EP2032727A1 - PROCÉDÉ ET APPAREIL DE PRODUCTION DE Ti DANS UN ÉLECTROLYTE À SEL FONDU - Google Patents
PROCÉDÉ ET APPAREIL DE PRODUCTION DE Ti DANS UN ÉLECTROLYTE À SEL FONDUInfo
- Publication number
- EP2032727A1 EP2032727A1 EP07747642A EP07747642A EP2032727A1 EP 2032727 A1 EP2032727 A1 EP 2032727A1 EP 07747642 A EP07747642 A EP 07747642A EP 07747642 A EP07747642 A EP 07747642A EP 2032727 A1 EP2032727 A1 EP 2032727A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode
- electrolyte
- metal
- potential
- anode
- 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- Withdrawn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
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
- C22B34/129—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
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- 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
Definitions
- Titanium and its alloys exhibit excellent mechanical properties, unrivalled corrosion resistance and outstanding biocompatibility; however, annual global titanium production is dwarfed by commodity metals such as steel and aluminium.
- Kroll process One needs only to examine the complex and discontinuous production method, the Kroll process, to correlate the high price of titanium with its low consumption.
- alternate processing routes have been sought, in vain; titanium oxides are extremely stable compounds that are bound with increasing tenacity to oxygen as the latter concentration decreases.
- a high solubility for oxygen in metallic titanium necessitates carbo-chlorination of titanium dioxide to produce an oxygen-free, chloride feedstock (TiCI 4 ), which is subsequently metallothermically reduced with liquid magnesium.
- the present invention describes a process in which, a metal, M 1 , is produced in an electrolytic cell consisting of a molten electrolyte, M Z Y - M Z O, at least one anode and at least one cathode, characterised in that the passage of current between said anode(s) and cathode(s) through said electrolyte, produces a metal, M 1 , from a raw material, M 1 X, containing a non-metallic species, X, under conditions such that the potential at the cathode causes the reduction of the M z cation and the formation of M z at activities less than one.
- the M z produced in this manner reduces the raw material, M-
- the raw material feed may also contain both species M 1 and X, in a ternary or higher order oxide, of the form M 2 M 1 X, by way of example.
- E is measured in volts versus the standard state potential for the reduction of Ca 2+ to Ca 0
- R is the universal gas constant (8,3144 J-mol "1 -K "1)
- the melt contains neither calcium metal as a discrete phase nor the high concentrations of Ca 0 necessary to constitute a "strongly reducing molten salt".
- Operation of the electrolysis cell such that the cathode potential is less negative than that corresponding to saturated calcium formation, which results in the reduction of the electrolyte cation to produce calcium in the solvated state, is equally effective for reduction of the metal oxide.
- Figure 1 is a current versus potential plot of TiO 2 and Mo in CaCI 2 at 900 3 C.
- Figure 2 is a predominance diagram showing the conditions of electrode potential and melt oxide content corresponding to a given electrochemical reaction for a system with a CaCI 2 -CaO electrolyte and a graphite electrode(s).
- Figure 3 is a predominance diagram showing the conditions of electrode potential and melt oxide content corresponding to a given electrochemical reaction for a system with a CaCI 2 -CaO electrolyte, a graphite anode(s), and a cathode consisting of titanium oxide.
- FIG. 4 is a schematic diagram of the electrochemical cell used in conjunction with the present invention.
- Figure 5 is the x-ray diffraction pattern of cathode material produced after 24 hours with a cell voltage of 50OmV.
- Figure 6 is the x-ray diffraction pattern of cathode material produced after 24 hours with a cell voltage of 75OmV.
- Figure 7 is the x-ray diffraction pattern of cathode material produced after 24 hours with a cell voltage of 100OmV.
- Figure 8 is an optical image of partially reduced cathode material exhibiting a metallic shell and a core consisting of oxides.
- Figure 9 is a potential versus time plot for TiO 2 reduced under constant current
- FIG. 10 Scanning electron micrograph of Ti-10V-2Fe-3AI alloy produced via the present invention.
- Table 1 lists the standard state reduction potential for Ca 2+ to Ca 0 , and the potentials calculated from Equation 1 corresponding to selected dissolved activities of Ca 0 at 900 g C.
- a molten salt reactor depicted in Figure 4, was assembled using vertical tube furnace with temperatures recorded using a thermocouple (1 ) within the cell and a PC-based data acquisition unit.
- a sealed lnconel reaction (2) vessel housed alumina crucibles (3), which contained the CaCI 2 -CaO electrolyte (4). This electrolyte was obtained by mixing thermally dried CaCI 2 -2H 2 O and 1 wt% CaO, and was subsequently heated in the retort under flowing argon (5, 6) to 1173 K.
- Example 2 Reduction of TiO? under conditions of constantly high Ca activity
- the experimental apparatus used in Example 1 was reproduced identically, except for the electrolysis voltage, which was fixed at 3V, and the duration of electrolysis, which was 12 hours.
- the sample was removed from the electrolyte, allowed to cool, and washed in water.
- a cross section of the sample ( Figure 8) revealed a metallic ⁇ -titanium case that enclosed a darker powder, which was identified by x-ray diffraction as a titanium sub-oxide.
- the thickness of the metallic layer was approximately 100-200 microns, which effectively acted as a diffusion barrier preventing full reduction of the titanium dioxide pellet.
- Example 2 An identical reactor to that used in Example 1 was employed to reduce 10-micron thick TiO 2 layers thermally formed on a titanium substrate.
- a potentiostat was used in conjunction with a graphite counter electrode, nickel/nickel chloride reference electrode and TiO 2 working electrodes.
- a constant reduction current was applied to the working electrode and the potential, with respect to the reference electrode, was recorded over time ( Figure 9). The reduction current was terminated when the working electrode potential reached a steady state value that did not continue to decrease over a long period of time. Since the TiO 2 layer was of finite thickness, the reduction current at the conclusion of the experiment must have been comprised primarily of calcium formation.
- Example 4 Production of conventional titanium alloy (Ti-10V-2Fe-3AI) Reagent grade oxide powders from Alfa Aesar (TiO 2 99.5 %, FeTiO 3 99.8 %, AI 2 O 3 99.9 % and V 2 O 5 99 %, 1-2 ⁇ m particle size) were mixed, as-received, with a small amount of distilled water, which acted as a binding agent, to achieve a final composition of 10 wt% V, 2 wt% Fe, 3 wt% Al with the balance of titanium. The powder was then ground with a mortar and pestle for 5 minutes to break down large agglomerates prior to uniaxial compaction on a 15 mm diameter die at 100 MPa to obtain the desired preform shape.
- Alfa Aesar TiO 2 99.5 %, FeTiO 3 99.8 %, AI 2 O 3 99.9 % and V 2 O 5 99 %, 1-2 ⁇ m particle size
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO20062776A NO20062776L (no) | 2006-06-14 | 2006-06-14 | Fremgangsmåte, apparatur samt midler for produksjon av materiale i en smeltet salt elektrolytt |
PCT/NO2007/000183 WO2007145526A1 (fr) | 2006-06-14 | 2007-05-30 | PROCÉDÉ ET APPAREIL DE PRODUCTION DE Ti DANS UN ÉLECTROLYTE À SEL FONDU |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2032727A1 true EP2032727A1 (fr) | 2009-03-11 |
EP2032727A4 EP2032727A4 (fr) | 2012-09-12 |
Family
ID=38831961
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07747642A Withdrawn EP2032727A4 (fr) | 2006-06-14 | 2007-05-30 | PROCÉDÉ ET APPAREIL DE PRODUCTION DE Ti DANS UN ÉLECTROLYTE À SEL FONDU |
Country Status (4)
Country | Link |
---|---|
US (1) | US20100006448A1 (fr) |
EP (1) | EP2032727A4 (fr) |
NO (1) | NO20062776L (fr) |
WO (1) | WO2007145526A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109594100A (zh) * | 2018-12-07 | 2019-04-09 | 东华大学 | 一种C3N4负载Cu/Sn合金材料及其制备和应用 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB201208698D0 (en) * | 2012-05-16 | 2012-06-27 | Metalysis Ltd | Electrolytic method,apparatus and product |
CN104775137A (zh) * | 2014-01-13 | 2015-07-15 | 赣州飞腾轻合金有限公司 | 一种液态阴极熔盐电解法制备铝钐中间合金的方法 |
CN105274576B (zh) * | 2014-05-28 | 2017-12-22 | 奥勇新材料科技(上海)有限公司 | 一种熔盐介质中连续还原制备金属的方法 |
CN104313645B (zh) * | 2014-10-28 | 2017-08-08 | 苏州萨伯工业设计有限公司 | 含钪铝合金材料的制备装置及制备工艺 |
CN108467970B (zh) * | 2018-03-23 | 2020-12-25 | 中国石油天然气集团公司管材研究所 | 一种用于高腐蚀性油气开发的含铁钛合金管及其制备方法 |
WO2020061551A1 (fr) * | 2018-09-23 | 2020-03-26 | Massachusetts Institute Of Technology | Électrolyse de métaphosphate fondu pour la production de phosphore blanc |
CN109778010A (zh) * | 2019-03-25 | 2019-05-21 | 杭州辰卓科技有限公司 | 一种具有马氏体结构的高阻尼高导热单相α钛合金及工艺 |
CN114045535A (zh) * | 2021-11-23 | 2022-02-15 | 上海大学 | 一种CoCrNi中熵合金制备方法 |
Citations (3)
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 |
WO2002040725A2 (fr) * | 2000-11-15 | 2002-05-23 | Cambridge University Technical Services Limited | Poudres metalliques et d'alliages et fabrication de ces poudres |
WO2003076690A1 (fr) * | 2002-03-13 | 2003-09-18 | Bhp Billiton Innovation Pty Ltd | Reduction d'oxydes metalliques dans une cellule electrolytique |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080190777A1 (en) * | 2004-09-09 | 2008-08-14 | British Titanium Plc. | Electro-Deoxidation Method, Apparatus and Product |
-
2006
- 2006-06-14 NO NO20062776A patent/NO20062776L/no not_active Application Discontinuation
-
2007
- 2007-05-30 US US12/308,367 patent/US20100006448A1/en not_active Abandoned
- 2007-05-30 WO PCT/NO2007/000183 patent/WO2007145526A1/fr active Application Filing
- 2007-05-30 EP EP07747642A patent/EP2032727A4/fr not_active Withdrawn
Patent Citations (3)
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 |
WO2002040725A2 (fr) * | 2000-11-15 | 2002-05-23 | Cambridge University Technical Services Limited | Poudres metalliques et d'alliages et fabrication de ces poudres |
WO2003076690A1 (fr) * | 2002-03-13 | 2003-09-18 | Bhp Billiton Innovation Pty Ltd | Reduction d'oxydes metalliques dans une cellule electrolytique |
Non-Patent Citations (1)
Title |
---|
See also references of WO2007145526A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109594100A (zh) * | 2018-12-07 | 2019-04-09 | 东华大学 | 一种C3N4负载Cu/Sn合金材料及其制备和应用 |
Also Published As
Publication number | Publication date |
---|---|
US20100006448A1 (en) | 2010-01-14 |
WO2007145526A1 (fr) | 2007-12-21 |
NO20062776L (no) | 2007-12-17 |
EP2032727A4 (fr) | 2012-09-12 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 20090114 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
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AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: ROSENKILDE, CHRISTIAN Inventor name: LORENTSEN, ODD-ARNE Inventor name: HAGEN, EIRIK Inventor name: DRING, KEVIN |
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RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: NORSK TITANIUM TECHNOLOGY AS |
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DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20120813 |
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RIC1 | Information provided on ipc code assigned before grant |
Ipc: C22C 14/00 20060101ALI20120807BHEP Ipc: C25C 3/28 20060101ALI20120807BHEP Ipc: C22B 34/12 20060101AFI20120807BHEP |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20130716 |