CN101701345A - Electrolytic cell in electro-deoxidization metallurgy process - Google Patents
Electrolytic cell in electro-deoxidization metallurgy process Download PDFInfo
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- CN101701345A CN101701345A CN200910237259A CN200910237259A CN101701345A CN 101701345 A CN101701345 A CN 101701345A CN 200910237259 A CN200910237259 A CN 200910237259A CN 200910237259 A CN200910237259 A CN 200910237259A CN 101701345 A CN101701345 A CN 101701345A
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- deoxidization
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Abstract
The invention discloses an electrolytic cell in electro-deoxidization metallurgy process, which is divided into a negative electrode region and a positive electrode region, which have the effect of isolating the flow of fused salts while achieving free exchange of ions, thus suppressing the occurrence of side reaction of positive and negative electrode products; the positive electrode in the electrolytic cell is rotated to accelerate the deoxidization speed and simultaneously, the emission of tail gas in the positive electrode region is quickened up in a manner of oriented-circulating protective gas stream in order to avoid overhigh content of the tail gas within the electrolytic cell; the electrodes of the electrolytic cell are changed into be arrayed in parallel, which breaks the limitation of traditional single electrode, the negative electrode and the positive electrode correspondingly form counter electrodes so as to polarize the electro-deoxidization task of the electrodes. The parallel-type electrodes can also adjust the array number of the counter electrodes according to requirement so as to change production ability without more improvements on equipment and production conditions, and to guarantee product quality as well. The electrolytic cell according to the invention has large production ability and short production period and is capable of realizing semi-continuous product.
Description
Technical field
The present invention relates to the design of electrolysis cells that the metal oxide electrochemical deoxidation prepares metal simple-substance or alloy, particularly a kind of electrolytic cell in electro-deoxidization metallurgy process technological design.
Background technology
The method of generally using in world's titanium sponge industrial production is a Kroll technology.The Kroll method mainly adopts metal M g reduction TiCl
4Operation-vacuum separation operation is made metal titanium, and this technology can make highly purified metal titanium.But this technology owing to thermal reduction process flow length, complex procedures, can not continuous production etc. reason make the titanium production cost high, the environmental pollution in the production process has in addition restricted the widespread use of titanium greatly.Improve although a lot of researchists attempt that Kroll technology is carried out some, the improvement of some technical elements of presentation of results can not change the expensive defective of this method.Therefore, adopting novel titanium extractive technique to replace the Kroll traditional technology is important prerequisite of titanium industrial development.
At present, " metal oxide and sosoloid molten salt electrodeoxidation method " (FFC method, international patent 99808568.5) all obtained certain achievement in the research aspect technology and the basic theory in recent years.The FFC method has broken through that people thought in the past can only be TiCl
4Dissolve in thought in the ionogen as raw material, directly utilize solid phase t iO
2As negative electrode, the chlorination in the traditional technology, refining TiCl have been saved
4, complicated procedures of forming such as magnesium reduction and vacuum distilling, particularly do not have the chlorine discharging, have save energy, pollute advantages such as few.
At present the FFC electro-deoxiedation prepares and exists side reaction ratio problem bigger than normal in the metal titanium technology, and this problem causes electrolysis production process reaction overlong time, current efficiency is low excessively, product quality is not high.
Summary of the invention
Order of the present invention provides a kind of electrolytic cell in electro-deoxidization metallurgy process, and on the basis that guarantees production level and product quality, the carrying out that effectively stops side reaction eliminated the unfavorable factor that side reaction brings, and eliminates the potential safety hazard in the production process.
Cell body of the present invention adopts stainless steel trough body, in graphite linings is arranged, electrolyzer inside is divided into cathodic area and positive column by dividing plate, two districts are relatively independent but can carry out ion-exchange freely, a plurality of titanium oxide cathode bar parallel waies are adopted in the access of electrode, anode adopt rotating electrode and with the corresponding one by one composition of negative electrode electrode pair, the electrolyzer top cover adopts stainless steel equally and is furnished with circuit, air-path interface.
Another technical scheme of the present invention is that described dividing plate is Al
2O
3, MgO, Al
2O
3One of-MgO material, its porosity show porosity 10～30% 40%～70%, show aperture, hole 0.1～2mm level, thickness 2mm～10mm.
Another technical scheme of the present invention is that described anode rotating speed generally is controlled at 60～180rpm.
Consider the serious side reaction carbon-coating problem of influence in the electrolytic process, introduce Al
2O
3Or MgO or Al
2O
3-MgO material dividing plate is divided into negative and positive two polar regions with electrolyzer, and interval, the two poles of the earth is realizing having again fused salt mobile buffer action when ion freely exchanges, thereby the side reaction that suppresses negative and positive the two poles of the earth product takes place, and negative and positive two polar region areas are about 6: 4 than design.Wherein the cathodic area is as the reduction zone, and the reduction reaction of high price titanium is carried out in this district, the oxygen in the former titanium oxide in the titanium reduction process from electrode interior progress into fused salt mutually, reach separating of metal and oxygen; The positive column is designed to the deoxidation district, and the oxygen in the fused salt is discharged in positive column discharge and with gas form, and the continuous reduction of oxygen concn makes the oxygen in cathodic area constantly be shifted in mutually to fused salt by electrode interior, thus realization deep deoxidation purpose.
The electrolyzer top cover comprises the parallel interface that is complementary with arrangement of electrodes, and protection gas (argon gas) inserts the tail gas outlet orifice on hole, anode top, and wherein electrode interface all is furnished with insulativity excellent protection pad.Total interface can satisfy the resistance to air loss requirement in the production all by screw thread and sealing-ring fixing seal.Because production process is to carry out in high-temperature fusion salt, and is too high for fear of the temperature of top cover, be equipped with water-cooling circulating system, prevent the premature aging and the corrosion of equipment.
A plurality of titanium oxide cathode bar parallel waies are adopted in the collocation of adjustment electrode, and electric deoxidation process hyperchannel is carried out.The cathode and anode interpole gap is controlled at more than the 200mm.
The invention advantage
The present invention is on the basis that guarantees production level and product quality, the carrying out that effectively stops side reaction, eliminate the unfavorable factor that side reaction brings, eliminate the potential safety hazard in the production process, and electrolyzer throughput of the present invention big, with short production cycle, can realize semi-continuous production.
Description of drawings
The left view of the electrolyzer process diagram that Fig. 1 designs for the inventor.
The vertical view of the electrolyzer process diagram that Fig. 2 designs for the inventor.
Wherein (1) is the stainless steel electrolytic cell body, and liner is the graphite linings that thickness is about 20mm; (2) be cathode sheets group rod, each group rod is made of the cathode sheets of some Φ 20mm*5mm, and the quantity of cathode sets rod is determined by the actual production demand; (3) be the rotation graphite anode, form counter electrode with negative electrode (2) and finish main electrolysis production process; (4) for rotating the drive part of graphite anode (3); (5), electrolyzer inside is divided into two polar regions of negative and positive, and satisfies the ionic trafficability characteristic for the inventor designs dividing plate; (6) and (7) be the cell gas circulation device, directed flow inertia protection gas (Ar) mainly is provided in electrolyzer, in time discharge electrolysis tail gas.
The titanium electrolysis process schema that Fig. 3 designs for the inventor.
Embodiment
Example 1
Electric tank cathode adopts the titanium oxide cathode bar, and this cathode bar is mixed in proportion forming and sintering by the smart powder of titanium dioxide, PVA binding agent etc. and forms, and every cathode bar oxide mass is about 100g, and the cathodic area is installed in parallel 3 groups of above-mentioned cathode bars.The positive column takes the mode corresponding with negative electrode 3 rotation graphite anodes in parallel as electrolytic anode, and cathode and anode spacing is 200mm, and the anode bar speed setting is 120rpm.The cancellation dividing plate.Adopt CaCl
2Fused salt, fused salt CaCl
2The degree of depth is 140mm, and temperature is controlled at 950 ℃, and protection gas argon flow amount is set at 5L/min, bath voltage 3.1V, electrolysis time 36h.Whole electrolysis process flow process is seen Fig. 3.
Shape of product does not have to change substantially, and density is higher, and color is grey black, and there is the grey layering in centre portions, and it is mainly intermediate product TiO, Ti after testing
2O, quality is about the outer product of 10g. and obtains the titanium sponge powder after fragmentation, pickling, cleaning, and titanium content is 99.07%, current efficiency 51%.There are relatively large black caking carbon-coating, the about 2mm of thickness in the fused salt surface in the electrolyzer.Remaining relatively large uncombined carbon in the inner sampling of fused salt.
Example 2
Electric tank cathode adopts the titanium oxide cathode bar, and this cathode bar is mixed in proportion forming and sintering by the smart powder of titanium dioxide, PVA binding agent etc. and forms, and every cathode bar oxide mass is about 100g, and the cathodic area is installed in parallel 3 groups of above-mentioned cathode bars.The positive column takes the mode corresponding with negative electrode 3 rotation graphite anodes in parallel as electrolytic anode, and cathode and anode spacing is 200mm, and the anode bar speed setting is 180rpm.Dividing plate adopts Al
2O
3Material, porosity show porosity 30% 55%, thickness 2mm, height 300mm.The electrolyzer integral matching as depicted in figs. 1 and 2.Adopt CaCl in the electrolyzer
2Fused salt, fused salt CaCl
2The degree of depth is 140mm, and temperature is controlled at 950 ℃, and protection gas argon flow amount is set at 5L/min, bath voltage 3.1V, electrolysis time 36h.Whole electrolysis process flow process is seen Fig. 3.
Shape of product does not have to change substantially, and density increases, and color is grey black, obtains the titanium sponge powder after fragmentation, pickling, cleaning, and titanium content is 99.27%, reaches national level Four titanium standard.Current efficiency 67.4%.Separator material burn into do not occur and melts phenomenon, and fused salt is white translucent CaCl through sampling analysis substantially in the electrolyzer
2Crystal does not have carbon or other impurity to be mingled with; There is a small amount of black caking district on the surface, can proceed to produce after simple the removing.
Example 3
Electric tank cathode adopts the titanium oxide cathode bar, and this cathode bar is mixed in proportion forming and sintering by the smart powder of titanium dioxide, PVA binding agent etc. and forms, and every cathode bar oxide mass is about 100g, and the cathodic area is installed in parallel 3 groups of above-mentioned cathode bars.The positive column takes the mode corresponding with negative electrode 3 rotation graphite anodes in parallel as electrolytic anode, and cathode and anode spacing is 200mm, and the anode bar speed setting is 120rpm.Dividing plate adopts the MgO material, and porosity shows porosity 15% 50%, thickness 5mm, height 300mm.The electrolyzer integral matching as depicted in figs. 1 and 2.Adopt CaCl in the electrolyzer
2Fused salt, fused salt CaCl
2Controlling depth is 140mm, and temperature is controlled at 950 ℃, and protection gas argon flow amount is set at 5L/min, bath voltage 3.1V, electrolysis time 28h.Whole electrolysis process flow process is seen Fig. 3.
Shape of product does not have to change substantially, and density increases, and color is grey black, obtains titanium sponge powder 130g after fragmentation, pickling, cleaning, and titanium content is 99.27%, reaches national level Four titanium standard, current efficiency 71%.Separator material burn into do not occur and melts phenomenon, and fused salt is white translucent CaCl through sampling analysis substantially in the electrolyzer
2Crystal does not have carbon or other impurity to be mingled with; There is a small amount of black caking district on the surface, can reuse after simple the removing.
Example 4
Electric tank cathode adopts the titanium oxide cathode bar, and this cathode bar is mixed in proportion forming and sintering by the smart powder of titanium dioxide, PVA binding agent etc. and forms, and every cathode bar oxide mass is about 100g, and the cathodic area is installed in parallel 4 groups of above-mentioned cathode bars.The positive column takes the mode corresponding with negative electrode 4 rotation graphite anodes in parallel as electrolytic anode, and cathode and anode spacing is 200mm, and the graphite anode speed setting is 120rpm.Dividing plate adopts Al
2O
3-MgO mixing material, porosity show porosity 15% 59%, thickness 5mm, height 300mm.The electrolyzer integral matching as depicted in figs. 1 and 2.Adopt CaCl in the electrolyzer
2Fused salt, fused salt CaCl
2Controlling depth is 140mm, and temperature is controlled at 950 ℃, and protection gas argon flow amount is set at 5L/min, bath voltage 3.1V, electrolysis time 28h.Whole electrolysis process flow process is seen Fig. 3.
Shape of product does not have to change substantially, and density increases, and color is grey black, obtains titanium sponge powder 181g after fragmentation, pickling, cleaning, and titanium content is 99.27%, reaches national level Four titanium standard, current efficiency 75.4%.Separator material burn into do not occur and melts phenomenon, and fused salt is white translucent CaCl through sampling analysis substantially in the electrolyzer
2Crystal does not have carbon or other impurity to be mingled with, and can directly produce again.
Example 5
Electric tank cathode adopts the titanium oxide cathode bar, and this cathode bar is mixed in proportion forming and sintering by the smart powder of titanium dioxide, PVA binding agent etc. and forms, and every cathode bar oxide mass is about 100g, and the cathodic area is installed in parallel 4 groups of above-mentioned cathode bars.The positive column takes the mode corresponding with negative electrode 4 rotation graphite anodes in parallel as electrolytic anode, and cathode and anode spacing is 200mm, and the graphite anode speed setting is 60rpm.Dividing plate adopts Al
2O
3-MgO mixing material, porosity show porosity 30% 59%, thickness 10mm, height 300mm.The electrolyzer integral matching as depicted in figs. 1 and 2.Adopt CaCl in the electrolyzer
2Fused salt, fused salt CaCl
2Controlling depth is 140mm, and temperature is controlled at 950 ℃, and protection gas argon flow amount is set at 5L/min, bath voltage 3.1V, electrolysis time 36h.Whole electrolysis process flow process is seen Fig. 3.
Shape of product does not have to change substantially, and density increases, and color is grey black, obtains titanium sponge powder 179g after fragmentation, pickling, cleaning, and titanium content is 99.27%, reaches national level Four titanium standard, current efficiency 74.4%.Separator material burn into do not occur and melts phenomenon, and fused salt is white translucent CaCl through sampling analysis substantially in the electrolyzer
2Crystal does not have carbon or other impurity to be mingled with, and can directly produce again.
Claims (3)
1. electrolytic cell in electro-deoxidization metallurgy process, it is characterized in that cell body adopts stainless steel trough body, in graphite linings is arranged as the fused salt carrier, electrolyzer inside is divided into cathodic area and positive column by dividing plate, two districts are relatively independent but can carry out ion-exchange freely, a plurality of titanium oxide cathode bar parallel waies are adopted in the access of electrode, anode adopt rotating anode and with the corresponding one by one composition of negative electrode electrode pair.
2. described a kind of electrolytic cell in electro-deoxidization metallurgy process as claimed in claim 1 is characterized in that described dividing plate is Al
2O
3, MgO, Al
2O
3One of-MgO material, its porosity show porosity 10～30% 40%～70%, show aperture, hole 0.1～2mm level, and thickness is 2～10mm.
3. described a kind of electrolytic cell in electro-deoxidization metallurgy process as claimed in claim 1 is characterized in that described rotating anode rotating speed is controlled at 60～180rpm.
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| CN101701345B CN101701345B (en) | 2011-08-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104499034A (en) * | 2014-12-22 | 2015-04-08 | 常熟市伟达电镀有限责任公司 | Novel electroplating device |
| 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 |
| CN105531401A (en) * | 2014-06-30 | 2016-04-27 | 东邦钛株式会社 | Metal production method and production method for high-melting-point metal |
| CN108441893A (en) * | 2018-06-13 | 2018-08-24 | 重庆大学 | A kind of molten-salt electrolysis TiO2The method for preparing Titanium |
-
2009
- 2009-11-11 CN CN2009102372597A patent/CN101701345B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105531401A (en) * | 2014-06-30 | 2016-04-27 | 东邦钛株式会社 | Metal production method and production method for high-melting-point metal |
| CN105531401B (en) * | 2014-06-30 | 2018-09-04 | 东邦钛株式会社 | The method for manufacturing the method for metal and manufacturing refractory metal |
| CN104499034A (en) * | 2014-12-22 | 2015-04-08 | 常熟市伟达电镀有限责任公司 | Novel electroplating device |
| 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 |
| CN108441893A (en) * | 2018-06-13 | 2018-08-24 | 重庆大学 | A kind of molten-salt electrolysis TiO2The method for preparing Titanium |
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Granted publication date: 20110824 Termination date: 20181111 |