CN101289754A - Process for preparing metallic titanium and titanium master alloy - Google Patents
Process for preparing metallic titanium and titanium master alloy Download PDFInfo
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- CN101289754A CN101289754A CNA2008100116820A CN200810011682A CN101289754A CN 101289754 A CN101289754 A CN 101289754A CN A2008100116820 A CNA2008100116820 A CN A2008100116820A CN 200810011682 A CN200810011682 A CN 200810011682A CN 101289754 A CN101289754 A CN 101289754A
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Abstract
The invention relates to the non-ferrous metal metallurgy fused salt electrolysis field, a method mainly comprises the steps of: preparing titanium dioxide, titanium tetrachloride, titanium dichloride and fluotitanate as raw materials, electrolyzing one or a plurality of combinations of TiO2, TiC14 and the fluotitanate in an electrolysis bath, preparing metallic titanium or titanium-based master alloy through an electrolysis method or a thermal reduction-electrolysis combined method, performing the TiO2 and connecting direct current to deoxidize or adopting metal (or metallic compound) for heat reducing the TiO2 beforehand, preparing the metallic titanium which contains oxygen (O) with certain concentration, and then electrolyzing aluminium, alkali metal, alkaline earth, rare earth metal, metallic copper, metallic zinc or metallic lead to deoxidize finally in the electrolysis bath. The purpose of the method is to reduce the production cost of the metallic titanium, simplify the production procedures and lower the environmental pollution in the production process, especially the titanium dioxide taken as the raw materials, the production flow is shortened, the storage and the transportation are convenient, none chlorine gas takes part in the reaction, and green metallurgy of the metallic titanium can be realized.
Description
Technical field:
The present invention relates to field, Non-ferrous Metallurgy fused salt electrolysis field, this method is a raw material with main development titanium dioxide, titanium tetrachloride, titanium dichloride and fluotitanate, electrolysis TiO in electrolyzer
2, TiCl
4With one or more multiple combinations of fluotitanate, preparation metal titanium or titanium base master alloy; Or adopt metal (or metallic compound) thermal reduction TiO in advance
2, prepare the metal titanium that contains finite concentration oxygen (O), final deoxygenation is carried out in electrolysis in the aluminium cell then.
Background technology:
It is little that titanium has density, the specific tenacity height, and advantage such as anti-oxidant, antifatigue, erosion resistance is outstanding 26S Proteasome Structure and Function material, enjoys good reputations such as " all can metal ", " moving towards the rare giant of 21 century ".Used widely in fields such as national defence, aerospace, navigation, oil, chemical industry, medical treatment, metallurgy.
The content of titanium in the earth's crust is very abundant, is only second to aluminium, iron, magnesium in the structural metal, occupies the 4th, and nisi rare.Because the metallurgical technology more complicated of titanium causes titanium and products thereof production cost too high, and its range of application is very restricted.But according to its reserves and performance, titanium probably becomes the 3rd kind of practical metal after iron, aluminium, therefore exploitation prospect is very wide, and the research association that titanium is extracted the research, particularly low-cost extracting process of metallurgical technology and technology receives concern more and more widely.The main method of producing metal titanium at present has:
1. hot reducing method
1.1 magnesium reduction process
Kroll method (magnesium reduction TiCl
4Method)
This method is that 1940W.J.Kroll proposes, and principle is Mg+TiCl
4=MgCl
2+ Ti, its advantage is to use the easy to handle titanium tetrachloride, and product purity is higher, and reductive agent magnesium can utilize etc. again.The Kroll method is given birth to technology: the operational path that adopts " titanium mineral (rutile/titanium slag/ilmenite → titanium slag) → titanium tetrachloride → titanium sponge ".
Produce titanium slag: under 1600～1900 ℃ high temperature, ilmenite is that reductive agent carries out selective reduction with refinery coke or hard coal in electric arc furnace, the titanium slag and the byproduct pig iron, the two separates by density difference is different, titanium is enriched in the slag.
Preparation titanium tetrachloride: titanium slag or natural/artificial rutile are mixed with refinery coke, generate crude titanic chloride with chlorine reaction and remove high-boiling-point impurity by distillation method then; Remove lower-boiling impurity by rectification method then, vanadium generally adopts copper method, aluminium method or hydrogen sulfide method to remove.
The reducing metal titanium is under the atmosphere of 800-900 ℃ and protection of inert gas, in the reactor of airtight steel, puts into TiCl with certain flow velocity
4With the fused reactive magnesium, obtain the spongy metal titanium, byproduct MgCl
2Can be used as the raw material of electrolytic magnesium.
1.2 sodium thermoreduction method and other hot reducing method (Hunter method)
The Hunter method is the method for producing the high pure metal titanium the earliest, and ultimate principle is:
TiCl
4(g)+4Na＝Ti(s)+4NaCl
Sodium reduction TiCl
4Method one-stage process and two-stage method are arranged.The result lacks than the titanium of producing with the Kroll method of same scale with the titanium amount that the Hunter method is produced.The Hunter method does not enlarge because of capacity of equipment in recent years, and the electrolytic sodium production technology does not have major progress and abandoned.
2.TiCl
4Electrolytic process
TiCl
4Electrolytic reduction once be considered to unique method that might replace Kroll technology, the mechanism of titanium tetrachloride reduction of fused salts titanium is as follows:
Ti
4++e→Ti
3+
Ti
3++e→Ti
2+
Ti
2++e→Ti
Total reaction is: TiCl
4=Ti+2Cl
2
According to the electrolysis temperature difference, warm electrolysis and high-temperature electrolysis method are two kinds in can being divided into.
2.1 middle temperature electrolysis: adopting the muriate of basic metal or alkaline-earth metal is ionogen, and electrolysis temperature is 600～1000 ℃, electrolysis TiCl under protection of inert gas
4, but exist such as TiCl
4Solubleness in melting salt is lower, current efficiency is low, produce technical problems such as chlorine contaminate environment, the easy oxidation of metal powder can't carry out problems such as suitability for industrialized production.
2.2 high-temperature electrolysis: when being higher than 1700 ℃, titanium (fusing point 1943K) becomes liquid state, can equally realize serialization production to electrolytic aluminum, and the purity of metal titanium is higher, but working condition is comparatively harsh.
3.TiO
2Electrolytic reduction
With TiCl
4Compare, reduction titanium dioxide has shortened Production Flow Chart, and be convenient to store and transportation, and do not have chlorine and participate in reaction, be a kind of novel pollution-free green metallurgical technology, caused widely and paid close attention to.
4.FFC Cambridge technology
Its mechanism is: when calcium is deposited on the titanium dioxide negative electrode, can generate CaO with the oxygen reaction on the negative electrode, CaO then is dissolved in CaCl
2Melt in the salt.Another kind explanation to mechanism is: with calcium sediment-filled phase ratio, the ionization of oxygen can take place under low relatively cathode potential, and titanium oxide just can directly be reduced into metal titanium by electrochemical process, rather than by realizing with the chemical reaction of calcium.
FFC Cambridge technological principle is: electrolytic trial is at 850 ℃～950 ℃, under the condition of argon shield, with fused CaCl
2Be electrolytic solution, graphite is anode, agglomerating TiO
2Battery lead plate is a negative electrode, at fused electrolyte CaCl
2Middle electrochemical reaction, the negative electrode TiO as a result of taking place
2Ionization goes out oxonium ion and anode migration, and titanium metal has been stayed, and obtains pure metallic titanium at negative plate place, and oxygen level constantly reduces with the increase of electrolysis time (can reach 6.0 * 10
-6Wt%).Since this technology can be from fused salt direct electrolysis TiO
2To titanium, its technical process is short, simple fast, cost is low, save the chlorination in the traditional technology, refining TiCl
4, magnesium reduction and vacuum complicated procedures of forming such as heat up in a steamer, and can reduce the cost of titanium sponge greatly, do not have chlorine especially to discharge, be a kind of pollution-free green metallurgical technology, have great superiority, be expected to obtain the Kroll method to produce cheap metal titanium, caused common concern.The technology that electrolysis TiO2 such as OS method, EMR/MSE method successively occurred.
Though the reserves of titanium in the earth's crust are bigger, the production technique of titanium sponge has multiple, really realizes the industrialized Hunter of having only method and Kroll method, and other method still rests on laboratory stage at present mostly.But the most effective production technique of extracting metal titanium at present is the Kroll method, owing to extensively adopt the Kroll method, makes that the metal titanium production cost is too high to influence its application.
Summary of the invention:
Goal of the invention: the invention provides the method that in electrolyzer, prepares metal titanium and titanium base alloy, or thermal reduction-electrolysis integrated process prepares metal titanium, its purpose is to reduce the production cost of metal titanium, simplifies production process, reduces the environmental pollution that causes in the production process.Be raw material with titanium dioxide especially, shortened Production Flow Chart, be convenient to store and transportation, and do not have chlorine and participate in reaction, can realize the green metallurgical of metal titanium.
Technical scheme: the present invention is achieved through the following technical solutions:
A kind of method for preparing metal titanium and titanium base alloy, it is characterized in that: this method is a raw material with titanium dioxide, titanium tetrachloride, titanium dichloride and fluotitanate, by electrolysis or thermal reduction-electrolysis integrated process, ionogen wherein is mainly sodium aluminum fluoride, fluotitanate, silicofluoride, sodium phosphate, Sodium Tetraborate, fluorochemical, muriate, Li
2One or more compositions among O, Quilonum Retard, the CaO, anode adopts carbon anode, negative electrode adopts a kind of solid state cathode in charcoal negative electrode, titanium negative electrode, stainless steel cathode, molybdenum negative electrode, the tungsten cathode, electrolysis under 600～1800 ℃ condition, at cathode surface or hold and cover liquid metal in the container of metal in advance and absorb the metal titanium that electrolysis produces, direct production metal titanium or titanium base alloy in electrolyzer; Or other metal in the separation titanium base alloy prepares metal titanium.
With titanium dioxide, in titanium tetrachloride or the fluotitanate one or more are raw material, adopt heavy ionogen in aluminium cell or in the electrolyzer of basic metal or alkaline-earth metal, heavy electrolytical density is greater than metallic aluminium or basic metal or alkaline-earth metal, and less than metal titanium, make the basic metal or the alkaline-earth metal that produce in the electrolytic process float to heavy electrolytical upper surface, make sink under the metal titanium heavy electrolytical below, impel basic metal or alkaline-earth metal in the electrolyzer to separate with metal titanium, at cathode surface or hold and cover liquid metal in the container of metal in advance and absorb the metal titanium that electrolysis produces, direct production metal titanium or titanium base alloy, or other metal that separates in the titanium base alloy prepares metal titanium.
With titanium dioxide is raw material, directly electrolysis titanium dioxide prepares metal titanium in electrolyzer, place the metal titanium of liquid metal or alloy absorption electrolysis generation in advance at cathode surface, and in electrolytic process, in electrolyzer, add low-melting metal or alloy, direct production metal titanium or titanium base master alloy in electrolyzer, utilize vacuum distilling, electrorefining, zone melting, density difference, electrolysis-original position smelting process, vacuum consumable smelting method or physical method, chemical process and electrochemical method are isolated other metal or alloy, prepare metal titanium or prepare the higher titanium base master alloy of other metal content.
With high-purity titanium dioxide is raw material, with TiO
2Pre-formedly pass to electric current or be that reductive agent carries out deoxidation just earlier with metal and alloy; Final deoxygenation is carried out in electrolysis in fused electrolyte.
With TiO
2The pre-formed galvanic current that passes to carries out deoxidation just, or under the protection of inert gas or in the electrolyzer under the vacuum condition, with metal M g, Ca, Sr, Li, Na, K, Al, CaC, CaH
2, a kind of in single rare earth or the mishmetal or their reductive agent that is combined as carry out deoxidation just.
The product of deoxidation just carries out final deoxygenation in the electrolysis of ice crystal ground mass; Or the titanium of first deoxidation is pre-formed, in the electrolytic process of metallic aluminium, metallic zinc, metallic lead, basic metal, alkaline-earth metal, rare earth metal and metal titanium, link to each other as negative electrode or with negative electrode, finish final deoxygenation as electrolytic byproduct, the preparation metal titanium.
With titanium tetrachloride and titanium dichloride is raw material, electrolysis under 600～1200 ℃ condition, the form that adopts catholyte and anolyte to separate, before electrolysis begins, cover liquid metal or alloy in advance on the surface of negative electrode, and in electrolytic process, add low-melting metal and alloy, absorb electrolytic metal titanium, direct production titanium base master alloy in electrolyzer, utilize vacuum distilling, electrorefining, zone melting, density difference, electrolysis-original position smelting process, vacuum consumable smelting method or physical method, chemical process and electrochemical method are isolated other metal or alloy, prepare metal titanium or prepare the higher titanium base master alloy of other metal content.
Add low-melting metal and alloy in the electrolytic process, and the liquid metal and the alloy that cover liquid state on the charcoal negative electrode have: the single metal or alloy of zinc, strontium, lead, tin, rare earth, aluminum silicon alloy, Sn-Al alloy, manganese or copper base, or in electrolytic process, cover the single metal or alloy of zinc, strontium, aluminium, tin, manganese and copper base in the container of splendid attire metal titanium, in the process of preparation titanium, form liquid titanium base alloy with metal titanium, after treating that liquid titanium alloy in the electrolyzer reaches finite concentration, take out liquid titanium base alloy from electrolyzer, this method is convenient to continuous production.
Ionogen in the electrolyzer is mainly sodium aluminum fluoride, fluotitanate, silicofluoride, sodium phosphate, Sodium Tetraborate, fluorochemical [BaF
2, CaF
2, SrF
2, MgF
2, AlF
3, REF
3(single or blended rare earth fluoride), ZnF
4, TiF
4, LiF, NaF, KF] and mouthful muriate (CaCl
2, MgCl
2, BaCl
2, SrCl
2, NaCl, KCl, LiCl, AlCl
3, RECl
3(single or blended rare earth fluoride), TiCl
4), Li
2One or more compositions such as O (or Quilonum Retard), CaO.
The structure of electrolyzer can adopt the structure of the parallel placement of anode and cathode; Also can adopt the vertical structure of placing of anode and cathode; Also can adopt the dual-electrode electrolysis groove; Alternating oxidation and reduction for avoiding titanium ion cause low-down current efficiency, can adopt anode and cathode electrolytic solution separated structures; The side-wall material of electrolyzer adopts SiC, SiC in conjunction with Si
3N
4, graphite or stupalith.
Advantage and effect:
The present invention's preparation metal titanium can reduce the production cost of metal titanium, shortened process greatly.With TiO
2Be the feedstock production metal titanium,, can produce huge economic benefit, but the also consumption of labor savings is raised labour efficiency making the production of metal titanium be transformed into environmental type by contamination type.
Description of drawings:
Accompanying drawing 1 is the structural representation of electrolyzer 1 of the present invention;
Accompanying drawing 2 is the structural representation of electrolyzer 2 of the present invention;
Accompanying drawing 3 is the structural representation of electrolyzer 3 of the present invention;
Accompanying drawing 4 is the structural representation of electrolyzer 4 of the present invention;
Accompanying drawing 5 is the structural representation of electrolyzer 5 of the present invention;
Accompanying drawing 6 is the structural representation of electrolyzer 6 of the present invention.
Embodiment:
The present invention will be further described in conjunction with the accompanying drawings below by embodiment:
The present invention is a raw material with titanium dioxide, titanium tetrachloride, titanium dichloride and fluotitanate mainly, prepares the method for metal titanium or titanium base alloy, is specially by electrolysis or thermal reduction-electrolysis integrated process:
(1) electrolytic process:
(a) this method is mainly with titanium dioxide (TiO
2) or titanium tetrachloride (TiCl
4) or one or more of fluotitanate be raw material;
(b) in aluminium cell, basic metal, alkaline-earth metal electrolyzer, (mainly adopt aluminium cell here), if with Al
2O
3And TiO
2When going out for the raw material eutectoid, adopt heavy ionogen, be that electrolytical density is greater than metallic aluminium and less than metal titanium, make on the metallic aluminium that produces in the electrolytic process or other the light metal and float to electrolytical surface, sink in the electrolyzer under the metal titanium and make, impel metallic aluminium in the electrolyzer etc. to separate with metal titanium; If not with Al
2O
3And TiO
2When going out, can adopt electrolytic aluminum ionogen commonly used or heavy ionogen for the raw material eutectoid.
(c) negative electrode adopts metallic cathode or adopts the single metal or alloy that covers liquid zinc, strontium, aluminium, silicon, lead, tin, rare earth or copper base on the charcoal negative electrode, in electrolyzer, form liquid titanium base alloy with metal titanium in the process of preparation titanium, directly prepare titanium base alloy, or from titanium alloy, separate other metal, prepare metal titanium.
(2) thermal reduction-electrolysis integrated process:
This method is with titanium dioxide (TiO
2) be raw material; Adopting electrolysis or its alloy of metal is that reductive agent is to TiO
2Carry out deoxidation just, then in electrolyzer to the product electrolysis of first deoxidation, or it is the titanium of first deoxidation is pre-formed, in the electrolytic process of basic metal, alkaline-earth metal, rare earth metal, metallic zinc, metallic lead, metallic aluminium and metal titanium as negative electrode (or link to each other with negative electrode), finish final deoxygenation as electrolytic byproduct, the preparation metal titanium.
(3) titanium tetrachloride (TiCl
4) and titanium dichloride (TiCl
2) electrolytic process
This method is with titanium tetrachloride (TiCl
4) or titanium dichloride (TiCl
2) be ionogen, in 600-1200 ℃ temperature range, the form that adopts catholyte and anolyte to separate, cathode surface covers the single metal or alloy of liquid Zn, strontium, lead, tin, rare earth or copper base, preparation metal titanium and titanium base alloy adopt the method for vacuum distilling or electrorefining to prepare metal titanium then.
Example 1 (Al and Ti codeposition are produced the Zn-Ti alloy):
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below; The 2nd, metallic rod, the double anode rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, the corundum liner; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, zinc titanium alloy liquid.
Black patch below the metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.The effect of plumbago crucible 6 is splendid attire electrolytic solution double as graphite cathodes, and the ionogen in the electrolytic solution 7 is mainly the sodium aluminum fluoride of 30-70wt%, the TiO of 1～5wt%
2, the CaF of 10～15wt%
2, the BaF of 17～45wt%
2And other ionogen of 2～5wt%, other ionogen comprises lithium fluoride, magnesium fluoride, sodium-chlor or the like.In the electrolytic process, added a certain amount of Al in the clockwise electrolytic solution every 20 minutes
2O
3And TiO
2, to replenish the Al in the electrolyzer
2O
3And TiO
2Consume, and in electrolytic process, in electrolyzer, add zinc granule.Before electrolysis begins, in electrolyzer, add industrial-purity zinc in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, the purity that improves metal titanium, makes the form formation liquid cathode of the metal titanium of electrolysis and thermal reduction generation with the Ti-Zn alloy, prevents the bottom of electrolytic tank crust simultaneously.Be added with corundum liner 5 in the electrolyzer, the corundum liner plays insulating effect, thereby increases current density, helps the gathering of metal titanium.Electrolysis finishes the back and forms zinc titanium alloy liquid 8, and just required Zn-Ti alloy liquid (titaniferous amount 10-30wt%) takes out Zn-Ti alloy liquid from electrolyzer, carry out the vacuum distilling dezincify, just can prepare metal titanium.Electrolysis byproduct metallic aluminium swims in bath surface.The electrolytic process cathode current density is 0.3～2.0A/cm
2, interpole gap is 25-45mm, and bath voltage is 2.8-6.5V, and electrolysis temperature is 640～900 ℃.
Reaction in the electrolyzer can be summarized as: 2Al
2O
3=4Al+3O
2(electrolysis).
TiO
2=O
2+ Ti (electrolysis)
4Al+3TiO
2＝3Ti+2Al
2O
3
Example 2 (Al and Ti codeposition are produced metal titanium)
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below; The 2nd, metallic rod, the double anode rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, SiC is ceramic-lined; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, metal titanium.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.Plumbago crucible 6 effects are splendid attire electrolytic solution double as negative electrodes, and the ionogen in the electrolytic solution 7 is mainly 48%AlF
3, 18%NaF, 18%BaF
2, 16%CaF
2In the electrolytic process, added a certain amount of Al in the clockwise electrolytic solution every 20 minutes
2O
3And TiO
2, to replenish the Al in the electrolyzer
2O
3And TiO
2Consume.
Negative electrode is vertical with anode to be placed in the electrolyzer, is added with corundum liner 5 in the electrolyzer, ceramic-lined 5 insulating effects of SiC, thus increase current density, help the gathering of metal titanium.Forming metal titanium 8 after the electrolysis is exactly required product.Electrolysis byproduct metallic aluminium swims in bath surface.The electrolysis cathode current density is 0.3～2.0A/cm
2, interpole gap is 30-45mm, and bath voltage is 2.8-4.5V, and electrolysis temperature is 680～980 ℃.
Reaction in the electrolyzer can be summarized as: 2Al
2O
3=4Al+3O
2(electrolysis).
TiO
2=O
2+ Ti (electrolysis)
4Ai+3TiO
2＝3Ti+2Al
2O
3
Test result shows: electrolytic process is steady, and Ti content can reach 99.1wt% in the metal alloy.
Example 3 (electrolysis TiO
2Produce metal titanium)
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below, the double cathode collector bar of doing; The 2nd, metallic rod, the double anode rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, insulated liner; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, metal titanium.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.Plumbago crucible 6 effects are splendid attire electrolytic solution double as graphite cathodes, and the ionogen in the electrolytic solution 7 is mainly 48%AlF
3, 18%NaF, 18%BaF
2, 16%CaF
2[or 95-99wt%CaCl
2+ (1-5wt%) CaO].Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2, to replenish the TiO in the electrolyzer
2Consume.
Be added with insulated liner 5 in the electrolyzer, 5 insulating effects of insulated liner, thus increase current density, help the gathering of metal titanium.Form metal titanium 8 after the electrolysis, from electrolyzer, take out metal titanium.The electrolysis cathode current density is 0.3～2.0A/cm
2, interpole gap is 35-45mm, and bath voltage is 2.8-4.5V, and electrolysis temperature is 600～1000 ℃.
Reaction in the electrolyzer can be summarized as: TiO
2=O
2+ Ti (electrolysis)
Test result shows: electrolytic process is steady, and Ti content can reach 99.0wt% in the metal alloy.
Example 4 (electrolysis TiO
2Production of copper-titanium alloy)
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below; The 2nd, metallic rod, the double anode rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, the corundum liner; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, copper-titanium alloy liquid.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.Plumbago crucible 6 effects are splendid attire electrolytic solution double as graphite cathodes, and the ionogen in the electrolytic solution 7 is mainly the sodium aluminum fluoride of 70-95wt%, the TiO of 1～5wt%
2, 2～5wt% CaF
2And other ionogen [or 95-99wt%CaCl of 2～20wt%
2+ (1-5wt%) CaO].In the electrolytic process, added a certain amount of TiO in the clockwise electrolytic solution every 20 minutes
2, to replenish the TiO in the electrolyzer
2Consume, and in electrolyzer, add a spot of metallic copper.In electrolyzer, add an amount of copper (or copper base alloy such as copper-titanium alloy, gunmetal, copper zinc alloy) in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, the purity double as negative electrode that improves metal titanium, make the form formation liquid cathode of the metal titanium of electrolysis generation, prevent the bottom of electrolytic tank crust simultaneously with the Ti-Cu alloy of liquid state.5 insulating effects of corundum liner, thus current density increased, help the gathering of metal titanium.Form Cu-Ti alloy liquid 8 (content of titanium is 20-70wt% in the alloy liquid) after the electrolysis, just required copper-titanium alloy liquid.Bath voltage in the electrolytic process is 2.8-8.5V, and cathode current density is 0.1～2.0A/cm
2, interpole gap is 25-45mm, electrolysis temperature is 800～1200 ℃.
Through electrorefining Cu-Ti alloy, just obtain metal titanium.Refining process is: in the molten salt system that NaCl-KCl (or the fluorochemical of other basic metal or alkaline-earth metal and muriate) forms, and the titanium generation electrochemical dissolution in the metal Cu-Ti anode, the anodic current density is less than 0.5A/cm
2, guarantee that titanium mainly enters fused salt with the divalence titanium ion, the low price titanium ion that is dissolved in fused salt discharges on negative electrode, is reduced into metal titanium.Impurity such as undissolved copper then remains in anode or is deposited on bottom of electrolytic tank in the anode, and is recyclable.
Example 5 (TiO
2Electrolysis production copper-titanium alloy)
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below; The 2nd, metallic rod, the double anode rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, SiC is in conjunction with Si
3N
4Liner; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, copper zinc titanium alloy liquid.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.Plumbago crucible 6 effects are splendid attire electrolytic solution double as graphite cathodes, and the ionogen in the electrolytic solution 7 is mainly (50-80wt%) NaCl-(20-50wt%) Na
4P
2O
7[or (50-80wt%) NaCl-(20-50wt%) K
2TiF
6Or (50-80wt%) NaCl-(20-50wt%) Na
2B
4O
7].Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2, to replenish the TiO in the electrolyzer
2Consume.In electrolyzer, add an amount of copper-30wt% zinc alloy in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, the purity double as negative electrode that improves metal titanium, make the form formation liquid cathode of the metal titanium of electrolysis generation, prevent the bottom of electrolytic tank crust simultaneously with the Cu-Zn-Ti alloy of liquid state.SiC is in conjunction with Si
3N
45 insulating effects of liner, thus current density increased, help the gathering of metal titanium.Form Cu-Zn-Ti alloy liquid 8 after the electrolysis, just required copper-titanium alloy, the massfraction of metal titanium is 20-70wt% in the alloy.Bath voltage is 2.8-8.5V, and cathode current density is 0.1～2.0A/cm
2, interpole gap is 25-45mm, electrolysis temperature is 800～1000 ℃.Through vacuum dezincification, preparation Cu-Zn-Ti (titaniferous amount 20-70wt%) alloy through electrorefining Cu-Ti alloy, just obtains metal titanium.
Example 6 (electrolysis TiO
2Production of copper-titanium alloy)
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below; The 2nd, metallic rod, the double anode utmost point guide rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, the corundum liner; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, copper-titanium alloy liquid.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.Plumbago crucible 6 effects are splendid attire electrolytic solution double as graphite cathodes, and the ionogen in the electrolytic solution 7 is mainly 95-99wt%CaCl
2+ (1-5wt%) CaO[or ionogen are 100%CaCl
2Or be the sodium aluminum fluoride of 70-95wt%, the TiO of 1～5wt%
2, 2～5wt% CaF
2And other ionogen of 2～20wt%].Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2And metallic copper.In electrolyzer, add an amount of copper-10wt% titanium (Ti) alloy in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, the purity double as negative electrode that improves metal titanium, make the form formation liquid cathode of the metal titanium of electrolysis generation, prevent the bottom of electrolytic tank crust simultaneously with the Ti-Cu alloy of liquid state.5 insulating effects of corundum liner, thus current density increased, help the gathering of metal titanium.Form Cu-Ti alloy liquid after the electrolysis, just required copper-titanium alloy liquid 8, the massfraction of metal titanium is 20-70wt% in the alloy.Bath voltage is 2.8-8.5V, and cathode current density is 0.1～2.0A/cm
2, interpole gap is 25-45mm, electrolysis temperature is 800～1200 ℃.The Al-Cu alloy of preparation through electrorefining, is removed metallic copper, just obtains metal titanium.
Example 7 (electrolysis TiO
2Produce tin-titanium master alloy)
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below; The 2nd, metallic rod, the double anode utmost point guide rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, the corundum liner; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, zinc-tin titanium alloy liquid.
The following black patch 4 of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.Plumbago crucible 6 effects are splendid attire electrolytic solution double as graphite cathodes, and the ionogen in the electrolytic solution 7 is mainly the sodium aluminum fluoride of 70-95wt%, the TiO of 1～5wt%
2, 2～5wt% CaF
2And other ionogen of 2～20wt%.Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2And red brass.In electrolyzer, add an amount of tin-zinc alloy (zinc content is 30-50wt%) in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, the purity double as negative electrode that improves metal titanium, make the form formation liquid cathode of the metal titanium of electrolysis generation, prevent the bottom of electrolytic tank crust simultaneously with the Ti-Cu alloy of liquid state.5 insulating effects of corundum liner, thus current density increased, help the gathering of metal titanium.For avoiding TiO
2Oxidizing metallic titanium using did not add TiO in electrolytic last 1 hour in electrolyzer
2, form Zn-Sn-Ti alloy liquid after the electrolysis through vacuum dezincification, prepare the Ti-Sn master alloy.
Example 8 (electrolysis TiO
2Produce tin-titanium alloy)
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below; The 2nd, metallic rod, the double anode rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, the corundum liner; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, tin titanium alloy liquid.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.Plumbago crucible 6 effects are splendid attire electrolytic solution double as graphite cathodes, and the ionogen in the electrolytic solution 7 is mainly the sodium aluminum fluoride of 30-70wt%, the TiO of 1～5wt%
2, the CaF of 10～15wt%
2, the BaF of 17～45wt%
2And other ionogen of 2～5wt%.Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2, to replenish the TiO in the electrolyzer
2Consume.In electrolyzer, add an amount of tin and tin-based alloy in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, the purity double as negative electrode that improves metal titanium, make the form formation liquid cathode of the metal titanium of electrolysis and thermal reduction generation, prevent the bottom of electrolytic tank crust simultaneously with the Ti-Sn alloy of liquid state.5 insulating effects of corundum liner, thus current density increased, help the gathering of metal titanium.Form tin titanium alloy liquid 8 after the electrolysis, just required Sn-Ti alloy liquid (titaniferous amount 10-30wt%).Extract metallic tin and just obtain metal titanium or tin titanium alloy.
In the electrolytic process, bath voltage is 2.8-4.5V, and cathode current density is 0.1～2.0A/cm
2, interpole gap is 25-45mm, electrolysis temperature is 700～1200 ℃.
Example 9 (electrolysis TiO
2The preparation metal titanium)
As shown in Figure 2, the 1st, anode rod is metallic crucible below; The 2nd, metallic rod, the double cathode collector bar of doing, the black patch below the metallic rod is a graphite cathode; The 3rd, process furnace; The 4th, ceramic crucible; The 5th, plumbago crucible, double as anode; The 6th, electrolytic solution; The 7th, metal titanium.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is negative electrode.Plumbago crucible 5 effects are splendid attire electrolytic solution double as graphite anodes, and the ionogen in the electrolytic solution 6 is mainly the sodium aluminum fluoride of 30-70wt%, the TiO of 1～5wt%
2, the CaF of 10～15wt%
2, the BaF of 17～45wt%
2And other ionogen of 2～5wt%, add the TiO that accounts for electrolyte weight 2～6% in the electrolyzer in advance
2Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2, to replenish the TiO in the electrolyzer
2Consume.Ceramic crucible 4 plays collects the metal titanium effect, and avoids the gas cyaniding metal titanium of crucible bottom.Just can prepare metal titanium 7 after the electrolysis.Cathode current density is 0.3～2.0A/cm
2, interpole gap is 25-45mm, electrolysis temperature is 700～1100 ℃.
Example 10 (electrolysis TiO
2Preparation metal titanium alloy)
As shown in Figure 2, the 1st, anode rod is metallic crucible below; The 2nd, metallic rod, the double cathode collector bar of doing, the black patch below the metallic rod is a graphite cathode; The 3rd, process furnace; The 4th, ceramic crucible; The 5th, plumbago crucible, double as anode; The 6th, electrolytic solution; The 7th, zinc titanium (copper titanium, tin titanium) alloy.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is negative electrode.Plumbago crucible 5 effects are splendid attire electrolytic solution double as graphite anodes, and the ionogen in the electrolytic solution 6 is mainly the sodium aluminum fluoride of 30-70wt%, the TiO of 1～5wt%
2, the CaF of 10～15wt%
2, the BaF of 17～45wt%
2And other ionogen [or 95-99wt%CaCl of 2～5wt%
2+ (1-5wt%) CaO].Add the TiO that accounts for electrolyte weight 2～6% in the electrolyzer in advance
2Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2, to replenish the TiO in the electrolyzer
2Consume.Behind the electrolyte melting, add the pure zinc of appropriate amount of industrial (or lead, copper, tin) in advance in crucible 4, purpose is to absorb the metal titanium that electrolysis and thermal reduction produce.Ceramic crucible 4 plays collects the metal titanium effect, and avoids the gas cyaniding metal titanium of crucible bottom.Form zinc titanium alloy liquid 7 after the electrolysis, just required Zn-Ti (or plumbous titanium, copper titanium, tin titanium) alloy liquid, Zn-Ti (or plumbous titanium, copper titanium, tin titanium) alloy liquid is taken out from electrolyzer, carry out vacuum dezincification (or remove other metal), just can prepare metal titanium by other method.In the electrolytic process, cathode current density is 0.3～2.0A/cm
2, interpole gap is 25-45mm, electrolysis temperature is 700～1200 ℃.
Example 11 (electrolysis TiO
2Preparation lead-zinc-titanium ternary alloy)
As shown in Figure 2, the 1st, metallic crucible, the double anode rod of doing; The 2nd, metallic rod, the double cathode collector bar of doing, the black patch below the metallic rod is a graphite cathode; The 3rd, process furnace; The 4th, ceramic crucible; The 5th, plumbago crucible double as anode; The 6th, electrolytic solution; The 7th, lead-zinc-titanium alloy.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is negative electrode.Plumbago crucible 5 effects are splendid attire electrolytic solution double as graphite anodes, and the ionogen in the electrolytic solution 6 is mainly the sodium aluminum fluoride of 30-70wt%, the TiO of 1～5wt%
2, the CaF of 10～15wt%
2, the BaF of 17～45wt%
2And other ionogen [or 95-99wt%CaCl of 2～5wt%
2+ (1-5wt%) CaO], add the TiO that accounts for electrolyte weight 2～6% in the electrolyzer in advance
2Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2, to replenish the TiO in the electrolyzer
2Consume.Behind the electrolyte melting, add an amount of zinc-lead alloy in advance in crucible 4, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation.Ceramic crucible 4 plays splendid attire lead-zinc alloy and collects the metal titanium effect, and the gas cyaniding metal titanium of avoiding crucible bottom.Form zinc-lead-titanium alloy liquid 7 after the electrolysis, just required Pb-Zn-Ti (titaniferous amount 10-40wt%) alloy liquid takes out Pb-Zn-Ti alloy liquid from electrolyzer, carry out the vacuum distilling dezincify, takes off lead, just can prepare metal titanium.In the electrolytic process, cathode current density is 0.3～2.0A/cm
2, interpole gap is 25-45mm, electrolysis temperature is 800～900 ℃.
Example 12
As shown in Figure 3, the 1st, plumbago crucible, the double anode of doing; The 2nd, the outer steel shell of electric furnace; The 3rd, earthenware porcelain receptacle; The 4th, aluminum oxide powder; The 5th, electric furnace; The 6th, electrolytic solution; 7 metal titaniums; The 8th, negative electrode (comprising charcoal negative electrode, titanium negative electrode, stainless steel cathode, molybdenum negative electrode, tungsten cathode etc.) and protective tube, the 9th, anode rod.
Adopting high purity graphite crucible 1 in present method is anode, and double as is the effect of splendid attire electrolytic solution, the main sodium aluminum fluoride+CaF of the ionogen in the electrolytic solution 6
2(4mass%)+LiF (3mass%) [or 95-99wt%CaCl
2+ (1-5wt%) CaO].Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2(or fluotitanate or titanium tetrachloride) is to replenish the TiO in the electrolyzer
2(or fluotitanate or titanium tetrachloride) consumes.Negative electrode 8 (comprising graphite anode, titanium negative electrode, stainless steel cathode, molybdenum negative electrode and tungsten cathode), earthenware porcelain receptacle 3 play collects the metal titanium effect, and avoids the gas cyaniding metal titanium of crucible bottom, electrolysis to finish the back and take out earthenware porcelain receptacle 3, just can obtain metal titanium 7.Cathode current density is 0.1～2.0A/cm in the electrolytic process
2, interpole gap is 25-45mm, electrolysis temperature is 700～1000 ℃.
Example 13
As shown in Figure 4,1-graphite anode; 2-graphite (or Ti, Mo, W or stainless steel) negative electrode; The 3-plumbago crucible; The 4-Zn-Ti alloy; The 5-magnesia crucible; 6-pottery blue (or metallic blue or vitrified pipe); The 7-resistance furnace; The 8-catholyte; The 9-anolyte.
Adopting high purity graphite in present method is anode 1 and negative electrode 2.The effect of magnesia crucible 5 is splendid attire electrolytic solution and alloy liquid, the main effect of pottery blue 6 is that part is isolated negative electrode and anolyte, avoid high price titanyl compound and titanyl compound mixing at a low price, and prevent anodic gas secondary pollution metal titanium, improve current efficiency, play buffer action simultaneously, thereby increase current density, help the gathering of metal titanium.Ionogen is mainly the sodium aluminum fluoride of 30-70wt%, the TiO of 1～5wt%
2, the CaF of 10～15wt%
2, the BaF of 17～45wt%
2And other his ionogen [or 95-99wt%CaCl of 2～5wt%
2+ (1-5wt%) CaO].Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2And metallic zinc (or tin, copper).Before electrolysis begins, in electrolyzer, add the pure zinc of appropriate amount of industrial (or tin, copper) in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, the purity double as negative electrode that improves metal titanium, make the form formation liquid cathode of the metal titanium of electrolysis and thermal reduction generation, prevent the bottom of electrolytic tank crust simultaneously with Ti-Zn (or tin, copper etc.) alloy 4 of liquid state.Electrolysis finishes the back and forms titanium alloy liquid 4, and just required Ti-Zn (or tin, copper) alloy liquid takes out Ti-Zn (or tin, copper) alloy liquid from electrolyzer, carry out vacuum distilling dezincify (or electrorefining removes out other metal), just can prepare metal titanium.
Example 14
As shown in Figure 4,1-graphite anode; 2-graphite (or Ti, Mo, W or stainless steel) negative electrode; The 3-plumbago crucible; The 4-Sr-Ti alloy; The 5-corundum crucible; 6-pottery blue (or metallic blue or vitrified pipe); The 7-resistance furnace; The 8-catholyte; The 9-anolyte.
Present method is with TiCl
4Or TiCl
2Be starting material, adopting high purity graphite is anode 1 and negative electrode 2.The effect of corundum crucible 5 is splendid attire electrolytic solution and alloy liquid, the main effect of pottery blue 6 is that part is isolated catholyte 8 and anolyte 9, and prevent anodic gas secondary pollution metal titanium, avoid the muriate of high price titanium and the muriate mixing of titanium at a low price, improve current efficiency, play buffer action simultaneously, thereby increase current density, help the gathering of metal titanium.The ionogen main component is (10.0～90.0) wt%KCl-(10.0～90) wt%SrCl
2[or (10.0～90.0) wt%NaKCl-(10.0～90) wt%SrCl
2)].
Added a certain amount of TiCl every 20 minutes in the clockwise electrolytic solution
4And Preparation of Metallic Strontium.Before electrolysis begins, in electrolyzer, add an amount of pure Sr (strontium) in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, and with metal titanium and electrolytic solution isolation, improve the purity double as negative electrode of metal titanium, the metal titanium that electrolysis and thermal reduction are produced is deposited on the metal Sr bottom with liquid state.Ti-Sr alloy liquid 4 is taken out from electrolyzer, carry out the distillation of classification final vacuum and take off strontium, just can prepare metal titanium, also can obtain the high-purity strontium of byproduct.
The electrolysis cathode current density is 0.3～2.0A/cm
2, interpole gap is 25-45mm, and bath voltage is 2.8-9.5V, and electrolysis temperature is 770～1100 ℃.
Ionogen in this experiment can adopt NaCl-LiCl, NaCl-KCl, NaCl-CaCl
2, NaCl-BaCl
2, KCl-BaCl
2, KCl-CaCl
2, NaCl-KCl-SrCl
2, NaCl-CaCl
2-BaCl
2-SrCl
2Deng chloride system and fluorochloride composition density system less than Preparation of Metallic Strontium.
The metal that adds in advance in the electrolyzer in this experiment also can add Zn, Pb, Sn, Cu, low-melting single or mishmetal, or the alloy of above-mentioned metal composition etc.Ionogen can adopt NaCl-LiCl, NaCl-KCl, NaCl-CaCl
2, NaCl-BaCl
2, KCl-BaCl
2, KCl-CaCl
2, NaCl-KCl-SrCl
2, NaCl-CaCl
2-BaCl
2-SrCl
2System Deng chloride system and fluorochloride composition.
Example 15
As shown in Figure 5, the 1st, the pottery of the state of cooling blue (or metallic blue) and metal titanium (or titanium alloy); The 2nd, the galvanic protection pipe; The 3rd, slideway; The 4th, ionogen; The 5th, the pottery blue (or metallic blue) of electrolysis state; The 6th, graphite anode; The 7th, insulated liner, the 8th, the crucible of splendid attire metal titanium, the hybrid alloys of 9 Preparation of Metallic Strontium and metal titanium (top is Preparation of Metallic Strontium, and the bottom is a metal titanium).
The ionogen main component is (10.0～90.0) wt%KCl-(10.0～90.0) wt%SrCl
2[or (10.0～90.0) wt%NaKCl-(10.0～90) wt%SrCl
2)].
Added a certain amount of TiCl every 20 minutes in the clockwise electrolytic solution
4, to replenish TiCl in the electrolyzer
4Consumption.Before electrolysis begins, add an amount of pure Sr (strontium) in electrolyzer in advance, purpose is the metal titanium that absorbs electrolysis and thermal reduction generation, and metal titanium and electrolytic solution are isolated, improve the purity of metal titanium, make the metal titanium of generation be deposited on metal Sr bottom with liquid state.Ti-Sr alloy liquid is taken out from electrolyzer, carry out vacuum distilling and take off strontium, just can prepare metal titanium.
The electrolysis cathode current density is 0.3～2.0A/cm
2, interpole gap is 25-45mm, and bath voltage is 2.8-9.5V, and electrolysis temperature is 770～1100 ℃.
Example 16
This method in two steps
(a) deoxidation (metallic reducing part) just
With titanium dioxide (TiO
2) be raw material; With TiO
2The pre-formed direct current that passes to carries out deoxidation just, or with metal M g, Ca (or CaC, CaH
2), single metal such as Sr, single rare earth or mishmetal, Na, K, Al or its alloy be that reductive agent is to TiO
2Carry out in vacuum (or under helium, argon shield or in electrolyzer) deoxidation just, the oxygen level in the metal titanium of first deoxidation is less than 5wt%.
(b) final deoxygenation (electrolysis section)
Among Fig. 6,1-cathode collector bar, below are iron crucible; The 2-anode rod; The 3-thermopair; The 4-graphite anode; 5-corundum cover; 6-electrolytic solution; The 7-plumbago crucible; The metal titanium of 8-deoxidation just; The 9-resistance furnace
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.The effect of plumbago crucible 7 is splendid attire electrolytic solution double as negative electrodes, and the ionogen in the electrolytic solution 6 is mainly the CaF of sodium aluminum fluoride and 1.0～15wt%
2, the BaF of 17～45wt%
2And other ionogen of 2～5wt% (or ionogen is CaCl
2), treat that ionogen melts fully after, at the beginning of the metal titanium 8 of deoxidation put into ionogen, metal titanium 8 oxygen level of first deoxidation are higher, are placed on the TiO that helps in the sodium aluminum fluoride wherein
2Be fused to sodium aluminum fluoride and melt in the salt, feed electric current then and carry out deoxidation, the preparation metal titanium.
Example 17
(a) deoxidation (metallic reducing part) just
With titanium dioxide (TiO
2) be raw material; With TiO
2Pre-formedly pass to galvanic current or be that reductive agent is to TiO with single metals such as metal M g, Ca (or CaC, CaH2), Sr, single rare earth or mishmetal, Na, K, Al or its alloy
2Carry out in vacuum (or under helium, argon shield or in electrolyzer) deoxidation just.
As shown in Figure 3, the 1st, plumbago crucible, the double anode of doing; The 2nd, electric furnace; The 3rd, earthenware porcelain receptacle; The 4th, powdered carbon; The 5th, insulating material; The 6th, electrolytic solution; 7 metal-rare-earths; The 8th, the titanium negative electrode and the protective tube of deoxidation just, the 9th, anode rod.
Ionogen in the electrolytic solution 6 is mainly RECl
3-NaCl (KCl) (or RE
2O
3-REF
3), treat that ionogen melts fully after, at the beginning of the metal titanium 8 of deoxidation put into ionogen as cathode material, the electrolysis rare earth, in the process of electrolysis rare earth, the metal titanium negative electrode of first deoxidation carries out complete deoxidation, obtains the higher metal titanium of purity.
This method is being produced basic metal, and alkaline-earth metal is also tested in the electrolyzer of electrolytic metal lead, metallic zinc and metallic copper, and the purity of metal titanium can reach 99.0-99.9wt% after the deoxidation.
Example 18 (electrolysis TiO
2Production of copper-titanium alloy)
As shown in Figure 1, the 1st, cathode collector bar is metallic crucible below; The 2nd, metallic rod, the double anode utmost point guide rod of doing; The 3rd, process furnace; The 4th, graphite anode; The 5th, insulated liner; 6 plumbago crucibles; The 7th, electrolytic solution; The 8th, copper-titanium alloy liquid.
The following black patch of metallic rod 2 is a carbon anode, and adopting high purity graphite in present method is anode.Plumbago crucible 6 effects are splendid attire electrolytic solution double as graphite cathodes, and the ionogen in the electrolytic solution 7 is mainly 95-99wt%CaCl
2+ (1-5wt%) CaO (or ionogen is 100%CaCl
2).Added a certain amount of TiO every 20 minutes in the clockwise electrolytic solution
2, to replenish the TiO in the electrolyzer
2Consume.Adding titanium content in electrolyzer in advance is 10wt% copper-titanium (Ti) alloy.Forming titanium content after the electrolysis is the Cu-Ti alloy liquid 8 of 20-70wt%, just required copper-titanium alloy liquid.Bath voltage is 2.8-8.5V, and cathode current density is 0.1～2.0A/cm
2, interpole gap is 25-45mm, electrolysis temperature is 800～1200 ℃.After the content of titanium reaches 50-70wt% in the Al-Cu alloy of preparation, the transposing anode and cathode is carried out refining, graphite anode 4 during with electrolysis changes titanium negative electrode (or charcoal negative electrode into, stainless steel cathode, the molybdenum negative electrode, tungsten cathode etc.), carry out the refining decopper(ing), after the refining, metal titanium deposits on the titanium negative electrode (or other negative electrodes), metallic copper (metal titanium and other impurity that contain 10wt%) then is deposited on the bottom of electrolyzer with the form of liquid metal, the titanium negative electrode is taken out, be put into (or under vacuum condition) cooling in the rare gas element, be the pure metallic titanium of preparation after the cooling, electrode is changed Graphite Electrodes; Conversion anode and cathode is afterwards carried out round-robin electrolysis next time and refining.
Above-mentioned experiment, to titanium dioxide (comprising rutile-type, brookite type, Detitanium-ore-type and technical grade and high-purity titanium dioxide), fluotitanate (comprising potassium fluotitanate, titanium sodium fluoride, hydrofluotitanic acid lithium, hydrofluotitanic acid rubidium, hydrofluotitanic acid magnesium, hydrofluotitanic acid calcium, hydrofluotitanic acid strontium, hydrofluotitanic acid barium, hydrofluotitanic acid rare earth etc.) and titanium tetrachloride (TiCl
4) can obtain expected effect.
In embodiment 16,17, under protection of inert gas or under vacuum condition or in electrolyzer, with metal M g, Ca (CaC, CaH
2), single metal such as Sr, single rare earth or mishmetal, Li, Na, K, Al or their reductive agent that is combined as carry out deoxidation just.The product of deoxidation just carries out final deoxygenation in the electrolysis of ice crystal ground mass; Or the titanium of first deoxidation is pre-formed, in the electrolytic process of basic metal, alkaline-earth metal, rare earth metal and metal titanium,, finish final deoxygenation, the preparation metal titanium as electrolytic byproduct as negative electrode (or link to each other with negative electrode).
In the above embodiments, negative electrode can cover that Pure Silicon Metal, manganese, aluminum silicon alloy, Sn-Al alloy are prepared in the middle of the titanium silicon, titanium manganese master alloy, aluminium silicon titanium master alloy and aluminium tin titanium master alloy.Electrolysis temperature can change between 600～1800 ℃ according to the metal or alloy difference that adds.
The above embodiments, the ionogen in the electrolyzer are mainly sodium aluminum fluoride, fluotitanate, silicofluoride, sodium phosphate, Sodium Tetraborate, fluorochemical [BaF
2, CaF
2, SrF
2, MgF
2, AlF
3, REF
3(single or blended rare earth fluoride), ZnF
4, TiF
4, LiF, NaF, KF] and muriate (CaCl
2, MgCl
2, BaCl
2, SrCl
2, NaCl, KCl, LiCl, AlCi
3, RECl
3(single or blended rare earth fluoride), TiCl
4), Li
2One or more compositions such as O (or Quilonum Retard), CaO can be implemented the technical program.
The structure of electrolyzer can adopt the parallel displacement structure of anode and cathode; Also can adopt the vertical displacement structure of anode and cathode; Also can adopt the dual-electrode electrolysis groove; Alternating oxidation and reduction for avoiding titanium ion cause low-down current efficiency, can adopt anode and cathode electrolytic solution separated structures; The side-wall material of electrolyzer adopts SiC or SiC in conjunction with Si
3N
4Or materials such as graphite or pottery.
Extraction to metal titanium and alloy thereof, utilize vacuum distilling, electrorefining, zone melting, density difference or other physical method, chemical process and electrochemical method to isolate other metal or alloy, prepare metal titanium or prepare the higher titanium base master alloy of other metal content.
The crucible that holds metal titanium and other metal can be ceramic crucible, metallic crucible and plumbago crucible, and the bottom of metallic crucible and plumbago crucible places insulation layer in case the crucible conduction.
Claims (10)
1, a kind of method for preparing metal titanium and titanium base alloy, it is characterized in that: this method is a raw material with titanium dioxide, titanium tetrachloride, titanium dichloride and fluotitanate, by electrolysis or thermal reduction-electrolysis integrated process, ionogen wherein is mainly sodium aluminum fluoride, fluotitanate, silicofluoride, sodium phosphate, Sodium Tetraborate, fluorochemical, muriate, Li
2One or more compositions among O, Quilonum Retard, the CaO, anode adopts carbon anode, negative electrode adopts a kind of solid state cathode in charcoal negative electrode, titanium negative electrode, stainless steel cathode, molybdenum negative electrode, the tungsten cathode, electrolysis under 600～1800 ℃ condition, at cathode surface or hold and cover liquid metal in the container of metal in advance and absorb the metal titanium that electrolysis produces, direct production metal titanium or titanium base alloy in electrolyzer; Or other metal in the separation titanium base alloy prepares metal titanium.
2, the method for preparing metal titanium and titanium base alloy according to claim 1, it is characterized in that: with titanium dioxide, in titanium tetrachloride or the fluotitanate one or more are raw material, adopt heavy ionogen in aluminium cell or in the electrolyzer of basic metal or alkaline-earth metal, heavy electrolytical density is greater than metallic aluminium or basic metal or alkaline-earth metal, and less than metal titanium, make the basic metal or the alkaline-earth metal that produce in the electrolytic process float to heavy electrolytical upper surface, make sink under the metal titanium heavy electrolytical below, impel basic metal or alkaline-earth metal in the electrolyzer to separate with metal titanium, at cathode surface or hold and cover liquid metal in the container of metal in advance and absorb the metal titanium that electrolysis produces, direct production metal titanium or titanium base alloy, or other metal that separates in the titanium base alloy prepares metal titanium.
3, the method for preparing metal titanium and titanium base alloy according to claim 1, it is characterized in that: be raw material with titanium dioxide, directly electrolysis titanium dioxide prepares metal titanium in electrolyzer, place the metal titanium of liquid metal or alloy absorption electrolysis generation in advance at cathode surface, and in electrolytic process, in electrolyzer, add low-melting metal or alloy, direct production metal titanium or titanium base master alloy in electrolyzer, utilize vacuum distilling, electrorefining, zone melting, density difference, electrolysis-original position smelting process, vacuum consumable smelting method or physical method, chemical process and electrochemical method are isolated other metal or alloy, prepare metal titanium or prepare the higher titanium base master alloy of other metal content.
4, the method for preparing metal titanium and titanium base alloy according to claim 1, it is characterized in that: with high-purity titanium dioxide is raw material, with TiO
2Pre-formedly pass to electric current or be that reductive agent carries out deoxidation just earlier with metal and alloy; Final deoxygenation is carried out in electrolysis in fused electrolyte.
5, the method for preparing metal titanium and titanium base alloy according to claim 4 is characterized in that: with TiO
2The pre-formed galvanic current that passes to carries out deoxidation just, or under the protection of inert gas or in the electrolyzer under the vacuum condition, with metal M g, Ca, Sr, Li, Na, K, Al, CaC, CaH
2, a kind of in single rare earth or the mishmetal or their reductive agent that is combined as carry out deoxidation just.
6, the method for preparing metal titanium and titanium base alloy according to claim 4 is characterized in that: the product of first deoxidation carries out final deoxygenation in the electrolysis of ice crystal ground mass; Or the titanium of first deoxidation is pre-formed, in the electrolytic process of metallic aluminium, metallic zinc, metallic lead, basic metal, alkaline-earth metal, rare earth metal and metal titanium, link to each other as negative electrode or with negative electrode, finish final deoxygenation as electrolytic byproduct, the preparation metal titanium.
7, the method for preparing metal titanium and titanium base alloy according to claim 1, it is characterized in that: with titanium tetrachloride and titanium dichloride is raw material, electrolysis under 600～1200 ℃ condition, the form that adopts catholyte and anolyte to separate, before electrolysis begins, cover liquid metal or alloy in advance on the surface of negative electrode, and in electrolytic process, add low-melting metal and alloy, absorb electrolytic metal titanium, direct production titanium base master alloy in electrolyzer, utilize vacuum distilling, electrorefining, zone melting, density difference, electrolysis-original position smelting process, vacuum consumable smelting method or physical method, chemical process and electrochemical method are isolated other metal or alloy, prepare metal titanium or prepare the higher titanium base master alloy of other metal content.
8, according to claim 2,3,4, the 7 described methods that prepare metal titanium and titanium base alloy, it is characterized in that: add low-melting metal and alloy in the electrolytic process, and the liquid metal and the alloy that cover liquid state on the charcoal negative electrode have: zinc, strontium, plumbous, tin, rare earth, aluminum silicon alloy, Sn-Al alloy, the single metal or alloy of manganese or copper base, or in electrolytic process, cover zinc in the container of splendid attire metal titanium, strontium, aluminium, tin, the single metal or alloy of manganese and copper base, in the process of preparation titanium, form liquid titanium base alloy with metal titanium, after treating that liquid titanium alloy in the electrolyzer reaches finite concentration, take out liquid titanium base alloy from electrolyzer, this method is convenient to continuous production.
9, according to claim 2,3,4, the 7 described methods that prepare metal titanium and titanium base alloy, it is characterized in that: the ionogen in the electrolyzer is mainly sodium aluminum fluoride, fluotitanate, silicofluoride, sodium phosphate, Sodium Tetraborate, fluorochemical, ZnF
4, TiF
4, LiF, NaF, KF, muriate, Li
2One or more compositions among O, Quilonum Retard, the CaO; Fluorochemical wherein is BaF
2, CaF
2, SrF
2, MgF
2, AlF
3, REF
3Muriate wherein is CaCl
2, MgCl
2, BaCl
2, SrCl
2, NaCl, KCl, LiCl, AlCl
3, RECl
3, TiCl
4
10, according to claim 2,3,4, the 7 described methods that prepare metal titanium and titanium base alloy, it is characterized in that: the structure of electrolyzer can adopt the structure of the parallel placement of anode and cathode; Also can adopt the vertical structure of placing of anode and cathode; Also can adopt the dual-electrode electrolysis groove; Alternating oxidation and reduction for avoiding titanium ion cause low-down current efficiency, can adopt anode and cathode electrolytic solution separated structures; The side-wall material of electrolyzer adopts SiC, SiC in conjunction with Si
3N
4, graphite or stupalith.
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|---|---|---|---|---|
| CN101628337B (en) * | 2009-08-06 | 2011-05-11 | 昆明理工大学 | Method for preparing metallic titanium powder by reducing titanium dioxide with magnesium |
| CN102586629A (en) * | 2012-02-22 | 2012-07-18 | 深圳市新星轻合金材料股份有限公司 | Recycling preparation method for producing titanium sponge and co-producing potassium cryolite with potassium fluotitanate as intermediate raw material |
| CN103219068A (en) * | 2013-03-25 | 2013-07-24 | 扬州腾飞电缆电器材料有限公司 | Antiseptic and anti-oxidation aluminum foil and processing technique thereof |
| WO2013107110A1 (en) * | 2012-01-18 | 2013-07-25 | 深圳市新星轻合金材料股份有限公司 | Method using sodium fluorotitanate as raw material for preparing titanium sponge |
| CN103451681A (en) * | 2013-09-03 | 2013-12-18 | 广州有色金属研究院 | Method for extracting metal titanium |
| CN103484721A (en) * | 2013-09-12 | 2014-01-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing ferro-titanium |
| CN103834971A (en) * | 2012-11-23 | 2014-06-04 | 宁波创润新材料有限公司 | Electrode and molten salt electrolysis device |
| CN103882477A (en) * | 2012-12-21 | 2014-06-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Electrolyte and molten salt for preparing metal titanium, and metal titanium preparation method |
| CN105420762A (en) * | 2015-11-25 | 2016-03-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Electrolytic bath structure and molten salt electrolysis method |
| CN105624735A (en) * | 2016-03-29 | 2016-06-01 | 东北大学 | Preparing method for titanium tin alloy |
| CN106591888A (en) * | 2016-12-26 | 2017-04-26 | 宝纳资源控股(集团)有限公司 | Preparation method and device of low-valence titanium ion molten salt electrolyte |
| CN106894059A (en) * | 2017-04-12 | 2017-06-27 | 攀钢集团研究院有限公司 | Metallic titanium powder molten-salt electrolysis recovery method |
| CN106917114A (en) * | 2017-04-12 | 2017-07-04 | 攀钢集团研究院有限公司 | Metallic titanium powder molten-salt electrolysis retracting device |
| CN107130262A (en) * | 2017-05-02 | 2017-09-05 | 攀钢集团研究院有限公司 | Fused salt electrolysis process prepares the electrolytic medium additive of the ultra-pure titanium of target as sputter |
| CN107274944A (en) * | 2017-06-29 | 2017-10-20 | 中国科学院上海有机化学研究所 | A kind of two-part FLiNaK fused salts depth method of deoxidation |
| CN107475751A (en) * | 2017-09-22 | 2017-12-15 | 湖南金纯新材料有限公司 | A kind of device and method that pure titanium is prepared by the use of liquid alloy as electrode |
| CN107587168A (en) * | 2017-10-31 | 2018-01-16 | 成都先进金属材料产业技术研究院有限公司 | The method that molten-salt electrolysis prepares Titanium |
| CN108138343A (en) * | 2016-07-20 | 2018-06-08 | 忠南大学校产学协力团 | Utilize electroreduction and the method for refining metal of electrorefining process |
| CN109023431A (en) * | 2018-09-30 | 2018-12-18 | 成都先进金属材料产业技术研究院有限公司 | The method for preparing titanium-aluminium alloy |
| CN109055994A (en) * | 2018-09-26 | 2018-12-21 | 北京科技大学 | A kind of method of titanium-containing blast furnace slag serialization electrolytic preparation high purity titanium |
| CN109628960A (en) * | 2019-02-01 | 2019-04-16 | 孟静 | The device of aluminium alloy is prepared in situ in electrolysis |
| CN109706482A (en) * | 2017-10-26 | 2019-05-03 | 遵义市吉祥富康门窗有限公司 | A kind of preparation method of titanium-aluminium alloy |
| CN109825854A (en) * | 2019-03-26 | 2019-05-31 | 北京科技大学 | A kind of molten-salt electrolysis-high temperature distillation prepares the device and method of high-purity titanium |
| CN110199039A (en) * | 2016-10-21 | 2019-09-03 | 通用电气公司 | Titanium alloy material is manufactured by reduction titanium tetrachloride |
| CN110198798A (en) * | 2016-10-21 | 2019-09-03 | 通用电气公司 | Titanium alloy material is manufactured by reduction titanium tetrahalide |
| CN110199040A (en) * | 2016-10-21 | 2019-09-03 | 通用电气公司 | Titanium alloy material is manufactured by reduction titanium tetrachloride |
| CN110284158A (en) * | 2019-06-24 | 2019-09-27 | 北京科技大学 | A kind of method of liquid cathode electrolysis Ti-containing slag step separation titanium copper and titanium silicon |
| CN112246769A (en) * | 2020-10-13 | 2021-01-22 | 马俊保 | Equipment is dispeled to chinese-medicinal material washing impurity of exempting from |
| CN112941567A (en) * | 2018-07-10 | 2021-06-11 | 东北大学 | Electrochemical method and apparatus for high temperature molten salt electrolysis in humid atmosphere |
| CN114672850A (en) * | 2022-05-07 | 2022-06-28 | 华北理工大学 | Method for preparing metal titanium by separating titanium-aluminum alloy through molten salt electrolytic deoxidation |
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2008
- 2008-06-04 CN CNA2008100116820A patent/CN101289754A/en active Pending
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628337B (en) * | 2009-08-06 | 2011-05-11 | 昆明理工大学 | Method for preparing metallic titanium powder by reducing titanium dioxide with magnesium |
| WO2013107110A1 (en) * | 2012-01-18 | 2013-07-25 | 深圳市新星轻合金材料股份有限公司 | Method using sodium fluorotitanate as raw material for preparing titanium sponge |
| CN102586629A (en) * | 2012-02-22 | 2012-07-18 | 深圳市新星轻合金材料股份有限公司 | Recycling preparation method for producing titanium sponge and co-producing potassium cryolite with potassium fluotitanate as intermediate raw material |
| CN103834971A (en) * | 2012-11-23 | 2014-06-04 | 宁波创润新材料有限公司 | Electrode and molten salt electrolysis device |
| CN103882477A (en) * | 2012-12-21 | 2014-06-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Electrolyte and molten salt for preparing metal titanium, and metal titanium preparation method |
| CN103882477B (en) * | 2012-12-21 | 2016-12-28 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of electrolyte for preparing Titanium and fused salt and the preparation method of Titanium |
| CN103219068B (en) * | 2013-03-25 | 2017-11-14 | 扬州腾飞电缆电器材料有限公司 | The anti-oxidation aluminium foil of anti-corrosion and its processing technology |
| CN103219068A (en) * | 2013-03-25 | 2013-07-24 | 扬州腾飞电缆电器材料有限公司 | Antiseptic and anti-oxidation aluminum foil and processing technique thereof |
| CN103451681A (en) * | 2013-09-03 | 2013-12-18 | 广州有色金属研究院 | Method for extracting metal titanium |
| CN103451681B (en) * | 2013-09-03 | 2016-06-08 | 广州有色金属研究院 | The extracting method of a kind of metal titanium |
| CN103484721A (en) * | 2013-09-12 | 2014-01-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing ferro-titanium |
| CN105420762A (en) * | 2015-11-25 | 2016-03-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Electrolytic bath structure and molten salt electrolysis method |
| CN105420762B (en) * | 2015-11-25 | 2018-11-16 | 成都先进金属材料产业技术研究院有限公司 | Cell construction and molten salt electrolysis method |
| CN105624735A (en) * | 2016-03-29 | 2016-06-01 | 东北大学 | Preparing method for titanium tin alloy |
| CN108138343A (en) * | 2016-07-20 | 2018-06-08 | 忠南大学校产学协力团 | Utilize electroreduction and the method for refining metal of electrorefining process |
| CN108138343B (en) * | 2016-07-20 | 2021-04-23 | 济隆科技有限公司 | Metal refining method using electrolytic reduction and electrolytic refining process |
| CN110199039A (en) * | 2016-10-21 | 2019-09-03 | 通用电气公司 | Titanium alloy material is manufactured by reduction titanium tetrachloride |
| CN110199039B (en) * | 2016-10-21 | 2022-10-04 | 通用电气公司 | Titanium alloy material production by reduction of titanium tetrachloride |
| CN110198798A (en) * | 2016-10-21 | 2019-09-03 | 通用电气公司 | Titanium alloy material is manufactured by reduction titanium tetrahalide |
| US11193185B2 (en) | 2016-10-21 | 2021-12-07 | General Electric Company | Producing titanium alloy materials through reduction of titanium tetrachloride |
| CN110199040A (en) * | 2016-10-21 | 2019-09-03 | 通用电气公司 | Titanium alloy material is manufactured by reduction titanium tetrachloride |
| CN106591888A (en) * | 2016-12-26 | 2017-04-26 | 宝纳资源控股(集团)有限公司 | Preparation method and device of low-valence titanium ion molten salt electrolyte |
| CN106917114A (en) * | 2017-04-12 | 2017-07-04 | 攀钢集团研究院有限公司 | Metallic titanium powder molten-salt electrolysis retracting device |
| CN106894059A (en) * | 2017-04-12 | 2017-06-27 | 攀钢集团研究院有限公司 | Metallic titanium powder molten-salt electrolysis recovery method |
| CN107130262A (en) * | 2017-05-02 | 2017-09-05 | 攀钢集团研究院有限公司 | Fused salt electrolysis process prepares the electrolytic medium additive of the ultra-pure titanium of target as sputter |
| CN107274944A (en) * | 2017-06-29 | 2017-10-20 | 中国科学院上海有机化学研究所 | A kind of two-part FLiNaK fused salts depth method of deoxidation |
| CN107475751A (en) * | 2017-09-22 | 2017-12-15 | 湖南金纯新材料有限公司 | A kind of device and method that pure titanium is prepared by the use of liquid alloy as electrode |
| CN109706482A (en) * | 2017-10-26 | 2019-05-03 | 遵义市吉祥富康门窗有限公司 | A kind of preparation method of titanium-aluminium alloy |
| CN107587168A (en) * | 2017-10-31 | 2018-01-16 | 成都先进金属材料产业技术研究院有限公司 | The method that molten-salt electrolysis prepares Titanium |
| CN112941567B (en) * | 2018-07-10 | 2024-02-23 | 东北大学 | Electrochemical method and device for high-temperature molten salt electrolysis in humid atmosphere |
| CN112941567A (en) * | 2018-07-10 | 2021-06-11 | 东北大学 | Electrochemical method and apparatus for high temperature molten salt electrolysis in humid atmosphere |
| CN109055994A (en) * | 2018-09-26 | 2018-12-21 | 北京科技大学 | A kind of method of titanium-containing blast furnace slag serialization electrolytic preparation high purity titanium |
| US20210340685A1 (en) * | 2018-09-30 | 2021-11-04 | Chengdu Advanced Metal Material Industrial Technology Research Institute Co., Ltd. | Method for preparing a titanium-aluminum alloy |
| CN109023431A (en) * | 2018-09-30 | 2018-12-18 | 成都先进金属材料产业技术研究院有限公司 | The method for preparing titanium-aluminium alloy |
| CN109628960B (en) * | 2019-02-01 | 2020-05-08 | 广西鲁板铝合金模板有限公司 | Device for preparing aluminum alloy in situ by electrolysis |
| CN109628960A (en) * | 2019-02-01 | 2019-04-16 | 孟静 | The device of aluminium alloy is prepared in situ in electrolysis |
| CN109825854A (en) * | 2019-03-26 | 2019-05-31 | 北京科技大学 | A kind of molten-salt electrolysis-high temperature distillation prepares the device and method of high-purity titanium |
| CN110284158A (en) * | 2019-06-24 | 2019-09-27 | 北京科技大学 | A kind of method of liquid cathode electrolysis Ti-containing slag step separation titanium copper and titanium silicon |
| CN112246769A (en) * | 2020-10-13 | 2021-01-22 | 马俊保 | Equipment is dispeled to chinese-medicinal material washing impurity of exempting from |
| CN114672850A (en) * | 2022-05-07 | 2022-06-28 | 华北理工大学 | Method for preparing metal titanium by separating titanium-aluminum alloy through molten salt electrolytic deoxidation |
| CN114672850B (en) * | 2022-05-07 | 2023-08-29 | 华北理工大学 | Method for preparing metallic titanium by separating titanium-aluminum alloy through molten salt electrolytic deoxidation |
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