CN101163804A - Electrochemical method and apparatus for removing oxygen from a compound or metal - Google Patents
Electrochemical method and apparatus for removing oxygen from a compound or metal Download PDFInfo
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- CN101163804A CN101163804A CNA2006800137065A CN200680013706A CN101163804A CN 101163804 A CN101163804 A CN 101163804A CN A2006800137065 A CNA2006800137065 A CN A2006800137065A CN 200680013706 A CN200680013706 A CN 200680013706A CN 101163804 A CN101163804 A CN 101163804A
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- 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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
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Abstract
A cathode comprising an oxygen-containing compound, or a metal containing dissolved oxygen, is arranged in contact with a melt comprising a hydroxide of an alkali metal. An inert anode, advantageously comprising nickel, is also arranged in contact with the melt and a potential is applied between the anode and the cathode such that oxygen is removed from the compound or the metal.
Description
The present invention relates to from the compound that comprises metal and oxygen or from metal or alloy, remove the method and apparatus of deoxidation by electrolysis process.
The electricity of solid chemical compound decomposes or electroreduction is described among International Patent Application PCT/GB99/01781 for example and D.J.Fray and G.Z.Chen " Extraction oftitanium from solid titanium dioxide in molten salts ", TMS (TheMinerals, Metals and Materials Society) 2004, in the 9-17 page or leaf, the full content with them is attached to herein by reference.In this method that is also referred to as the FFC method, the compound between electrolytic reduction metal (use in this article this term comprise metal and semi-metal the two) and another material (for example oxygen).The negative electrode that will comprise or contact this solid chemical compound immerses or the contact fused salt, and negative electrode with also and between the anode that contacts of this salt apply voltage, make this substance dissolves in salt.For example, can use this method from solid metal compound, to extract metal.Also can handle, to form alloy or intermetallic compound the negative electrode that comprises or contact the mixture of solid metal compound mixture or one or more compounds and one or more metals.
This method is called as the electricity decomposition in this article, but also is known as the term that other comprises electric deoxidation or electroreduction.
Because calcium has great electropositivity, calcium chloride commonly used is as ionogen in electric decomposition method.This fused salt serves as ionogen in electric decomposition method.The term fused salt can for example ionogen, melting salt and melt exchange use with other Essential Terms in this area.
By using CaCl
2The base melt carries out electricity decomposition, might reduce most of metal oxides.Yet, be provided in CaCl
2Have enough inert anode materials aspect in the base melt and produced problem.
At present, do not have and for example to be used as the suitable material of inert anode in the calcium chloride at the muriate melt, so generally use carbon anode.In electric decomposition method, use carbon anode to cause emitting CO and/or CO
2In addition, carbon anode is consumed and electric degradation production can be by Prevent Carbon Contamination.
Summary of the invention
As defined in the appended independent claim that should mention at present, the invention provides method and apparatus that from the compound that comprises metal and oxygen or from metal or alloy, removes deoxidation and the anode that is used for electric decomposition method.Preferred or favorable characteristics of the present invention is defined in the dependent claims.
In first aspect, the present invention can advantageously provide from the compound that comprises metal and oxygen the method for removing deoxidation, and it comprises the negative electrode that comprises or contact this compound is arranged to and the contacted step of melt that comprises alkali metal hydroxide.Also anode arrangement is become to contact with melt and between anode and negative electrode, apply the electromotive force that is enough to from this solid chemical combination except that deoxidation.This compound can be an intermetallic compound.In similar method, negative electrode comprises or contacts the metal or alloy that contains dissolved oxygen, and the electromotive force that is applied is enough to oxygen is removed from this metal or alloy.This compound, metal or alloy be solid preferably.
Preferred this melt also comprises alkalimetal oxide and this oxide compound especially preferably is soluble in the oxyhydroxide.Comprising the melt that is dissolved in the alkalimetal oxide in the alkali metal hydroxide is the melt system that can advantageously support oxygen-ion conductive.Good oxygen-ion conductive may be favourable by melt transfer from the solid chemical compound of negative electrode aspect emitting at the anode place with oxygen effectively.
Preferably decomposing cathode during place's electromotive force (on magnitude) at electricity is lower than and is used for emitting continuously hydrogen or from the alkali-metal electromotive force of melt successive sedimentation.Preferably, the electromotive force between negative electrode and the anode (voltage that is applied) is lower than the electromotive force of the continuous decomposition that is used for melt.
Though alkali metal hydroxide can be any alkali metal hydroxide, it is preferably sodium hydroxide and this basic metal is sodium, and perhaps this oxyhydroxide is that potassium hydroxide and this basic metal are potassium.Oxide compound then is preferably sodium oxide or potassium oxide respectively.Can use and comprise different cationic oxyhydroxide and/or hopcalite.
Though solid chemical compound can be any stable solid chemical compound that comprises metal and oxygen of alkalimetal oxide that do not have, but the present invention is being used to reduce low stable oxide compound for example when ferriferous oxide or cobalt, nickel, copper, zinc or plumbous oxide compound,, may be particularly advantageous perhaps being used for when metal or the alloy that comprises this metal remove deoxidation.
If when the precursor material at negative electrode place comprises the mixture of the mixture of metallic compound or one or more metallic compounds and one or more metals, then can make the alloy or the intermetallic compound that comprise the metallics in the precursor material.
Melt can comprise more than a kind of alkali-metal oxyhydroxide or hopcalite, but can comprise other negatively charged ion or cationic substance in addition.Yet this material should preferably not be to cause that the corrosive of inert anode is the sort of.
The fusing point of sodium hydroxide is about 320 ℃.Electricity in calcium chloride melt decomposes, and this can advantageously make electric decomposition method be carried out at low temperatures.For example this reaction can be lower than 650 ℃ or be lower than under 500 ℃ the temperature and carry out.Can be to carry out this electricity under any temperature of fused to decompose particularly advantageously at ionogen.
Advantageously, add the fusing point that a spot of sodium iodide or Sodium Bromide can reduce sodium hydroxide.This electricity is decomposed be able in addition lower temperature under carry out, can reduce that therefore melt is maintained energy required under the working temperature, and can reduce the etching problem in the electric decomposer.
The removal of oxygen from (one or more) compound, (one or more) metal or (one or more) alloy of negative electrode can comprise diffusion.Depend on the included material and the geometric condition of material therefor (for example particle size of negative electrode place material), can quicken this process by elevated temperature, and therefore under the low temperature operation can reduce speed of reaction unfriendly.Therefore, can advantageously use temperature greater than 500 ℃ or 550 ℃.The boiling point of NaOH for example is 1390 ℃, can use in principle so to be higher than 500 ℃ temperature, as long as the speed of reaction increase of any acquisition suitably balance any increase of the corrosion of equipment under comparatively high temps.
Anode preferably is inertia for melt substantially under working conditions.For example, decompose if use the sodium hydroxide melt that has wherein dissolved the small part sodium oxide to carry out electricity under 650 ℃, then anode should be inertia basically to this melt under this temperature.Think that the anode that comprises nickel or nickel oxide for example is inertia in the fused sodium hydroxide basically at the causticity melt.Anode preferably for example make by the nickeliferous material of bag by nickel oxide or nickelalloy or rich nickelalloy.Inconel
TMCan be fit to.Usually, the metal of formation indifferent oxide layer can be suitable as the inert anode in the oxyhydroxide melt.
The inert anode of mentioning herein should be considered to, and as those skilled in the art think, has comprised basic inert anode.Therefore, inert anode should have enough inertia in practice so that can be used for the time of proper extension.
Therefore, another aspect of the present invention can advantageously provide from the solid chemical compound that comprises metal and oxygen the method for removing deoxidation, and it comprises the negative electrode that comprises or contact this solid chemical compound is arranged to and the contacted step of melt that comprises alkali metal hydroxide.Also anode arrangement is become to contact with this melt, and apply between anode and negative electrode be enough to electromotive force that oxygen is removed from solid chemical compound, wherein this anode comprises the metal or alloy of formation indifferent oxide layer or comprises nickel, nickel oxide or nickelalloy.
When comparing with normally used carbon anode in the electric decomposition method, inertia or basic inert anode can provide many favorable characteristics.The gas of emitting at inert anode during electricity decomposes can be pure oxygen substantially.Carbon anode is emitted carbon monoxide or carbonic acid gas usually, and if these gases be discharged in the atmosphere with the issuable amount of commercial plant, can have deleterious effect to environment.Any oxygen that produces can be discharged in the atmosphere or can be collected as the product of this electricity decomposition method.
Because inert anode does not react during electricity decomposes, so they are not consumed by this method or are consumed with favourable slow speed.This can allow the groove anode cost longer, that the groove design is simpler and total working time of this method of enforcement lower.In addition, melt and resultant metal can be not by from the anodic material contamination, the number that this can increase the working life of melt and can reduce the required post-processing step of product.
This method advantageously, when work during enough time, its end product is a metal; For example, if Fe
2O
3Be this solid chemical compound, then product is Fe.The electricity of the solid chemical compound from the oxide compound to the pure metal decomposes and can be undertaken by many intermediate compounds.If this method not operation can be reduced to enough time of metal fully, desirablely go out the product that any of these intermediate compound is used as this method.
If basic metal will be obtained and/or be dissolved in the melt at negative electrode with metallic forms, the electronic conductance of melt can increase.This can reduce the electrical efficiency of this method unfriendly.Making basic metal under the condition at negative electrode place, advantageously not carry out this method as the metal successive sedimentation from oxyhydroxide.Melt can comprise more than a kind of basic metal material, and in this case, the electromotive force that is applied between anode and the negative electrode preferably is not enough to become metal for any basic metal that is present in the melt in the negative electrode successive sedimentation.Do not exist dissolved basic metal advantageously to have reduced in the melt or basically eliminate the electronic conductance of melt.
During the electricity of oxyhydroxide melt decomposes, think under the low cathode potential of electromotive force that may be required than alkalimetal ion reduction the becoming basic metal that exists in melt, can discharge hydrogen potentially on the negative electrode.Any this basic metal that produces at negative electrode can be dissolved in the melt potentially and can for example change the character of melt by the electronic conductance that increases melt unfriendly.Preferred releasing hydrogen gas can advantageously prevent the reduction of alkalimetal ion.
Can monitor the reaction at negative electrode place by the electromotive force of measuring negative electrode with respect to reference electrode.This example comprise true reference electrode for example the Ag/AgCl electrode or by for example cyclic voltammetry carry out gauged vacation (psuedo) reference electrode or dynamically reference electrode for example comprise the electrode of the metal identical with basic metal material in the melt.
Be used to implement to have sodium hydroxide melt and the nickeliferous anode of bag that comprises some sodium oxides according to the groove of the method for particularly preferred embodiment of the present invention.
In one embodiment, in comprising the melt that is dissolved in the sodium oxide in the sodium hydroxide, can electric decomposing oxidation iron.About this embodiment, following reaction equation and standard electric chemical potential have illustrated the suitability of disclosed method.
Gathered theoretical standard electrochemical potential below for the decomposition reaction of various ferriferous oxides.Numeral given below be calculate by the tabular thermodynamic data and be temperature and unit activity (unitactivity) for 600 ℃; Negative potential is corresponding to positive free energy and indicated and need energy input so that reaction can proceed to right hand side from the left-hand side.
1.Fe
2O
3＝2Fe+1.5O
2 E°＝-1.022V
2.Fe
3O
4＝3Fe+2O
2 E°＝-1.075V
3.FeO＝Fe+0.5O
2 E°＝-1.074V
4.Fe
2O
3＝2FeO+0.5O
2 E°＝-0.919V
5.3Fe
2O
3＝2Fe
3O
4+0.5O
2 E°＝-0.601V
6.Fe
3O
4＝3FeO+0.5O
2 E°＝-1.077V
If during electricity decomposes, chemically or electrochemically reached before electricity decomposes or during formed the mixed oxide that comprises sodium, iron and oxygen, then need to consider following reaction formula and standard electric chemical potential.
7.Na
2Fe
2O
4＝2Fe+1.5O
2+Na
2O E°＝-1.351V
Think and to determine electrolytical stability by following reaction formula and standard electric chemical potential.This numeral is meant 600 ℃ and unit activity.
8.Na
2O＝2Na+0.5O
2 E°＝-1.434V
9.2NaOH＝Na
2O+0.5O
2+H
2 E°＝-1.650V
10.2NaOH＝2Na+0.5O
2+H
2O E°＝-2.050V
11.2NaOH＝2Na+O
2+H
2 E°＝-3.084V
In this embodiment, sodium oxide is diluted by sodium hydroxide, so its validity score electrolytic potential is than the electromotive force low (negative value is bigger) with regard to standard conditions calculated.Adopt quantitative term, for order of magnitude of the every reduction of concentration under saturation concentration, the decomposition voltage of sodium oxide increases 173mV 600 ℃ of following negative values.In this embodiment, possiblely be, concentration can be in a saturated order of magnitude, so decomposition voltage will be in the magnitude of-1.434-0.173=-1.607V.
About sodium hydroxide, best decomposition reaction has caused the generation (reaction 9) of hydrogen, and the sedimentary reaction (reaction 10 and 11) that relates to the sodium metal needs significantly bigger electromotive force of negative value.
By as can be seen above-mentioned, the electricity of ferriferous oxide decomposes the formation should cause iron in the sodium hydroxide melt, preferably is enough to make oxygen to remove (reaction 1-6) but deficiency so that hydrogen or sodium emit or deposit the bath voltage of (reacting 8 and 9) continuously at negative electrode from ferriferous oxide by applying.It should be noted, emit continuously or deposit that bath voltage must fully be higher than corresponding to reaction 8 or 9 voltage so that overcome voltage loss in the groove in order to cause this of hydrogen or sodium.
Since the standard free energy that reacts below on the occasion of, the iron product should not react with sodium hydroxide.
12.Fe+2NaOH＝FeO+Na
2O+H
2 ΔG°＝+111kJ/mol
13.3Fe+8NaOH＝Fe
3O
4+4Na
2O+4H
2 ΔG°＝+444kJ/mol
14.2Fe+6NaOH＝Fe
2O
3+3Na
2O+3H
2 ΔG°＝+363kJ/mol
Usually, can advantageously use and embody method of the present invention and come from compound, metal or alloy, to remove deoxidation, as long as oxygen or the oxide compound in this compound, the metal or alloy is unstable for the compound that forms between oxygen and the positively charged ion in the melt.
The description of specific embodiments
Description is also described specific embodiments of the present invention by embodiment, wherein:
Fig. 1 has shown and has been used for the groove of electric decomposition method according to embodiments of the present invention.
Fig. 1 shown and has been used for the groove 10 that electricity decomposes, its comprise consist of 98% NaOH and The melt 20 of 2% sodium oxide molybdena. Iron basket 40 forms comprise Fe2O
3 Negative electrode 30 quilts of particle 50 Be immersed in the melt. The anode 60 of commercial pure nickel is also entered into melt, wherein this anode and Negative electrode all is connected to power supply 70.
At work, melt is heated to for example 400 ℃ of its operating temperatures. At anode and negative electrode Between apply for example 2.5 to 3.0V work potential. Under this work potential, Fe2O
3In Oxygen migrates to this melt and is transferred to anode, and it is released as oxygen at this anode.
In second embodiment, melt is heated to 550 ℃ working temperature.Other all reaction conditionss as mentioned above.This embodiment with the speed that is higher than first embodiment with Fe
2O
3Be reduced to Fe.Think that this is because the increase of rate of diffusion in the negative electrode place material.
In order to form the negative electrode that comprises solid metal compound or solid metal, advantageously this compound or metal are made porous form, for example by with this compound or metal with powder-form slip casting (and optional sintering).In this this structure, the material at negative electrode place should contain the infiltration of intercommunication hole with the permission melt, and particle size should be enough little of to allow the oxygen diffusion.In fact, can prepare the material at negative electrode place by any way with any geometry, still, if use unfavorable thickness of material cross section, speed of reaction can be subjected to that the rate of diffusion of oxygen limits in the material.
Claims (30)
1. method of removing deoxidation from compound, metal or alloy comprises step:
The negative electrode that will comprise this compound, metal or alloy is arranged to contact with the melt that comprises alkali metal hydroxide;
Inert anode is arranged to contact with this melt, and this anode comprises nickel; With
Applying between this anode and negative electrode is enough to electromotive force that oxygen is removed from this compound, metal or alloy.
2. according to the process of claim 1 wherein that anode comprises for example nickel oxide of nickel, nickelalloy, nickeliferous intermetallic compound or nickel compound.
3. according to the method for claim 1 or 2, wherein anode comprises the nickel of enough ratios, so that anode is inertia basically in melt.
4. according to each method in the aforementioned claim, wherein anode is inertia basically for the melt under working conditions.
5. according to each method in the aforementioned claim, wherein negative electrode place electromotive force is lower than the electromotive force that is used for emitting continuously from melt hydrogen.
6. according to each method in the aforementioned claim, wherein negative electrode place electromotive force is lower than and is used for the alkali-metal electromotive force of successive sedimentation.
7. according to each method in the aforementioned claim, wherein melt also comprises alkalimetal oxide, and this oxide compound is preferably dissolved in the oxyhydroxide.
8. according to each method in the aforementioned claim, wherein basic metal is sodium or potassium.
9. according to each method in the aforementioned claim, wherein metal is iron, cobalt, nickel, copper, zinc or lead.
10. according to each method in the aforementioned claim, its product is a metal.
11. according to each method in the aforementioned claim, wherein compound or the metal therefrom removed of oxygen is solid chemical compound or solid metal.
12. according to each method in the aforementioned claim, wherein the compound therefrom removed of oxygen comprises metal and oxygen.
13. according to each method in the aforementioned claim, wherein this compound, metal or alloy have formed the part of the precursor material at negative electrode place, this precursor material comprises more than a kind of metal or metallic compound.
14. according to the method for claim 13, its product is the alloy or the intermetallic compound of the metal that exists in the precursor material.
15. according to each method in the aforementioned claim, wherein melt is in and is lower than 650 ℃ temperature during operation.
16. according to each method in the aforementioned claim, wherein melt is in and is higher than 500 ℃ temperature during operation.
17. according to each method in the aforementioned claim, it comprises other step: reference electrode is arranged to contact with this melt, be used for control cathode and/or anodic electromotive force and/or be applied to anode and negative electrode between electromotive force or voltage.
18. according to each method in the aforementioned claim, wherein the electromotive force between anode and the negative electrode is lower than the electromotive force that is used for decomposing continuously alkali metal hydroxide.
19. according to the method for claim 7, wherein the electromotive force between anode and the negative electrode is lower than the electromotive force that is used for decomposing alkalimetal oxide continuously or is used for removing from this melt continuously alkalimetal oxide.
20., wherein do not have electronic conductance basically in the melt during operation according to each method in the aforementioned claim.
21., wherein during operation, do not have basic metal to be dissolved in the melt basically as metallics according to each method in the aforementioned claim.
22. a method of removing deoxidation from compound, metal or alloy comprises step:
The negative electrode that will comprise this compound, metal or alloy is arranged to contact with the melt that comprises alkali metal hydroxide;
Inert anode is arranged to contact with this melt; With
Applying between anode and negative electrode is enough to electromotive force that oxygen is removed from this solid chemical compound.
23. according to the method for claim 22, wherein inert anode comprises nickel.
24. according to the method for claim 22 or 23, wherein this compound, metal or alloy comprise one or more in iron, cobalt, nickel, copper, zinc or the lead.
25. according to each method in the claim 22 to 24, wherein this melt comprises sodium hydroxide and sodium oxide, perhaps contains potassium hydroxide and potassium oxide.
26. be used for the device that electricity decomposes, comprise:
Be used to comprise the container of the melt of alkali metal hydroxide;
Inert anode; With
Be used at inert anode and comprise the power supply that applies electric decomposition voltage between the negative electrode that is used for the solid chemical compound that electricity decomposes.
27. according to the device of claim 26, wherein anode comprises nickel.
28. be used for anode according to the device that is used for the electricity decomposition of claim 26 or 27.
29. be used in according to the anode in each the method in the claim 1 to 25.
30. use metal, intermetallic compound or alloy according to each method preparation in the claim 1 to 25.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0504444.1 | 2005-03-03 | ||
| GBGB0504444.1A GB0504444D0 (en) | 2005-03-03 | 2005-03-03 | Method and apparatus for removing oxygen from a solid compound or metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101163804A true CN101163804A (en) | 2008-04-16 |
Family
ID=34430598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800137065A Pending CN101163804A (en) | 2005-03-03 | 2006-03-03 | Electrochemical method and apparatus for removing oxygen from a compound or metal |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20080302655A1 (en) |
| EP (1) | EP1866448A1 (en) |
| JP (1) | JP2008531854A (en) |
| CN (1) | CN101163804A (en) |
| AU (1) | AU2006219725A1 (en) |
| EA (1) | EA200701896A1 (en) |
| GB (2) | GB0504444D0 (en) |
| WO (1) | WO2006092615A1 (en) |
| ZA (1) | ZA200707266B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112941567A (en) * | 2018-07-10 | 2021-06-11 | 东北大学 | Electrochemical method and apparatus for high temperature molten salt electrolysis in humid atmosphere |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO20060806L (en) * | 2006-02-17 | 2007-08-20 | Norsk Titanium Metals As | Method and apparatus for metal production |
| WO2010069685A1 (en) * | 2008-12-18 | 2010-06-24 | Silicon Fire Ag | Silicon or elemental metals as energy carriers |
| WO2010069622A1 (en) | 2008-12-18 | 2010-06-24 | Silicon Fire Ag | Method and plant for providing an energy carrier using carbon dioxide as a carbon supplier and using electricity |
| AR076567A1 (en) * | 2009-05-12 | 2011-06-22 | Metalysis Ltd | METHOD AND APPARATUS FOR REDUCTION OF SOLID RAW MATERIAL |
| US20110048665A1 (en) * | 2009-08-09 | 2011-03-03 | Max Eric Schlienger | Corrosion resistance for a leaching process |
| US8764962B2 (en) * | 2010-08-23 | 2014-07-01 | Massachusetts Institute Of Technology | Extraction of liquid elements by electrolysis of oxides |
| BR112013011941A2 (en) * | 2010-11-18 | 2016-11-01 | Metalysis Ltd | method and system for electrolytically reducing a solid feedstock |
| EA034483B1 (en) | 2010-11-18 | 2020-02-12 | Металисиз Лимитед | Electrolysis apparatus |
| US8900439B2 (en) | 2010-12-23 | 2014-12-02 | Ge-Hitachi Nuclear Energy Americas Llc | Modular cathode assemblies and methods of using the same for electrochemical reduction |
| GB201223375D0 (en) * | 2012-12-24 | 2013-02-06 | Metalysis Ltd | Method and apparatus for producing metal by electrolytic reduction |
| NL2015759B1 (en) | 2015-11-10 | 2017-05-26 | Stichting Energieonderzoek Centrum Nederland | Additive manufacturing of metal objects. |
| 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 |
| CN113802149B (en) * | 2021-08-11 | 2023-06-27 | 华北理工大学 | Method for extracting metallic iron from zinc kiln slag |
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|---|---|---|---|---|
| BE621887A (en) * | 1961-08-30 | |||
| SU651602A1 (en) * | 1977-09-26 | 1980-01-05 | Институт общей и неорганической химии АН Украинской ССР | Method of producing bismuth powder by electrolysis |
| DE2914094C2 (en) * | 1979-04-07 | 1983-02-10 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Porous nickel electrode for alkaline electrolysis, process for producing the same and its use |
| US4454015A (en) * | 1982-09-27 | 1984-06-12 | Aluminum Company Of America | Composition suitable for use as inert electrode having good electrical conductivity and mechanical properties |
| JPS59177865A (en) * | 1983-03-29 | 1984-10-08 | Japan Storage Battery Co Ltd | Gas diffusion electrode |
| GB9812169D0 (en) * | 1998-06-05 | 1998-08-05 | Univ Cambridge Tech | Purification method |
| US6372099B1 (en) * | 1998-07-30 | 2002-04-16 | Moltech Invent S.A. | Cells for the electrowinning of aluminium having dimensionally stable metal-based anodes |
| US6540902B1 (en) * | 2001-09-05 | 2003-04-01 | The United States Of America As Represented By The United States Department Of Energy | Direct electrochemical reduction of metal-oxides |
| US6911134B2 (en) * | 2002-09-06 | 2005-06-28 | The University Of Chicago | Three-electrode metal oxide reduction cell |
-
2005
- 2005-03-03 GB GBGB0504444.1A patent/GB0504444D0/en not_active Ceased
-
2006
- 2006-03-03 AU AU2006219725A patent/AU2006219725A1/en not_active Abandoned
- 2006-03-03 EA EA200701896A patent/EA200701896A1/en unknown
- 2006-03-03 WO PCT/GB2006/000765 patent/WO2006092615A1/en active Application Filing
- 2006-03-03 GB GBGB0604348.3A patent/GB0604348D0/en not_active Ceased
- 2006-03-03 US US11/817,458 patent/US20080302655A1/en not_active Abandoned
- 2006-03-03 JP JP2007557592A patent/JP2008531854A/en active Pending
- 2006-03-03 CN CNA2006800137065A patent/CN101163804A/en active Pending
- 2006-03-03 EP EP06709988A patent/EP1866448A1/en not_active Withdrawn
-
2007
- 2007-08-28 ZA ZA200707266A patent/ZA200707266B/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112941567A (en) * | 2018-07-10 | 2021-06-11 | 东北大学 | Electrochemical method and apparatus for high temperature molten salt electrolysis in humid atmosphere |
| CN112941567B (en) * | 2018-07-10 | 2024-02-23 | 东北大学 | Electrochemical method and device for high-temperature molten salt electrolysis in humid atmosphere |
Also Published As
| Publication number | Publication date |
|---|---|
| US20080302655A1 (en) | 2008-12-11 |
| GB0504444D0 (en) | 2005-04-06 |
| AU2006219725A1 (en) | 2006-09-08 |
| WO2006092615A1 (en) | 2006-09-08 |
| JP2008531854A (en) | 2008-08-14 |
| ZA200707266B (en) | 2008-09-25 |
| GB0604348D0 (en) | 2006-04-12 |
| EP1866448A1 (en) | 2007-12-19 |
| EA200701896A1 (en) | 2008-02-28 |
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