CN101949038B - Method for preparing TiCxOy composite anode with electrolysis method - Google Patents
Method for preparing TiCxOy composite anode with electrolysis method Download PDFInfo
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- CN101949038B CN101949038B CN201010288550XA CN201010288550A CN101949038B CN 101949038 B CN101949038 B CN 101949038B CN 201010288550X A CN201010288550X A CN 201010288550XA CN 201010288550 A CN201010288550 A CN 201010288550A CN 101949038 B CN101949038 B CN 101949038B
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Abstract
The invention provides a method for preparing a TiCxOy composite anode with an electrolysis method, comprising the following steps: taking titanium containing material and carbonaceous reducing agent as raw materials; evenly mixing the raw materials according to chemical reaction metering proportion; preparing a composite anode primary product by pressure shaping; taking the composite anode as a cathode, graphite electrode as an anode and alkali metal chloride fused salt as electrolyte to form an electrolytic cell to perform electrolysis; separating out parts of oxygen of titanium dioxide in the composite anode primary product in the mode of ion, transporting to the anode, and generating O2 and CO or/ and CO2 on the anode; causing the other part of oxygen to react with carbon in the raw materials to generate CO; and finally, obtaining the finished product of the TiCxOy composite anode. The method can realize the continuous production of the TiCxOy composite anode and greatly lowers the production cost of the TiCxOy composite anode.
Description
Technical field
The present invention relates to the method that a kind of electrolytic process prepares carbon oxygen titanium composite anode, the finished product of the present invention are carbon oxygen titanium composite anode, and carbon oxygen titanium composite anode can belong to rare metal refinement technique field directly as the raw materials for production of electrolytic process production metallic titanium powder.
Background technology
Metal titanium is as a kind of new metal, has a series of advantageous properties such as low density, good solidity to corrosion, plasticity-, high specific strength.Titanium and alloy thereof are widely used in fields such as aerospace, man-made satellite, military project, chemical industry, oil, metallurgy, light industry, electric power, sea water desaltination, naval vessels, weaving and medical treatment.
At present, the industrial process of titanium sponge still is TiCl
4The Mg hot reducing method, this technology with titanium mineral through enrichment, chlorination, produce TiCl
4, then in inert atmospheres such as argon gas or helium, use magnesium reduction TiCl
4Be titanium sponge, carry out the vacuum distilling separation then and remove magnesium and MgCl
2, be the finished product titanium sponge through product treatment at last.This method production capacity is big, easily realizes commercialization, so up to the present also there is not other technology to substitute.A series of shortcomings such as but technical process is long, the cycle is long, reduction ratio is low, the reductive agent price is higher, the difficult realization serialization of process cause cost of sponge Titanium too high.And invention does not have big improvement to this technology so far from the forties in last century.
Along with the titanium industrial expansion, the smelting of metal titanium has produced the FFC Cambridge technology (WO09964638) based on fused salt electrolysis process, and the technological line of FFC technology is: with solid TiO
2Make negative electrode, the fused chloride of alkaline-earth metal is (as CaCl
2) make ionogen, when impressed voltage was lower than the decomposition voltage of fused salt, the oxygen on the negative electrode entered ionogen with ionic species, emits O at anode
2And CO
2Gas stays pure metallic titanium on the negative electrode.The estimated cost of this method is lower than Kroll method, and is considered to nontoxic, environmental friendliness, and technology is simple, and is with short production cycle.By continuing research, FFC technology remains at following problem: TiO
2The electrode resistance rate is very big, is difficult to realize that stable electrolysis, current efficiency are low; Negative electrode is TiO
2In impurity will all remain in the titanium, this is high-purity Ti O with regard to the raw material that requires technology
2, and high purity Ti O
2Production cost is higher, causes the economy of integrated artistic route to reduce.In addition, the suboxide that FFC technology is not considered the reduction titanium obtains the required electrochemical energy of metal titanium and lacks than reducing titanium dioxide, therefore, obtains metal titanium from more feasible economically with the suboxide of titanium as cathodic reduction.
The electrolysis of TiOmTiC sosoloid soluble anode is the research focus that electrolytic process prepares metal titanium equally.The research of relevant this respect the earliest by the investigator of USSR (Union of Soviet Socialist Republics) last century the seventies propose, think have only carbon, current potential that the oxygen ratio is approximately 1 oxidation of coal titanium is only very stable.TiOmTiC sosoloid electrolytic process is with TiO
2Mix with C at high temperature that reduction makes TiOmTiC sosoloid, again this sosoloid anode is carried out electrorefining in the alkali molten salt system and obtain pure metallic titanium.This technology does not produce the anode sludge in electrolytic process, the electrorefining refining effect is good, but this technology solubility composite anode making is a process that multistep is rapid, comparatively loaded down with trivial details, and the thermal reduction energy consumption is higher.Be conceived to low cost, scale operation metal titanium, composite anode preparation technology still will optimize improvement.
MER technology (WO2005/019501) is mentioned TiO
2Mix by stoichiometric ratio with C, obtain the suboxide of titanium and the mixture of carbon 1100 ℃～1300 ℃ thermal reductions, again with this as composite anode electrolysis in the alkali molten salt system, obtain metal titanium at negative electrode.It is temperature required higher that this method prepares anode, and this will influence the economy of technology.This technology is the combination of thermal and electrochemical process, is difficult to realize the continuity of technology.
Summary of the invention
At above-mentioned deficiency, the objective of the invention is to overcome the defective and the deficiency of prior art, provide a kind of titaniferous material and carbonaceous reducing agent of using to be raw material, prepare carbon oxygen titanium (TiC with electrolytic process
xO
y, 0＜x≤1,1≤y＜2 wherein) and the method for composite anode.Use this composite anode as the soluble anode electrolysis, finally obtain the metal titanium of purity greater than 99.0wt% at negative electrode.
For achieving the above object, the present invention adopts following technical scheme:
A) be raw material with titaniferous material and carbonaceous reducing agent, press chemical reaction metering proportion uniform mixing, prepare the composite anode first product by pressure forming;
B) be negative electrode with the composite anode first product, Graphite Electrodes is an anode, and the alkaline earth metal chloride fused salt is an ionogen, forms electrolyzer and carries out electrolysis;
C) part of the oxygen in the titanium dioxide in the composite anode first product is separated out with ionic species; A part migrates to anode, generates O at anode
2With CO or/and CO
2, the carbon reaction in another part and the raw material generates CO;
D) finally obtain carbon oxygen titanium composite anode finished product TiC at negative electrode
xO
y
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, titaniferous material can comprise metatitanic acid, titanium dioxide.
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, carbonaceous reducing agent can comprise the carbonaceous reducing agent such as Graphite Powder 99, refinery coke, charcoal etc.
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, the chemical reaction metering proportion of titaniferous material and carbonaceous reducing agent is with TiO
2With C by mass ratio can be set at 100: 4～100: 22.5.
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, the force value that pressure forming is set can be 500kg/cm
2～1000kg/cm
2
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, the force value that pressure forming is set can be 500kg/cm
2～800kg/cm
2
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, the alkaline earth metal chloride fused salt can adopt CaCl
2
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, cathode current density can be set at 0.01A/cm in the electrolytic process
2～2A/cm
2
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, cathode current density can be set at 0.1A/cm in the electrolytic process
2～1.0A/cm
2
Prepare the method for carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment, electrolysis temperature can be set at 800 ℃～850 ℃ in the electrolytic process.
Embodiment
Below in conjunction with exemplary embodiment the specific embodiment of the present invention is described further, does not therefore limit the present invention in the described exemplary embodiment scope.Carbonaceous reducing agent refers to carbon to be the reductive agent of main component among the present invention, for example Graphite Powder 99, refinery coke, charcoal etc.
The method for preparing carbon oxygen titanium composite anode according to the electrolytic process of exemplary embodiment may further comprise the steps: with titaniferous material and carbonaceous reducing agent is raw material, presses chemical reaction metering proportion uniform mixing, prepares the composite anode first product by pressure forming; With the composite anode first product is negative electrode, and Graphite Electrodes is an anode, and the alkaline earth metal chloride fused salt is an ionogen, forms electrolyzer and carries out electrolysis; Oxygen part in the titanium dioxide in the composite anode first product is separated out with ionic species; A part migrates to anode, generates O at anode
2With CO or/and CO
2, the carbon reaction in another part and the raw material generates CO; Finally obtain carbon oxygen titanium composite anode finished product TiC at negative electrode
xO
y, wherein, 0＜x≤1,1≤y＜2.
Electrolytic process according to exemplary embodiment prepares in the method for carbon oxygen titanium composite anode, and titaniferous material can comprise metatitanic acid, titanium dioxide, and carbonaceous reducing agent can comprise such as Graphite Powder 99, refinery coke, charcoal etc.; The chemical reaction metering proportion of titaniferous material and carbonaceous reducing agent is with TiO
2With C by mass ratio can be set at 100: 4～100: 22.5; The force value that pressure forming is set can be 500kg/cm
2～1000kg/cm
2, here, if force value is lower than 500kg/cm
2The raw material bulk strength is low excessively, then easily produces physics and cave in fused salt, if force value is higher than 1000kg/cm
2, then intensity is too high, and is too fine and close, is unfavorable for deoxidation, and more excellent scope is 500kg/cm
2～800kg/cm
2Can adopt CaCl as electrolytical alkaline earth metal chloride fused salt
2Cathode current density can be set at 0.01A/cm in the electrolytic process
2～2A/cm
2If cathode current density is higher than 2A/cm
2, can cause electrolytic bath to press to be higher than the calcium chloride decomposition voltage, like this will electrolytic chlorination calcium, be unfavorable for the negative electrode deoxidation if current density is low excessively, and be lower than 0.01 extremely difficult control that preferably, cathode current density can be set at 0.1A/cm
2～1.0A/cm
2Electrolysis temperature can be set at 800 ℃～850 ℃ in the electrolytic process, and the setting of electrolysis temperature is mobile best based on calcium chloride fused salt in this scope mainly, the too high equipment of temperature can not bear and economy not good yet.
Below, will provide the specific embodiment that electrolytic process prepares carbon oxygen titanium composite anode, but embodiment only is exemplary, the invention is not restricted to this.
Embodiment one
Take by weighing titanium dioxide (TiO
298wt%) 102g, Graphite Powder 99 (C content 99wt%) 4.1 grams mix in planetary ball mill, with 1000kg/cm
2Pressure compression moulding as negative electrode, graphite rod is an anode.With the calcium chloride fused salt is ionogen, and electrolyzer is with argon shield, 800 ℃ of electrolysis.Cathode current density is 0.01A/cm
2, electrolysis time 2 hours.After electrolysis is finished, take out negative electrode with the residual ionogen of 0.5% dilute hydrochloric acid flush away, clean chlorion with deionized water again, oven dry is Ti through the main thing of XRD material phase analysis mutually
4O
7With a small amount of C, chemical constitution is TiC
0.18O
1.75
Embodiment two
Take by weighing titanium dioxide (TiO
298wt%) 102g, refinery coke (C content 90wt%) 7.8 grams mix in planetary ball mill, with 500kg/cm
2Pressure compression moulding as negative electrode, graphite rod is an anode.With the calcium chloride fused salt is ionogen, and electrolyzer is with argon shield, 820 ℃ of electrolysis.Cathode current density is 0.1A/cm
2, electrolysis time 5 hours.After electrolysis is finished, take out negative electrode with the residual ionogen of 0.5% dilute hydrochloric acid flush away, clean chlorion with deionized water again, oven dry contains Ti mutually through the main thing of XRD material phase analysis
3O
5, Ti
2O
3And C, chemical constitution is TiC
0.35O
1.63
Embodiment three
Take by weighing titanium dioxide (TiO
298wt%) 102g, charcoal (C content 74wt%) 16.2 grams mix in planetary ball mill, with 800kg/cm
2Pressure compression moulding as negative electrode, graphite rod is an anode.With the calcium chloride fused salt is ionogen, and electrolyzer is with argon shield, 840 ℃ of electrolysis.Cathode current density is 0.4A/cm
2, electrolysis time 10 hours.After electrolysis is finished, take out negative electrode with the residual ionogen of 0.5% dilute hydrochloric acid flush away, clean chlorion with deionized water again, oven dry is Ti through the main thing of XRD material phase analysis mutually
2O
3And C, a small amount of Ti
3O
5, chemical constitution is TiC
0.71O
1.54
Embodiment four
Take by weighing titanium dioxide (TiO
298wt%) 102g, Graphite Powder 99 (C content 99wt%) 22.7 grams mix in planetary ball mill, with 800kg/cm
2Pressure compression moulding as negative electrode, graphite rod is an anode.With the calcium chloride fused salt is ionogen, and electrolyzer is with argon shield, 840 ℃ of electrolysis.Cathode current density is 1.0A/cm
2, electrolysis time 24 hours.After electrolysis is finished, take out negative electrode with the residual ionogen of 0.5% dilute hydrochloric acid flush away, clean chlorion with deionized water again, oven dry is TiO and C through the main thing of XRD material phase analysis mutually, and chemical constitution is TiC
0.99O.
Embodiment five
Take by weighing metatitanic acid (TiO (OH)
298wt%) 125g, Graphite Powder 99 (C content 99wt%) 22.7 grams mix in planetary ball mill, with 800kg/cm
2Pressure compression moulding as negative electrode, graphite rod is an anode.With the calcium chloride fused salt is ionogen, and electrolyzer is with argon shield, 850 ℃ of electrolysis.Cathode current density is 2.0A/cm
2, electrolysis time 24 hours.After electrolysis is finished, take out negative electrode with the residual ionogen of 0.5% dilute hydrochloric acid flush away, clean chlorion with deionized water again, oven dry is TiO and C through the main thing of XRD material phase analysis mutually, and chemical constitution is TiCO.
Embodiment six
The carbon oxygen titanium composite anode that obtains with embodiment one, embodiment two, embodiment three, embodiment four or embodiment five is directly as anode, and carbon steel is a negative electrode, with NaCl-CaCl
2-KCl eutectic mixture is that ionogen is carried out electrolysis, adds the TiCl of massfraction 3% in the electrolytic solution
x(2≤x＜3), wherein anode initial current density is 0.12A/cm
2, negative electrode initial current density is 0.80A/cm
2Electrolysis time 4 hours, 720 ℃ of electrolysis temperatures, normal temperature takes out cathode product, cleans residual ionogen with 0.5% hydrochloric acid, and deionized water is cleaned chlorion, oven dry, chemical analysis shows that product is that purity is greater than the 99.0wt% metallic titanium powder.
The invention provides a kind of titaniferous material and carbonaceous reducing agent of using and be raw material, prepare carbon oxygen titanium composite anode (TiC with electrolytic process
xO
y, 0＜x≤1,1≤y＜2 wherein) method.Use this composite anode as the soluble anode electrolysis, finally can obtain the metal titanium of purity greater than 99.0wt% at negative electrode.This method can realize the serialization production of carbon oxygen titanium composite anode, significantly reduces the production cost of carbon oxygen titanium composite anode.
Claims (9)
1. an electrolytic process prepares the method for carbon oxygen titanium composite anode, it is characterized in that may further comprise the steps:
With metatitanic acid and/or titanium dioxide and carbonaceous reducing agent is raw material, presses chemical reaction metering proportion uniform mixing, prepares the composite anode first product by pressure forming; With the composite anode first product is negative electrode, and Graphite Electrodes is an anode, and the alkaline earth metal chloride fused salt is an ionogen, forms electrolyzer and carries out electrolysis, obtains carbon oxygen titanium composite anode at negative electrode.
2. the method for claim 1 is characterized in that carbonaceous reducing agent comprises Graphite Powder 99, refinery coke, charcoal.
3. the method for claim 1, the chemical reaction metering proportion that it is characterized in that metatitanic acid and/or titanium dioxide and carbonaceous reducing agent is with TiO
2With C by mass ratio be set at 100: 4～100: 22.5.
4. the method for claim 1 is characterized in that the force value that pressure forming is set is 500kg/cm
2～1000kg/cm
2
5. the method for claim 1 is characterized in that the force value that pressure forming is set is 500kg/cm
2～800kg/cm
2
6. the method for claim 1 is characterized in that the alkaline earth metal chloride fused salt adopts CaCl
2
7. the method for claim 1 is characterized in that cathode current density is set at 0.01A/cm in the electrolytic process
2～2A/cm
2
8. the method for claim 1 is characterized in that cathode current density is set at 0.1A/cm in the electrolytic process
2～1.0A/cm
2
9. the method for claim 1 is characterized in that electrolysis temperature is set at 800 ℃～850 ℃ in the electrolytic process.
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| CN102586809B (en) * | 2012-03-22 | 2014-12-10 | 北京科技大学 | A method for improving the deoxidation process of TiO2 cathode by using carbonaceous additives |
| CN102912379A (en) * | 2012-10-25 | 2013-02-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metal titanium |
| CN102925929B (en) * | 2012-10-25 | 2015-04-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing metal titanium by molten salt electrolysis |
| CN105220180B (en) * | 2015-11-12 | 2017-10-24 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of composite anode during electroextraction Titanium |
| CN109650893A (en) * | 2019-01-14 | 2019-04-19 | 浙江海虹控股集团有限公司 | A kind of method of low temperature preparation titaniferous composite anode |
| CN110387562B (en) * | 2019-09-03 | 2021-11-05 | 郑州大学 | An electrochemical method and electrochemical device for preparing metal zirconium with zirconium dioxide |
| CN113881977B (en) * | 2021-11-12 | 2023-04-11 | 东北大学 | Method for preparing zinc-titanium alloy at low temperature by taking titanium oxycarbide as anode |
| CN113913882B (en) * | 2021-11-12 | 2023-04-11 | 东北大学 | Method for preparing aluminum-titanium alloy by taking titanium oxycarbide as raw material through low-temperature electrodeposition |
| GB2613588A (en) * | 2021-12-07 | 2023-06-14 | Chinuka Ltd | Treatment of metal ores |
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| US7410562B2 (en) * | 2003-08-20 | 2008-08-12 | Materials & Electrochemical Research Corp. | Thermal and electrochemical process for metal production |
| CN100415940C (en) * | 2005-05-08 | 2008-09-03 | 北京科技大学 | Method for producing pure titanium by anodic electrolysis of titanium monoxide/titanium carbide soluble solid solution |
| JP2007247002A (en) * | 2006-03-16 | 2007-09-27 | Keio Gijuku | Method for electrochemical reduction of titanium oxide |
| WO2008091806A1 (en) * | 2007-01-22 | 2008-07-31 | Materials & Electrochemical Research Corp. | Metallothermic reduction of in-situ generated titanium chloride |
| US7628937B2 (en) * | 2007-12-17 | 2009-12-08 | E.I. Du Pont De Nemours And Company | Processes for making titanium production anodes |
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