Eco-friendly smelting process for reactor-grade zirconium using raw ore metal reduction and electrolytic refining integrated process

Patent metadata

Field	Value
Publication number	US-9238873-B2
Application number	US-201113813271-A
Country	US
Kind code	B2
Filing date	Jul 29, 2011
Priority date	Jul 30, 2010
Publication date	Jan 19, 2016
Grant date	Jan 19, 2016

Abstract

The manufacturing method for high-purity Zirconium is characterized by self-propagating high temperature synthesis (SHS) of a raw material having zirconium raw ore containing ZrO 2 , ZrSiO 4 , KZr 2 (PO 4 ) 3 , or a mixture thereof and a reducing agent that is metal powder, to prepare zirconium intermetallic compound or zirconium nitride, followed by the recovery of high-purity Zr by electrolytic refining the reaction product of the SHS.

First claim

The invention claimed is:

1. A manufacturing method for high-purity Zirconium comprising self-propagating high temperature synthesis (SHS, self-sustained combustion synthesis) of a raw material having zirconium raw ore containing ZrSiO 4 and a reducing agent that is metal powder, to prepare Zr x Si y (x is a real number of 1 to 5, and y is a real number of 1 to 4), followed by the recovery of high-purity Zr by electrolytic-refining Zr x Si y .

2. The manufacturing method for high-purity Zirconium of claim 1 , wherein the raw material further contains zirconium oxide.

3. A manufacturing method for high-purity Zirconium comprising self-propagating high temperature synthesis (SHS, self-sustained combustion synthesis) of a material containing zirconium raw ore containing ZrO 2 , ZrSiO 4 , KZr 2 (PO 4 ) 3 , or a mixture thereof and a reducing agent that is metal powder, in the presence of nitrogen to prepare a mixture of HfN and ZrN, followed by the recovery of high-purity Zr by electrolytic-refining the mixture of HfN and ZrN.

4. The manufacturing method for high-purity Zirconium of claim 3 , wherein at the time of the SHS, Si 3 N 4 is volatilized and removed.

5. The manufacturing method for high-purity Zirconium of claim 1 , wherein the reducing agent is Al, Mg, or a mixture thereof.

6. The manufacturing method for high-purity Zirconium of claim 1 , wherein at the time of the SHS, pressure of atmospheric gas is 2 to 250 atm.

7. The manufacturing method for high-purity Zirconium of claim 1 , wherein at the time of the SHS, a liquid phase is formed.

8. The manufacturing method for high-purity Zirconium of claim 1 , after SHS, further comprising removing metal oxide produced by oxidation of the reducing agent using acid leaching.

9. The manufacturing method for high-purity Zirconium of claim 1 , wherein the electrolytic refining is performed using molten salts in which 3 to 10 weight % of zirconium halide is added to LiCl—KCl, LiF—KF or LiF—KF—NaF eutectic salts.

10. The manufacturing method for high-purity Zirconium of claim 9 , wherein at the time of the electrolytic refining, cell potential is 0.5 to 2V.

11. The manufacturing method for high-purity Zirconium of claim 9 , wherein at the time of the electrolytic refining, a mole ratio of hafnium ions to zirconium ions (Hf 4+ /Zr 4+ or Hf 3+ /Zr 3+ ) in the eutectic salt is 0.5 or less.

12. The manufacturing method for high-purity Zirconium of claim 1 , wherein high-purity Zirconium recovered by electrolytic refining contains Hf at a concentration of 100 weight ppm or less.

13. The manufacturing method for high-purity Zirconium of claim 9 , wherein the molten salt is purified by a Czochralski method to sequentially and directionally solidify the molten salt using the fact that a content of thermally stable impurities is changed according to the temperature in a two phase region in which a solid phase and a liquid phase co-exist in a phase diagram of substances configuring molten salts and reused.

Assignees

• Lee Jong Hyeon
• Lee Yoon Sang
• Lee Han Soo
• Kim Seon Jin
• Chung Sun Kyo
• Hayk H Nersisyan
• Iac In Nat Univ Chungnam

Inventors

• Lee Jong Hyeon
• Lee Yoon Sang
• Lee Han Soo
• Kim Seon Jin
• Chung Sun Kyo
• Hayk H Nersisyan

Classifications

• C22B34/14

  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 title

• C25C3/26 Primary

  of titanium, zirconium, hafnium, tantalum or vanadium · CPC title

• C22B5/04

  by aluminium, other metals or silicon · CPC title

• C22B9/00

  General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals · CPC title

• C22B34/129

  obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc · CPC title