CN101270480B - Method for preparing metallic titanium or plated titanium by electrolyzing titanic chloride with ion liquid - Google Patents
Method for preparing metallic titanium or plated titanium by electrolyzing titanic chloride with ion liquid Download PDFInfo
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- CN101270480B CN101270480B CN200710064623A CN200710064623A CN101270480B CN 101270480 B CN101270480 B CN 101270480B CN 200710064623 A CN200710064623 A CN 200710064623A CN 200710064623 A CN200710064623 A CN 200710064623A CN 101270480 B CN101270480 B CN 101270480B
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Abstract
The invention relates to a method for preparing metal titanium or plating the metal titanium through electrolyzing titanium tetrachloride by room temperature ion liquid. An organic solvent is added inthe mixture of one or one than one ion liquids to prepare electrolytic liquid; the metal titanium, a carbon steel or a platinum sheet are taken as a deposition cathode in an electrobath; a platinum electrode is taken as a working cathode at a feed position; the deposition cathode and the working cathode at the feed position as well as the working cathode at the feed position and an anode are spaced by porous isolating films; a bi-potentiostat is used to control the constant potentials of the working cathode at the feed position of the electrobath and the deposition cathode to respectively carry out pre-electrolyzing relative to the reference electrode of minus 1.0V vs.Pt; the titanium tetrachloride is added into the electrolyzing liquid; the potential of the working cathode at the feed position is minus 1.0 to minus 0.2 V vs.Pt, the potential of the deposition cathode is minus 2.0 to minus 1.0 V vs.Pt and constant potential electrolyzing is carried out under the situation of maintaining the potentials to prepare the metal titanium or plating the metal titanium.
Description
Technical field
The invention belongs to the nonferrous materials field, particularly a kind of ionic liquid at room temperature electrolysis titanium tetrachloride prepares the method for metal titanium or plated metal titanium.
Background technology
Titanium density is little, and the intensity height has well heat-resisting, low temperature resistant and corrosion resistance nature simultaneously, uses increasingly extensive in aviation, ocean, oil, the energy, chemical industry and field such as medical.The industrialized preparing process that with the titanium tetrachloride is the raw material production metal titanium at present has magnesium reduction process (Kroll method) and sodium thermoreduction method (Hunter method).These two kinds of methods use MAGNESIUM METAL or sodium under 800～1000 ℃ titanium tetrachloride to be reduced to titanium respectively.Reducing metal (magnesium or sodium) the cost height that these two kinds of methods are used, reaction needed high temperature makes energy consumption higher simultaneously, and facility investment is big, can only periodical operation, so the titanium production cost of these two kinds of methods is very high.That the investigator attempts to develop is new, continuous process to be to solve the expensive problem of Kroll method and Hunter method cheaply.U.S. Pat 3114685 has proposed a kind of method that adopts the direct electrolysis titanium tetrachloride of fused salt to produce metal titanium, but operate continuously.But temperature of reaction is more than 700 ℃, and energy consumption is still very high, and reactor material requires also high, has increased production cost.International monopoly WO99/64638 has reported that a kind of calcium chloride molten salt electrochemistry reduction of titanium dioxide prepares the method for titanium, owing to use titanium dioxide to make the cost titanium tetrachloride be lower than electrolytic process as raw material, but the same high temperature fused salt electrolysis that uses, cost is higher.Development in recent years use ionic liquid at room temperature electrolysis titanium tetrachloride to prepare the method for titanium, reported a kind of apparatus and method of utilizing ionic liquid electrolytic titanium iron cpd to prepare ferro-titanium as international monopoly WO2005/103338.The electrolysis of this ionic liquid method can be lower than under 200 ℃ to be carried out, and avoids using high-temperature molten salt, and simultaneously ion liquid electrochemical window broad makes current efficiency higher, thus energy consumption far below fused salt electrolysis, application prospect is very extensive.But, because the reduction of titanium is a proceed step by step, the metal titanium that the titanium tetrachloride ionic liquid electrolysis process of present report obtains contains intermediate product titanous chloride or titanium dichloride, thereby purity is not high, simultaneously can only obtain powder or titanium sponge, be difficult to realize the good plating of metal titanium on base electrode.So, overcome the not high shortcoming of purity that present ionic liquid electrolytic process is produced metal titanium, particularly can realize simultaneously the plating of metal titanium, significant aspect metal finishing.
Summary of the invention
The objective of the invention is to prepare shortcomings such as the not high and coating of metal titanium purity is bad, by providing the electrolytic method of a kind of ionic liquid to realize preparation or electroplating the high purity metal titanium at present ionic liquid electrolysis titanium tetrachloride.
The method that ionic liquid electrolysis titanium tetrachloride of the present invention prepares metal titanium or plated metal titanium may further comprise the steps:
(1) with ionic liquid vacuum hydro-extraction 24～48 hours, the organic solvent that can make the titanium uniform deposition that adds quality then and be ionic liquid quality 0.5%～5% is mixed with electrolytic solution as leveling reagent;
(2) in the electrolyzer that an anode and two negative electrodes are installed, with the polishing (as use sand papering) cleaning after base electrodes such as metal titanium, carbon steel or platinized platinum as the deposition cathode in the electrolyzer, with the platinum electrode after the polished and cleaned (as using sand papering) as reinforced place's work negative electrode in the electrolyzer, between deposition cathode and reinforced place's work negative electrode, and between reinforced place's work negative electrode and anode, separate with porous diaphragm; With platinum filament as reference electrode;
(3) electrolytic solution with step (1) joins in the electrolyzer of step (2); Under high pure nitrogen or high-purity argon gas protection gas, keep the reaction liquid temperature at 20～100 ℃; Start agitator and recycle pump in the electrolyzer; Use the reinforced place's work negative electrode of double potentiostat control electrolyzer and the constant potential of deposition cathode with respect to reference electrode to be-1.0V vs.Pt respectively, under this current potential, carry out constant potential preelectrolysis, in electrolytic solution, drip titanium tetrachloride then continuously;
(4) after step (3) adds titanium tetrachloride, use double potentiostat earlier the reinforced place's work negative electrode of control current potential with respect to reference electrode be-1.0～-0.2V vs.Pt, carrying out potentiostatic deposition under this current potential after 1～2 hour, the current potential of controlling deposition cathode again with respect to reference electrode be-2.0～-1.0V vs.Pt, this moment, reinforced place's work negative electrode still kept former constant potential, keep carrying out under the above-mentioned current potential potentiostatic deposition in reinforced place's work negative electrode and deposition cathode and prepare metal titanium or plated metal titanium, the deposition cathode electrolysis was taken out after 2～6 hours, the deposition cathode that more renews.
Described porous diaphragm is sintered glass core or porous ceramics, and the aperture is 1～20 μ m.
Described reinforced place's work negative electrode or anodic electrode area are 1.5～3 times of deposition cathode area.
Described anode is platinum electrode or Graphite Electrodes etc.
Described ionic liquid is selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate ([C
2Mim] [BF
4]), 1-ethyl-3-Methylimidazole trifluoromethyl acetate ([C
2Mim] [TA]), two trifluoromethane sulfimide the salt ([C of 1-ethyl-3-Methylimidazole
2Mim] [Tf
2N]), two trifluoromethane sulfimide the salt ([P of ethyl-butyl pyrroles
14] [Tf
2N]), 1-ethyl-3-Methylimidazole trifluoromethyl sulfonic acid ([C
2Mim] [TfO]), 1-ethyl-3-Methylimidazole dicyan amide salt ([C
2Mim] [N (CN)
2]), 1-ethyl-3-Methylimidazole three cyanogen methane salt ([C
2Mim] [C (CN)
3]) etc. in one or more mixing liquid.
Described organic solvent is selected from one or more the mixture in benzene,toluene,xylene etc.
Temperature during described ionic liquid vacuum hydro-extraction is 80～130 ℃.
After base electrodes such as described metal titanium, carbon steel or the platinized platinum polishings, put into the sulphuric acid soln that concentration is 30～50wt% successively, hydrochloric acid, water, acetone and the benzene of 2～30wt% cleans the back as deposition cathode.
After the described platinum electrode polishing, put into the sulphuric acid soln that concentration is 30～50wt%, hydrochloric acid, water, acetone and the reinforced place's work negative electrode of benzene cleaning back conduct of 2～30wt% successively.
The rotating speed of the described agitator of step (3) is 50～2000rpm, and the pumping capacity of recycle pump is 25～200mL/h.
The described preelectrolysis time of step (3) is 10～30 minutes.
The purity of described nitrogen or argon gas is greater than 99.99%.
The used electrolyzer of the inventive method can be electrolyzer as shown in Figure 1, this electrolyzer is an airtight groove, the shell material of this electrolyzer can be glass or tetrafluoroethylene, has the import of air outlet 6, circulation fluid import 7, circulation fluid outlet 8, feeding device 9, the import of whipping appts 10, the socket of anode 11, the socket of depositing electrode 12, the socket of reinforced place's work negative electrode 13 and the socket of reference electrode 14 on it; And the feeding device 9 that feeds in the electrolyzer is installed in the ingress of feeding device 9, ingress at whipping appts 10 is equipped with the whipping appts 10 that feeds in the electrolyzer, spigot at anode 11 is equipped with the anode 11 that feeds in the electrolyzer, spigot at depositing electrode 12 is equipped with the depositing electrode 12 that feeds in the electrolyzer, spigot at reinforced place's work negative electrode 13 is equipped with the reinforced place's work negative electrode 13 that feeds in the electrolyzer, at the spigot of reference electrode 14 reference electrode 14 that feeds in the electrolyzer is installed; All electrodes, feeding device, whipping appts and interface all seal; Between deposition cathode and reinforced place's work negative electrode, separate, between reinforced place's work negative electrode and anode, separate with porous diaphragm 4 with porous diaphragm 5; Whole electrolyzer is divided into cathode compartment 1 (zone between porous diaphragm 5 adjacent with deposition cathode and electrolyzer one sidewall), cathode compartment 2 (zones between 2 porous diaphragms) and anolyte compartment 3 (porous diaphragm 4 adjacent with reinforced place's work negative electrode and the zone between another sidewall of electrolyzer);
Described air outlet 6 is positioned at the top of anolyte compartment's 3 housings, and the socket of anode 11 is positioned on the housing at 3 tops, anolyte compartment; Described circulation fluid outlet 8 is positioned on the housing of cathode compartment 1 bottom, and the socket of reinforced place's work negative electrode 12 is positioned on the housing at cathode compartment 1 top; Described circulation fluid import 7 is positioned on the housing of cathode compartment 2 bottoms, and the import of the import of feeding device 9, whipping appts 10, the socket of reinforced place's work negative electrode 13 and the socket of reference electrode 14 are positioned on the housing at cathode compartment 2 tops;
The positive potential output terminal of one double potentiostat is connected with anode by lead, and the negative potential output terminal is connected with deposition cathode with reinforced place's work negative electrode by lead respectively, and the reference potential output terminal is connected with reference electrode by lead.
Described circulation fluid outlet links to each other with the import of a reciprocal pump of constant delivery type, and pump outlet connects the circulation fluid import.
The purity that method of the present invention can prepare titanium is 90～98wt%, and current efficiency is 70～85%.The present invention uses ionic liquid as electrolytic solution, good conductivity, and electrolysis temperature is low, and energy consumption is low, and reactor material requires low, and cost is low, obtains the product purity height, the current efficiency height.
Description of drawings
Fig. 1. used electrolyzer synoptic diagram in the inventive method.
Reference numeral
1. cathode compartment 2. cathode compartments 3. anolyte compartments 4,5. barrier film
6. 7. circulation fluid imports, 8. circulation fluids in air outlet export 9. feeding devices
10. reinforced place's work negative electrodes of whipping appts 11. anodes 12. deposition cathode 13.
14. reference electrode
Embodiment
The structure of the used electrolyzer of following examples please refer to accompanying drawing 1, the CMBP-1 type double potentiostat that adopts Jiangsu Electrical Analysis Instrument Factory to produce.
Embodiment 1.
With ionic liquid [C
2Mim] [BF
4] 120 ℃ of following vacuum hydro-extractions 24 hours, add the benzene that quality is ionic liquid quality 5wt% then.Behind base electrode platinized platinum usefulness sand paper polishing grinding, be successively placed in 50wt% sulphuric acid soln, 30wt% hydrochloric acid, water, acetone and the benzene and cleaned 10 minutes, as deposition cathode; Reinforced place's work negative electrode and anode also adopt platinized platinum, and be identical with the deposition cathode treatment process.Reinforced place's work negative electrode and anodic electrode area are 3 times of deposition cathode, and reference electrode uses platinum filament; Between deposition cathode in electrolyzer and the reinforced place's work negative electrode, and between reinforced place's work negative electrode and anode, be that the sintered glass core barrier film of 1～20 μ m separates with the aperture.Ionic liquid is added in the electrolyzer, and protection gas is high purity nitrogen (purity is 99.999%), keeps the reaction liquid temperature at 20 ℃, starts agitator and recycle pump, and agitator speed is 50rpm, and pumping capacity is 25mL/h.
Carry out red-tape operati with double potentiostat, reinforced place's work negative electrode of control and deposition cathode were carried out constant potential preelectrolysis 30 minutes under current potential-1.0V vs.Pt (promptly with respect to reference electrode), drip titanium tetrachloride continuously by charging opening then.After adding titanium tetrachloride, the reinforced place's work negative electrode of control carries out potentiostatic deposition after 1 hour under current potential-1.0Vvs.Pt (promptly with respect to reference electrode), control deposition cathode again and carry out potentiostatic deposition under current potential-2.0V vs.Pt (promptly with respect to reference electrode), electrolysis was taken out after 6 hours.
The content of titanium is 97wt%, and current efficiency is greater than 75%.
Embodiment 2.
With ionic liquid [C
2Mim] [TA] 80 ℃ of following vacuum hydro-extractions 48 hours, add the toluene that quality is ionic liquid quality 5wt% then.Behind base electrode metal titanium sheet usefulness sand paper polishing grinding, be successively placed in 30wt% sulphuric acid soln, 2wt% hydrochloric acid, water, acetone and the benzene and cleaned 2 minutes, as deposition cathode; Reinforced place's work negative electrode and anode adopt platinized platinum, and be identical with the deposition cathode treatment process.Reinforced place's work negative electrode and anodic electrode area are 1.5 times of deposition cathode, and reference electrode uses platinum filament; Between deposition cathode in electrolyzer and the reinforced place's work negative electrode, and between reinforced place's work negative electrode and anode, be that the sintered glass core barrier film of 1～20 μ m separates with the aperture.Ionic liquid is added in the electrolyzer, and protection gas is high-purity argon gas (purity is 99.999%), keeps the reaction liquid temperature at 50 ℃, starts agitator and recycle pump, and agitator speed is 300rpm, and pumping capacity is 30mL/h.
Carry out red-tape operati with double potentiostat, reinforced place's work negative electrode of control and deposition cathode were carried out constant potential preelectrolysis 30 minutes under current potential-1.0V vs.Pt (promptly with respect to reference electrode), drip titanium tetrachloride continuously by charging opening then.After adding titanium tetrachloride, the reinforced place's work negative electrode of control carries out potentiostatic deposition after 1.5 hours under current potential-0.2Vvs.Pt (promptly with respect to reference electrode), control deposition cathode again and carry out potentiostatic deposition under current potential-1.9V vs.Pt (promptly with respect to reference electrode), electrolysis was taken out after 2 hours.
The content of titanium is 95wt%, and current efficiency is greater than 70%.
Embodiment 3.
With ionic liquid [P
14] [Tf
2N] 110 ℃ of following vacuum hydro-extractions 36 hours, add the dimethylbenzene that quality is ionic liquid quality 2.5wt% then.Behind base electrode platinized platinum usefulness sand paper polishing grinding, be successively placed in 40wt% sulphuric acid soln, 15wt% hydrochloric acid, water, acetone and the benzene and cleaned 8 minutes, as deposition cathode; Reinforced place's work negative electrode also adopts platinized platinum, and is identical with the deposition cathode treatment process, and counter electrode adopts Graphite Electrodes.Reinforced place's work negative electrode and anodic electrode area are 2 times of deposition cathode, and reference electrode uses platinum filament; Between deposition cathode in electrolyzer and the reinforced place's work negative electrode, and between reinforced place's work negative electrode and anode, be that the porous ceramics barrier film of 1～20 μ m separates with the aperture.Ionic liquid is added in the electrolyzer, and protection gas is high purity nitrogen (purity is 99.999%), keeps the reaction liquid temperature at 100 ℃, starts agitator and recycle pump, and agitator speed is 2000rpm, and pumping capacity is 200mL/h.
Carry out red-tape operati with double potentiostat, reinforced place's work negative electrode of control and deposition cathode were carried out constant potential preelectrolysis 30 minutes under current potential-1.0V vs.Pt (promptly with respect to reference electrode), drip titanium tetrachloride continuously by charging opening then.After adding titanium tetrachloride, the reinforced place's work negative electrode of control carries out potentiostatic deposition after 2 hours under current potential-0.95Vvs.Pt (promptly with respect to reference electrode), control deposition cathode again and carry out potentiostatic deposition under current potential-1.5V vs.Pt (promptly with respect to reference electrode), electrolysis was taken out after 4 hours.
The content of titanium is 96wt%, and current efficiency is greater than 78%.
Embodiment 4.
With ionic liquid [C
2Mim] [TfO] 130 ℃ of following vacuum hydro-extractions 36 hours, adding quality then was the benzene of ionic liquid quality 0.5wt% and the toluene of 1.0wt%.Behind base electrode platinized platinum usefulness sand paper polishing grinding, be successively placed in 40wt% sulphuric acid soln, 20% hydrochloric acid, water, acetone and the benzene and cleaned 5 minutes, as deposition cathode; Reinforced place's work negative electrode and anode also adopt platinized platinum, and be identical with the deposition cathode treatment process.Reinforced place's work negative electrode and anodic electrode area are 2 times of deposition cathode, and reference electrode uses platinum filament; Between deposition cathode in electrolyzer and the reinforced place's work negative electrode, and between reinforced place's work negative electrode and anode, be that the sintered glass core barrier film of 1～20 μ m separates with the aperture.Ionic liquid is added in the electrolyzer, and protection gas is high purity nitrogen (purity is 99.999%), keeps the reaction liquid temperature at 50 ℃, starts agitator and recycle pump, and agitator speed is 1000rpm, and pumping capacity is 100mL/h.
Carry out red-tape operati with double potentiostat, reinforced place's work negative electrode of control and deposition cathode were carried out constant potential preelectrolysis 20 minutes under current potential-1.0V vs.Pt (promptly with respect to reference electrode), drip titanium tetrachloride continuously by charging opening then.After adding titanium tetrachloride, the reinforced place's work negative electrode of control carries out potentiostatic deposition after 1.2 hours under current potential-0.5Vvs.Pt (promptly with respect to reference electrode), control deposition cathode again and carry out potentiostatic deposition under current potential-1.8V vs.Pt (promptly with respect to reference electrode), electrolysis was taken out after 3 hours.
The content of titanium is 97wt%, and current efficiency is greater than 85%.
Embodiment 5.
With ionic liquid [C
2Mim] [N (CN)
2] 120 ℃ of following vacuum hydro-extractions 48 hours, adding quality then was the benzene of ionic liquid quality 1.0wt% and the dimethylbenzene of 2.0wt%.Behind base electrode carbon steel coupon usefulness sand paper polishing grinding, be successively placed in 45wt% sulphuric acid soln, 25wt% hydrochloric acid, water, acetone and the benzene and cleaned 8 minutes, as deposition cathode; Reinforced place's work negative electrode and anode adopt platinized platinum, and be identical with the deposition cathode treatment process.Reinforced place's work negative electrode and anodic electrode area are 2.5 times of deposition cathode, and reference electrode uses platinum filament; Between deposition cathode in electrolyzer and the reinforced place's work negative electrode, and between reinforced place's work negative electrode and anode, be that the sintered glass core barrier film of 1～20 μ m separates with the aperture.Ionic liquid is added in the electrolyzer, and protection gas is high purity nitrogen (purity is 99.999%), keeps the reaction liquid temperature at 40 ℃, starts agitator and recycle pump, and agitator speed is 500rpm, and pumping capacity is 50mL/h.
Carry out red-tape operati with double potentiostat, reinforced place's work negative electrode of control and deposition cathode were carried out constant potential preelectrolysis 25 minutes under current potential-1.0V vs.Pt (promptly with respect to reference electrode), drip titanium tetrachloride continuously by charging opening then.After adding titanium tetrachloride, the reinforced place's work negative electrode of control carries out potentiostatic deposition after 1.8 hours under current potential-0.2Vvs.Pt (promptly with respect to reference electrode), control deposition cathode again and carry out potentiostatic deposition under current potential-1.0V vs.Pt (promptly with respect to reference electrode), electrolysis was taken out after 5 hours.
The content of titanium is 95wt%, and current efficiency is greater than 70%.
Embodiment 6.
With mixed ionic liquid [C
2Mim] [Tf
2N]/[C
2Mim] [TfO] (mol ratio is 2: 1) add the dimethylbenzene that quality is ionic liquid quality 2wt% then 120 ℃ of following vacuum hydro-extractions 48 hours.Behind base electrode platinized platinum usefulness sand paper polishing grinding, be successively placed in 35wt% sulphuric acid soln, 10wt% hydrochloric acid, water, acetone and the benzene and cleaned 5 minutes, as deposition cathode; Reinforced place's work negative electrode and anode also adopt platinized platinum, and be identical with the deposition cathode treatment process.Reinforced place's work negative electrode and anodic electrode area are 2 times of deposition cathode, and reference electrode uses platinum filament; Between deposition cathode in electrolyzer and the reinforced place's work negative electrode, and between reinforced place's work negative electrode and anode, be that the sintered glass core barrier film of 1～20 μ m separates with the aperture.Ionic liquid is added in the electrolyzer, and protection gas is high purity nitrogen (purity is 99.999%), keeps the reaction liquid temperature at 80 ℃, starts agitator and recycle pump, and agitator speed is 100rpm, and pumping capacity is 80mL/h.
Carry out red-tape operati with double potentiostat, reinforced place's work negative electrode of control and deposition cathode were carried out constant potential preelectrolysis 20 minutes under current potential-1.0V vs.Pt (promptly with respect to reference electrode), drip titanium tetrachloride continuously by charging opening then.After adding titanium tetrachloride, the reinforced place's work negative electrode of control carries out potentiostatic deposition after 2 hours under current potential-1.0Vvs.Pt (promptly with respect to reference electrode), control deposition cathode again and carry out potentiostatic deposition under current potential-1.8V vs.Pt (promptly with respect to reference electrode), electrolysis was taken out after 6 hours.
The content of titanium is 96wt%, and current efficiency is greater than 80%.
Claims (6)
1. an ionic liquid electrolysis titanium tetrachloride prepares the method for metal titanium, it is characterized in that described method may further comprise the steps:
(1) with ionic liquid vacuum hydro-extraction 24～48 hours, the organic solvent that can make the titanium uniform deposition that adds quality then and be ionic liquid quality 0.5%～5% is mixed with electrolytic solution as leveling reagent;
(2) in the electrolyzer that an anode and two negative electrodes are installed, wherein, described two negative electrodes are respectively as the deposition cathode in the electrolyzer with the metal titanium after the polished and cleaned, carbon steel or platinized platinum base electrode, with the platinum electrode after the polished and cleaned as reinforced place's work negative electrode in the electrolyzer, between deposition cathode and reinforced place's work negative electrode, and between reinforced place's work negative electrode and anode, separate with porous diaphragm; With platinum filament as reference electrode;
(3) electrolytic solution with step (1) joins in the electrolyzer of step (2); Under high pure nitrogen or high-purity argon gas protection gas, keep the reaction liquid temperature at 20～100 ℃; Start agitator and recycle pump in the electrolyzer; Use the reinforced place's work negative electrode of double potentiostat control electrolyzer and the constant potential of deposition cathode all to be-1.0V vs.Pt, under this current potential, carry out constant potential preelectrolysis, in electrolytic solution, drip titanium tetrachloride then continuously with respect to reference electrode;
(4) after step (3) adds titanium tetrachloride, use double potentiostat earlier the reinforced place's work negative electrode of control current potential with respect to reference electrode be-1.0～-0.2V vs.Pt, carrying out potentiostatic deposition under this current potential after 1～2 hour, the current potential of controlling deposition cathode again with respect to reference electrode be-2.0～-1.0V vs.Pt, this moment, reinforced place's work negative electrode still kept former constant potential, kept carrying out under the above-mentioned current potential potentiostatic deposition in reinforced place's work negative electrode and deposition cathode and prepared metal titanium;
Described reinforced place is meant the electrolytic solution part that adds step (1);
Described reinforced place's work negative electrode is between anode and deposition cathode;
Described porous diaphragm is sintered glass core or porous ceramics, and the aperture is 1～20 μ m;
Described organic solvent is selected from more than one in the benzene,toluene,xylene.
2. method according to claim 1 is characterized in that: described anode is platinum electrode or Graphite Electrodes.
3. method according to claim 1 is characterized in that: described ionic liquid is selected from more than one in 1-ethyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-Methylimidazole trifluoromethyl acetate, the two trifluoromethane sulfimide salt of 1-ethyl-3-Methylimidazole, the two trifluoromethane sulfimide salt of ethyl-butyl pyrroles, 1-ethyl-3-Methylimidazole trifluoromethyl sulfonic acid, 1-ethyl-3-Methylimidazole dicyan amide salt, the 1-ethyl-3-Methylimidazole three cyanogen methane salt.
4. method according to claim 1 is characterized in that: the temperature during described ionic liquid vacuum hydro-extraction is 80～130 ℃.
5. method according to claim 1 is characterized in that: the rotating speed of the described agitator of step (3) is 50～2000rpm, and the pumping capacity of recycle pump is 25～200mL/h.
6. method according to claim 1 is characterized in that: the described preelectrolysis time of step (3) is 10～30 minutes.
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| CN102191517B (en) * | 2010-03-10 | 2014-04-30 | 中国科学院过程工程研究所 | Method of electroplating zinc, nickel, molybdenum and their alloys by using ionic liquid |
| CN101994128A (en) * | 2010-11-26 | 2011-03-30 | 昆明理工大学 | Method for preparing Al-Ti alloy or plated Al-Ti alloy by low-temperature electrolytic deposition of ionic liquid |
| CN104928720B (en) * | 2015-07-13 | 2018-08-14 | 成都先进金属材料产业技术研究院有限公司 | A kind of electrolytic method of titanium soluble anode |
| CN108264125A (en) * | 2018-03-06 | 2018-07-10 | 辽宁海润环保技术股份有限公司 | A kind of advanced treatment method for sewage water |
| CN108754605B (en) * | 2018-06-22 | 2019-11-12 | 东北大学 | The device and method of electro-deposition oriented growth metal single crystal in aqueous electrolyte |
| CN109440158A (en) * | 2018-12-28 | 2019-03-08 | 南京时恒电子科技有限公司 | A kind of Cu-Ti-Co combination electrode and preparation method thereof |
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