CN100415940C - Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis - Google Patents
Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis Download PDFInfo
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- CN100415940C CN100415940C CNB2005100116846A CN200510011684A CN100415940C CN 100415940 C CN100415940 C CN 100415940C CN B2005100116846 A CNB2005100116846 A CN B2005100116846A CN 200510011684 A CN200510011684 A CN 200510011684A CN 100415940 C CN100415940 C CN 100415940C
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Abstract
The present invention provides a method for directly preparing pure titanium in an electrolysis mode by sosoloid TiO-mTiC anode, wherein the sosoloid anode has metallic conductivity. Carbon and titanium dioxide or titanium carbide and titanium dioxide are taken as raw materials, and the raw materials are mixed according to chemically reaction stoichiometry into powdery. The powdery raw materials are shaped by pressing and are prepared into a TiO-mTiC anode with metallic conduction by a vacuum reaction with the temperature range of 600 DEG C to 1600 DEG C. Alkali or alkaline earth metal halide molten salts are used as an electrolyte, and the raw materials are electrolyzed at 400 DEG C to 1000 DEG C. Carbon and oxygen contained in the anode in the electrolytic process are formed into oxycarbide gas CO, CO2 or oxygen to release, titanium simultaneously enters into the molten salt in a low-vament ion mode, and pure titanium is obtained by depositing in a cathode. The present invention has the advantages that the electrolytic process continuously carries out, anode slime does not generate, and the technology is simple.
Description
Technical field
The invention belongs to electrolytic process and produce pure titanium technical field, the method that a kind of titanium monoxide/titanium carbide solubility sosoloid anode electrolysis is produced pure titanium particularly is provided.With soluble anode TiOmTiC (wherein 0≤m≤1) direct pure titanium of electrolytic preparation in basic metal and/or alkaline earth metal halide fused salt, in the method, anode institute's carbon containing and oxygen are with carbon oxide gas (CO, CO
2) or the form of oxygen emit, titanium dissolves into fused salt and obtains pure titanium in cathodic deposition with the low price ionic species.Adopt this method can under the prerequisite that the anode sludge do not occur, finish the technological process of the pure titanium of continuity electrolysis production, will reduce the production cost of the metal of titanium significantly.
Background technology
Metal titanium has very excellent physics, chemical property, and its density is littler by 43% than steel, specific tenacity height, fusing point height, high-temperature corrosion resistance and toxicological harmless.At present, titanium has become excellent lightweight structural material, new function material and important bio-medical material.Titanium has been widely used in civil areas such as aerospace, military project and chemical industry, boats and ships, automobile, sports equipment, medicine equipment, building.It is described as " following metal ", " the 3rd metal ".Yet, the price of titanium greatly limited the utilization of titanium, although the reserves of titanium in the earth's crust abundant (0.44%, in all metallic elements, arrange the 8th, be only second to magnesium 2.0%), owing to the existing metallurgical process of titanium is loaded down with trivial details, its price can't be reduced.
The main flow production technique of metal current titanium is the Kroll method, produces the titanium sponge available electron bundle melting that obtains and purifies.It at first is by carburizing chlorination producing titanium tetrachloride t 5 bx (TiCl with titanium dioxide that the Kroll method is produced the metal titanium process
4), obtain titanium sponge with MAGNESIUM METAL by thermal reduction then, MAGNESIUM METAL then is to obtain by electrolytic chlorination magnesium, the chlorine of electrolysis gained is used for producing of titanium chloride again, so whole process of production comprises the electrolysis of magnesium chloride, the titanium oxide chlorination, and three major portions of magnesiothermic reduction, complex steps, energy consumption is big, and the magnesiothermic reduction step of core is a batch operation, productivity effect is very low, owing to these reasons have caused costing an arm and a leg of metal titanium, the price of the titanium sponge of producing with this method is about 5.6～10.0US$/kg, and its price is far above the price of iron and steel, and the unit weight price also is more than 3 times of metallic aluminium.
In order to reduce the price of titanium sponge, in the past nearly 70 years, the metallurgists of countries in the world are multi-faceted to seek new low-cost pure titanium smelting technology, comprising chemical heat reduction, methods such as electrolysis.
The titanium electrolysis process of studying mainly contains TiCl
4Electrolysis and titanium oxide electrolysis (document: M.V.Ginatta.Process for the electrolytic production of metals[P] .US6074545,2000; M.V.Ginatta, G.Orsello, R.Berruti.Method and cell for the electrolytic production of a polyvalent metal[P] .US5015342,1991; Ni Fusheng, Lu Qingtao, the balance in the old generation official .LiCl-NaCl-KCl system between titanium and the lower chloride. rare metal .111 (1984): 23-28; Du Jihong, Qi and state the electrochemical reduction of .Ti (IV) in the muriate melt. Rare Metals Materials and engineering, 27 (1998): 165-168.)。
Because TiCl
4Be the covalent linkage molecule, the solubleness in melting salt is lower, is difficult to satisfy need of industrial production.Titanium is typical transiting group metal elements in addition, the current efficiency that titanium ion can reduce electrolytic process in the incomplete discharge and the migration of different valence state ion between cathode and anode of negative electrode.
At the initial stage in this century, univ cambridge uk has proposed a kind of with TiO with the research group headed by the D.J.Fray
2Produce the novel process (document: G.Z.Chen of titanium sponge for raw material negative electrode deoxidation in fused calcium chloride, D.J.Fray, T.W.Farthing.Direct electrochemical reduction of titanium dioxide to titanium in moltencalcium chloride.Nature, 407 (2000): 361-364).The estimated cost of this method is lower than Kroll method, and is considered to nontoxic.Thus, oxide electrolysis direct production titanium sponge becomes the research focus (document: G.Z.Chen that titanium metal is smelted, D.J.Fray, T.W.Farthing.Direct electrochemical reduction of titaniumdioxide to titanium in molten calcium chloride.Nature, 407 (2000): 361-364; D.J.Fray.Emerging molten salt technologies for metals production.JOM, 53 (2001): 26-31; G.Z.Chen, D.J.Fray.Electro-deoxidation of metal oxides.Light Metals, 2001:1147-1151).But produce titanium sponge and have following problem about this method that studies have shown that of FFC technology recently:
(1) adopts the higher CaCl of oxygen dissolving power
2Melt the titanium sponge too high oxygen level that salt system makes generation, reduce oxygen level and must carry out excessive electrolysis, this has caused current efficiency extremely low again;
(2) preparation of raw material negative electrode is very inconvenient, TiO
2Be semi-conductor, the electrolysis initial stage must be born the conducting of electrode by other metallic substance, as the raw material negative electrode too the Nature can cause very big volts lost, and the carrying out of impeded electrode process;
(3) oxonium ion solid phase diffusion speed causes polarization to make the current density of negative electrode very low too slowly, and along with the electrolytic electrode area that carries out gradually changes, also can be even carry out Faradaic current along with TiO in the mode of permanent electromotive force
2Therefore the increase of the amount of being reduced and increasing is difficult to realize stable electrolysis on industrial production;
(4) because raw material TiO
2With the product metal titanium be same negative electrode, whole technology can only be step, also can only replace another TiO with the electrode taking-up after finishing a catholyte even that is to say electrolysis success
2Electrolysis again behind the electrode.
(5) the product metal titanium is raw material TiO
2Progressively reduce gained, most impurity will enter into the product metal titanium in the raw material.It is just necessary with highly purified raw material TiO to obtain highly purified metal
2Yet, produce high purity Ti O
2Cost is not low, and this will bring the raising of whole process production cost.
So the industrialized possibility of FFC technology still remains to be discussed, only just might practicability after the problem more than having solved, and be difficult to see the approach (M.F.Liu that addresses these problems in itself on the reality, Z.C.Guo, W.C.Lu.An investigation into electrochemical reduction of TiO
2Pellet.Transaction of the institute of mining and metallurgy, sectrion C.In press).
Japanology personnel hilllock portion (Okabe) and little open country (Ono) etc. are same, and electrolysis has obtained metal titanium (document: T.H.Okabe as ionogen with fused calcium chloride, M.Nakamura, T.Oishi et al.Electrochemicaldeoxidation of titanium.Met.Trans., 24B (1993): 449-455; K.Ono, R.O.Suzuki.a newconcept for producing Ti sponge:calciothermic reduction.JOM, 54 (2002) (2): 59-61), different is that they are not with raw material TiO
2Directly contact with negative electrode, so they think to obtain to restore after the calcium metal by electrolysis to obtain metal titanium, this method is a kind of combination of electrolysis and thermal reduction, and this method has been saved in the FFC method and prepared TiO
2The step of negative electrode, but exist how with the calcium metal of cathode product and the TiO of raw material
2Problems such as mixing rationally and extraction product titanium; And the problem of other parts of FFC method equally still exists in this method.
Therefore to obtain the sufficiently high metal titanium of quality and still oxygen and product titanium metal must be isolated, and raw material titanium successive can be provided in the electrolytic solution.The high-purity titanium titanium sponge is that anode passes through the acquisition of melting salt (mostly being muriate) electrorefining on the reality, but these raw material anodes obtain by the Kroll method, that is to say this only refining process, in all senses, do not reach the purpose that reduction is extracted.Because TiC is a kind of compound with metallic conduction performance, also can be used as the resolvability anode is used for fusion electrolysis and prepares high purity titanium, titanium enters fused salt with the low price ionic species in the electrolytic process, and obtains pure titanium in cathodic deposition, but the positive column residual carbon has a strong impact on electrolytic carrying out.Remain the carbon problem for solving above-mentioned anode, the fifties in last century, E.Wainer (document: E.Wainer.Cell feed material for the production of titanium[P] .US2868703,1959.; E.Wainer, C.Heights, O.Assignor.Production of titanium[P] .US2722509,1955.) be after raw material mixes with TiC and TiO, thermal treatment forms the sosoloid (TiCTiO) of TiC and TiO under 2100 ℃ high temperature, at the muriate fusion electrolysis, discovering has CO gas to emit and the positive column does not have resultant product (anode sludge) on the anode as anode, can obtain pure titanium in cathodic deposition through after the electrolysis.Here the TiO that uses is the metallic conductivity compound of a kind of similar TiC, so TiC and TiO sosoloid can be used for being similar to the soluble anode of metal, and anodic product is hydrocarbon gas (CO, CO under suitable condition
2), titanium then dissolves in the electrolytic solution with the ionic form.But the scheme that Wainer carried need be a raw material with TiC and TiO, wherein TiO is not easy preparation and control, and the sosoloid melting that he proposed is adopted under the arc melting high temperature (＞2100 ℃) and is finished, and obviously still has problems on the practical application meaning.
Japanology researchist bridge this (Y.Hashimoto) is with excessive carbon and TiO
2For raw material mixes, (＞1700 ℃) make oxygen doping titanium carbide (TiC doped by Oxygen) under high arc temperature, and be anode electrolysis, the fusion electrolysis cathodic deposition obtain pure titanium (document: the molten salt Electricity that melts of this Yong Yan of Bridge .Ti-C-O alloy ま は The Yang Very と The Ru Ti separates. the Japanese metal Chi of association, 32 (1968): 1327-1333.; This Yong Yan of Bridge. チ Application is molten to melt low-grade (the δ)-Ti-C-O of salt System And-chain To お け Ru solubility Yang Very チ Application Yang Very stripping.The Japan metal Chi of association, 35 (1971): 480-486.; This Yong Yan of Bridge. the Ti-C-O お of ア one Network It unit I び TiC solubility Yang Very I り Ti extracts out. the Japanese metal Chi of association, 35 (1971): 282-289.; This Yong Yan of Bridge. the molten salt Electricity that melts of チ Application separates System And-chain To お け Ru solubility Yang Very と て baked knot TiC To つ い て. the Japanese metal Chi of association, 35 (1971): 487-493.; This Yong Yan of Bridge. high Pure degree TiC powder end System makes To Seki The Ru research (the 1st Reported)--TiO
2Vacuum charing To I Ru micro mist TiC System makes To つ い て. powder お I び powder metallurgy, 17 (1970): 168-175.).But its anodic preparation process still depends on very pyritous reductive condition, does not reach the low-cost purpose of extracting titanium in itself.And its electrolytic experiment all is based on the titanium carbide of hypoxemia, a large amount of anode sludge of the too high generation of anode carbon content, and continuous electrolysis can't normally carry out.
Summary of the invention
The objective of the invention is to: provide the method that titanium monoxide/titanium carbide solubility sosoloid anode electrolysis is produced pure titanium, promptly a kind of method with direct pure titanium of electrolytic preparation of sosoloid anode TiOmTiC (wherein 0≤m≤1) of metallic conductivity.Realized low-energy consumption preparing TiOmTiC (wherein 0≤m≤1) sosoloid soluble anode, and in the halogenide fused salt to electrolysis, carbon and oxygen contained in the anode are combined into carbon carrier of oxygen (CO, CO
2) form or oxygen emit, and contained titanium enters fused salt and obtains pure titanium in cathodic deposition with the low price ionic species.
The present invention is a raw material with carbon and titanium dioxide or with titanium carbide and titanium dioxide, be mixed into powder by the chemical reaction metering, compression moulding then, vacuum reaction is made the TiOmTiC anode with metallic conduction performance, wherein 0≤m≤1 in 600 ℃～1600 ℃ temperature range; Halogenide fused salt with basic metal or alkaline-earth metal is an electrolytic solution, electrolysis under 400 ℃～1000 ℃ temperature; Contained carbon and the oxygen of anode forms carbon oxide gas CO, CO in the electrolytic process
2Or oxygen emits, and titanium enters fused salt and obtains pure titanium in cathodic deposition with the low price ionic species simultaneously; After electrolysis is finished cathode product normal temperature is removed down the muriate of clearing out from electrolytic solution for 5～8 times with deionized water; This electrolytic process carries out continuously, and does not have anode sludge generation.Specific embodiment is as follows:
1. with the carbon and the TiO of chemical reaction metering
2Be raw material, with 100kg/cm
2～1000kg/cm
2Pressure forming, the preferred 600kg/cm of forming pressure
2～1000kg/cm
2Vacuum reaction is made TiOmTiC (wherein 0≤m≤1) anode with metallic conduction performance in 600 ℃～1600 ℃ temperature range.
With carbon and titanium dioxide or with titanium carbide and titanium dioxide be raw material respectively by the stoichiometric ratio of following reaction with the raw material uniform mixing;
2TiO
2+4C＝Ti
2CO+3CO
3TiO
2+5C＝Ti
3CO
2+4CO
4TiO
2+6C＝Ti
4CO
3+5CO
.
.
.
.
.
.
TiO
2+C＝TiO+CO
Or
2TiO
2+4TiC＝3Ti
2CO+CO
4TiO
2+5TiC＝3Ti
3CO
2+2CO
2TiO
2+2TiC＝Ti
4CO
3+CO
.
.
.
.
.
.
2TiO
2+TiC＝3TiO+CO
3. with the TiC and the TiO of chemical reaction metering
2Be raw material, with 100kg/cm
2～1000kg/cm
2Pressure forming, the preferred 600kg/cm of forming pressure
2～1000kg/cm
2Vacuum reaction is made TiOmTiC (wherein 0≤m≤1) anode with metallic conduction performance in 600 ℃～1600 ℃ temperature range.
4. select basic metal or alkaline earth metal halide molten salt system, preferred fluorinated thing or muriate, more preferably muriate eutectic system.
5. the TiOmTiC (wherein 0≤m≤1) with step 1 and 2 preparations is an anode, selects a kind of metallic substance as negative electrode, and preferred titanium, carbon steel, nickel are negative electrode.
6. the electrode selected for use as electrolytic solution and step 4 of the fused salt of selecting for use with step 3 is formed electrolyzer, electrolysis under 400 ℃～1000 ℃ temperature.
7. the current density range during electrolysis is respectively: anode, 0.05A/cm
2～1.00A/cm
2, preferred 0.20A/cm
2～0.5A/cm
2Negative electrode, 0.10A/cm
2～1.00A/cm
2, preferred 0.10A/cm
2～0.4A/cm
2
8. add solubility sosoloid anode continuously, each electrolysis was checked cathode product after 15 hours.
9. after electrolysis is finished cathode product normal temperature is removed down, go out muriate from electrolytic solution for six times with washed with de-ionized water.
The invention has the advantages that: prepare anode TiOmTiC (wherein 0≤m≤1) electrolysis in the halogenide fused salt with metallic conduction performance being lower than under 1600 ℃ the condition, negative electrode obtains pure titanium and the positive column does not have the anode sludge to produce.So can finish the continuity electrolytic process.
Description of drawings
Fig. 1 prepares the x-ray diffraction pattern of anode material for example 1 of the present invention.
Fig. 2 prepares the x-ray diffraction pattern of anode material for example 2 of the present invention.
Fig. 3 is the stereoscan photograph of example 3 cathode products of the present invention.
Fig. 4 is the x-ray diffraction pattern of example 3 cathode products of the present invention.
Fig. 5 is the x-ray diffraction pattern of example 4 cathode products of the present invention
Fig. 6 is the stereoscan photograph of example 5 cathode products of the present invention.
Fig. 7 is the stereoscan photograph of example 6 cathode products of the present invention.
Embodiment
Embodiment 1
Anode preparation
Raw material: carbon dust, titanium dioxide mixes with following reactive chemistry metering ratio.
2TiO
2+4C＝Ti
2CO+3CO
Preparation process condition (seeing the following form)
Resistance is 38 ohmcms before the block thermal treatment that compacting obtains, and resistance is sharply reduced to 0.1 ohmcm after the thermal treatment.To material element analysis revealed after the thermal treatment, the atom proportioning form that it has should be Ti
2CO, the constituent of this material of employing X-ray diffraction means analysis, it the results are shown in accompanying drawing 1, and the structure generation considerable change of material after the thermal treatment as seen from the figure is mainly the TiCTiO sosoloid with metallic conduction performance.
Anode preparation
Raw material: titanium carbide, titania powder mixes with following reactive chemistry metering ratio.
2TiO
2+4TiC＝3Ti
2CO+CO
Preparation process condition (seeing the following form)
Resistance is 72 ohmcms before the block thermal treatment that compacting obtains, and resistance is sharply reduced to 0.05 ohmcm after the thermal treatment.Adopt the constituent of this material of X-ray diffraction means analysis, it the results are shown in accompanying drawing 2, is TiCTiO sosoloid as seen from the figure after the thermal treatment.
Embodiment 3
The block materials that obtains with embodiment 1 is an anode, and carbon steel is a negative electrode, and the NaCl-KCl fused salt is that electrolytic solution carries out electrolysis, and concrete implementing process sees the following form:
Be explanation anodic reaction mechanism, adopt gas chromatographicanalyzer device antianode process to generate gas in the electrolytic process and detect that the carrier gas of being adopted is an argon gas, the concentration that obtains all gases sees the following form
Produce carbon oxide gas at anode in the last table data declaration electrolytic process, and under experiment condition based on CO.Cathodic deposition obtained pure titanium after electrolysis was finished, and it is received and kept with 5 seasoninies of washed with de-ionized water with dilute hydrochloric acid (1wt%) washing back, and calculating cathode efficiency by faraday's theorem is 90%; The electron scanning micrograph of accompanying drawing 3 examples 3 cathode products.Accompanying drawing 4 examples 3 are the x-ray diffraction pattern of cathode product, and as can be seen from the figure, cathode product has the crystalline structure of pure titanium.
Embodiment 4
The block materials that obtains with embodiment 2 is an anode, and carbon steel is a negative electrode, and the LiCl-KCl fused salt is that electrolytic solution carries out electrolysis, and concrete implementing process sees the following form:
The pure titanium that negative electrode obtained after electrolysis was finished is received and kept it for 8 times with washed with de-ionized water with dilute hydrochloric acid (1wt%) washing back, and calculating cathode efficiency by faraday's theorem is 85%; The electron scanning micrograph of accompanying drawing 5 examples 4 cathode products.
Embodiment 5
Anode preparation
Raw material: carbon dust, titanium dioxide mixes with following reactive chemistry metering ratio.
3TiO
2+5C＝Ti
3CO
2+4CO
Preparation process condition (seeing the following form)
Resistance is 46 ohmcms before the block thermal treatment that compacting obtains, and resistance is sharply reduced to 0.07 ohmcm after the thermal treatment.
With this block materials is anode, and it is as follows that carbon steel is that negative electrode NaCl-KCl fused salt is that the electrolytic condition of electrolytic solution following table carries out electrolysis gas chromatographic detection anodic gas analytical results:
It is 89% that faraday's theorem is calculated current efficiency, the electron scanning micrograph of accompanying drawing 6 examples 5 cathode products.Results of elemental analyses shows that oxygen level is 210ppm in the cathode product.
Embodiment 6
Anode preparation
Raw material: carbon dust, titanium dioxide mixes with following reactive chemistry metering ratio.
TiO
2+C＝TiO+CO
Preparation process condition (seeing the following form)
Resistance is 43 ohmcms before the block thermal treatment that compacting obtains, and resistance is sharply reduced to 0.2 ohmcm after the thermal treatment.
With this block materials is anode, and carbon steel is a negative electrode, and the LiF-NaF-KF fused salt is that electrolytic solution following table electrolytic condition electrolysis gas chromatographic detection anodic gas analytical results is as follows.
It is 87% that faraday's theorem is calculated current efficiency, the electron scanning micrograph of accompanying drawing 7 examples 6 cathode products.Results of elemental analyses shows that oxygen level is 380ppm in the cathode product.
Claims (6)
1. method that titanium monoxide/titanium carbide solubility sosoloid anode electrolysis is produced pure titanium is characterized in that: with carbon and titanium dioxide or with titanium carbide and titanium dioxide is raw material, is mixed into powder by the chemical reaction metering, then with 100kg/cm
2～1000kg/cm
2Pressure forming, vacuum reaction is made the TiOmTiC anode with metallic conduction performance, wherein 0≤m≤1 in 600 ℃～1600 ℃ temperature range; Halogenide fused salt with basic metal or alkaline-earth metal is an electrolytic solution, electrolysis under 400 ℃～1000 ℃ temperature; Contained carbon and the oxygen of anode forms carbon oxide gas CO, CO in the electrolytic process
2Or oxygen emits, and titanium enters fused salt and obtains pure titanium in cathodic deposition with the low price ionic species simultaneously; After electrolysis is finished cathode product is removed down the muriate of clearing out from electrolytic solution for 5～8 times with deionized water; This electrolytic process carries out continuously, and does not have anode sludge generation; With carbon and titanium dioxide or with titanium carbide and titanium dioxide be raw material respectively by the stoichiometric ratio of following reaction with the raw material uniform mixing;
2TiO
2+4C＝Ti
2CO+3CO
3TiO
2+5C＝Ti
3CO
2+4CO
4TiO
2+6C＝Ti
4CO
3+5CO
TiO
2+C＝TiO+CO
Or
2TiO
2+4TiC＝3Ti
2CO+CO
4TiO
2+5TiC＝3Ti
3CO
2+2CO
2TiO
2+2TiC＝Ti
4CO
3+CO
2TiO
2+TiC＝3TiO+CO。
2. the method for claim 1, it is characterized in that: forming pressure is 600kg/cm
2～1000kg/cm
2
3. the method for claim 1, it is characterized in that: the halogenide fused salt of described basic metal or alkaline-earth metal is fluorochemical or muriate.
4. the method for claim 1, it is characterized in that: with TiOmTiC is anode, selects a kind of metallic substance as negative electrode, described metallic substance is titanium, carbon steel or nickel.
5. the method for claim 1 is characterized in that: as electrolytic solution and electrode composition electrolyzer, the current density range during electrolysis is respectively: anode is 0.05A/cm with fused salt
2～1.00A/cm
2, negative electrode is 0.10A/cm
2～1.00A/cm
2
6. the method for claim 1, it is characterized in that: the current density range during electrolysis is respectively: anode is 0.20A/cm
2～0.5A/cm
2Negative electrode is 0.10A/cm
2～0.4A/cm
2
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