Process for separating zirconium and hafnium tetrachlorides from mixtures

Patent metadata

Field	Value
Publication number	US-9005556-B2
Application number	US-201113813696-A
Country	US
Kind code	B2
Filing date	Aug 2, 2011
Priority date	Aug 2, 2010
Publication date	Apr 14, 2015
Grant date	Apr 14, 2015

Abstract

A simple, inexpensive and non-corrosive industrial separation method making it possible to separate zirconium and hafnium tetrachlorides from mixtures thereof, a simple industrial method allowing the zirconium/hafnium separation, and a method making it possible to produce fractions enriched with zirconium and containing hafnium at a trace level are disclosed.

First claim

The invention claimed is:

1. A method for separating hafnium tetrachloride and zirconium tetrachloride, from a mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes, comprising:
carrying out liquid-liquid extraction to separate hafnium tetrachloride and zirconium tetrachloride from a mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes, with a Zr/Hf enrichment of at least 100/1 (expressed by mass), using an ionic liquid, the melting point of which is below 100° C., with a non-nucleophilic anion, under anhydrous conditions.

2. The method according to claim 1 , in which the liquid-liquid extraction is carried out with a hydrocarbon or a mixture of hydrocarbons.

3. The method according to claim 1 , in which the temperature at which said method is carried out is less than approximately 100° C.

4. The method according to claim 1 , in which said aromatic compound has the following formula:

in which Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 represent independently of each other:
a hydrogen atom,
a linear or branched alkyl containing from 1 to 20 carbon atoms, or
an aryl.

5. The method according to claim 1 , in which the ionic liquid is a stoichiometric mixture of methylbutylimidazolium chloride and aluminium chloride.

6. The method according to claim 2 , in which the hydrocarbon is chosen from:
linear or branched alkanes with 4 to 12 carbon atoms,
cycloalkanes and substituted cycloalkanes, with 5 to 12 carbon atoms,
aromatics substituted by alkyl and/or cycloalkyl chains, the alkyl radicals having 1 to 12 carbon atoms or
mixtures thereof.

7. A method for separating hafnium tetrachloride and zirconium tetrachloride, comprising the following steps:
bringing into contact under anhydrous conditions:
a mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes with an ionic liquid, the melting point of which is below 100° C.,

the Zr tetrachloride/aromatic compound complex being molecular, and the Hf tetrachloride/aromatic compound complex being ionic
recovery of the Zr tetrachloride/aromatic compound complex in a solvent, said solvent being such that:
the solvent contains the mixture of complexes,
or the solvent is added to the mixture of complexes at the same time as the ionic liquid is brought into contact with the mixture of complexes, or it is added to the mixture of complexes after the ionic liquid is brought into contact with the mixture of complexes,
in order to separate hafnium tetrachloride and zirconium tetrachloride.

8. The method according to claim 7 , in which the mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes is contained in the solvent, or
in which the solvent is added to the mixture of complexes at the same time as the ionic liquid is brought into contact with the mixture of complexes.

9. The method according to claim 7 , in which the solvent is added to the mixture of complexes after the ionic liquid is brought into contact with the mixture of complexes.

10. The method according to claim 7 for separating hafnium tetrachloride and zirconium tetrachloride, comprising the following steps:
bringing into contact under anhydrous conditions:
a mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes with an ionic liquid,
the Zr tetrachloride/aromatic compound complex being molecular, and the Hf tetrachloride/aromatic compound complex being ionic,
if the mixture of complexes contains no solvent, the addition of a solvent at the end of the previous step, in order to obtain an anhydrous reaction mixture such that:

if the ionic liquid is not miscible with the solvent, the mixture contains a phase comprising the solvent and a phase comprising the ionic liquid,
and if the ionic liquid is miscible with the solvent, the mixture contains an added alkane allowing the formation of a phase comprising the solvent and a phase comprising the ionic liquid,
and thus to carry out a liquid-liquid extraction by the addition of the ionic liquid to the mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes, and
recovery of the ionic complex: Hf tetrachloride/aromatic compound solubilized in the ionic liquid, and that of the molecular complex: Zr tetrachloride/aromatic compound in the solvent.

11. The method according to claim 7 , in which recovery of the molecular complex: Zr tetrachloride/aromatic compound in the solvent is carried out by decantation between the phase comprising the solvent and the phase comprising the ionic liquid, when these two phases are not miscible with each other.

12. The method according to claim 7 , in which recovery of the molecular complex Zr tetrachloride/aromatic compound in the solvent is carried out by the addition of an alkane, making it possible to obtain the phase comprising the solvent and the phase comprising the ionic liquid.

13. The method according to claim 7 , in which the step of bringing the mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes into contact with the ionic liquid is preceded by a step of treatment of the hafnium tetrachloride and the zirconium tetrachloride with an aromatic compound in order to obtain the mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes.

14. The method according to claim 7 , comprising a step of removal of the aromatic compound from said complexes by vacuum distillation or by vacuum distillation in the presence of an alkane.

15. The method according to claim 7 , comprising the following steps:
treatment of a mixture of hafnium tetrachloride and zirconium tetrachloride with hexamethylbenzene in solution in toluene for 48 hours at ambient temperature with stirring in order to obtain a mixture of Zr tetrachloride/aromatic compound and Hf tetrachloride/aromatic compound complexes in solution in toluene,
cooling down the solution obtained in the previous step at 4° C. in order to obtain a solid,
recovery of the solid formed in the previous step,
evaporation of the toluene in order to obtain a mixture of complexes,
dissolution of the mixture of complexes in a stoichiometric mixture of methylbutylimidazolium chloride and aluminium chloride , and the addition of toluene in order to obtain a reaction mixture,
addition of pentane to the reaction mixture in order to form two phases,
separation of the two phases by decantation and recovery of the ionic complex Hf tetrachloride/aromatic compound and the molecular complex: Zr tetrachloride/aromatic compound.

Assignees

• Santini-Scampucci Catherine
• Chauvin Yves
• Campbell Paul
• Centre Nat Rech Scient

Inventors

• Santini-Scampucci Catherine
• Chauvin Yves
• Campbell Paul

Classifications

• C22B3/42

  by ion-exchange extraction · CPC title

• C22B3/20 Primary

  Treatment or purification of solutions, e.g. obtained by leaching (C22B3/18 takes precedence) · CPC title

• C01P2002/86

  by NMR- or ESR-data · CPC title

• C01G27/04

  Halides · CPC title

• 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