CN1936088A - Method and apparatus for directly preparing refractory metal and alloy from metal oxide - Google Patents
Method and apparatus for directly preparing refractory metal and alloy from metal oxide Download PDFInfo
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- CN1936088A CN1936088A CN 200610116383 CN200610116383A CN1936088A CN 1936088 A CN1936088 A CN 1936088A CN 200610116383 CN200610116383 CN 200610116383 CN 200610116383 A CN200610116383 A CN 200610116383A CN 1936088 A CN1936088 A CN 1936088A
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Abstract
The invention relates to a method to directly make refractory metal and alloy from metal oxide. The feature is that it forms metal liquid, refractory metal oxide particle and molten salt melt from up to down, and the metal liquid, refractory metal oxide and graphite cathode leader form cathode system. The technology includes the following steps: sintering refractory metal oxide ball at 1000-1200 degree centigrade for 7-9h, adding metal powder, refractory metal oxide and halide molten salt, heating crucible furnace to temperature of electrolysis and taking electrolysis to gain the refractory metal and alloy. The invention lowers the request to molten salt electrolyte, has short technology process. It is low energy consumption and has low request to device.
Description
Technical field
The present invention relates to a kind ofly directly prepare the method and the isolated plant thereof of refractory metal and alloy, belong to electrolytic process and prepare the alloying technology field by metal oxide.
Background technology
Refractory metal is meant titanium (Ti), zirconium (Zr), the hafnium (Hf) of IV family subgroup in the periodic table of elements, the vanadium (V) of V family subgroup, niobium (Nb), tantalum (Ta), the chromium (Cr) of VI family subgroup, tungsten (W), molybdenum (Mo), ten kinds of fusing points such as the rhenium (Re) of VII family subgroup are higher than the general name of 1650 ℃ of metallic elements.At present the main preparation methods of refractory metal is exactly a hot reducing method, comprises metallothermic reduction, carbothermic reduction etc., but that hot reducing method is produced is discontinuous, to reactor require high, pollute the widespread use that shortcoming such as big has restricted this metalloid.The preparation of refractory metal mainly contains two megatrend, and the first is further perfect on original method basis, comprises maximization, automatization etc.; The 2nd, develop a kind of novel method to replace traditional method.Researcher gains enlightenment from electrolytic aluminum, hope can replace hot reducing method with electrolytic process, thereby reduce cost significantly, but with the electrolytic aluminum electrolytic magnesium is the preparation that the traditional electrical solution of representative can not directly apply to refractory metal, mainly has a following difficulty: (1) is difficult to find sodium aluminum fluoride-aluminum oxide good electrolyte system (aluminum oxide melting degree therein reaches 10%) like that; (2) the refractory metal high-melting-point make resultant with the disperse of powder shape in fused salt, be difficult to collect; (3) refractory metal all has the multivalence attitude, causes metal ion not exclusively to discharge at negative electrode, reduces current efficiency greatly.Cambridge University achieved success in the metal titanium preparation with a kind of new fused salt electrolysis in 2000, and this method has advantages such as process simplification, cost is low, pollution is little, but its maximum shortcoming is that the negative electrode preparation is complicated, current efficiency is low, and decomposition voltage is wayward.
Summary of the invention
The objective of the invention is the shortcoming at existing preparation refractory metal technology, the electrolysis process that proposes a kind of novelty realizes directly being prepared by metal oxide the method for refractory metal or alloy.Another object of the present invention provides a kind of isolated plant that is directly prepared the method for refractory metal or alloy by metal oxide.
For achieving the above object, the present invention takes following technical scheme:
A kind of method that directly prepares refractory metal and alloy by metal oxide, it is characterized in that placing the metal-powder of crucible, spherical refractory metal oxide and fused salt block from bottom to top at high temperature by forming metal liquid, spherical refractory metal oxide and the layering of fused fused salt from bottom to top in proper order, metal liquid, spherical refractory metal oxide and graphite cathode guide rod are formed cathod system; Its processing step is as follows: with the refractory metal oxide pelletizing, particle diameter is 5～10mm, at 1000～1200 ℃ of following sintering 7～9h; An amount of metal-powder is placed the crucible bottom, on metal-powder, insert the good spherical refractory metal oxide of pellet sintering, add the halogenide fused salt again; When heating crucible to electrolysis temperature, graphite anode is fallen by system by rise fall of electrodes, graphite anode is immersed in the fused fused salt, graphite anode and graphite cathode guide rod are connected on respectively on the positive and negative electrode of direct supply, carry out electrolysis, electrolysis voltage is 2.0～3.8V, and Faradaic current is 0.1～3.0A, obtains the refractory metal alloy of refractory metal particle and crucible bottom at last.
The electrolytic process of the inventive method is to carry out in the used isolated plant of the present invention.The structure of this device comprises: high-temperature heating equipment (1), corundum crucible (2), graphite cathode guide rod (3), metal-powder (4), spherical refractory metal oxide (5), fused salt (6), flake graphite anode (7), direct supply (8), rise fall of electrodes system (9) is characterized in that metal-powder (4), spherical refractory metal oxide (5), fused salt (6) divide from the bottom to top to be placed in the corundum crucible (2); Graphite cathode guide rod (3) is positioned at corundum crucible (2) lower curtate middle position, and flake graphite anode (7) is fixed in the rise fall of electrodes system (9); The heating unit (1) peripheral by corundum crucible (2) carries out heat, when temperature rises to electrolysis temperature, regulates rise fall of electrodes system (9), and flake graphite anode (7) is immersed in the fused fused salt (6); Flake graphite anode (7) and graphite cathode guide rod (3) are connected on respectively on the positive and negative electrode of direct supply (8).
The present invention is a kind of method that directly prepares refractory metal and alloy thereof from refractory metal oxide, it is characterized in that the metal of selecting for use density suitable, make that spherical refractory metal oxide is suspended on the liquid metal under hot conditions, form cathod system with molten metal, graphite cathode guide rod, under electronic action, the refractory metal oxide ionization produces the oxygen room, the oxonium ion that generates is under electric field action, separate out at graphite anode by molten salt electrolyte, generate pure refractory metal and alloy thereof at negative electrode.
The mechanism of the inventive method is: under electronic action, nonconducting refractory metal oxide can the oxygen ionization, produce oxonium ion and generate the oxygen room and become semi-conductor, the oxonium ion that generates is under electric field action, fused salt by ionophore migrates to anode and separates out, along with the oxygen in the oxide compound constantly " is driven away ", stay pure metal at last.Concrete electrode reaction is as follows:
Anodic reaction: 2O
2-+ C → CO
2+ 4e
Cathodic reaction: MeO
x+ 2xe → Me+xO
2-
Characteristics of the present invention are: select the suitable metal of density, refractory metal oxide, fused salt for use, and the feasible layering that at high temperature forms from bottom to top, order is metal liquid-spherical refractory metal oxide-fused fused salt; Liquid metal has been formed a cathod system with spherical refractory metal oxide and graphite cathode guide rod, because refractory metal oxide and electronic conductor molten metal contact area are very big, thereby has increased current density, has improved electrolytic efficiency; No longer need metal oxide to be fused in the fused salt in this method, reduced the requirement to molten salt electrolyte, product is collected easily, does not have electrolysis repeatedly and incomplete electric discharge phenomena; Technical process is short, and equipment requirements is not high, and energy consumption is low, can realize serialization production.
Description of drawings
Fig. 1 is the isolated plant structural representation of the inventive method electrolysis process.
Each digital code table is as follows among the figure:
1. spherical refractory metal oxide 6. fused salts 7. flake graphite anodes 8. direct supplys of high-temperature heating equipment 2. corundum crucible 3. graphite cathode guide rods, 4. metal-powders 5. 9. rise fall of electrodes systems.
Embodiment
Now reach in conjunction with the accompanying drawings embodiment with the present invention be described in detail in after.
Embodiment one
With refractory metal oxide (tantalum pentoxide is an example) 20g pelletizing, particle diameter is 5～10mm, sintering 8h under 1000 ℃ of conditions; The 40g copper powder is placed the crucible bottom, on copper powder, place the good spherical tantalum pentoxide of 20g pellet sintering, insert 80g MgF again
2-CaF
2Fused salt, it consists of 55.5%MgF
2-44.5%CaF
2(massfraction); Behind the heating crucible to 1200 ℃, graphite anode is fallen by system by rise fall of electrodes, and graphite anode is immersed in the fused fused salt, and the graphite cathode guide rod of graphite anode and crucible bottom is connected on respectively on the positive and negative electrode of direct supply; Carry out electrolysis, electrolysis voltage is 3.2V, and Faradaic current is 0.1～3.0A, and behind electrolysis 8～10h, electric current is reduced to below the 0.1A, stops electrolysis, finally obtains pure metal tantalum, and because the part metals tantalate solid solution in copper liquid, has formed the copper tantalum alloy.
Embodiment two
With refractory metal oxide (titanium dioxide is example) 20g pelletizing, particle diameter is 5～10mm, sintering 8h under 1000 ℃ of conditions; The 40g aluminium powder is placed the crucible bottom, on aluminium powder, place the good spherical titanium dioxide of 20g pellet sintering, insert 80gCaCl again
2Fused salt; Behind the heating crucible to 900 ℃, graphite anode is fallen by system by rise fall of electrodes, and graphite anode is immersed in the fused fused salt, and the graphite cathode guide rod of graphite anode and crucible bottom is connected on respectively on the positive and negative electrode of direct supply; Carry out electrolysis, electrolysis voltage is 2.8V, and Faradaic current is 0.1～3.0A, behind electrolysis 8～10h, below the near 0.1A of electric current, stops electrolysis, finally obtains pure metal titanium, and the solid solution of part metals titanium forms aluminum titanium alloy in aluminium liquid.
Claims (3)
1. method that directly prepares refractory metal and alloy by metal oxide, it is characterized in that placing the metal-powder of crucible, spherical refractory metal oxide and fused salt block from bottom to top at high temperature by forming metal liquid, spherical refractory metal oxide and the layering of fused fused salt from bottom to top in proper order, metal liquid, spherical refractory metal oxide and graphite cathode guide rod are formed cathod system; Its processing step is as follows: with the refractory metal oxide pelletizing, particle diameter is 5～10mm, at 1000～1200 ℃ of following sintering 7～9h; An amount of metal-powder is placed the crucible bottom, on metal-powder, insert the good spherical refractory metal oxide of pellet sintering, add the halogenide fused salt again; When heating crucible to electrolysis temperature, graphite anode is fallen by system by rise fall of electrodes, graphite anode is immersed in the fused fused salt, graphite anode and graphite cathode guide rod are connected on respectively on the positive and negative electrode of direct supply, carry out electrolysis, electrolysis voltage is 2.0～3.8V, and Faradaic current is 0.1～3.0A, obtains the refractory metal alloy of refractory metal particle and crucible bottom at last.
2. directly prepare the method for refractory metal and alloy by claim 1 is described by metal oxide, it is characterized in that described metal-powder is copper powder, aluminium powder etc.
3. by the described isolated plant that directly prepares the method for refractory metal and alloy by metal oxide of claim 1, the structure of this device comprises: high-temperature heating equipment (1), corundum crucible (2), graphite cathode guide rod (3), metal-powder (4), spherical refractory metal oxide (5), fused salt (6), flake graphite anode (7), direct supply (8), rise fall of electrodes system (9) is characterized in that metal-powder (4), spherical refractory metal oxide (5), fused salt (6) divide from the bottom to top to be placed in the corundum crucible (2); Graphite cathode guide rod (3) is positioned at corundum crucible (2) lower curtate middle position, and flake graphite anode (7) is fixed in the rise fall of electrodes system (9); The heating unit (1) peripheral by corundum crucible (2) carries out heat, when temperature rises to electrolysis temperature, regulates rise fall of electrodes system (9), and flake graphite anode (7) is immersed in the fused fused salt (6); Flake graphite anode (7) and graphite cathode guide rod (3) are connected on respectively on the positive and negative electrode of direct supply (8).
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| CNB2006101163834A CN100535196C (en) | 2006-09-21 | 2006-09-21 | Method and apparatus for directly preparing refractory metal and alloy from metal oxide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967660A (en) * | 2010-11-09 | 2011-02-09 | 上海大学 | Method for preparing Nb3Al superconducting material by using electrical co-deoxidization method |
| CN102424986A (en) * | 2011-11-24 | 2012-04-25 | 中国船舶重工集团公司第七二五研究所 | Method for preparation of titanium-tungsten alloy through molten salt electrolysis |
| CN101928964B (en) * | 2010-01-21 | 2012-05-02 | 上海大学 | Method for directly preparing Ti5Si3 high-temperature alloy from titaniferous blast furnace slag and electrolytic bath device thereof |
| CN103741170A (en) * | 2014-01-15 | 2014-04-23 | 广西贺州金广稀土新材料有限公司 | Arcing and electrolysis integrated furnace for preparing rare earth metal |
| CN106978612A (en) * | 2017-03-16 | 2017-07-25 | 广东省稀有金属研究所 | A kind of metallurgical method of metallic compound |
| CN110284158A (en) * | 2019-06-24 | 2019-09-27 | 北京科技大学 | A kind of method of liquid cathode electrolysis Ti-containing slag step separation titanium copper and titanium silicon |
| CN115142096A (en) * | 2021-03-30 | 2022-10-04 | 中国科学院过程工程研究所 | Method for improving electrolysis efficiency of refractory metal prepared by molten salt electrolysis and purifying molten salt |
-
2006
- 2006-09-21 CN CNB2006101163834A patent/CN100535196C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928964B (en) * | 2010-01-21 | 2012-05-02 | 上海大学 | Method for directly preparing Ti5Si3 high-temperature alloy from titaniferous blast furnace slag and electrolytic bath device thereof |
| CN101967660A (en) * | 2010-11-09 | 2011-02-09 | 上海大学 | Method for preparing Nb3Al superconducting material by using electrical co-deoxidization method |
| CN101967660B (en) * | 2010-11-09 | 2012-05-02 | 上海大学 | Method for preparing Nb3Al superconducting material by using electrical co-deoxidization method |
| CN102424986A (en) * | 2011-11-24 | 2012-04-25 | 中国船舶重工集团公司第七二五研究所 | Method for preparation of titanium-tungsten alloy through molten salt electrolysis |
| CN102424986B (en) * | 2011-11-24 | 2014-10-29 | 中国船舶重工集团公司第七二五研究所 | Method for preparation of titanium-tungsten alloy through molten salt electrolysis |
| CN103741170A (en) * | 2014-01-15 | 2014-04-23 | 广西贺州金广稀土新材料有限公司 | Arcing and electrolysis integrated furnace for preparing rare earth metal |
| CN103741170B (en) * | 2014-01-15 | 2016-02-24 | 广西贺州金广稀土新材料有限公司 | One is prepared rare earth metal and is beaten arc electrolysis all-in-one oven |
| CN106978612A (en) * | 2017-03-16 | 2017-07-25 | 广东省稀有金属研究所 | A kind of metallurgical method of metallic compound |
| CN110284158A (en) * | 2019-06-24 | 2019-09-27 | 北京科技大学 | A kind of method of liquid cathode electrolysis Ti-containing slag step separation titanium copper and titanium silicon |
| CN115142096A (en) * | 2021-03-30 | 2022-10-04 | 中国科学院过程工程研究所 | Method for improving electrolysis efficiency of refractory metal prepared by molten salt electrolysis and purifying molten salt |
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| CN100535196C (en) | 2009-09-02 |
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