CN103422122B - A kind of method of titanium dioxide direct Preparation of Titanium - Google Patents
A kind of method of titanium dioxide direct Preparation of Titanium Download PDFInfo
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- CN103422122B CN103422122B CN201310385439.6A CN201310385439A CN103422122B CN 103422122 B CN103422122 B CN 103422122B CN 201310385439 A CN201310385439 A CN 201310385439A CN 103422122 B CN103422122 B CN 103422122B
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Abstract
A kind of method that the present invention relates to titanium dioxide direct Preparation of Titanium, belongs to non-ferrous metallurgy technology field.Prereduction titanium dioxide electrodes is prepared after first passing through titanium dioxide powder, carbon dust and binding agent mix homogeneously, wherein binding agent is water or PVA, then it is negative electrode by prereduction titanium dioxide electrodes, graphite or other inert material are anode, electrolyte be ionic liquid, decomposition voltage be 2.8～3.2V, electrolysis temperature be 25～120 DEG C under conditions of carry out electroreduction 12～48h, then take out negative electrode, rinse and drying to obtain cathode product Titanium.Present invention reduces technological process, significantly reduce energy consumption, it is achieved cleaning produces.
Description
Technical field
A kind of method that the present invention relates to titanium dioxide direct Preparation of Titanium, belongs to non-ferrous metallurgy technology field.
Background technology
Titanium has that specific strength is big, density is little, high temperature resistant, anticorrosive, be widely used in the fields such as space flight, oil, the energy, traffic, chemical industry, biomedicine without excellent performances such as magnetic, and its application the most constantly extends.
The production method of titanium mainly has two kinds at present: magnesium reduction process (Kroll method) and sodium thermoreduction method (Hunter method).Because Hunter method is higher than Kroll method production cost, so titanium produces, commonly use is Kroll method.Kroll method is the titanium sponge production technique with magnesium-reduced vacuum distillation method as representative.Titanium ore is enriched with chlorination and produces TiCl4 by it, then with magnesium, TiCl4 is reduced to titanium sponge in argon or helium atmosphere, then carries out vacuum distilling and is separated off magnesium and MgCl2, eventually passes product treatment and obtains finished product titanium sponge.This technological process there are two important circulations, i.e. magnesium circulation and chlorine circulate, and the outer circulation of magnesium and chlorine circulation are obtained by high-temperature molten salt electrolytic chlorine magnesium.Therefore this technological process is long, operation complexity, and production cost is high, and environmental pollution is serious.Through the development of decades, Kroll method has been also carried out a series of improvement, but research work for many years proves, the technique improvement of some local cannot change this present situation of high cost.Therefore, it is necessary to research flow process is short, low cost and environment amenable preparation method, make Titanium can be applied in more field.For seeking the titanium preparation technology of new low cost, the most all do substantial amounts of research work.The new technology of research has fused salt electrolysis process (FFC method).First TiO2 is fired into negative electrode by the method, then uses CaCl2 high-temperature molten salt system as electrolyte, and direct at 800～1000 DEG C is Titanium by its electroreduction.Owing to this method directly obtains Titanium from TiO2 electrolysis, greatly simplifiing technological process and equipment, therefore can substantially reduce energy consumption and production costs (according to estimates, the production cost of this method is only 1/3rd of Kroll method).But; up to the present the method simply succeeds at laboratory; large-scale production to be realized; first have to solve the problem that prepared by TiO2 negative electrode and electric conductivity is bad; its secondary the airtight of electrolysis bath and atmosphere protection of realizing, then must also overcome the titanium ion variation of valence impact on current efficiency in electrolytic process.And to solve problem above simultaneously, also have the biggest difficulty in practice.And molten-salt electrolysis to be carried out at a temperature of 800 DEG C, need to consume certain energy etching apparatus.Therefore, the titanium new preparation technology of low cost simple, energy-conservation in the urgent need to a kind of technique of development, and the appearance of ionic liquid provides new possibility undoubtedly for this.
Ionic liquid is the abbreviation of ionic liquid at room temperature, is a kind of composition anions and canons, at the organic salt that room temperature or near room temperature are in a liquid state.It has electrochemical window width, good conductivity, liquid state range width, without the excellent properties such as vapour pressure, good stability, be a kind of green solvent.In terms of electro-deposition, the advantage that ionic liquid has merged high-temperature molten salt and aqueous solution: there is wider electrochemical window and good electric conductivity, the most i.e. can get ability electro-deposition goes out in high-temperature molten salt metal and alloy, but there is no severe corrosive as high-temperature molten salt；Going back electrodepositable in ionic liquid obtains most of metal that can obtain in aqueous simultaneously, and without side reaction, thus the metal quality obtained is more preferably, current efficiency is higher, particularly aluminum, titanium, silicon and germanium etc. is difficult to electro-deposition obtains in aqueous metal and alloy thereof all the more so.The above-mentioned characteristic of ionic liquid and good electrical conductivity thereof make the brand-new liquid of electro-deposition research, are more and more applied in terms of electrodeposit metals.
Summary of the invention
The problem existed for above-mentioned prior art and deficiency, the present invention provides a kind of method of titanium dioxide direct Preparation of Titanium.Compared with existing Titanium preparation method, present invention reduces technological process, significantly reduce energy consumption, it is achieved cleaning produces, and the present invention is achieved through the following technical solutions.
A kind of method of titanium dioxide direct Preparation of Titanium, it specifically comprises the following steps that
(1) prereduction titanium dioxide electrodes is prepared: first by titanium dioxide powder, carbon dust and PVA according to mass percent 100:(12～16): (1～2) mix homogeneously is also pressed into block mixture, then block mixture is calcined in reducing atmosphere under conditions of temperature is 1200～1300 DEG C 1～4h and obtains prereduction titanium dioxide electrodes；Or first by titanium dioxide powder, water and carbon dust according to mass percent 100:(6～10): (12～16) mix homogeneously and be pressed into a diameter of 1～10mm ball doughy mix, then in reducing atmosphere, ball doughy mix is calcined under conditions of temperature is 1200～1300 DEG C 1～2h and obtains prereduction titanium dioxide pelletizing, in finally pelletizing is loaded titanium basket, i.e. obtain prereduction titanium dioxide electrodes；
(2) Titanium is prepared: the prereduction titanium dioxide electrodes obtained with step (1) is as negative electrode, graphite or other inert material are anode, electrolyte be ionic liquid, decomposition voltage be 2.8～3.2V, electrolysis temperature be 25～120 DEG C under conditions of carry out electroreduction 12～48h, then take out negative electrode, rinse and drying to obtain cathode product Titanium.
The mesh mesh number of described titanium basket is 100～200 mesh.
Described ionic liquid is alkalescence chloro 1-butyl-3-Methylimidazole .-aluminum chloride (BmimCl-AlCl3), alkalescence chloro 1-ethyl-3-methylimidazole-aluminum chloride (EmimCl-AlCl3), 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim] BF4), 1-ethyl-3-methylimidazole tetrafluoroborate ([Emim] BF4) or 1-butyl-3-Methylimidazole. hexafluorophosphate ([Bmim] PF6).
Above-mentioned ionic liquid is all commercial analytical pure.
The invention has the beneficial effects as follows: titanium dioxide is directly converted into Titanium by (1) present invention, and product metal titanium oxygen content is relatively low, and compared with traditional Titanium production method, present invention reduces technological process, significantly reduces energy consumption；(2) compared with the FCC method of existing research, electroreduction temperature of the present invention is low, uses ionic liquid electroreduction temperature below 130 DEG C, and high temperature fused salt electrolysis temperature is more than 800 DEG C, reduce 670 DEG C, the most cost-effective, reduce energy consumption and slow down the corrosion to equipment；(3) due to titanium dioxide poorly conductive, titanium dioxide is calcined under carbon reducing atmosphere by the present invention, titania molecule part deoxidation is made to become quasiconductor, improve the electric conductivity of negative electrode, improve the electrochemical deoxidising efficiency in electrolytic process, and negative electrode titanium dioxide is used pelletizing shape, reaction rate can be further speeded up, improve electrochemical deoxidising efficiency.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
Embodiment 1
The method of this titanium dioxide direct Preparation of Titanium, it specifically comprises the following steps that
(1) prepare prereduction titanium dioxide electrodes: first titanium dioxide powder, carbon dust and PVA according to mass percent 100:16:2 mix homogeneously and are pressed into block mixture, then in reducing atmosphere, block mixture is calcined under conditions of temperature is 1200 DEG C 1h and obtains prereduction titanium dioxide electrodes；
(2) Titanium is prepared: the prereduction titanium dioxide electrodes obtained with step (1) is as negative electrode, graphite is anode, electrolyte be ionic liquid, decomposition voltage be 2.8V, electrolysis temperature be 25 DEG C under conditions of carry out electroreduction 12h, then take out negative electrode, rinse and drying to obtain cathode product Titanium.Wherein ionic liquid is [Bmim] Cl-AlCl3, the oxygen content of Titanium is less than 1%.
Embodiment 2
The method of this titanium dioxide direct Preparation of Titanium, it specifically comprises the following steps that
(1) prepare prereduction titanium dioxide electrodes: first titanium dioxide powder, carbon dust and PVA according to mass percent 100:12:1 mix homogeneously and are pressed into block mixture, then in reducing atmosphere, block mixture is calcined under conditions of temperature is 1300 DEG C 4h and obtains prereduction titanium dioxide electrodes；
(2) Titanium is prepared: the prereduction titanium dioxide electrodes obtained with step (1) is as negative electrode, platinum electrode is anode, electrolyte be ionic liquid, decomposition voltage be 3.2V, electrolysis temperature be 120 DEG C under conditions of carry out electroreduction 48h, then take out negative electrode, rinse and drying to obtain cathode product Titanium.Wherein ionic liquid is [Bmim] BF4, the oxygen content of Titanium is less than 1%.
Embodiment 3
The method of this titanium dioxide direct Preparation of Titanium, it specifically comprises the following steps that
(1) prepare prereduction titanium dioxide electrodes: first titanium dioxide powder, carbon dust and PVA according to mass percent 100:14:1 mix homogeneously and are pressed into block mixture, then in reducing atmosphere, block mixture is calcined under conditions of temperature is 1250 DEG C 2h and obtains prereduction titanium dioxide electrodes；
(2) Titanium is prepared: the prereduction titanium dioxide electrodes obtained with step (1) is as negative electrode, graphite is anode, electrolyte be ionic liquid, decomposition voltage be 3.0V, electrolysis temperature be 100 DEG C under conditions of carry out electroreduction 24h, then take out negative electrode, rinse and drying to obtain cathode product Titanium.Wherein ionic liquid is EmimCl-AlCl3, the oxygen content of Titanium is less than 1%.
Embodiment 4
The method of this titanium dioxide direct Preparation of Titanium, it specifically comprises the following steps that
(1) prereduction titanium dioxide electrodes is prepared: first by titanium dioxide powder, water and carbon dust according to mass percent 100:10:16 mix homogeneously the ball doughy mix that is pressed into a diameter of 1mm, then in reducing atmosphere, ball doughy mix is calcined under conditions of temperature is 1200 DEG C 1h and obtains the titanium dioxide pelletizing of prereduction, in finally pelletizing is loaded the titanium basket of mesh 100 mesh with electric conductivity, i.e. obtain prereduction titanium dioxide electrodes；
(2) Titanium is prepared: the prereduction titanium dioxide electrodes obtained with step (1) is as negative electrode, platinum electrode is anode, electrolyte be ionic liquid, decomposition voltage be 2.8V, electrolysis temperature be 25 DEG C under conditions of carry out electroreduction 12h, then take out negative electrode, rinse and drying to obtain cathode product Titanium.Wherein ionic liquid is BmimCl-AlCl3, the oxygen content of Titanium is less than 1%.
Embodiment 5
The method of this titanium dioxide direct Preparation of Titanium, it specifically comprises the following steps that
(1) prereduction titanium dioxide electrodes is prepared: first by titanium dioxide powder, water and carbon dust according to mass percent 100:6:12 mix homogeneously the ball doughy mix that is pressed into a diameter of 10mm, then in reducing atmosphere, ball doughy mix is calcined under conditions of temperature is 1300 DEG C 2h and obtains the titanium dioxide pelletizing of prereduction, in finally pelletizing is loaded the titanium basket of mesh 200 mesh with electric conductivity, i.e. obtain prereduction titanium dioxide electrodes；
(2) Titanium is prepared: the prereduction titanium dioxide electrodes obtained with step (1) is as negative electrode, graphite is anode, electrolyte be ionic liquid, decomposition voltage be 3.2V, electrolysis temperature be 120 DEG C under conditions of carry out electroreduction 48h, then take out negative electrode, rinse and drying to obtain cathode product Titanium.Wherein ionic liquid is [Emim] BF4, the oxygen content of Titanium is less than 1%.
Embodiment 6
The method of this titanium dioxide direct Preparation of Titanium, it specifically comprises the following steps that
(1) prereduction titanium dioxide electrodes is prepared: first by titanium dioxide powder, water and carbon dust according to mass percent 100:8:14 mix homogeneously the ball doughy mix that is pressed into a diameter of 5mm, then in reducing atmosphere, ball doughy mix is calcined under conditions of temperature is 1250 DEG C 1.5h and obtains the titanium dioxide pelletizing of prereduction, in finally pelletizing is loaded the titanium basket of mesh 120 mesh with electric conductivity, i.e. obtain prereduction titanium dioxide electrodes；
(2) Titanium is prepared: the prereduction titanium dioxide electrodes obtained with step (1) is as negative electrode, platinum electrode is anode, electrolyte be ionic liquid, decomposition voltage be 3.0V, electrolysis temperature be 100 DEG C under conditions of carry out electroreduction 24h, then take out negative electrode, rinse and drying to obtain cathode product Titanium.Wherein ionic liquid is [Bmim] PF6, the oxygen content of Titanium is less than 1%.
Claims (2)
1. the method for a titanium dioxide direct Preparation of Titanium, it is characterised in that specifically comprise the following steps that
(1) prereduction titanium dioxide electrodes is prepared: first by titanium dioxide powder, carbon dust and PVA according to mass percent 100:(12～16): (1～2) mix homogeneously is also pressed into block mixture, then block mixture is calcined in reducing atmosphere under conditions of temperature is 1200～1300 DEG C 1～4h and obtains prereduction titanium dioxide electrodes；Or first by titanium dioxide powder, water and carbon dust according to mass percent 100:(6～10): (12～16) mix homogeneously and be pressed into a diameter of 1～10mm ball doughy mix, then in reducing atmosphere, ball doughy mix is calcined under conditions of temperature is 1200～1300 DEG C 1～2h and obtains prereduction titanium dioxide pelletizing, in finally pelletizing is loaded titanium basket, i.e. obtain prereduction titanium dioxide electrodes；
(2) Titanium is prepared: the prereduction titanium dioxide electrodes obtained with step (1) is as negative electrode, graphite or other inert material are anode, electrolyte be ionic liquid, decomposition voltage be 2.8～3.2V, electrolysis temperature be 25～120 DEG C under conditions of carry out electroreduction 12～48h, then take out negative electrode, rinse and drying to obtain cathode product Titanium；
Wherein ionic liquid is alkalescence chloro 1-butyl-3-Methylimidazole .-aluminum chloride, alkalescence chloro 1-ethyl-3-methylimidazole-aluminum chloride, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate or 1-butyl-3-Methylimidazole. hexafluorophosphate.
The method of titanium dioxide direct Preparation of Titanium the most according to claim 1, it is characterised in that: the mesh mesh number of described titanium basket is 100～200 mesh.
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| CN104131312A (en) * | 2014-07-08 | 2014-11-05 | 昆明理工大学 | Method utilizing eutectic solvent to carry out in-situ reduction on lead oxide to produce lead |
| CN104213151B (en) * | 2014-09-05 | 2017-05-10 | 昆明理工大学 | Method for preparing lead-antimony alloy by directly electrolyzing lead-antimony oxide |
| CN104451781A (en) * | 2014-12-08 | 2015-03-25 | 中国铝业股份有限公司 | Preparation method of anode for producing metallic titanium by electrolysis |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101166838A (en) * | 2002-10-09 | 2008-04-23 | Bhp比利顿创新公司 | Electrochemical reduction of metal oxides |
| CN102656287A (en) * | 2009-08-06 | 2012-09-05 | 齐诺卡有限公司 | Treatment of titanium ores |
| CN102995065A (en) * | 2012-12-07 | 2013-03-27 | 山东理工大学 | Method for preparing metal titanium by taking ionic liquid as electrolyte and performing electro-deoxidization at room temperature |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101166838A (en) * | 2002-10-09 | 2008-04-23 | Bhp比利顿创新公司 | Electrochemical reduction of metal oxides |
| CN102656287A (en) * | 2009-08-06 | 2012-09-05 | 齐诺卡有限公司 | Treatment of titanium ores |
| CN102995065A (en) * | 2012-12-07 | 2013-03-27 | 山东理工大学 | Method for preparing metal titanium by taking ionic liquid as electrolyte and performing electro-deoxidization at room temperature |
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