CN101302630B - Method for preparing metal by means of solid oxide electrolytic cell - Google Patents
Method for preparing metal by means of solid oxide electrolytic cell Download PDFInfo
- Publication number
- CN101302630B CN101302630B CN2008100327342A CN200810032734A CN101302630B CN 101302630 B CN101302630 B CN 101302630B CN 2008100327342 A CN2008100327342 A CN 2008100327342A CN 200810032734 A CN200810032734 A CN 200810032734A CN 101302630 B CN101302630 B CN 101302630B
- Authority
- CN
- China
- Prior art keywords
- anode
- oxide
- solid oxide
- cathode
- metal
- 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.)
- Expired - Fee Related
Links
Abstract
The invention provides a method for preparing metal by a solid oxide electrolyte bath, belonging to the material technical field. The concrete steps of the method are as follows: in the electrolyte bath formed by a metal oxide cathode, solid oxide electrolytes and a composite material anode based on oxides with perovskite structure, the cathode end is injected with inert gases and the anode end is inserted with an air pipe, and the electrolyte bath is heated; the cathode end and the anode end are electrified for electrolysis, and oxygen with a purity of more than 99.9 percent can be collected on the anode end; after electrolysis, metals with purity of more than 99 percent can be collected on the cathode end. The method avoids the corrosion dissolution of the carbon anode and the possible generation of greenhouse gasses such as carbon dioxide, etc.
Description
Technical field
What the present invention relates to is the method in a kind of material technology field, particularly a kind of method with preparing metal by means of solid oxide electrolytic cell.
Background technology
Titanium is one of the abundantest element of content in the earth's crust, accounts for the 4th in the structural metal.Titanium and alloy thereof have excellent properties such as density is low, corrosion-resistant, high temperature resistant.Except being suitable as the space flight spare part, also obtained certain application at civil areas such as petroleum industry, the energy, traffic, chemical industry, biochemistry, medicine.In order to make titanium become the metal of widespread use, both at home and abroad all in the research of carrying out the titanium reducing process.
Find through literature search prior art, China Patent No. is ZL 01805455.2, denomination of invention is the patent of " produce the method for metal, semi-metal or alloy and be used for the raw material of this method ", introduced under the condition of anaerobic, in the mixture of the melting salt of basic metal or alkaline earth metal chloride or salt, by electrolysis, from metal oxide, remove deoxidation, thereby obtain the method for metal.Concrete grammar is: be negative electrode with titanium dioxide, the carbon of graphite or other kinds is anode, with fused calcium chloride is ionogen, under 800-1000 ℃ temperature, carry out electrolysis, negative electrode titanium dioxide is reduced into metal titanium, oxonium ion in anodic oxidation, generates oxygen or carbon monoxide and carbonic acid gas from the cathodic migration to the anode.Adopt this method to prepare metal titanium, exist following problem: one, in electrolytic process, because constantly leaving away of oxonium ion and metal titanium stays, might cause that impurity element deposits in the metal titanium in the melting salt, influence the purity of metal titanium; Its two, on negative electrode except the ionization reaction that oxygen occurs, deposition and the calcium and the reactive metal oxide of calcium might appear also, generate the oxide compound of metal and calcium, like this, both influenced the purity of metal titanium, also can the control of Electric potentials of follow-up electrolytic reaction be impacted; Its three, adopt carbon anode, exist ablation problem, increased the content of carbon in the melting salt.Its four, do ionogen with the melting salt of basic metal or alkaline earth metal chloride, exist the high temperature corrosion problem.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of method of preparing metal by means of solid oxide electrolytic cell is provided.Still (MO is as titanium oxide TiO with metal oxide in the present invention
2) as negative electrode, with have perovskite structure oxide be the matrix material of base as anode, thereby obtain highly purified metal.
The present invention is achieved by the following technical solutions, method with preparing metal by means of solid oxide electrolytic cell involved in the present invention, be specially: by metal oxide cathode, solid oxide electrolyte, have in the electrolyzer that perovskite structure oxide forms for the based composites anode, feed rare gas element at cathode terminal, insert airway at positive terminal, and electrolyzer heated, add that at the anode and cathode two ends voltage carries out electrolysis, collect oxygen at positive terminal then, after electrolysis finishes, obtain metal more than 99% at cathode terminal.
Described metal oxide cathode is made of metal oxide and pairing metal.Metal oxide through after the reduction reaction, generates needed metal as reaction electrode.Pairing metal, as collector electrode, the transmission cathodic current.
Described metal oxide, can be selected from the pairing oxide compound of a kind of metal among Ti, Zr, Hf, Al, M, gU, Nd, Mo, Cr, Nb, Ce, P, As, Si, Sb, the Sm, its shape can be metal oxide granule, metal oxide sintered sheets (piece), the pre-adult of foamed metal oxide compound.
Described solid oxide electrolyte is made up of good oxygen ion conductor.Such as, the powder of ScSZ (scandium doped zirconia), CGO (gadolinium doped cerium oxide) by the method for flow casting molding, forms 200 μ m-300 μ m thick films.
Described to have perovskite structure oxide be the based composites anode, is divided into anode active layer and anode contact layer.The anode active layer is by the LSFC (La of 50% (weight percent)
0.58Sr
0.4Fe
0.8Co
0.2O
3-δ) and the mixture of the CGO of 50% (weight percent) form; Monophasic LSFC is as the anode contact layer.
Described heating, its temperature are 500 ℃-800 ℃.
Means of solid oxide electrolytic cell of the present invention, be mixed into slurry by powder after, process with the method for conventional casting method, spraying method and silk screen printing, help suitability for industrialized production and making in the future.Feeding rare gas element at cathode compartment, is in order to guarantee fresh reductive metal, not by the oxidation of high temperature air institute.Inserting airway in the anolyte compartment, is in order to collect the oxygen of generation.
The electrolyzer that adopts solid oxide electrolyte of the present invention to constitute carries out the method for extracting metals, make the electrochemical reaction of in electrolyzer, carrying out, the reduction of metal oxide is only arranged at negative electrode, at anode separating out of oxygen only arranged, there is not the existence of other side reactions, improve current efficiency greatly, thereby also reduced energy consumption.
Adopt the method for solid electrolyte, overcome in the molten salt electrolyte, fused salt impurity is to the influence of metal purity, and the deposition that the fused salt metal ion may be on negative electrode; Fine and close solid electrolyte strictly makes a distinction cathode compartment and anolyte compartment, makes separately reactant and reaction product, can the phase mutual interference; Simultaneously, the etching problem of also having avoided high-temperature molten salt to cause.
Compared with prior art, the present invention is that basic matrix material is made anode with having perovskite structure oxide, can obtain highly purified oxygen in the anolyte compartment, the also economically valuable of by product that makes electrolytic reaction, avoided the corrosion dissolution of carbon anode, and issuable carbonic acid gas isothermal chamber gas.Adopt the present invention can obtain purity in the metal more than 99% and purity at the oxygen more than 99.9%.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Following examples prepare high pure metal with solid oxide electrolyte electrolytic tank electrolysis metal oxide.Negative electrode is a metal oxide, and anode is to have the matrix material of perovskite structure oxide for base, and ionogen is a solid oxide electrolyte.Feed rare gas element (as nitrogen or argon gas) at cathode compartment, insert airway in the anolyte compartment, add that at negative electrode and anode two ends voltage carries out electrolysis, just can obtain highly purified metal, obtain highly purified oxygen at positive terminal at cathode terminal.Concrete reaction formula is as follows:
Anode: O
2*→ 1/2O
2(g)+2e
-
Negative electrode: MO+2e
-→ O
2*+ M (s)
Total reaction: MO+ electric energy → M (s)+1/2O
2(g)
Embodiment 1
At first, preparation negative electrode.
With the titanium dioxide and the ti-alloy mesh compression moulding together of granular or powder type, under argon atmospher, 800 ℃ of sintering 1 hour, the cooling back is as negative electrode.
Then, half electrolyzer of preparation ionogen and anode formation.
The solid oxide electrolyte powder, ScSZ (or CGO) powder, by the method for flow casting molding, behind the formation biscuit, under oxidizing atmosphere, at 1400 ℃, sintering obtained the compact solid electrolytic thin-membrane after 3 hours behind the naturally cooling; Behind the solid electrolyte film naturally cooling, continue the anode active layer of silk screen printing last layer thickness at 5 μ m, this active layer is by the LSFC (La of 50% (weight percent)
0.58Sr
0.4Fe
0.8Co
0.2O
3-δ) and the mixture of the CGO of 50% (weight percent) form; Then, on the anode active layer, silk screen printing last layer thickness is at the single-phase LSFC of 50 μ m, as the anode contact layer.Half electrolyzer finished of preparation is under air atmosphere, and 1000 ℃ of sintering 2 hours become half electrolyzer that is made of ionogen and anode.
Then, negative electrode is closely contacted with solid oxide electrolyte in half electrolyzer, form means of solid oxide electrolytic cell.
At last, feed rare gas element such as nitrogen at cathode terminal, insert airway at positive terminal, and electrolyzer is heated to 500 ℃, add that at the anode and cathode two ends voltage carries out electrolysis, collect oxygen at positive terminal then, after electrolysis finished, obtaining purity at cathode terminal was that metal titanium powder more than 99% and purity are the oxygen more than 99.9%.
Embodiment 2
At first, preparation negative electrode.
Form slurry with the titanium dioxide of granular or powder type and foam of polymers, dry post-heating to 400 ℃ removing organism, and then continues to be warmed up to 1500 ℃, sintering under nitrogen atmosphere, the preform behind the sintering as negative electrode.
Then, according to the method among the embodiment 1, half electrolyzer that preparation ionogen and anode constitute.
Then, negative electrode is closely contacted with solid oxide electrolyte in half electrolyzer, form means of solid oxide electrolytic cell.
At last, feed rare gas element such as nitrogen at cathode terminal, insert airway at positive terminal, and electrolyzer is heated to 800 ℃, add that at the anode and cathode two ends voltage carries out electrolysis, collect oxygen more than 99.9% at positive terminal then, after electrolysis finished, obtaining purity at cathode terminal was metal foam titanium more than 99%.
Embodiment 3
At first, preparation negative electrode.
Use titania powder, after aluminium sesquioxide powder (mol ratio is 2: the 1) compression moulding, under the nitrogen atmosphere that contains 3% hydrogen 900 ℃, sintering 1.5 hours, the cooling back is as negative electrode.
Then, half electrolyzer that constitutes according to embodiment 1 preparation ionogen and anode.
Then, negative electrode is closely contacted with solid oxide electrolyte in half electrolyzer, form means of solid oxide electrolytic cell.
At last, feed rare gas element such as nitrogen at cathode terminal, insert airway at positive terminal, and electrolyzer is heated to 650 ℃, add that at the anode and cathode two ends voltage carries out electrolysis, collect oxygen more than 99.9% at positive terminal then, after electrolysis finished, the titanium aluminum alloy that obtains at cathode terminal accounted for more than 99% of total mass.
Claims (3)
1. the method for a preparing metal by means of solid oxide electrolytic cell, it is characterized in that, by titanium oxide or titanium aluminum alloy oxide cathode, solid oxide electrolyte, have in the electrolyzer formed of matrix material anode that perovskite structure oxide is a base, feed rare gas element at cathode terminal, insert airway at positive terminal, and electrolyzer heated, add that at the anode and cathode two ends voltage carries out electrolysis, collecting purity at positive terminal then is oxygen more than 99.9%, after electrolysis finished, the titanium or the titanium aluminum alloy that obtain at cathode terminal accounted for more than 99% of total mass;
Described matrix material anode with perovskite structure oxide for base is divided into anode active layer and anode contact layer;
Described anode active layer is made up of the mixture of the CGO of the LSFC of 50% weight percent and 50% weight percent;
Described anode contact layer is monophasic LSFC;
Described solid oxide electrolyte is the scandium doped zirconia be made up of oxygen ion conductor or the powder of gadolinium doped cerium oxide.
2. the method for preparing metal by means of solid oxide electrolytic cell according to claim 1 is characterized in that, described oxide cathode, and its shape is granule, sintered sheets or the pre-adult of spumescence.
3. the method for preparing metal by means of solid oxide electrolytic cell according to claim 1 is characterized in that, described heating, and its temperature is 500 ℃-800 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100327342A CN101302630B (en) | 2008-01-17 | 2008-01-17 | Method for preparing metal by means of solid oxide electrolytic cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100327342A CN101302630B (en) | 2008-01-17 | 2008-01-17 | Method for preparing metal by means of solid oxide electrolytic cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101302630A CN101302630A (en) | 2008-11-12 |
| CN101302630B true CN101302630B (en) | 2010-11-10 |
Family
ID=40112722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100327342A Expired - Fee Related CN101302630B (en) | 2008-01-17 | 2008-01-17 | Method for preparing metal by means of solid oxide electrolytic cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101302630B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4170067A3 (en) * | 2021-10-25 | 2023-05-10 | Airbus Defence and Space GmbH | System and method for extracting oxygen from powdered metal oxides |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956203B (en) * | 2010-10-28 | 2012-06-06 | 北京科技大学 | New method for preparing oxygen in situ by using lunar surface soil |
| CN105926020B (en) * | 2016-06-14 | 2018-05-11 | 中山大学 | A kind of preparation method of super hydrophilic titanium foam for water-oil separating |
| CN107841759A (en) * | 2017-09-25 | 2018-03-27 | 杨家华 | Low-temp methanol washs oxygenerator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404530A (en) * | 2000-02-22 | 2003-03-19 | 秦内蒂克有限公司 | Electrolytic reduction of metal oxides such as titanium dioxide and process application |
| CN1450205A (en) * | 2003-04-22 | 2003-10-22 | 上海大学 | Process for preparing titanium sponge from titanium oxide composite ore |
-
2008
- 2008-01-17 CN CN2008100327342A patent/CN101302630B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404530A (en) * | 2000-02-22 | 2003-03-19 | 秦内蒂克有限公司 | Electrolytic reduction of metal oxides such as titanium dioxide and process application |
| CN1450205A (en) * | 2003-04-22 | 2003-10-22 | 上海大学 | Process for preparing titanium sponge from titanium oxide composite ore |
Non-Patent Citations (2)
| Title |
|---|
| 胡小锋，许茜，李海滨，马青梅，任东琦.熔盐电脱氧法制备金属Ti的最新研究进展.材料导报20 8.2006,20(8),101-103. |
| 胡小锋,许茜,李海滨,马青梅,任东琦.熔盐电脱氧法制备金属Ti的最新研究进展.材料导报20 8.2006,20(8),101-103. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4170067A3 (en) * | 2021-10-25 | 2023-05-10 | Airbus Defence and Space GmbH | System and method for extracting oxygen from powdered metal oxides |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101302630A (en) | 2008-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103451682B (en) | A kind of method of titaniferous soluble anode electroextraction by molten salt electrolysis titanium | |
| CN100415940C (en) | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis | |
| US8658007B2 (en) | Oxygen-producing inert anodes for SOM process | |
| CN104593804B (en) | A kind of high-temperature electrolysis CO 2/ H 2o prepares synthetic gas system and application thereof | |
| CN101949038B (en) | Method for preparing TiCxOy composite anode with electrolysis method | |
| CN103290433B (en) | Device and the technique thereof of pure titanium are prepared in a kind of pair of electrolyzer fused salt electrolysis | |
| CN108336316A (en) | A kind of lithium-rich anode material and preparation method thereof being modified based on the surfaces MOFs | |
| US20210285113A1 (en) | Process that can withstand high currents, for producing ammonia | |
| CN111244470B (en) | Nano composite cathode and preparation and application thereof | |
| CN101302630B (en) | Method for preparing metal by means of solid oxide electrolytic cell | |
| CN101906646B (en) | Method for preparing iron metal by molten salt electrolysis of iron ore | |
| CN103290424A (en) | Preparation method of TiC powder | |
| CN105386076A (en) | Improvement method for carbon nano tube preparation system based on high-temperature electrolysis of CO2 | |
| CN103482625B (en) | A kind of preparation method of niobium carbide and carbonization tantalum electrode | |
| CN113832473A (en) | Molten salt electrochemical method for co-production of metal/carbon composite material and hydrogen | |
| US20020125125A1 (en) | Cathode for aluminum production and electrolytic cell | |
| Ando et al. | Electrochemical reforming of CH4–CO2 mixed gas using porous yttria-stabilized zirconia cell | |
| CN102995065A (en) | Method for preparing metal titanium by taking ionic liquid as electrolyte and performing electro-deoxidization at room temperature | |
| CN107119283B (en) | The electrochemical preparation method of mesoporous carbon nanocoils | |
| CN111394748B (en) | For CO2Electrolytic iron-nickel alloy in-situ desolventizing layered perovskite cathode material | |
| CN101302631B (en) | Making method for solid oxide electrolytic cell | |
| CN102358943B (en) | Method for synthesizing ethylene and oxalic acid from acetylene by bipolar electrochemical technology | |
| CN111364065A (en) | Method for preparing uranium by utilizing uranium oxide | |
| CN108977853A (en) | A kind of electrolytic aluminium anode and preparation method thereof with coated conductive oxide layer | |
| CN112501636B (en) | Preparation method of Ti-Mn porous anode material for electrolytic manganese dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101110 Termination date: 20130117 |