EP2770086A2 - Réduction d'oxydes métalliques dans une cellule électrolytique - Google Patents
Réduction d'oxydes métalliques dans une cellule électrolytique Download PDFInfo
- Publication number
- EP2770086A2 EP2770086A2 EP20140163470 EP14163470A EP2770086A2 EP 2770086 A2 EP2770086 A2 EP 2770086A2 EP 20140163470 EP20140163470 EP 20140163470 EP 14163470 A EP14163470 A EP 14163470A EP 2770086 A2 EP2770086 A2 EP 2770086A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- electrolyte
- cathode
- metal oxide
- potential
- 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.)
- Withdrawn
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 36
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 36
- 230000009467 reduction Effects 0.000 title description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 23
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 23
- 239000001110 calcium chloride Substances 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- -1 oxygen anions Chemical class 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000005012 migration Effects 0.000 claims description 3
- 238000013508 migration Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 description 12
- 239000008188 pellet Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007248 cellular mechanism Effects 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 2
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 229910000953 kanthal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
-
- 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
- C22B34/129—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
- 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
- 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
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/18—Electrolytes
Definitions
- the present invention relates to reduction of metal oxides in a solid state in an electrolytic cell.
- the present invention was made during the course of an on-going research project on solid state reduction of titania (TiO 2 ) carried out by the applicant.
- the Cambridge International application discloses two potential applications of a "discovery" in the field of metallurgical electrochemistry.
- One application is the direct production of a metal from a metal oxide.
- the "discovery” is the realisation that an electrolytic cell can be used to ionise oxygen contained in a metal oxide so that the oxygen dissolves in an electrolyte.
- the Cambridge International application discloses that when a suitable potential is applied to an electrolytic cell with a metal oxide as a cathode, a reaction occurs whereby oxygen is ionised and is subsequently able to dissolve in the electrolyte of the cell.
- the allowed claims of the European patent application inter alia define a method of electrolytically reducing a metal oxide (such as titania) that includes operating an electrolytic cell at a potential at an electrode formed from the metal oxide that is lower than the deposition potential of cations in the electrolyte at a surface of the electrode.
- a metal oxide such as titania
- the Cambridge European patent application does not define what is meant by deposition potential and does not include any specific examples that provide values of the deposition potential for particular cations.
- page 5 of the submissions state that:
- the experimental work was carried out using a CaCl 2 -based electrolyte at a cell potential below the decomposition potential of CaCl 2 .
- the applicant believes that the initial deposition of Ca metal on the cathode was due to the presence of Ca ++ cations and O -- anions derived from CaO in the electrolyte.
- the decomposition potential of CaO is less than the decomposition potential of CaCl 2 .
- the cell operation is dependent, at least during the early stages of cell operation, on decomposition of CaO, with Ca ++ cations migrating to the cathode and depositing as Ca metal and O -- anions migrating to the anode and forming CO and/or CO 2 (in a situation in which the anode is a graphite anode).
- the applicant also believes that at later stages of the cell operation part of the Ca metal that deposited on the cathode was deposited directly on partially deoxidised titanium and thereafter participated in chemical reduction of titanium.
- the cathode is formed at least in part from the metal oxide.
- the method includes operating the cell at the potential that is above the potential at which cations of the metal that is capable of chemically reducing the metal oxide deposit as the metal on the cathode so that the metal deposits on the cathode.
- the metal deposited on the cathode is soluble in the electrolyte and can dissolve in the electrolyte and thereby migrate to the vicinity of the metal oxide.
- the electrolyte be a CaCl 2 -based electrolyte that includes CaO as one of the constituents of the electrolyte.
- the present invention does not require the addition of substantial amounts of CaO to the electrolyte.
- the cell potential be above a potential at which Ca metal can deposit on the cathode, i.e. at a potential that is above the decomposition potential of CaO.
- the decomposition potential of CaO can vary over a considerable range depending on factors such as the composition of the anode, the electrolyte temperature and electrolyte composition.
- the cell potential be below the potential at which Cl - anions can deposit on the anode and form chlorine gas, i.e. the decomposition potential of CaCl 2 .
- the decomposition potential of CaCl 2 can vary over a considerable range depending on factors such as the composition of the anode, the electrolyte temperature and electrolyte composition.
- the cell potential be between 1.3 and 3.5V.
- the CaCl 2 -based electrolyte may be a commercially available source of CaCl 2 , such as calcium chloride dihydrate, that partially decomposes on heating and produces CaO or otherwise includes CaO.
- the CaCl 2 -based electrolyte may include CaCl 2 and CaO that are added separately or pre-mixed to form the electrolyte.
- the anode be graphite or an inert anode.
- Carbon in the titanium is an undesirable contaminant.
- carbon transfer was partially responsible for low energy efficiency of the cell. Both problems could present significant barriers to commercialisation of electrolytic reduction technology.
- the dominant mechanism of carbon transfer is electrochemical rather than erosion and that one way of minimising carbon transfer and therefore contamination of titanium produced at the cathode by electrochemical reduction of titania is to position a membrane that is permeable to oxygen anions and is impermeable to carbon in ionic and non-ionic forms between the cathode and the anode and thereby prevent migration of carbon to the cathode.
- the electrolytic cell includes a membrane that is permeable to oxygen anions and is impermeable to carbon in ionic and non-ionic forms positioned between the cathode and the anode to thereby prevent migration of carbon to the cathode.
- the membrane may be formed from any suitable material.
- the membrane is formed from a solid electrolyte.
- One solid electrolyte tested by the applicant is yttria stabilised zirconia.
- an electrolytic cell as described above and operating in accordance with the above described method.
- the electrolytic cell is shown in Figure 1 .
- the electrochemical cell included a graphite crucible equipped with a graphite lid.
- the crucible was used as the cell anode.
- a stainless steel rod was used to secure electrical contact between a d/c power supply and the crucible.
- the cell cathode consisted of Kanthal or platinum wire connected at one end to the power supply and TiO 2 pellets suspended from the other end of the wire.
- An alumina tube was used as an insulator around the cathode.
- the cell electrolyte was a commercially available source of CaCl 2 , namely calcium chloride dihydrate, that partially decomposed on heating at the operating temperature of the cell and produced CaO.
- a thermocouple was immersed in the electrolyte in close proximity to the pellets.
- pellets Two types were used. One type was slip-cast and the other type was pressed. Both types of pellets were made from analytical grade TiO 2 powder. Both types of pellets were sintered in air at 850°C. One pressed and one slip-cast pellet were used in the experiment.
- the power-supply maintained a constant voltage throughout the experiment.
- the voltage and resulting cell current were logged using LabVIEW (TM) data acquisition software.
- the constant voltage (3V) used in the experiment produced an initial current of approximately 1.2A. A continuous drop in the current was observed during the initial 2 hours. After that a gradual increase in the current up to 1A was observed.
- the invention is not so limited and extends to reduction of other titanium oxides and to oxides of other metals and alloys.
- examples of other potentially important metals are aluminium, silicon, germanium, zirconium, hafnium, magnesium and molybdenum.
- suitable electrolytes will be salts and oxides that are soluble in salts.
- suitable electrolyte is BaCl 2 .
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPS1071A AUPS107102A0 (en) | 2002-03-13 | 2002-03-13 | Electrolytic reduction of metal oxides |
| AUPS3049A AUPS304902A0 (en) | 2002-06-19 | 2002-06-19 | Reduction of metal oxides in an electrolytic cell |
| EP03743767A EP1492905A4 (fr) | 2002-03-13 | 2003-03-13 | Reduction d'oxydes metalliques dans une cellule electrolytique |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03743767A Division EP1492905A4 (fr) | 2002-03-13 | 2003-03-13 | Reduction d'oxydes metalliques dans une cellule electrolytique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2770086A2 true EP2770086A2 (fr) | 2014-08-27 |
| EP2770086A3 EP2770086A3 (fr) | 2014-10-29 |
Family
ID=27805836
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14163470.9A Withdrawn EP2770086A3 (fr) | 2002-03-13 | 2003-03-13 | Réduction d'oxydes métalliques dans une cellule électrolytique |
| EP03743767A Withdrawn EP1492905A4 (fr) | 2002-03-13 | 2003-03-13 | Reduction d'oxydes metalliques dans une cellule electrolytique |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03743767A Withdrawn EP1492905A4 (fr) | 2002-03-13 | 2003-03-13 | Reduction d'oxydes metalliques dans une cellule electrolytique |
Country Status (12)
| Country | Link |
|---|---|
| EP (2) | EP2770086A3 (fr) |
| JP (1) | JP4658479B2 (fr) |
| KR (2) | KR20110025237A (fr) |
| CN (1) | CN1650051B (fr) |
| BR (1) | BR0308384B1 (fr) |
| CA (1) | CA2479048C (fr) |
| EA (1) | EA007046B1 (fr) |
| MX (1) | MXPA04008887A (fr) |
| NO (1) | NO340277B1 (fr) |
| NZ (1) | NZ531467A (fr) |
| WO (1) | WO2003076690A1 (fr) |
| ZA (1) | ZA200407434B (fr) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPS117002A0 (en) * | 2002-03-13 | 2002-04-18 | Bhp Billiton Innovation Pty Ltd | Minimising carbon transfer in an electrolytic cell |
| GB0219640D0 (en) * | 2002-08-23 | 2002-10-02 | Univ Cambridge Tech | Electrochemical method and apparatus |
| AU2002951962A0 (en) * | 2002-10-09 | 2002-10-24 | Bhp Billiton Innovation Pty Ltd | Electrolytic reduction of metal oxides |
| AU2002952083A0 (en) | 2002-10-16 | 2002-10-31 | Bhp Billiton Innovation Pty Ltd | Minimising carbon transfer in an electrolytic cell |
| JP4513297B2 (ja) * | 2003-09-30 | 2010-07-28 | 日本軽金属株式会社 | 金属酸化物の還元方法及び金属酸化物の還元装置 |
| JP4502617B2 (ja) * | 2003-09-30 | 2010-07-14 | 日本軽金属株式会社 | 金属酸化物の還元方法及び金属酸化物の還元装置 |
| JP2007529631A (ja) * | 2004-03-22 | 2007-10-25 | ビーエイチピー ビリトン イノベーション プロプライアタリー リミテッド | 金属酸化物の電気化学的還元 |
| BRPI0512782A (pt) * | 2004-06-28 | 2008-04-08 | Bhp Billiton Innovation Pty | método para produzir metal de titánio e produtos de metal de titánio semi-acabados ou prontos para o uso |
| EA014138B1 (ru) * | 2005-08-01 | 2010-10-29 | БиЭйчПи БИЛЛИТОН ИННОВЕЙШН ПТИ ЛТД. | Электрохимическое восстановление оксидов металлов |
| NO20062776L (no) * | 2006-06-14 | 2007-12-17 | Norsk Titanium Tech As | Fremgangsmåte, apparatur samt midler for produksjon av materiale i en smeltet salt elektrolytt |
| CN100532653C (zh) * | 2006-11-03 | 2009-08-26 | 西北有色金属研究院 | 一种熔盐电解提取钛的方法 |
| GB0714021D0 (en) * | 2007-07-18 | 2007-08-29 | Green Metals Ltd | Improvements in anode materials |
| GB0902486D0 (en) * | 2009-02-13 | 2009-04-01 | Metalysis Ltd | A method for producing metal powders |
| GB201010772D0 (en) * | 2010-06-26 | 2010-08-11 | Fray Derek J | Method for texturing silicon surfaces |
| NZ610339A (en) | 2010-11-18 | 2015-11-27 | Metalysis Ltd | Method and system for electrolytically reducing a solid feedstock |
| GB201019615D0 (en) | 2010-11-18 | 2010-12-29 | Metalysis Ltd | Electrolysis apparatus and method |
| MY180279A (en) | 2010-11-18 | 2020-11-26 | Metalysis Ltd | Electrolysis apparatus |
| GB201102023D0 (en) | 2011-02-04 | 2011-03-23 | Metalysis Ltd | Electrolysis method, apparatus and product |
| RU2466216C1 (ru) * | 2011-06-17 | 2012-11-10 | Государственное образовательное учреждение высшего профессионального образования "Национальный исследовательский Томский политехнический университет" | Способ получения металлического титана электролизом |
| CA2850339C (fr) | 2011-10-04 | 2021-07-27 | Metalysis Limited | Production electrolytique de poudre |
| GB201223375D0 (en) | 2012-12-24 | 2013-02-06 | Metalysis Ltd | Method and apparatus for producing metal by electrolytic reduction |
| KR101526298B1 (ko) * | 2013-04-22 | 2015-06-10 | 서울대학교산학협력단 | 산화티타늄 전극의 제조방법, 이를 포함하는 활성산소종 생성 시스템, 염소 생성 시스템, 염료감응형 태양전지 및 전기이중층 커패시터 |
| GB201411433D0 (en) | 2014-06-26 | 2014-08-13 | Metalysis Ltd | Method and apparatus for electrolytic reduction of a feedstock comprising oxygen and a first metal |
| KR101740424B1 (ko) | 2015-08-18 | 2017-05-26 | 충남대학교산학협력단 | 일메나이트 원광을 이용한 금속 티타늄의 제조방법 |
| NL2015759B1 (en) | 2015-11-10 | 2017-05-26 | Stichting Energieonderzoek Centrum Nederland | Additive manufacturing of metal objects. |
| WO2017141044A1 (fr) * | 2016-02-17 | 2017-08-24 | Metalysis Limited | Procédés de fabrication de matériaux en graphène |
| GB201615659D0 (en) | 2016-09-14 | 2016-10-26 | Metalysis Ltd | Method of producing a powder |
| GB201615660D0 (en) | 2016-09-14 | 2016-10-26 | Metalysis Ltd | Method of producing a powder |
| GB201615658D0 (en) | 2016-09-14 | 2016-10-26 | Metalysis Ltd | Method of producing a composite material |
| NL2018890B1 (en) | 2017-05-10 | 2018-11-15 | Admatec Europe B V | Additive manufacturing of metal objects |
| NL2021611B1 (en) | 2018-09-12 | 2020-05-06 | Admatec Europe B V | Three-dimensional object and manufacturing method thereof |
| CN109763146B (zh) * | 2019-03-27 | 2021-03-26 | 贵州省过程工业技术研究中心 | 一种铝电解用钛基复合材料阳极制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999064638A1 (fr) | 1998-06-05 | 1999-12-16 | Cambridge University Technical Services Limited | Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS322357B1 (fr) * | 1954-12-29 | 1957-04-18 | ||
| ITTO970080A1 (it) * | 1997-02-04 | 1998-08-04 | Marco Vincenzo Ginatta | Procedimento per la produzione elettrolitica di metalli |
| GB2359564B (en) * | 2000-02-22 | 2004-09-29 | Secr Defence | Improvements in the electrolytic reduction of metal oxides |
| AUPR443801A0 (en) * | 2001-04-10 | 2001-05-17 | Bhp Innovation Pty Ltd | Removal of oxygen from metal oxides and solid metal solutions |
| AUPR602901A0 (en) * | 2001-06-29 | 2001-07-26 | Bhp Innovation Pty Ltd | Removal of oxygen from metals oxides and solid metal solutions |
| AUPR712101A0 (en) * | 2001-08-16 | 2001-09-06 | Bhp Innovation Pty Ltd | Process for manufacture of titanium products |
| JP2003129268A (ja) * | 2001-10-17 | 2003-05-08 | Katsutoshi Ono | 金属チタンの精錬方法及び精錬装置 |
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2003
- 2003-03-13 KR KR1020117003330A patent/KR20110025237A/ko not_active Abandoned
- 2003-03-13 CA CA2479048A patent/CA2479048C/fr not_active Expired - Fee Related
- 2003-03-13 JP JP2003574882A patent/JP4658479B2/ja not_active Expired - Fee Related
- 2003-03-13 NZ NZ531467A patent/NZ531467A/en not_active IP Right Cessation
- 2003-03-13 BR BRPI0308384-5A patent/BR0308384B1/pt not_active IP Right Cessation
- 2003-03-13 KR KR1020047014399A patent/KR101038701B1/ko not_active Expired - Fee Related
- 2003-03-13 EP EP14163470.9A patent/EP2770086A3/fr not_active Withdrawn
- 2003-03-13 EA EA200401203A patent/EA007046B1/ru not_active IP Right Cessation
- 2003-03-13 EP EP03743767A patent/EP1492905A4/fr not_active Withdrawn
- 2003-03-13 CN CN038092735A patent/CN1650051B/zh not_active Expired - Fee Related
- 2003-03-13 WO PCT/AU2003/000306 patent/WO2003076690A1/fr not_active Ceased
- 2003-03-13 MX MXPA04008887A patent/MXPA04008887A/es active IP Right Grant
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2004
- 2004-09-15 NO NO20043857A patent/NO340277B1/no not_active IP Right Cessation
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999064638A1 (fr) | 1998-06-05 | 1999-12-16 | Cambridge University Technical Services Limited | Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040111408A (ko) | 2004-12-31 |
| EP1492905A4 (fr) | 2006-06-28 |
| NO20043857L (no) | 2004-12-08 |
| EA007046B1 (ru) | 2006-06-30 |
| KR101038701B1 (ko) | 2011-06-02 |
| WO2003076690A1 (fr) | 2003-09-18 |
| CA2479048A1 (fr) | 2003-09-18 |
| JP2005520045A (ja) | 2005-07-07 |
| ZA200407434B (en) | 2006-05-31 |
| BR0308384A (pt) | 2005-01-25 |
| NZ531467A (en) | 2007-06-29 |
| CA2479048C (fr) | 2012-07-10 |
| EA200401203A1 (ru) | 2005-06-30 |
| BR0308384B1 (pt) | 2014-02-04 |
| NO340277B1 (no) | 2017-03-27 |
| MXPA04008887A (es) | 2004-11-26 |
| JP4658479B2 (ja) | 2011-03-23 |
| EP2770086A3 (fr) | 2014-10-29 |
| CN1650051B (zh) | 2011-02-23 |
| KR20110025237A (ko) | 2011-03-09 |
| CN1650051A (zh) | 2005-08-03 |
| EP1492905A1 (fr) | 2005-01-05 |
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