accumulate in said residue and said leaching with alcohol is followed by contacting said alcohol solution with oxalic acid to precipitate chlorides of scandium, thorium, and lanthanides, and to retain chlorides of zirconium, silicon, and iron in said alcohol solution, whereby purified chlorides of scandium, thorium, and lanthanides are obtained.