CN101235520A - Method for preparing metallic titanium by electrolyzing TiCl4 molten salt and electrolysis bath thereof - Google Patents
Method for preparing metallic titanium by electrolyzing TiCl4 molten salt and electrolysis bath thereof Download PDFInfo
- Publication number
- CN101235520A CN101235520A CNA2008100105417A CN200810010541A CN101235520A CN 101235520 A CN101235520 A CN 101235520A CN A2008100105417 A CNA2008100105417 A CN A2008100105417A CN 200810010541 A CN200810010541 A CN 200810010541A CN 101235520 A CN101235520 A CN 101235520A
- Authority
- CN
- China
- Prior art keywords
- titanium
- electrolysis
- electrolyzer
- ticl
- 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.)
- Granted
Links
Images
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
A method for preparing metallic titanium by TiCl4 fused salt electrolysis and an electrolysis bath for preparing the metallic titanium are disclosed, wherein the method comprises the following steps: pre-warming, adding electrolyte, pumping shielding gas, hollow electrolyzing, electrolyzing by adding TiCl4, electrolyzing, hollow electrolyzing, pumping shielding gas, discharging and after-treatment technology steps, wherein the anode of the electrolysis bath is graphite inside lining, the cathode is a steel bar, a baffle plate is arranged between the graphite anode and the steel bar cathode, and the baffle plate is submerged in molten electrolyte, a cylinder type airtight container with a cover is arranged on the baffle board, the steel bar cathode is arranged on the cover, electrolyte and TiCl4 feed inlet are further arranged on the cover, the electrolyte and a feed inlet are further mounted on the cover, a stainless steel discharging tube and a bleeding and pressure gauging pipe orifice are arranged on the bottom of the electrolysis bath, an argon gas inflating orifice is arranged on the side-wall of the cylinder container, an anode gas chamber is arranged between the upper portion of sides of the bath and the upper portion of the baffle plate, a Cl2 exhaust port is arranged on the chamber, a slope is arranged on the lower portion of the cathode chamber where the cathode chamber is arranged near to the baffle plate, space of the bottom of the graphite anode and the baffle plate is stamped by fireproof concrete. Compared with the traditional TiCl4 low-temperature fused salt electrolysis technology, the method has the advantages of solving the problems of high oxygen content in titanium powder in the electrolyzing products, can not proceed continuous production, great variation of the heat balance and the material balance of the electrolysis bath, and low efficiency of the electric current.
Description
Technical field
The invention belongs to the non-ferrous metallurgy technology field, particularly a kind of TiCl
4The electrolysis process and the electrolyzer of granulated metal titanium produced in fused salt electrolysis.
Background technology
At present, industrial metal titanium mainly uses Kroll (Kroll) method to produce both at home and abroad, the metal titanium of being produced is spongiform according to the method, be called titanium sponge, its main technique flow process is: with concentrate such as rutile or ilmenite obtained after treatment the higher-grade material---artificial rutile and titanium slag (contain TiO
2More than the 85%-90%) be raw material, through high-temp chlorination, make rough TiCl
4, after rectification and purification, make pure TiCl again
4After, in the vacuum reducing stove, use magnesium metal reduction TiCl
4, reduzate is the spongy metal titanium, fused MgCl
2The metal M g intact with unreacted.After reduction, with the liquid MgCl of reaction generation
2Extrude with MAGNESIUM METAL,, remove remaining MgCl through vacuum distilling
2Behind Mg, promptly obtain the satisfactory titanium sponge of product purity.Though the Kroll method has obtained using widely in industrial production, this method still has many shortcomings:
1.Kroll the method production cycle is long, productivity is low.Only with regard to TiCl
4The technological process of original production titanium sponge also, the process need a few days of producing pure titanium sponge.Single furnace output is generally the 2-5 ton, although there is the highest single furnace output of the external producer of bibliographical information can reach 10 tons, there are several large-scale reduction furnaces in a big metal titanium factory, and throughput can reach ton/years up to ten thousand, and its productivity still is not very high.Should be in the production of several main non-ferrous metals, the productivity that its Kroll method is produced titanium sponge is minimum.
2. reduction reaction is at high temperature carried out, and reactant and product be all muriate, and body of heater and equipment are had heavy corrosion.Reduction furnace long-time running meeting under the high-temperature vacuum condition deforms, and causes consumption.
3. energy consumption height.In non-ferrous metals industry, the smelting of non-ferrous metal (being commonly referred to as chemical metallurgy) is main energy consumption department.Wherein electrolytic aluminum is 3.72 tons of mark coal/TAl, and it is 6.94 tons of mark coal/TNi that nickel is smelted comprehensive energy consumption, and smart zinc comprehensive energy consumption is 1.69 tons of mark coal/TZn, and the electrolytic zinc comprehensive energy consumption is 2.01 tons of mark coal/TZn.It is 1.06 tons of mark coal/TCu that copper is smelted comprehensive energy consumption, and the titanium sponge comprehensive energy consumption is 15.32-17.8 ton mark coal/TTi.This shows that in the existing technology, the unit consumption of energy of producing titanium sponge is the highest.
4. can not realize serialization production.
5.TiCl
4The metal titanium sponge is produced in magnesium reduction, need be reductive agent with the MAGNESIUM METAL, though in theory, producing one ton of titanium sponge approximately needs 1 ton of MAGNESIUM METAL, and in fact required magnesium will be higher than this value.The reductive agent MAGNESIUM METAL can be used MgCl
2Fused salt electrolysis process production.Also can use the silicothermic process production of calcined dolomite.But the used reductive agent MAGNESIUM METAL of Large Titanium factories more both domestic and external is all produced with fused salt electrolysis process.Can consume TiCl in titanium station-service fused salt electrolysis process production MAGNESIUM METAL
4By product---the MgCl that titanium sponge generated is produced in magnesium reduction
2Simultaneously, the Cl of electrolysis generation
2Be again titanium slag chlorination production TiCl
4Raw material.The mode of production of above-mentioned self-built electrolytic magnesium factory of titanium factory is referred to as magnesium titanium associated enterprises usually, is considered to realize the technical process and the production and operation pattern of titanium sponge production economic benefit the best.The Mg-Ti integrated process can make the production cost of titanium reduce, but this also can make the construction investment of titanium factory increase undoubtedly.Because MgCl
2The main muriate of the waste residue that fused salt electrolysis produces is formed, and poisonous and unfavorable environmental protection has increased the waste residue processing costs.
In order to solve long problem of Kroll method production cycle, boost productivity, cut down the consumption of energy, reduce the production cost of metal titanium, since the Kroll method was born, people were studying other smelting process of metal titanium always.During this time, other that people explored produced not following tens kinds of the method for metal titanium, and many methods it is said succeeds in the laboratory, but all fails to realize producing in the large-scale industry.
In many non-Kroll refining titanium methods, that people were the most good in recent years is TiO
2Fused salt electrolysis process.This method ultimate principle is the TiO that will suppress and burn till
2Make negative electrode, graphite is made anode, carries out electrolysis in electrolysis of chloride plastome, and its anodic product is CO
2, negative electrode is a titanium.Also there is the investigator to pass through the research of anticathode electrolysis process, thinks that the electrochemical reaction mechanism of negative electrode generation metal titanium is still: basic metal or alkaline-earth metal ions generation exoelectrical reaction before this, basic metal that exoelectrical reaction generates or alkaline-earth metal reduction TiO
2Generate metal titanium.No matter but be that the titanium that generates on the negative electrode is the TiO of negative electrode
2The Direct Electrochemistry reaction generates, and still basic metal that is generated behind the cathodic discharge and alkaline-earth metal reduction back generates indirectly, and its last electrolysate Ti is attached to TiO with the skim metal titanium
2Electrode surface, the generation of this layer metal titanium can limit the TiO of metal titanium inside
2Reduction process, make that final negative electrode product can only be the metal titanium of skim, so fused salt electrolysis process is difficult in industrial replacement Kroll method at present.But, TiCl
4The low-temperature molten salt electrolytic process be considered to the most potential because this method can make the Production Flow Chart of titanium shorten dramatically, productivity improves greatly, production cost and energy consumption reduce greatly.
At existing TiCl
4In the low-temperature molten salt electrolysis tech, mainly there is following shortcoming:
(1) between the titanium valve particle that in the cathode electrolytic cell basketry, loosens, the muriate of titanium can not be by electrolysis completely at a low price, when electrolysis finishes, the loose porous muriatic electrolyte melt that contains the low price titanium, can in electrolyzer, be taken out together, in water washing process subsequently together with the loose titanium in the basketry, the muriate and the water generation hydrolysis of titanium at a low price generates TiO
2And TiO, cause the oxygen level in the electrolysate titanium valve to increase.
(2) can not continuous production.
(3) thermal equilibrium of electrolyzer and material balance change greatly.
(4) current efficiency is low.
Summary of the invention
At above-mentioned TiCl
4Fused salt electrolysis process is produced the weak point of the electrolyzer of metal titanium, the invention provides a kind of TiCl
4The method and the electrolyzer of granulated metal titanium produced in fused salt electrolysis.
TiCl of the present invention
4Its outside of fused-salt bath is the pot shell of a steel.Insulating brick and refractory brick are arranged at pot shell inwall and pot shell bottom, and the innermost liner of pot shell sidepiece is a synthetic graphite.The electrolytic anode of this graphite liner double as, the bottom of graphite anode is equipped with rod iron, and this rod iron is the conduction connector of anode electrolytic cell.The fused ionogen is arranged in the electrolyzer.The electric tank cathode of steel vertically is inserted in the bath of cell.Between the graphite anode and steel negative electrode of electrolyzer, lay its underpart and be the very big and top of open porosity for not having the hole comparatively pottery of compact structure or the dividing plate that refractory materials is made.Having the pottery of hole part or refractory materials dividing plate is immersed in the electrolyte melt and has the ion that can make in the electrolyte melt have mass transfer function preferably in hole.But this mass transfer is the diffusion mass transfer and the ionic electromigration mass transfer of particle in the fused salt in electrolyzer, and does not have convective mass transfer.Above the dividing plate that pottery or refractory materials are made, a cartridge type encloses container with a lid is installed, make by stainless steel plate.Seal with vaccum seal ring between the loam cake of container and the cylindrical shell.The steel negative electrode is installed in and covers, and in addition, adding ionogen and TiCl is installed also on lid
4The charging opening pipe.The bottom is provided with and is used to extrude the stainless steel tube that is mixed with metallic titanium powder and electrolyte melt, and the mouth of pipe that has venting and mensuration pressure concurrently.The sidewall of drum ladle than the upper part, installed one can applying argon gas aerating pipe port, be used for to TiCl
4The applying argon gas pressurization makes the bottom land product extrude outside the groove via stainless steel tube.Between the stainless steel cylinder on the top of groove sidepiece refractory materials or lagging material and dividing plate top an anodic gas chamber of being made by stainless steel plate is arranged, opening is arranged on the chamber, the gas that generates on the anode by deriving, and adds collection here.The bottom of cathode compartment is made the slope in the place near dividing plate with refractory materials, so that the titanium valve that generates on the negative electrode here compiles.Between the bottom and porous refractory dividing plate of graphite anode, make firm by ramming with refractory concrete.This refractory concrete plays the effect of reinforcing graphite anode and dividing plate, can prevent that again the electrolysis melt from leaking outside from bottom land.
Description of drawings
Accompanying drawing is low temperature TiCl of the present invention
4The structural representation of fused-salt bath.
Among the figure: 1. pot shell, the 2. insulating brick in the groove liner, the 3. refractory brick in the groove liner, 4. graphite anode, 5. cathode steel bar, 6. electrolyte melt, 7. row's chlorine mouth of anodic gas gather qi together chamber, 8. stainless steel cylinder, 9. argon gas feeds mouthful, 10. vacuum packing ring, the lid of 11. cathode compartment top feed compartments, 12.TiCl
4Charging opening, 13. ionogen charging opening, 14. the steel electric tank cathode, 15. gas valves, 16. connect the manometric mouth of pipe, 17. discharge the conduit that is mixed with the titanium valve electrolyte melt, 18. the bottom has the dividing plate that porous is made by pottery or refractory materials, the slope that 19. refractory materialss or refractory concrete are made, 20. refractory concretes, 21. anodic gas gather qi together chamber, the phase chamber of 22 tops, cathodic area that surround by dividing plate.
Embodiment
As shown in drawings, low temperature TiCl of the present invention
4Fused-salt bath, its cell body has the pot shell 1 of a steel, be lined with insulating brick 2 in the pot shell 1, be lined with refractory brick 3 in the insulating brick, with electrolyte melt 6 contacted lateral linings be graphite anode 4, the bottom of graphite anode 4 is connected with anode rod iron 5, and stretches out outside the pot shell, the electric tank cathode 14 of steel vertically is installed on the electrolyzer center, and its underpart extend in the electrolyte melt 6; Between the graphite anode 4 and steel negative electrode 14 of electrolyzer, there is its underpart to be that open porosity is very big and top does not have pore, erosion resistance is better, thermal shock resistance is the dividing plate 18 made of pottery or refractory materials preferably, what install above dividing plate 18 that pottery or refractory materials are made is a metal cylinder 8 that has crown cap 11, metal cylinder 8 and crown cap 11 are all made by abrasion-proof stainless steel, seal with vacuum packing ring 10 between the two, there is an inlet mouth 9 that can charge into the rare gas element argon gas in the outside of metal cylinder 8, steel negative electrode 14, be lifted on and cover on 11, on the lid 11 TiCl is installed also
413, one of filling tube 12 and ionogen charging openings can make ionogen product titanium valve together with electrolyte melt drainage conduit 17 outside the drain tank under the pressure effect of argon gas.Also have a Y-tube to be welded in addition to cover on 11 the hole, a mouth of pipe setting pressure valve 15 of Y-tube, another mouth of pipe 16 of Y-tube connects tensimeter.Electrolyte melt 6 upper surfaces, dividing plate 18 and on metal cylinder 8 and the lid above the tube 11 form a space and be called TiCl
4Phase chamber 22 is shaped on anodic gas Cl between refractory materials 3 or the metal cylinder above the lagging material 2 and above the groove internal partition 18 8
2 Collection chamber 21, Cl
2There is venting hole 7 collection chamber 21 tops.Dividing plate 18 is divided into two chambers with electrolyte melt in the groove, and the inside is a cathode compartment, and the outside is the anolyte compartment.There is a slope 19 by refractory materials or refractory concrete system the cathode compartment bottom near the position of dividing plate 18, is used to compile the product titanium valve of negative electrode.Bottom in the anolyte compartment, the refractory concrete 20 for making firm by ramming between graphite anode 4 and dividing plate 18, refractory concrete 20 have the effect of reinforcing graphite anode 4 and dividing plate 18, the effect that also has electrolyte melt of preventing 6 to spill from bottom land.
Adopt the step of this kind electrolyzer production titanium valve as follows:
Preheating: at first use the flame baking electrolyzer, and be heated to 600-700 ℃, meanwhile, the NaCl-LiCl-KCl electrolyte melt that will have the eutectic composition composition places in the plumbago crucible, and it is melted to 600-700 ℃.
Add ionogen: by ionogen charging opening 13, electrolyte melt is joined in the electrolyzer of inner preheating, ionogen will be added to given level height, does not have the hole part of dividing plate.
Logical protection gas: at TiCl
4Charging opening 12, ionogen charging opening 13 discharge nozzles 17 are under the situation that stainless steel gas valve 15 is opened, by argon gas inlet mouth 9, with the TiCl of argon gas with groove inner cathode district ionogen top
4Air in the phase chamber 22 is all driven away, again with argon gas inlet mouth 9, ionogen charging opening 13, and drainage conduit 17 and valve port 15 Close Alls.
Empty electrolysis: before the electrolysis, electrolyzer carries out 20～120 minutes empty electrolysis, and empty electrolysis is meant at TiCl
4Do not add fashionablely, the electrolysis of being carried out during without any the Ti ion of form in the electrolyte melt because electrolyte melt is LiCl-KCl and NaCl ternary eutectic melt, is the electrolysis of metallic lithium in empty electrolysis stage therefore;
Add TiCl4:TiCl
4Reinforced by its feed opening 12.
Electrolysis: direct current imported in the electrolyzer by anode rod iron 5 and steel negative electrode carry out electrolysis, and by adjusting the voltage of electrolyzer, little by little make the temperature of the electrolyte melt 6 in the electrolyzer remain on 500-550 ℃, realize the thermal equilibrium of electrolyzer, and under this electrolysis temperature and power strength, realize normal electrolysis production, because electrolysis temperature is low, the metal titanium that electrolysis generates is the powdered metal titanium, and titanium valve can be deposited to bottom land.
Empty electrolysis: after sinking to titanium valve on the bottom land and being accumulated to a certain degree, close TiCl
4Charging valve, and carry out the empty electrolysis of for some time, up to electrolyzer counter potential＞3.3V.
Logical protection gas: after the titanium in the electrolyte melt 6 is reduced fully (chemistry or electrochemical), open the air intake valve of argon gas, to TiCl
4Applying argon gas in the phase chamber 22 makes its pressure greater than 0.1MPa.
Discharging: open the valve port of drainage conduit, the powdery titanium that bottom land is generated is discharged in groove together with the electrolyte melt that mixes with it.
Aftertreatment: after the cooling, through washing, remove ionogen, obtain titanium valve after the oven dry, titanium valve purity is greater than 99%, the Cl that generates on anode 4 in the electrolytic process
2Enter Cl
2Collection chamber 21 is discharged and is collected by venting port 7, is used for titanium slag chlorination production TiCl
4
Each reaction equation is:
When just beginning, the surface of electric tank cathode district electrolyte melt 6 can generate metallic lithium in empty electrolytic process, join the TiCl in the phase chamber 22
4Can react with the metallic lithium that generates, generate powdered titanium Ti
4Li+TiCl
4→4LiCl+Ti (1)
TiCl
4+Ti＝2TiCl
2 (2)
The low price TiCl that reaction generates
2Be easy to be dissolved in the electrolyte melt, and be dissociated into Ti
2+And Cl
-Ti at a low price
2+In electrolytic process, on negative electrode, be reduced, generate metal titanium.
Ti
2++2e→Ti (3)
No matter press present electrolysis theoretical investigation electrolyte melt by chemical reaction (1), or the metal titanium of electrochemical reaction (3) generation, and the low price Ti that generates in the electrolyte melt
2+Ion can further quicken TiCl
4Dissolution rate in electrolyte melt.Therefore, cathode surface may exist following chemical reaction in the electrolyte melt:
Ti
4++4e→Ti
Ti
4++2e→Ti
2+
Ti
2++2e→Ti。
Claims (2)
1, a kind of TiCl
4The electrolyzer of metal titanium is produced in fused salt electrolysis, it is characterized in that this electrolyzer outside is the pot shell of a steel, insulating brick and refractory brick are arranged at pot shell inwall and pot shell bottom, the innermost liner of pot shell sidepiece is a synthetic graphite, the electrolytic anode of this graphite liner double as, the bottom of graphite anode is equipped with rod iron, this rod iron is the conduction connector of anode electrolytic cell, the fused ionogen is arranged in the electrolyzer, the electric tank cathode of steel vertically is inserted in the bath of cell, between the graphite anode and steel negative electrode of electrolyzer, lay its underpart and be the very big and top of open porosity and be the comparatively pottery of compact structure or the dividing plate that refractory materials is made, the pottery or the refractory materials dividing plate that have the hole part are immersed in the electrolyte melt, above the dividing plate that pottery or refractory materials are made, a cartridge type encloses container with a lid is installed, seal with vaccum seal ring between the loam cake of container and the cylindrical shell, the steel negative electrode is installed in and covers, and also is equipped with to add ionogen and TiCl on lid
4Charging opening, the bottom is provided with and is used to extrude the stainless steel tube that is mixed with metallic titanium powder and electrolyte melt, and the mouth of pipe that has venting and mensuration pressure concurrently, top at the sidewall of drum ladle, installed one can applying argon gas aerating pipe port, between the stainless steel cylinder on the top of groove sidepiece refractory materials or lagging material and dividing plate top, an anodic gas chamber of being made by stainless steel plate is arranged, opening is arranged on the chamber, the bottom of cathode compartment is in the place near dividing plate, make the slope with refractory materials, between the bottom and porous refractory dividing plate of graphite anode, make firm by ramming with refractory concrete.
2, adopt the described TiCl of claim 1
4The electrolyzer of metal titanium is produced in fused salt electrolysis, carries out the method that metal titanium is produced in the low-temperature molten salt electrolysis, it is characterized in that may further comprise the steps:
(1) preheating: at first use the flame baking electrolyzer, and be heated to 600-700 ℃, the NaCl-LiCl-KCl electrolyte melt that will have the eutectic composition composition simultaneously places in the plumbago crucible, makes its temperature of fusion reach 600-700 ℃;
(2) add ionogen: by the ionogen charging opening, electrolyte melt is joined in the electrolyzer of inner preheating, make electrolyte levels not have the hole part of dividing plate;
(3) logical protection gas: at TiCl
4Under the situation that charging opening, ionogen are reinforced, discharge nozzle and stainless steel gas valve are opened, with the TiCl of argon gas with groove inner cathode district ionogen top
4Air in the phase chamber is all driven away, again with argon gas inlet mouth, ionogen charging opening, drainage conduit and valve port Close All;
(4) empty electrolysis: electrolyzer need carry out 20～120 minutes empty electrolysis before the electrolysis;
(5) add TiCl
4: TiCl
4Reinforced by its feed opening;
(6) electrolysis: direct current is imported in the electrolyzer by anode rod iron and steel negative electrode, by adjusting the voltage of electrolyzer, little by little make the temperature of the electrolyte melt in the electrolyzer remain on 500-550 ℃, and under this electrolysis temperature and power strength, carrying out electrolysis, the granulated metal titanium of generation is deposited to bottom land;
(7) empty electrolysis: after sinking to titanium valve on the bottom land and being accumulated to a certain degree, close TiCl
4Charging valve, and carry out the empty electrolysis of for some time, up to electrolyzer counter potential＞3.3V;
(8) logical protection gas: after the titanium in the electrolyte melt is reduced fully, open the air intake valve of argon gas, to TiCl
4Applying argon gas in the phase chamber makes its pressure greater than 0.1MPa;
(9) discharging: open the valve port of drainage conduit, the powdery titanium that bottom land is generated is discharged in groove together with the electrolyte melt that mixes with it;
(10) aftertreatment: cooling, ionogen is removed in washing, obtains titanium valve after the oven dry, and titanium valve purity is greater than 99%, the Cl that generates on anode in the electrolytic process
2Enter Cl
2Collection chamber is discharged and is collected by venting port, is used for titanium slag chlorination production TiCl
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100105417A CN101235520B (en) | 2008-03-05 | 2008-03-05 | Method for preparing metallic titanium by electrolyzing TiCl4 molten salt and electrolysis bath thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100105417A CN101235520B (en) | 2008-03-05 | 2008-03-05 | Method for preparing metallic titanium by electrolyzing TiCl4 molten salt and electrolysis bath thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101235520A true CN101235520A (en) | 2008-08-06 |
| CN101235520B CN101235520B (en) | 2010-06-09 |
Family
ID=39919415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100105417A Expired - Fee Related CN101235520B (en) | 2008-03-05 | 2008-03-05 | Method for preparing metallic titanium by electrolyzing TiCl4 molten salt and electrolysis bath thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101235520B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014762A (en) * | 2012-12-31 | 2013-04-03 | 金坛市六九钛业科技有限公司 | Device for producing metal by fused salt electrolysis process |
| CN103334126A (en) * | 2013-06-14 | 2013-10-02 | 中国船舶重工集团公司第七二五研究所 | Method for preparing titanium sponge through resistance furnace by adopting molten salt electrolysis method |
| CN103484898A (en) * | 2013-10-10 | 2014-01-01 | 宝纳资源控股(集团)有限公司 | Vacuum high-temperature continuous electrolytic furnace system and electrolytic method |
| CN103759539A (en) * | 2014-02-11 | 2014-04-30 | 金坛市六九钛业科技有限公司 | Liquid material feeding device used for high temperature furnace for generating high-purity metal through molten salt electrolysis method |
| CN103834971A (en) * | 2012-11-23 | 2014-06-04 | 宁波创润新材料有限公司 | Electrode and molten salt electrolysis device |
| CN103911631A (en) * | 2014-04-01 | 2014-07-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Device for collecting products at cathode during molten salt electrolysis and molten salt electrolysis system |
| CN104313643A (en) * | 2014-07-31 | 2015-01-28 | 贵州重力科技环保有限公司 | High-purity antimony producing method by two-section fused salt electrolysis method |
| CN104928720A (en) * | 2015-07-13 | 2015-09-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Electrolyzing method for titanium soluble anode |
| CN105347041A (en) * | 2014-08-21 | 2016-02-24 | 中国科学院上海应用物理研究所 | Fused salt transporting method and device |
| CN106591888A (en) * | 2016-12-26 | 2017-04-26 | 宝纳资源控股(集团)有限公司 | Preparation method and device of low-valence titanium ion molten salt electrolyte |
| CN106702435A (en) * | 2017-03-30 | 2017-05-24 | 安徽工业大学 | Porous medium auxiliary molten salt electrolysis metal refining device |
| CN106835203A (en) * | 2016-12-26 | 2017-06-13 | 宝纳资源控股(集团)有限公司 | The purifier and method of a kind of fused salt |
| CN107475539A (en) * | 2017-08-18 | 2017-12-15 | 中南大学 | A kind of method that gaseous state electrochemistry prepares Titanium |
| CN107574318A (en) * | 2017-08-08 | 2018-01-12 | 山东默锐科技有限公司 | A kind of sodium slag method for purifying and separating and its equipment for purifying used |
| CN108441893A (en) * | 2018-06-13 | 2018-08-24 | 重庆大学 | A kind of molten-salt electrolysis TiO2The method for preparing Titanium |
| CN111020356A (en) * | 2019-12-30 | 2020-04-17 | 广州广钢新材料股份有限公司 | High-strength deformed steel bar and manufacturing method thereof |
| CN112996932A (en) * | 2018-07-11 | 2021-06-18 | 乌斯季卡面诺戈尔斯克钛和镁种植股份有限公司 | Device for chlorinating titanium-containing raw material in chloride salt melt |
| CN115161714A (en) * | 2022-08-01 | 2022-10-11 | 青岛国韬钛金属产业研究院有限公司 | Method for preparing metal titanium by molten salt solid-state deoxidation method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2789943A (en) * | 1955-05-05 | 1957-04-23 | New Jersey Zinc Co | Production of titanium |
| US2908619A (en) * | 1958-08-01 | 1959-10-13 | New Jersey Zinc Co | Production of titanium |
| NL131349C (en) * | 1960-02-19 | |||
| CN2298263Y (en) * | 1997-03-12 | 1998-11-25 | 石富 | Electric tank |
-
2008
- 2008-03-05 CN CN2008100105417A patent/CN101235520B/en not_active Expired - Fee Related
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834971A (en) * | 2012-11-23 | 2014-06-04 | 宁波创润新材料有限公司 | Electrode and molten salt electrolysis device |
| CN103834971B (en) * | 2012-11-23 | 2016-08-17 | 宁波创润新材料有限公司 | Electrode and fused salt electrolysis apparatus |
| CN103014762B (en) * | 2012-12-31 | 2015-09-16 | 金坛市六九钛业科技有限公司 | The raw metalliferous device of a kind of fused salt electrolysis process |
| CN103014762A (en) * | 2012-12-31 | 2013-04-03 | 金坛市六九钛业科技有限公司 | Device for producing metal by fused salt electrolysis process |
| CN103334126B (en) * | 2013-06-14 | 2016-04-13 | 中国船舶重工集团公司第七二五研究所 | A kind of method adopting fused salt electrolysis process to prepare titanium sponge in resistance furnace |
| CN103334126A (en) * | 2013-06-14 | 2013-10-02 | 中国船舶重工集团公司第七二五研究所 | Method for preparing titanium sponge through resistance furnace by adopting molten salt electrolysis method |
| CN103484898B (en) * | 2013-10-10 | 2016-04-27 | 宝纳资源控股(集团)有限公司 | A kind of vacuum high-temperature continuous electrolysis furnace system and electrolysis process |
| CN103484898A (en) * | 2013-10-10 | 2014-01-01 | 宝纳资源控股(集团)有限公司 | Vacuum high-temperature continuous electrolytic furnace system and electrolytic method |
| CN103759539B (en) * | 2014-02-11 | 2015-09-30 | 金坛市六九钛业科技有限公司 | The liquid material feeding device that the high temperature furnace that high pure metal is produced in molten-salt electrolysis uses |
| CN103759539A (en) * | 2014-02-11 | 2014-04-30 | 金坛市六九钛业科技有限公司 | Liquid material feeding device used for high temperature furnace for generating high-purity metal through molten salt electrolysis method |
| CN103911631A (en) * | 2014-04-01 | 2014-07-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Device for collecting products at cathode during molten salt electrolysis and molten salt electrolysis system |
| CN103911631B (en) * | 2014-04-01 | 2016-06-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Collect device and the fused salt electrolysis system of fused salt electrolysis cathode product |
| CN104313643A (en) * | 2014-07-31 | 2015-01-28 | 贵州重力科技环保有限公司 | High-purity antimony producing method by two-section fused salt electrolysis method |
| CN105347041A (en) * | 2014-08-21 | 2016-02-24 | 中国科学院上海应用物理研究所 | Fused salt transporting method and device |
| CN105347041B (en) * | 2014-08-21 | 2019-12-06 | 上海联和日环能源科技有限公司 | Molten salt transportation method and equipment |
| CN104928720A (en) * | 2015-07-13 | 2015-09-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Electrolyzing method for titanium soluble anode |
| CN106591888A (en) * | 2016-12-26 | 2017-04-26 | 宝纳资源控股(集团)有限公司 | Preparation method and device of low-valence titanium ion molten salt electrolyte |
| CN106835203A (en) * | 2016-12-26 | 2017-06-13 | 宝纳资源控股(集团)有限公司 | The purifier and method of a kind of fused salt |
| CN106835203B (en) * | 2016-12-26 | 2019-05-31 | 宝纳资源控股(集团)有限公司 | A kind of purification device and method of fused salt |
| CN106702435B (en) * | 2017-03-30 | 2018-10-09 | 安徽工业大学 | A kind of porous media auxiliary fused-salt electrolytic refining metal device |
| CN106702435A (en) * | 2017-03-30 | 2017-05-24 | 安徽工业大学 | Porous medium auxiliary molten salt electrolysis metal refining device |
| CN107574318A (en) * | 2017-08-08 | 2018-01-12 | 山东默锐科技有限公司 | A kind of sodium slag method for purifying and separating and its equipment for purifying used |
| CN107574318B (en) * | 2017-08-08 | 2019-08-23 | 山东默锐科技有限公司 | A kind of sodium slag method for purifying and separating and its equipment for purifying used |
| CN107475539B (en) * | 2017-08-18 | 2019-05-17 | 中南大学 | A kind of method that gaseous state electrochemistry prepares Titanium |
| CN107475539A (en) * | 2017-08-18 | 2017-12-15 | 中南大学 | A kind of method that gaseous state electrochemistry prepares Titanium |
| CN108441893A (en) * | 2018-06-13 | 2018-08-24 | 重庆大学 | A kind of molten-salt electrolysis TiO2The method for preparing Titanium |
| CN112996932A (en) * | 2018-07-11 | 2021-06-18 | 乌斯季卡面诺戈尔斯克钛和镁种植股份有限公司 | Device for chlorinating titanium-containing raw material in chloride salt melt |
| CN111020356A (en) * | 2019-12-30 | 2020-04-17 | 广州广钢新材料股份有限公司 | High-strength deformed steel bar and manufacturing method thereof |
| CN115161714A (en) * | 2022-08-01 | 2022-10-11 | 青岛国韬钛金属产业研究院有限公司 | Method for preparing metal titanium by molten salt solid-state deoxidation method |
| CN115161714B (en) * | 2022-08-01 | 2023-07-18 | 青岛国韬钛金属产业研究院有限公司 | Method for preparing metallic titanium by molten salt solid-state deoxidization method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101235520B (en) | 2010-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101235520B (en) | Method for preparing metallic titanium by electrolyzing TiCl4 molten salt and electrolysis bath thereof | |
| US5185068A (en) | Electrolytic production of metals using consumable anodes | |
| CN101914788B (en) | Method for preparing metallic titanium | |
| AU2002335251B2 (en) | Method and apparatus for smelting titanium metal | |
| CN103451682A (en) | Method for extracting metal titanium through molten salt electrolysis of titanium-containing soluble anode | |
| CN105088274B (en) | A kind of device for processing and reclaiming aluminium electroloysis solid waste | |
| CN103774180B (en) | A kind of apparatus and method producing metal and alloy integrating chlorination-electrolysis | |
| CZ297064B6 (en) | Process of producing metals by electrolysis | |
| CN102719857B (en) | Method and electrolytic tank for producing metal titanium through directive electrolysis of titanium dioxide | |
| WO2005080642A1 (en) | PROCESS FOR PRODUCING Ti OR Ti ALLOY BY REDUCTION OF Ca | |
| CN106929688B (en) | A kind of apparatus and method preparing rafifinal using aluminium lime-ash | |
| CN109267100B (en) | Device and method for preparing pure titanium through electrolysis-chlorination-electrolysis | |
| CN200952043Y (en) | Liquid cathode electrolytic tank for electrolytic production rare earth metal and alloy thereof | |
| CN110983378B (en) | Device and method for preparing metal aluminum and titanium tetrachloride in molten salt by soluble anode | |
| Yan et al. | Molten salt electrolysis for sustainable metals extraction and materials processing—A review | |
| CN104928719A (en) | Novel molten salt electrolysis smelting high-purity titanium device and smelting method thereof | |
| CN104711637B (en) | Method for recovering metal lead from solid lead oxide | |
| CN204982083U (en) | Novel fused salt electrolysis smelts high purity titanium device | |
| CN204959051U (en) | Aluminium electroloysis solid waste material's device is handled and retrieved | |
| CN212799663U (en) | Refining device for mixed molten salt product in titanium tetrachloride production | |
| CN202450165U (en) | Device for producing metal magnesium through electrolytic magnesium chloride | |
| JP4198434B2 (en) | Method for smelting titanium metal | |
| Withers et al. | The electrolytic production of Ti from a TiO2 feed (the DARPA sponsored program) | |
| CN103898555A (en) | Metal titanium production method | |
| CN209024654U (en) | A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100609 Termination date: 20110305 |