GB2362164A - Electrolytic reduction of sintered mass of metal oxide - Google Patents

Electrolytic reduction of sintered mass of metal oxide Download PDF

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Publication number
GB2362164A
GB2362164A GB0010873A GB0010873A GB2362164A GB 2362164 A GB2362164 A GB 2362164A GB 0010873 A GB0010873 A GB 0010873A GB 0010873 A GB0010873 A GB 0010873A GB 2362164 A GB2362164 A GB 2362164A
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GB
United Kingdom
Prior art keywords
metal oxide
feedstock
electrolytic reduction
sintered
microns
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.)
Granted
Application number
GB0010873A
Other versions
GB0010873D0 (en
GB2362164B (en
Inventor
Alastair Bryan Godfrey
Charles Malcolm Ward-Close
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UK Secretary of State for Defence
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UK Secretary of State for Defence
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by UK Secretary of State for Defence filed Critical UK Secretary of State for Defence
Priority to GB0010873A priority Critical patent/GB2362164B/en
Publication of GB0010873D0 publication Critical patent/GB0010873D0/en
Priority to EP01905907A priority patent/EP1257678B1/en
Priority to US10/204,465 priority patent/US20030047462A1/en
Priority to AU3387601A priority patent/AU3387601A/en
Priority to DE60130322T priority patent/DE60130322T2/en
Priority to PCT/GB2001/000661 priority patent/WO2001062995A1/en
Priority to AT01905907T priority patent/ATE372395T1/en
Priority to EP01905901A priority patent/EP1257677A1/en
Priority to US10/204,460 priority patent/US20030057101A1/en
Priority to AU2001233876A priority patent/AU2001233876B2/en
Priority to AU2001233871A priority patent/AU2001233871A1/en
Priority to PCT/GB2001/000653 priority patent/WO2001062994A1/en
Priority to JP2001561803A priority patent/JP4703931B2/en
Priority to GB0218516A priority patent/GB2376241B/en
Priority to EP08075215A priority patent/EP1956102B1/en
Priority to EP01905924A priority patent/EP1257679B1/en
Priority to EA200401129A priority patent/EA008264B1/en
Priority to JP2001561804A priority patent/JP4995392B2/en
Priority to ES01905924T priority patent/ES2231443T3/en
Priority to PCT/GB2001/000683 priority patent/WO2001062996A1/en
Priority to AT01905924T priority patent/ATE286150T1/en
Priority to DE60108081T priority patent/DE60108081T2/en
Priority to AU2001233890A priority patent/AU2001233890B2/en
Priority to KR1020027010919A priority patent/KR100767981B1/en
Priority to DK08075215.7T priority patent/DK1956102T3/en
Priority to EP04022898A priority patent/EP1489192A1/en
Priority to US10/204,547 priority patent/US6921473B2/en
Priority to UA2002097584A priority patent/UA74179C2/en
Priority to AU3389001A priority patent/AU3389001A/en
Priority to EA200601812A priority patent/EA013138B1/en
Priority to CNB018054552A priority patent/CN1279194C/en
Priority to EA200200895A priority patent/EA005348B1/en
Priority to CN2006101150285A priority patent/CN1982506B/en
Priority to CA2401034A priority patent/CA2401034C/en
Publication of GB2362164A publication Critical patent/GB2362164A/en
Application granted granted Critical
Publication of GB2362164B publication Critical patent/GB2362164B/en
Priority to US11/149,588 priority patent/US20060110277A1/en
Priority to US12/929,993 priority patent/US20110158843A1/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
    • 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
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • 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
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 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
    • 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
    • C22B5/00—General methods of reducing to metals
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • 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
    • 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
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/06—Alloys

Abstract

A method of electrolytic reduction of a metal oxide, in particular titanium dioxide, wherein said electrolysis is preformed on a sintered mass of a mixture of metal oxide substantially comprising particles of size greater than 20 microns and finer particles of less than 7 microns. The sintered mass is preferably formed by mixing binder and water. The finer particles may make up 5 - 70% by weight of the mass.

Description

2362164 Improved Feedstock for Electrolytic Reduction of Metal Oxide.
PCT Patent Application W099/64638 describes a method of removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt, and has particular application to titanium dioxide reduction.
The possibility of producing inexpensive Ti and Ti alloy powders is of tremendous economic importance. Several attempts have been made using the process described above with varying degrees of success. A problem with this process is that to get reduction of the oxide electrical contact must be maintained for some time at a temperature at which oxygen diffuses readily. Under these conditions the titanium will diffusion bond to itself resulting in clumps of material stuck together rather than free flowing powder.
It is an object of the invention to overcome this problem by providing a feedstock for the process which overcomes these problems.
The invention comprises a method of electrolytic reduction of a metal oxide wherein said electrolysis is preformed on a sintered mass of a mixture of metal oxide substantially comprising particles of size generally greater than 20 microns and finer particles of less than 7 microns.
Preferably the finer particles make up between 10 and 55% of the sintered block by weight.
High density granules of approximately the size required for the powder are manufactured and then are mixed with very fine unsintered titanium dioxide, binder and water in the appropriate ratios and formed into the required shape of feedstock. This feedstock is then sintered at to achieve the required strength for the reduction process. The resulting feedstock after sintering but before reduction consists of high density granules in a low density (porous) matrix.
The feedstock can be reduced as blocks using the usual method and the result is a friable block which can easily be broken up into powder. The reason for this is that the matrix shrinks considerably during the reduction resulting in a sponge-like structure, but the granules shrink to 2 form a more or less solid structure. The matrix can conduct electricity to the granules but is easily broken after reduction.
Example About 1 kg of rutile sand (titanium dioxide content 95%) from Richard Bay Minerals, South Africa, with an average particle size of 100 ptm was mixed with 10 wt.% rutile calciner discharge from the company TiOxide (made from the sulphate process) which had been ground in a pestle and mortar to ensure a fine particle agglomerate size. To this was added a further 2 wt.% binder (methyl cellulose) and the whole mix was shaken with a mechanical shaker for 30 minutes to ensure a homogenous feedstock. The resulting material was then mixed with distilled water until the consistency of the paste was about that of putty. This material was then flattened by hand onto a sheet of aluminium foil to a thickness of about 5 min and then scored, using a scalpel blade, into squares of side 30 mm. This material was then allowed to dry overnight in a drying oven at 700C. On removal from the oven it was then possible to peel off the foil and break the rutile into squares as marked by the scalpel blade. The binder gives significant strength to the feedstock thus enabling a 5 mm diameter hole to be drilled in the centre of each square for mounting on the electrode at a later stage. Since no shrinkage was anticipated in the sintering stage no allowance for shrinkage in the calculation of the hole size was necessary.
About 50 squares of the rutile were loaded up into a furnace in air at room temperature and the furnace was switched on and allowed to heat at its natural rate to 1300'C (time to heat up around 30 minutes). After 2 hours at this temperature the furnace was switched off and allowed to cool at its natural rate (about 200C per minute initially). When the rutile was below I OO'C it was unloaded from the furnace and stacked onto a M5 threaded stainless steel rod which was to be used as the current carrier. The total amount of rutile loaded was 387 g. The bulk density of the feedstock in this form was measured and found to be 2.33 0.07 kg/I (i.e. 55% dense), and its strength for handling was found to be quite sufficient.
The feedstock was then electrolysed using the process described in the above referenced patent application at up to 3V for 51 hours at an electrolyte temperature of 1000'C. The resulting material after cleaning and removal of the electrode rod had a weight of 214 g. Oxygen and 3 nitrogen analysis indicated that the levels of these interstitials were 800 ppm. and 5 ppm respectively. The form of the product was very similar to that of the feedstock except the colour change and slight shrinkage. Due to the process used to manufacture the feedstock the product was friable and could be crushed up using fingers and pliers to a reasonably fine powder. Some of the particles were large therefore the material was passed through a 250 gm sieve. Approximately 65% by weight of the material was small enough to pass through the 250 Lrn sieve after using this simple crushing technique.
The resulting powder was washed in hot water to remove the salt and very fine particles, then it was washed in glacial acetic acid to remove the CaO and then finally in water again to remove the acid. The powder was then dried in a drying oven overnight at 70 'C. The results can be expressed as the concentration of calciner discharge required to achieve useable strength of the feedstock after sintering. At 1300T about 10% was required, at 1200T about 25% was required and at 10000C at least 50% was required although this still gave a very weak feedstock.
The calciner discharge used can be replaced by cheaper amorphous Ti02. The key requirement for this 'matrix' material is that it sinters easily with significant shrinkage during the sintering process. Any oxide or mixture of oxides which fulfil these criteria would be usable. For Ti02 this means the particle size must be less than about 1 gm. It is estimated that at least 5% matrix material should be present in order to give any significant strength to the sintered product.
The starting granules need not be rutile sand but could be manufactured by a sintering and crushing process, and in principle there is no reason to suppose that alloy powders could not be made by this route. Other metal powders could also presumably be made by this route.
4

Claims (9)

Claims
1. A method of electrolytic reduction of a metal oxide wherein said electrolysis is preforined on a sintered mass of a mixture of metal oxide substantially comprising particles of size greater than 20 microns and finer particles of less than 7 microns.
2. A method of electrolytic reduction of metal oxide as claimed in claim I wherein said sintered mass is additionally formed by mixing binder and water.
3. A method as claimed in any preceding claim wherein said metal oxide is titanium oxide.
4. A method as claimed in any preceding claim wherein said finer particles make up between 5 and 70% of the sintered block by weight.
5. A method as claimed in any preceding claim wherein said finer particles make up between 10 and 55% of the sintered block by weight.
6. A feedstock for the electrolytic reduction of metal oxide, said feedstock comprising a sintered mass of a mixture of metal oxide particles of size greater than 20 microns and finer particles of less than 7 microns.
7. A feedstock as claimed in claim 6 wherein said metal oxide is titanium oxide.
8. A feedstock as claimed in claim 7 wherein said finer particles make up between 5 and 70% of the sintered block by weight.
9. A feedstock as claimed in claim 8 wherein said finer particles make up between 10 and 55% of the sintered block by weight.
GB0010873A 2000-02-22 2000-05-08 Improved feedstock for electrolytic reduction of metal oxide Expired - Fee Related GB2362164B (en)

Priority Applications (36)

Application Number Priority Date Filing Date Title
GB0010873A GB2362164B (en) 2000-05-08 2000-05-08 Improved feedstock for electrolytic reduction of metal oxide
AT01905907T ATE372395T1 (en) 2000-02-22 2001-02-19 METHOD FOR PRODUCING METAL FOAM BY ELECTROLYTIC REDUCTION OF POROUS OXIDIC PREFORMS
US10/204,465 US20030047462A1 (en) 2000-02-22 2001-02-19 Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction
AU3387601A AU3387601A (en) 2000-02-22 2001-02-19 Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
DE60130322T DE60130322T2 (en) 2000-02-22 2001-02-19 METHOD OF PREPARING METAL FOAM BY ELECTROLYTIC REDUCTION OF POROUS OXIDIC PREPARATIONS
PCT/GB2001/000661 WO2001062995A1 (en) 2000-02-22 2001-02-19 Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
EP01905907A EP1257678B1 (en) 2000-02-22 2001-02-19 Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
EP01905901A EP1257677A1 (en) 2000-02-22 2001-02-19 Method of manufacture for ferro-titanium and other metal alloys by electrolytic reduction
US10/204,460 US20030057101A1 (en) 2000-02-22 2001-02-19 Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
AU2001233876A AU2001233876B2 (en) 2000-02-22 2001-02-19 Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
AU2001233871A AU2001233871A1 (en) 2000-02-22 2001-02-19 Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction
PCT/GB2001/000653 WO2001062994A1 (en) 2000-02-22 2001-02-19 Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction
JP2001561803A JP4703931B2 (en) 2000-02-22 2001-02-19 Method for producing metal foam by electrolytic reduction of porous oxide preform
GB0218516A GB2376241B (en) 2000-02-22 2001-02-19 Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
ES01905924T ES2231443T3 (en) 2000-02-22 2001-02-20 ELECTROLYTIC REDUCTION OF OXIDES SUCH AS TITANIUM DIOXIDE AND APPLICATIONS OF THE PROCEDURE.
UA2002097584A UA74179C2 (en) 2000-02-22 2001-02-20 A method for electrolytic reduction of metals oxides or metalloids and application of the method
EA200401129A EA008264B1 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
JP2001561804A JP4995392B2 (en) 2000-02-22 2001-02-20 Electroreduction of metal oxides such as titanium dioxide and application of the method
EP08075215A EP1956102B1 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxide particles such as titanium dioxide
PCT/GB2001/000683 WO2001062996A1 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
AT01905924T ATE286150T1 (en) 2000-02-22 2001-02-20 METHOD FOR THE ELECTROLYTIC REDUCTION OF METAL OXIDES SUCH AS PARTICULAR TITANIUM DIOXIDE AND THE USE OF IT
DE60108081T DE60108081T2 (en) 2000-02-22 2001-02-20 Process for the electrolytic reduction of metal oxides such as titanium dioxide and its application
AU2001233890A AU2001233890B2 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
KR1020027010919A KR100767981B1 (en) 2000-02-22 2001-02-20 A method for recovering a metal, semi-metal or alloy from a metal oxide or semi-metal oxide or a mixture of oxides of alloying elements
DK08075215.7T DK1956102T3 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxide particles such as titanium dioxide
EP04022898A EP1489192A1 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
US10/204,547 US6921473B2 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
EP01905924A EP1257679B1 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
AU3389001A AU3389001A (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
EA200601812A EA013138B1 (en) 2000-02-22 2001-02-20 Method of electrolytic reduction of metal oxides such as titanium dioxide and method for use thereof
CNB018054552A CN1279194C (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process application
EA200200895A EA005348B1 (en) 2000-02-22 2001-02-20 Method of electrolytic reduction of metal oxides such as titanium dioxide and process applications
CN2006101150285A CN1982506B (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
CA2401034A CA2401034C (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
US11/149,588 US20060110277A1 (en) 2000-02-22 2005-06-10 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
US12/929,993 US20110158843A1 (en) 2000-02-22 2011-03-01 Electrolytic reduction of metal oxides such as titanium dioxide and process applications

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB0010873A GB2362164B (en) 2000-05-08 2000-05-08 Improved feedstock for electrolytic reduction of metal oxide

Publications (3)

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GB0010873D0 GB0010873D0 (en) 2000-06-28
GB2362164A true GB2362164A (en) 2001-11-14
GB2362164B GB2362164B (en) 2004-01-28

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004053201A1 (en) * 2002-12-12 2004-06-24 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
WO2005031041A1 (en) * 2003-09-26 2005-04-07 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
WO2005038092A1 (en) * 2003-10-14 2005-04-28 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
WO2005090640A1 (en) * 2004-03-22 2005-09-29 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
US7758740B2 (en) 2003-06-20 2010-07-20 Metalysis Limited Electrochemical reduction of metal oxides

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB781803A (en) * 1954-04-26 1957-08-28 Horizons Titanium Corp Electrolytic removal of oxygen from titanium, zirconium, vanadium, molybdenum, manganese and chromium
GB1362991A (en) * 1972-07-20 1974-08-14 Atomic Energy Authority Uk Processes of making nuclear fuel artefacts
GB1374832A (en) * 1972-04-11 1974-11-20 Magnesium Elektron Ltd Sintered zirconia bodies
US4157285A (en) * 1975-05-27 1979-06-05 Universite Libre De Bruxelles Method for preparing manganese chloride and manganese by igneous electrolysis of the manganese chloride obtained
US4187155A (en) * 1977-03-07 1980-02-05 Diamond Shamrock Technologies S.A. Molten salt electrolysis
EP0026666A1 (en) * 1979-09-28 1981-04-08 Sumitomo Aluminium Smelting Company Limited Method of producing sintered zirconia article
WO1998049371A1 (en) * 1997-04-30 1998-11-05 The Alta Group, Inc. Apparatus for producing titanium crystal and titanium
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1257677A1 (en) * 2000-02-22 2002-11-20 Qinetiq Limited Method of manufacture for ferro-titanium and other metal alloys by electrolytic reduction

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB781803A (en) * 1954-04-26 1957-08-28 Horizons Titanium Corp Electrolytic removal of oxygen from titanium, zirconium, vanadium, molybdenum, manganese and chromium
GB1374832A (en) * 1972-04-11 1974-11-20 Magnesium Elektron Ltd Sintered zirconia bodies
GB1362991A (en) * 1972-07-20 1974-08-14 Atomic Energy Authority Uk Processes of making nuclear fuel artefacts
US4157285A (en) * 1975-05-27 1979-06-05 Universite Libre De Bruxelles Method for preparing manganese chloride and manganese by igneous electrolysis of the manganese chloride obtained
US4187155A (en) * 1977-03-07 1980-02-05 Diamond Shamrock Technologies S.A. Molten salt electrolysis
EP0026666A1 (en) * 1979-09-28 1981-04-08 Sumitomo Aluminium Smelting Company Limited Method of producing sintered zirconia article
WO1998049371A1 (en) * 1997-04-30 1998-11-05 The Alta Group, Inc. Apparatus for producing titanium crystal and titanium
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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004053201A1 (en) * 2002-12-12 2004-06-24 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
US7470355B2 (en) 2002-12-12 2008-12-30 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
US7758740B2 (en) 2003-06-20 2010-07-20 Metalysis Limited Electrochemical reduction of metal oxides
WO2005031041A1 (en) * 2003-09-26 2005-04-07 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
WO2005038092A1 (en) * 2003-10-14 2005-04-28 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
EA009106B1 (en) * 2003-10-14 2007-10-26 Би Эйч Пи БИЛЛИТОН ИННОВЕЙШН ПТИ ЛТД. Electrochemical reduction of metal oxides
WO2005090640A1 (en) * 2004-03-22 2005-09-29 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides

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Publication number Publication date
GB0010873D0 (en) 2000-06-28
GB2362164B (en) 2004-01-28

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Legal Events

Date Code Title Description
732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
PCNP Patent ceased through non-payment of renewal fee

Effective date: 20060508