GB2395958A - Electrolytic separation of metals - Google Patents
Electrolytic separation of metals Download PDFInfo
- Publication number
- GB2395958A GB2395958A GB0228322A GB0228322A GB2395958A GB 2395958 A GB2395958 A GB 2395958A GB 0228322 A GB0228322 A GB 0228322A GB 0228322 A GB0228322 A GB 0228322A GB 2395958 A GB2395958 A GB 2395958A
- Authority
- GB
- United Kingdom
- Prior art keywords
- metal
- oxide
- oxides
- metals
- molten salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 150000002739 metals Chemical class 0.000 title claims abstract description 32
- 238000000926 separation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 54
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052768 actinide Inorganic materials 0.000 claims abstract description 8
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 8
- 150000001255 actinides Chemical class 0.000 claims abstract description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 5
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 5
- 239000007787 solid Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 5
- 238000005253 cladding Methods 0.000 abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 abstract description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical class [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 229910052770 Uranium Inorganic materials 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- -1 uranium ions Chemical class 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002915 spent fuel radioactive waste Substances 0.000 description 3
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 3
- 229910000439 uranium oxide Inorganic materials 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 229910000310 actinide oxide Inorganic materials 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- FLDALJIYKQCYHH-UHFFFAOYSA-N plutonium(iv) oxide Chemical class [O-2].[O-2].[Pu+4] FLDALJIYKQCYHH-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 150000003671 uranium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A process for the separation of metals, the metals being, comprised as the metal oxides in a mixed oxide sample, comprises (i), adding the mixed oxide to a molten salt electrolyte and cathodically electrolysing the oxide, the potential of the cathode being controlled so as to favour oxygen ionisation over deposition of metal from the cations present in the molten salt, and the applied potential difference being such as to facilitate selective reduction of one metal oxide at the expense of other metal oxides; and (ii) separating the metal from the remaining metal oxides. The process is applicable to mixed oxide samples comprising mixtures of two or more metal oxides, and is particularly useful for the separation of metals of the transition, lanthanide and/or actinide series comprised in mixed oxide samples. A particular application is in the separation of zirconium and hafnium comprised in mixed zirconium and hafnium oxides, the removal of hafnium facilitating the use of the zirconium in fuel cladding for use in the nuclear power industry.
Description
l SEPARATION OF METALS
Field of the Invention
This invention relates to a method for the separation of metals from mixtures of 5 metal oxides and relies on the selective reduction of certain oxides to the metals, whilst the other metals remain in the form of the oxides. The method of the present invention finds particular application in the separation of transition metals, lanthanides and actinides.
10 Background to the Invention
The prior art teaches the use of molten salts in the separation of metals and metal
oxides in molten salt media. As used herein, the term "molten salts" is intended to cover salts such as lithium chloride which melts at an elevated temperature and also ionic liquids which typically are liquid at room temperature or which melt at a 15 temperature up to about 300 C. Such techniques have found particular application in the nuclear industry, where two well-established processes are available for the treatment of irradiated nuclear fuel.
The first of these processes, the Dimitrovgrad SSC-RIAR process, makes use of 20 chemical oxidants (chlorine and oxygen gases) to react with powdered uranium dioxide fuel to form higher oxidation state compounds such as UO2CI2 which are soluble in the molten salt. In an electrochemical cell the uranium compounds are reduced to UO2 at the cathode, forming a solid deposit. This process has both technical and environmental limitations.
The second process, developed by the Argonne National Laboratory (ANL) is fundamentally an electrorefining technology which uses current flow to anodically oxidise uranium to form uranium ions in the molten salt electrolyte. At the cathode the uranium is reduced and electrodeposited as uranium metal.
r The ANL process requires a metal feed. If oxide fuels are to be treated, it is necessary to reduce the uranium oxide (usually UO2 pellets) to the metal. This reduction process is carried out chemically, using lithium metal in a LiCI or LiCI/KCI molten salt at 500 to 600 C. Alternatively, a salt transport process can be used 5 involving a Cu-Mg-Ca alloy and molten CaCI2 salt. However, in both reduction methods the by-products, Li2O and CaO respectively, need to be recovered from the molten salt phase by an electrolysis step. Effectively this means a two stage process.
A disadvantage of the lithium reduction process for producing a metallic feed from 10 an oxide is the production of Li2O by-product. This requires recycle to make the process economic, and this is done by an electrolytic recovery of lithium metal.
Hence this is a two stage process, comprising a reduction step followed by a lithium recovery stage.
15 More recently, in EP-A-1088113, there is proposed a method for the removal of oxygen from a metal oxide wherein an electrode comprising the metal oxide is contacted with a molten salt, and a potential is applied which is lower than the deposition potential of the cation of the molten salt, thereby facilitating removal of oxygen from the metal oxide.
Subsequently, in the PCT patent application published under No WO-A01/41152, there is disclosed a single step process for reducing to metallic form a metal oxide present in spent nuclear fuel, the process comprising cathodically electrolysing the oxide in the presence of a molten salt electrolyte, the potential of the cathode being 25 controlled so as to favour oxygen ionisation over deposition of the metal from the cations present in the molten salt.
The process thereby involves the use of a single electrochemical process to reduce the metal oxide fuel to a metallic form, with oxygen, carbon monoxide and carbon 30 dioxide produced as the only by-products. The potential of the cathode is maintained and controlled so that only oxygen ionisation occurs and not the deposition of the I.
l cations (eg Ca ions) in the fused salt. Typically, the oxide comprises an actinide oxide, such as uranium oxide or irradiated uranium oxide.
This process was then developed and applied to the separation of metals from a 5 mixture of metal oxides such as occurs in spent nuclear fuel, which is a frequent requirement in the nuclear power industry. Thus mixtures of uranium and plutonium oxides, together with the oxides of other actinide metals, may additionally be contaminated with oxides of other, chemically active, metals such as, for example, those associated with fission products. Co-pending patent application No lO PCT/GB02/02402 teaches a method for the treatment of irradiated fuel which allows for the separation of uranium, and metals more noble than uranium, from such mixtures as are found in spent nuclear fuel, and facihtates the provision of these metals in a form suitable for use as the feed in a molten salt electrorefining process, whilst ensuring that other, more electropositive, metals remain in the form of oxides.
The present inventors, however, recognised that there is frequently the requirement, both within the nuclear industry and the wider chemical industry, for the separation of metals from mixtures of metal oxides, and that the established technologies within these industries often provide inadequate means for the performance of such 20 separations. Thus, whilst the prior art, as previously discussed, has focused largely
on applications within the nuclear power industry and, most particularly, on processes involving actinide metals, it is often necessary, in a wide range of industries, to separate a large variety of metals, many of which are not members of the actinide series.
The present invention, therefore seeks to provide a method for the electrochemical separation of metals, the method relying on the different reduction potentials of different oxides which results in the reduction of one oxide to the free metal, whilst the other metal remains as the oxide. Examples of metals which might be separated 30 in this way include transition metals, lanthanides and actinides.
Statements of Invention
Thus, according to the present invention, there is provided a process for the separation of metals, said metals being comprised as the metal oxides in a mixed oxide sample, the process comprising: 5 (i) adding the mixed oxide to a molten salt electrolyte and cathodically electrolysing the oxide, the potential of the cathode being controlled so as to favour oxygen ionization over deposition of metal from the cations present in the molten salt, and the applied potential difference being such as to facilitate selective reduction of one metal oxide at the expense of other metal oxides; and 10 (ii) separating the metal from the remaining metal oxides.
The potential of the cathode is maintained and controlled so that only oxygen ionisation occurs and not the deposition of the cations (eg Ca ions) in the fused salt, and also to ensure that, whilst reduction of one of the metals occurs smoothly, the 15 other metals are not reduced and remain in the anode as oxides. The only by-
products which are produced are oxygen, carbon monoxide and carbon dioxide gases.
The process may be applied to the separation of a wide variety of metals. Specific examples of metals which may be successfully separated in this way include metals 20 of the transition, lanthanide and actinide series which are comprised as the oxides in mixed oxide samples. The broad usefulness and versatility of the method is illustrated by its applicability to the separation of metals from mixtures of two or
more metal oxides.
25 A specific example of a preferred application of the process is in the separation of hafnium, present as the oxide, in samples of zirconium oxide. Zirconium metal is widely used in the nuclear power industry in zircalloy cladding. However, haDnium serves as a poison in nuclear reactors and it is vital, therefore, that it should be removed from the zirconium metal prior to the incorporation of this material in 30 cladding. Its removal is facilitated by the process of the present invention, wherein a
suitable potential difference is applied in order to facilitate the reduction of zirconium oxide to zirconium metal whilst leaving the hafnium oxide unchanged.
The mixed oxide may be in any physical form, and this is generally dependent on the 5 particular application from which it has resulted. For example, it may be provided as solid pieces of irregular size and shape, but it may also comprise a powder, an amorphous mass, or a dense solid agglomerate. In any event, the material may be treated according to the method of the present invention by connection to an electrical circuit such that it serves as the cathode during electrolysis. Connection to 10 the circuit may be effected by any of the standard means well known to those skilled in the art.
Preferably the mixed oxide is in contact with the cathode of an electrochemical cell.
The cathode could be in the form of a mesh basket. The molten salt electrolyte may 15 be any suitable molten salt or mixture of such salts, for instance chloride salts, preferably CaCI2 and/or BaCl2. The anode may be any suitable inert anode, such as carbon. The separation step, whereby the metal is separated from the remaining metal oxides, 20 may comprise any of a number of techniques well known to those skilled in the art.
Thus, for example, simple dissolution and solvent extraction techniques may be applicable; alternatively, heating and slagging methods could be appropriate. As a further alternative, additional electrochemical means may be employed to effect the separation. Optionally, reduction of the selected metal oxide may be carried out in one particular molten salt, whilst separation of that metal from the other metal oxide or oxides is effected in a different molten salt composition. Alternatively, the two processes may be performed in the same molten salt.
Detailed description of the Invention
In order to carry out an embodiment of the present invention, an electrolytic cell is assembled which has a carbon anode and a mesh basket cathode. A mixed oxide sample is placed in the mesh basket. The electrolyte consists of a molten salt or a 5 mixture of such salts comprising, for example, chloride salts such as CaCl2 or BaCI2.
A voltage is applied between the cathode and the anode. At the cathode the reaction involves the diffusion of oxygen atoms to the surface of the solid, followed by ionisation according to the reaction: O + 2e- o2 10 The oxide ions which are produced dissolve in the electrolyte and are transferred to the anode where they are re-oxidised to produce oxygen gas. Further by-products include carbon monoxide and carbon dioxide. The potential at the cathode may be controlled, via a third reference electrode, to ensure that the reaction occurring at the cathode is oxygen ionisation and not deposition of the cations in the fused salt, and 15 that only a selected metal oxide is reduced. Electrolysis at elevated temperatures results in an increased rate of oxygen diffusion, thereby also encouraging ionisation rather than metal deposition.
After electrolysis the mixed oxide sample is left in the form of a metal/metal oxide 20 solid mixture at the cathode, with one of the metals having been reduced to the metallic form, whilst the other metals remain in the form of their oxides. This metallic/metal oxide product is then subjected to a suitable separation treatment.
Claims (13)
1. A process for the separation of metals, said metals being comprised as the metal oxides in a mixed oxide sample, the process comprising: 5 (i) adding the mixed oxide to a molten salt electrolyte and cathodically electrolysing the oxide, the potential of the cathode being controlled so as to favour oxygen ionisation over deposition of metal from the cations present in the molten salt, and the applied potential difference being such as to 10 facilitate selective reduction of one metal oxide at the expense of other metal oxides; and (ii) separating the metal from the remaining metal oxides.
2. A process as claimed in claim 1 wherein said mixed oxide sample comprises 15 a mixture of two or more metal oxides.
3. A process as claimed in claim I or 2 wherein metal oxides comprise oxides of metals from at least one of the transition metal, lanthanide or actinide series.
20
4. A process as claimed in claim 3 wherein said metals comprise zirconium and haLnium and said mixed oxide sample comprises mixed zirconium and haLnium oxides.
5. A process as claimed in any one of claims 1 to 4 wherein the mixed oxide is 25 provided as solid pieces of irregular size and shape, a powder, an amorphous mass, or a dense solid agglomerate.
6. A process as claimed in any preceding claim wherein the oxide is located in a mesh basket which forms the cathode.
7. A process as claimed in any preceding claim wherein the molten salt electrolyte comprises at least one chloride salt.
8. A process as claimed in claim 7 wherein the chloride salt is CaCI2 or BaCI2.
9. A process as claimed in any preceding claim wherein the anode is a carbon anode.
10. A process as claimed in any preceding claim wherein the step of separating 10 the metal from the remaining metal oxides is carried out by the use of dissolution and solvent extraction techniques, heating and slagging methods or electrochemical means.
11. A process as claimed in any preceding claim wherein said reduction of the 15 selected metal oxide is carried out in one molten salt whilst separation of the metal from the other metal oxide or oxides is effected in a different molten salt composition.
12. A process as claimed in any one of claims 1 to 10 wherein said reduction of 20 the selected metal oxide and said separation of the metal from the other metal oxide or oxides is performed in the same molten salt.
13. A process substantially as hereinbefore described and with reference to the accompanying description.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0228322A GB2395958A (en) | 2002-12-05 | 2002-12-05 | Electrolytic separation of metals |
| PCT/GB2003/005238 WO2004050955A2 (en) | 2002-12-05 | 2003-12-02 | Separation of metals |
| JP2004556519A JP2006509104A (en) | 2002-12-05 | 2003-12-02 | Metal separation |
| US10/537,744 US20060137992A1 (en) | 2002-12-05 | 2003-12-02 | Separation of metals |
| AT03778571T ATE323788T1 (en) | 2002-12-05 | 2003-12-02 | SEPARATION OF METALS |
| DE60304738T DE60304738D1 (en) | 2002-12-05 | 2003-12-02 | SEPARATION OF METALS |
| AU2003285572A AU2003285572A1 (en) | 2002-12-05 | 2003-12-02 | Separation of metals |
| EP03778571A EP1570114B1 (en) | 2002-12-05 | 2003-12-02 | Separation of metals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0228322A GB2395958A (en) | 2002-12-05 | 2002-12-05 | Electrolytic separation of metals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0228322D0 GB0228322D0 (en) | 2003-01-08 |
| GB2395958A true GB2395958A (en) | 2004-06-09 |
Family
ID=9949081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0228322A Withdrawn GB2395958A (en) | 2002-12-05 | 2002-12-05 | Electrolytic separation of metals |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20060137992A1 (en) |
| EP (1) | EP1570114B1 (en) |
| JP (1) | JP2006509104A (en) |
| AT (1) | ATE323788T1 (en) |
| AU (1) | AU2003285572A1 (en) |
| DE (1) | DE60304738D1 (en) |
| GB (1) | GB2395958A (en) |
| WO (1) | WO2004050955A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2298964A1 (en) * | 2008-06-30 | 2011-03-23 | Kabushiki Kaisha Toshiba | Process for producing metallic zirconium |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0113749D0 (en) * | 2001-06-06 | 2001-07-25 | British Nuclear Fuels Plc | Actinide production |
| GB0601697D0 (en) * | 2006-01-27 | 2006-03-08 | Pryde Neil Ltd | Garment affording protection against knocks or blows |
| US20100219344A1 (en) * | 2009-02-27 | 2010-09-02 | Battelle Memorial Institute | Electrochemically Modulated Separations for In-line and At-line Monitoring of Actinides in High-Volume Process Streams |
| JP5534700B2 (en) * | 2009-04-06 | 2014-07-02 | 株式会社東芝 | Electrolytic production apparatus and production method for metal |
| CN108277507A (en) * | 2018-02-06 | 2018-07-13 | 北京科技大学 | A kind of method of vanadium and chromium in electrolytic separation containing vanadium and chromium fused salt |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB945899A (en) * | 1960-08-22 | 1964-01-08 | Atomic Energy Commission | Separation of uranium and plutonium oxides |
| US4995948A (en) * | 1989-07-24 | 1991-02-26 | The United States Of America As Represented By The United States Department Of Energy | Apparatus and process for the electrolytic reduction of uranium and plutonium oxides |
| US5454914A (en) * | 1993-12-23 | 1995-10-03 | The United States Of America As Represented By The United States Department Of Energy | Method of removal of heavy metal from molten salt in IFR fuel pyroprocessing |
| US5478664A (en) * | 1993-04-05 | 1995-12-26 | Santoku Metal Industry Co., Ltd. | Method of recovering reusable metals from nickel-hydrogen rechargeable battery |
| WO1999064638A1 (en) * | 1998-06-05 | 1999-12-16 | Cambridge University Technical Services Limited | Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt |
| WO2001041152A2 (en) * | 1999-12-03 | 2001-06-07 | British Nuclear Fuels Plc | Actinide production |
| GB2359564A (en) * | 2000-02-22 | 2001-08-29 | Secr Defence | Electrolytic reduction of metal oxides |
| WO2002099815A2 (en) * | 2001-06-06 | 2002-12-12 | British Nuclear Fuels Plc | Actinide production |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762694A (en) * | 1987-05-01 | 1988-08-09 | The United States Of America As Represented By The United States Department Of Energy | Molten salt extraction process for the recovery of valued transition metals from land-based and deep-sea minerals |
| US4923577A (en) * | 1988-09-12 | 1990-05-08 | Westinghouse Electric Corp. | Electrochemical-metallothermic reduction of zirconium in molten salt solutions |
| GB0104253D0 (en) * | 2001-02-21 | 2001-04-11 | British Nuclear Fuels Plc | Process for separating metals |
-
2002
- 2002-12-05 GB GB0228322A patent/GB2395958A/en not_active Withdrawn
-
2003
- 2003-12-02 US US10/537,744 patent/US20060137992A1/en not_active Abandoned
- 2003-12-02 JP JP2004556519A patent/JP2006509104A/en active Pending
- 2003-12-02 WO PCT/GB2003/005238 patent/WO2004050955A2/en active IP Right Grant
- 2003-12-02 DE DE60304738T patent/DE60304738D1/en not_active Expired - Lifetime
- 2003-12-02 AT AT03778571T patent/ATE323788T1/en not_active IP Right Cessation
- 2003-12-02 EP EP03778571A patent/EP1570114B1/en not_active Expired - Lifetime
- 2003-12-02 AU AU2003285572A patent/AU2003285572A1/en not_active Abandoned
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB945899A (en) * | 1960-08-22 | 1964-01-08 | Atomic Energy Commission | Separation of uranium and plutonium oxides |
| US4995948A (en) * | 1989-07-24 | 1991-02-26 | The United States Of America As Represented By The United States Department Of Energy | Apparatus and process for the electrolytic reduction of uranium and plutonium oxides |
| US5478664A (en) * | 1993-04-05 | 1995-12-26 | Santoku Metal Industry Co., Ltd. | Method of recovering reusable metals from nickel-hydrogen rechargeable battery |
| US5454914A (en) * | 1993-12-23 | 1995-10-03 | The United States Of America As Represented By The United States Department Of Energy | Method of removal of heavy metal from molten salt in IFR fuel pyroprocessing |
| WO1999064638A1 (en) * | 1998-06-05 | 1999-12-16 | Cambridge University Technical Services Limited | Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt |
| WO2001041152A2 (en) * | 1999-12-03 | 2001-06-07 | British Nuclear Fuels Plc | Actinide production |
| GB2359564A (en) * | 2000-02-22 | 2001-08-29 | Secr Defence | Electrolytic reduction of metal oxides |
| WO2002099815A2 (en) * | 2001-06-06 | 2002-12-12 | British Nuclear Fuels Plc | Actinide production |
Non-Patent Citations (2)
| Title |
|---|
| Journal of Alloys and Compounds, vol 237, 1996, pages 150-154 * |
| Metallurgical Transactions B, vol 24B, 1993, pages 449-455 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2298964A1 (en) * | 2008-06-30 | 2011-03-23 | Kabushiki Kaisha Toshiba | Process for producing metallic zirconium |
| EP2298964A4 (en) * | 2008-06-30 | 2011-07-20 | Toshiba Kk | Process for producing metallic zirconium |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1570114B1 (en) | 2006-04-19 |
| US20060137992A1 (en) | 2006-06-29 |
| DE60304738D1 (en) | 2006-05-24 |
| WO2004050955A3 (en) | 2005-01-13 |
| AU2003285572A8 (en) | 2004-06-23 |
| WO2004050955A2 (en) | 2004-06-17 |
| EP1570114A2 (en) | 2005-09-07 |
| AU2003285572A1 (en) | 2004-06-23 |
| GB0228322D0 (en) | 2003-01-08 |
| ATE323788T1 (en) | 2006-05-15 |
| JP2006509104A (en) | 2006-03-16 |
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