CN109439902A - A kind of method that calcium original position distillation-deoxidation prepares high purity titanium - Google Patents
A kind of method that calcium original position distillation-deoxidation prepares high purity titanium Download PDFInfo
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- CN109439902A CN109439902A CN201811569164.0A CN201811569164A CN109439902A CN 109439902 A CN109439902 A CN 109439902A CN 201811569164 A CN201811569164 A CN 201811569164A CN 109439902 A CN109439902 A CN 109439902A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
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Abstract
The invention discloses the methods that a kind of calcium original position distillation-deoxidation for belonging to metal smelt technical field prepares high purity titanium.This method is that material system A, calcium reduction agent separation are placed in closed reaction vessel, it heats in an inert atmosphere, calcium is entered in material system A in fused salt in calcium reduction agent with the dissolution of high-purity calcium gas form, realizes to titanium material deoxidation, the high purity titanium of oxygen content≤0.10wt% is made；The material system A is the mixture of titanium material and anhydrous calcium chloride, and one or both of alkali halide, alkaline-earth halide are contained or not contain in material system A, and the titanium material is Titanium or titanium oxide；The calcium reduction agent is calcium metal or calcium alloy；The separated region placed that separates is mutually isolated simultaneously gas phase connection.The method of the present invention is simple and easy, good to the removal effect of oxygen, nitrogen, can satisfy the requirement in the fields such as aerospace, defence and military.
Description
Technical field
The invention belongs to metal smelt technical field, in particular to a kind of calcium original position distillation-deoxidation prepares the side of high purity titanium
Method.
Background technique
Titanium has many advantages, such as that density is small, intensity is high, nonmagnetic, corrosion-resistant, easy processing molding, becomes and rises abruptly after iron, aluminium
Rise " third metal ", therefore someone foretell 21 century by be titanium century.Titanium alloy is now widely used for aerospace, state
The fields such as anti-military project, chemical industry metallurgical, sea water desalination, biological medicine.The U.S., Russian two countries be whole world research titanium history it is longer,
Strongest country, always based on aerospace market, civilian industry is relatively fewer for titanium application, and China is then different, non-
Aerospace market accounts for about 90%, and aerospace market accounts for about 10%.In recent years, grew as Chinese comprehensive strength continues to develop, in aviation
The research and development in the fields such as space flight, military project and manufacture investment continue to increase, this just needs the quality of titanium to propose more in these fields
Harsh requirement.
The chemical activity of Titanium is very high to have very strong affinity to gaseous impurity especially oxygen, and therefore, titanium is in smelting
In refining, the processing especially hot and cold processing and welding process of titanium, oxygen is very easy to enter in titanium, causes titanium physical and chemical performance
Decline.Although iodate purifying technique can effectively remove the oxygen in titanium, that there are metal recovery rates is low, processing capacity is small,
Energy consumption is high, can not apply to the problems such as molded titanium.Therefore, find it is a kind of can effectively remove oxygen in Titanium it is simple,
Economic method is of great significance to the production and application of titanium and its alloy.In recent years, had metallurgy, material worker at this
Aspect carried out positive exploration and trial, and had made some progress: Chinese patent 200610030744.3 disclose titanium or
The method of titanium alloy melting liquid deoxidizing.This method is using rare earth element as cleanser, in a vacuum in frequency furnace, will by La, Ce, Nd, Pr,
Calmness 15 in titanium melt~be poured available hypoxemia after twenty minutes and contain is added at 1650~1720 DEG C in the cleanser of Y composition
The titanium or titanium alloy of amount.The maximum feature of this method is that refinement crystalline substance can also be played while removing Oxygen in Titanium Alloy using rare earth
Grain improves the effect of mechanical property；But the rare earth oxide and molten titanium generated in the technology coexists, and casting can after calmness
Rare earth oxide can be still suffered to be mixed in titanium, cause deoxidation effect unstable, be not suitable for the preparation of high purity titanium.
Chinese patent 201410843972.7 discloses the preparation method of Ultra Low-oxygen titanium valve.This method is in alumina crucible
The oxygen in titanium valve is eliminated using HDH method.The characteristics of this method is that hydrogen atom is able to enter metal inside for oxygen with H2O
Form take out of, can be to avoid the pollution in material preparation process using alumina crucible, the use when titanium valve is come out of the stove and is dispensed
Argon gas is protected from the secondary oxidation of titanium valve.But this method is suitble to the deoxidation of metal powder or sponge grease, if being used for titanium
Deoxidation material in hydrogenation and certain embodiments, which can become fragile, to be cracked, to cause the destruction of material.
Chinese patent 201110262991.7 discloses a kind of method of ferro-titanium deoxygenation refining.This method uses fused salt
The method of electrolysis is electrolyte at 600~850 DEG C using the villiaumite of alkali metal chloride and titanium using thick ferro-titanium as anode
Electrolysis.100ppm of the cathode product after the ferro-titanium oxygen content that washing obtains can be reduced to electrolysis by 5% before being electrolysed
Below.Although low energy consumption for this method, the removal effect of oxygen is good, electrolytic process Anodic dissolves, therefore this method is uncomfortable
Deoxidation for titanium.
In addition, using calcium to Titanium deoxidation when, to avoid the impurity in calcium in Titanium deoxidation process to Titanium
The pollution of bring impurity, conventional method is first to distill calcium metal, obtain silicon, oxygen, nitrogen content qualification high-purity calcium, then with high-purity
Calcium is to Titanium deoxidation.The first problem of this technique is to be distilled high-purity calcium of acquisition in packaging, storage, transport, high
Pure calcium can because absorb the oxygen in environment, nitrogen, water and introduce nitrogen, oxygen impurities, nitrogen, oxygen impurities can pollute titanium products；Second is asked
Topic is that the distillation of traditional handicraft and deoxidation are completed in two equipment respectively, and energy consumption is high.
Summary of the invention
The purpose of the present invention is to provide a kind of method that calcium original position distillation-deoxidation prepares high purity titanium, specific technical solutions
It is as follows:
A kind of method that calcium original position distillation-deoxidation prepares high purity titanium is to be placed in material system A, calcium reduction agent separation
It in closed reaction vessel, heats in an inert atmosphere, calcium enters material system A with the dissolution of high-purity calcium gas form in calcium reduction agent
In middle fused salt, the deoxidation to titanium material is realized, the high purity titanium of oxygen content≤0.10wt% is made；
The material system A is the mixture of titanium material and anhydrous calcium chloride, and alkali gold is contained or not contain in material system A
Belong to one or both of halide, alkaline-earth halide, the titanium material is Titanium or titanium oxide；The calcium reduction agent
For calcium metal or calcium alloy；
The separated region placed that separates is mutually isolated simultaneously gas phase connection.
Further, the titanium material is Titanium, and the oxygen content < 100ppm of high purity titanium is made.
Preferably, the closed reaction vessel includes Titanium crucible, stainless steel crucible, and the Titanium crucible is located at not
It becomes rusty in steel crucible, by the way that material system A to be placed in Titanium crucible, calcium reduction agent is placed in Titanium crucible and stainless steel crucible
Between gap in realize separate place.
The alkali halide, alkaline-earth halide are the salt that eutectic melt can be generated with calcium chloride；Preferably,
The alkali halide is potassium chloride.
The anhydrous calcium chloride is obtained by the way that calcium chloride to be dehydrated to 12~36h at 300~600 DEG C.
The titanium material is other special-shaped components or the powder such as bulk, plate, silk material, tubing, bar, band；The gold
Category calcium is high-purity calcium, distillation calcium, industrial calcium, and the calcium alloy is calcium silicon, calloy.
The calcium metal or calcium alloy are preferably clast, powder.
The mass ratio of titanium material and anhydrous calcium chloride is 1:5~1:40 in the material system A, it is to be understood that this
Titanium material should be able to be completely covered after anhydrous calcium chloride fusing in invention material system A.
The calcium reduction agent additional amount using the quality of calcium in calcium reduction agent as reaction temperature under calcium in anhydrous calcium chloride fused salt
Subject to 0.5~5 times of saturation solubility.
The additional amount of the alkali halide or alkaline-earth halide is the 50%~90% of anhydrous calcium chloride quality.
The reaction temperature is 700~1300 DEG C, and the reaction time is 12~120h；It is understood that in the present invention
Reaction temperature should be higher than that salt fusing point in reaction system, melt salt, and calcium in calcium reduction agent can be made to distil to form high-purity calcium gas.
After the completion of the deoxidation, raw material titanium is cleaned: first washing removal kish calcium, the salt (chlorination being added in raw material
Calcium, alkali halide or alkaline-earth halide), mixed acid surface clean 1~15 time of 0.5~10M is reused, then distinguish
With deionized water, ethyl alcohol and acetone surface clean 1~15 time；Wherein mixed acid is by two or more in hydrofluoric acid, nitric acid, hydrochloric acid
The mixed acid of composition.
The calcium original position distillation-deoxidation prepare the method for high purity titanium specifically includes the following steps:
(1) material filling: material system A, calcium reduction agent separation are placed in reaction vessel, sealed reaction vessel；
(2) it distills deoxidation: sealing reactor is packed into stainless-steel vacuum tank, vacuumize, logical inert gas, heating reaction
Container enters calcium in calcium reduction agent in material system A in fused salt with the dissolution of high-purity calcium gas form, realizes to titanium material deoxidation；
After reaction, cooled to room temperature；
(3) disassembly, cleaning: take out deoxidation after titanium material, washing removal kish calcium, salt, and carry out surface clean,
The high purity titanium of oxygen content≤0.10wt% is made in drying.
In the method for the present invention, calcium reduction agent calcium is by distillation, and dissolution enters anhydrous calcium chloride in the form of the high-purity calcium of gaseous state
In fused salt, to realize the deoxidation to titanium material.
The invention has the benefit that
(1) compared with traditional calcium distillation-high-purity calcium method of deoxidation, the present invention is by the distilation of calcium and titanium material
Calcium deoxidation merges in the same reaction vessel, effectively prevents high-purity calcium packaging, transport, packaging dismounting, dress in conventional method
To the pollution of high-purity calcium in furnace deoxidation process, while reducing the costs such as energy consumption；The present invention is by calcium reduction agent and is deoxidized titanium
Raw material is kept apart, and it is reducing agent that cheap industrial calcium, which can be used directly, and calcium melts and generate steam, steam at the reaction temperatures
Pressure can reach 102~1790Pa, and then high-purity calcium steam dissolution enters calcium chloride fused salt and reaches saturation, in the process,
The impurity such as silicon, oxygen, nitrogen in calcium reduction agent are not distilled and are stayed in calcium reduction agent, and pollution will not be brought to titanium material；Calcium saturation
Fused salt the deoxygenation of titanium occurs again at the reaction temperatures, due to calcium be it is excessive, calcium vapour pressure maintains always instead
Equilibrium vapor pressure at a temperature of answering, the activity of calcium can achieve maximum value in fused salt, be conducive to the removing of oxygen in raw material titanium；
(2) medium invention introduces anhydrous calcium chloride fused salt as calcium dissolution and deoxidation, firstly, fused calcium chloride pair
Reacting reducing agent calcium has preferable solubility, guarantees that there are activity adequately and uniformly metal calcium reductions on the surface of titanium material
Agent, while fused calcium chloride can reduce calcium oxide activity to reaction product calcium oxide solubility with higher, be conducive to depth
Remove the oxygen in titanium material；Secondly, titanium material is totally submerged by fused salt, one layer of buffer area itself can be used as, isolation is external
Pollution of the residual impurity to titanium material；The reaction of third, fused salt and titanium material belongs to liquid-solid reaction, and the uniformity of reaction is preferable,
Suitable for the deoxidation of other special-shaped components such as all kinds of titanium plate materials, wire rod, bulk, the direct-reduction deoxidation of titanium oxide is applied also for,
And the smelting and processing technology of existing titanium material (Titanium, titanium oxide) can be connected, had a wide range of application；
(3) although the method for the present invention uses technical grade calcium metal or calcium alloy, but actually occurs deoxidation
It is high-purity calcium by distillation, thus can effectively avoids pollution of the various impurity to titanium in industrial calcium using the method for the present invention,
Avoiding the calcium oxide on calcium metal surface from entering fused salt causes calcium oxide activity to rise, and reduces while guaranteeing deoxidation effect de-
The cost of oxygen；
(4) the method for the present invention is simple and easy, good to the removal effect of oxygen, nitrogen, and at low cost, a step can prepare high purity titanium,
It is long, at high cost to solve the problems, such as that existing deoxy technology oxygen content is difficult to reach titanium sponge standard, process flow；It is prepared by the present invention
Oxygen content≤0.10wt% in high purity titanium, wherein using Titanium as oxygen content < 100ppm in high purity titanium made from titanium material, most
Low oxygen content < 50ppm, reaches the level of iodide process purification, and the use that can satisfy the fields such as aerospace, defence and military is wanted
It asks.
Detailed description of the invention
Attached drawing 1 is the reaction vessel schematic diagram that calcium original position distillation-deoxidation prepares high purity titanium in the specific embodiment of the invention；
Label declaration: 1- anhydrous calcium chloride；2- titanium material；3- calcium reduction agent；4- Titanium crucible；5- stainless steel crucible；
6- elevated-temperature seal washer.
Specific embodiment
The present invention provides a kind of methods that calcium original position distillation-deoxidation prepares high purity titanium, below with reference to embodiment and attached drawing
The present invention is described further.
Embodiment 1
1 piece of metallic titanium plate, quality 15g, oxygen content 850ppm is taken, (CaCl is pressed2): m (Ti)=40:1 weighs anhydrous chlorination
Calcium 600g (is dehydrated 36h at 600 DEG C using preceding), and weighing high-purity calcium bits 60g, (at 1300 DEG C, calcium is full in anhydrous calcium chloride fused salt
With 0.5 times of solubility), Titanium and anhydrous calcium chloride are filled in titanium crucible, high-purity calcium bits are filled in titanium crucible and height
The gap location of temperature alloy crucible, it is then that high temperature alloy crucible is intact using elevated-temperature seal washer sealing, specifically such as 1 institute of attached drawing
Show.
The crucible being sealed is put into the high-temperature alloy vacuum tank of resistance stove heating, is evacuated to after covering bell
0.2Pa is then washed with argon gas.Under protection of argon gas, 5 DEG C/min is heated to 1300 DEG C, and keeps the temperature 12h at 1300 DEG C, protects
After temperature, it is furnace-cooled to room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out metal
Titanium；Mixing acid elution 15 times of the hydrofluoric acid of metallic titanium surface 0.5M, hydrochloric acid, then respectively with deionized water, ethyl alcohol, acetone punching
Wash surface 15 times, the Titanium then obtained by drying to oxygen content 85ppm.
Embodiment 2
1 piece of metallic titanium plate, quality 22g, oxygen content 840ppm is taken, (CaCl is pressed2): m (Ti)=20:1 weighs anhydrous chlorination
Calcium 440g (is dehydrated for 24 hours at 500 DEG C) using preceding, and weighing distillation calcium bits 176g, (at 1300 DEG C, calcium is full in anhydrous calcium chloride fused salt
With 2 times of solubility), Titanium and anhydrous calcium chloride are filled in titanium crucible, distillation calcium bits are filled in titanium crucible and high temperature
The gap location of alloy crucible, it is then that high temperature alloy crucible is intact using elevated-temperature seal washer sealing, it is specific as shown in Fig. 1.
The crucible being sealed is put into the high-temperature alloy vacuum tank of resistance stove heating, is evacuated to after covering bell
0.2Pa is then washed with argon gas.Under protection of argon gas, 5 DEG C/min is heated to 1300 DEG C, and keeps the temperature 12h at 1300 DEG C, protects
After temperature, it is furnace-cooled to room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out metal
Titanium；Mixing acid elution 6 times of the hydrofluoric acid of metallic titanium surface 4M, nitric acid, then deionized water, ethyl alcohol, acetone rinsing are used respectively
Surface 3 times, the Titanium then obtained by drying to oxygen content 55ppm, nitrogen content 15ppm, silicone content 10ppm.
Embodiment 3
Titanium silk 1, quality 15g, oxygen content 690ppm is taken, (CaCl is pressed2): m (Ti)=30:1 weighs anhydrous chlorination
Ca45 0g (is dehydrated 30h at 400 DEG C using preceding), and weighing industrial calcium bits 146g, (at 1000 DEG C, calcium is full in anhydrous calcium chloride fused salt
With 5 times of solubility), Titanium and anhydrous calcium chloride are filled in titanium crucible, industrial calcium bits are filled in titanium crucible and stainless
The gap location of steel crucible, it is then that stainless steel crucible is intact using elevated-temperature seal washer sealing, it is specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.4Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 1000 DEG C, and keeps the temperature 48h at 1000 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out Titanium；Metallic titanium surface
It is then dried with the hydrofluoric acid of 8M, mixing acid elution 4 times of hydrochloric acid, then respectively with deionized water, ethyl alcohol, acetone rinsing surface 6 times
It is dry to obtain oxygen content 42ppm, nitrogen content 21ppm, silicone content 11ppm Titanium.
Embodiment 4
1 piece of metallic titanium plate, quality 14g, oxygen content 660ppm is taken, (CaCl is pressed2): m (Ti)=40:1 weighs anhydrous chlorination
Calcium 560g (is dehydrated 36h at 300 DEG C using preceding), and weighing industrial calcium bits 145g, (at 900 DEG C, calcium is full in anhydrous calcium chloride fused salt
With 4 times of solubility), Titanium and anhydrous calcium chloride are filled in titanium crucible, industrial calcium bits are filled in titanium crucible and stainless
The gap location of steel crucible, it is then that stainless steel crucible is intact using elevated-temperature seal washer sealing, it is specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.1Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 900 DEG C, and keeps the temperature 64h at 900 DEG C, after heat preservation, is furnace-cooled to
Room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out Titanium.Metallic titanium surface is used
Mixing acid elution 1 time of the hydrofluoric acid of 10M, nitric acid, then then dried with deionized water, ethyl alcohol, acetone rinsing surface 4 times respectively
It is dry to obtain the Titanium of oxygen content 40ppm.
Embodiment 5
1 piece of Titanium block, quality 20g, oxygen content 910ppm is taken, (CaCl is pressed2): m (Ti)=25:1 weighs anhydrous chlorination
Calcium 500g (is dehydrated 36h at 300 DEG C using preceding), and weighing industrial calcium bits 37g, (at 1050 DEG C, calcium is full in anhydrous calcium chloride fused salt
With 1 times of solubility), Titanium and anhydrous calcium chloride are filled in titanium crucible, industrial calcium bits are filled in titanium crucible and stainless
The gap location of steel crucible, it is then that stainless steel crucible is intact using elevated-temperature seal washer sealing, it is specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.7Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 1050 DEG C, and keeps the temperature 28h at 1050 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out Titanium.Metallic titanium surface
With the hydrofluoric acid of 7M, mixing acid elution 4 times of hydrochloric acid, deionized water, ethyl alcohol, acetone rinsing surface 10 times are being used respectively, then
Titanium obtained by drying to oxygen content 44ppm.
Embodiment 6
Titanium silk 1, quality 18g, oxygen content 970ppm is taken, (CaCl is pressed2): m (Ti)=18:1 weighs anhydrous chlorination
Calcium 324g (is dehydrated 20h at 450 DEG C using preceding), weigh kalzium metal (calcium content 75wt%) 65g (at 1050 DEG C, anhydrous chlorine
2 times for changing calcium saturation solubility in calcium fused salt), Titanium and anhydrous calcium chloride are filled in titanium crucible, kalzium metal loads
It is then that stainless steel crucible is intact using elevated-temperature seal washer sealing in the gap location of titanium crucible and stainless steel crucible, specifically such as
Shown in attached drawing 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.8Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 1050 DEG C, and keeps the temperature 28h at 1050 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, the remaining kalzium metal of removal is washed with clear water and calcium chloride takes out Titanium.Titanium table
Mixing acid elution 10 times of the hydrofluoric acid of face 4M, nitric acid, then respectively with deionized water, ethyl alcohol, acetone rinsing surface 11 times, and
Titanium obtained by drying to oxygen content 50ppm afterwards.
Embodiment 7
1 piece of Titanium block, quality 22g, oxygen content 830ppm is taken, (CaCl is pressed2): m (Ti)=20:1 weighs anhydrous chlorination
Calcium 440g (is dehydrated 16h at 500 DEG C using preceding), weigh calcium-silicon (calcium content 42wt%) 194g (at 950 DEG C, anhydrous chlorine
3 times for changing calcium saturation solubility in calcium fused salt), Titanium and anhydrous calcium chloride are filled in titanium crucible, calcium-silicon loads
It is then that stainless steel crucible is intact using elevated-temperature seal washer sealing in the gap location of titanium crucible and stainless steel crucible, specifically such as
Shown in attached drawing 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.6Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 950 DEG C, and keeps the temperature 72h at 950 DEG C, after heat preservation, is furnace-cooled to
Room temperature.Crucible is opened after coming out of the stove, the remaining calcium-silicon of removal is washed with clear water and calcium chloride takes out Titanium.Metallic titanium surface
It is then dried with the hydrofluoric acid of 4M, mixing acid elution 8 times of nitric acid, then respectively with deionized water, ethyl alcohol, acetone rinsing surface 6 times
It is dry to obtain the Titanium of oxygen content 41ppm, nitrogen content 18ppm, silicone content 9ppm.
Embodiment 8
Titanium silk 1, quality 20g, oxygen content 920ppm is taken, (CaCl is pressed2): m (Ti)=30:1 weighs anhydrous chlorination
Calcium 600g (is dehydrated 36h at 500 DEG C using preceding), and is incorporated the potassium chloride of 50% anhydrous calcium chloride quality, weighs industrial calcium 96g
(at 800 DEG C, 4 times of calcium saturation solubility in anhydrous calcium chloride fused salt), Titanium, anhydrous calcium chloride and potassium chloride are filled in
In titanium crucible, industrial calcium bits are filled in the gap location of titanium crucible and stainless steel crucible, then that stainless steel crucible is close using high temperature
Seal washer sealing is intact, specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.6Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 800 DEG C, and keeps the temperature 86h at 800 DEG C, after heat preservation, is furnace-cooled to
Room temperature.Crucible is opened after coming out of the stove, washs removal residual metal calcium with clear water, potassium chloride calcium chloride takes out Titanium.Titanium
Deionized water, ethyl alcohol, acetone rinsing surface 11 times are being used in mixing acid elution 11 times of the hydrofluoric acid of surface 6M, hydrochloric acid respectively,
Titanium then obtained by drying to oxygen content 49ppm.
Embodiment 9
1 piece of metallic titanium plate, quality 25g, oxygen content 750ppm is taken, (CaCl is pressed2): m (Ti)=10:1 weighs anhydrous chlorination
Calcium 250g (is dehydrated for 24 hours at 300 DEG C) using preceding, and is incorporated the potassium chloride of 70% anhydrous calcium chloride quality, weighs industrial calcium 50g
(at 800 DEG C, 5 times of calcium saturation solubility in anhydrous calcium chloride fused salt), Titanium, anhydrous calcium chloride and potassium chloride are filled in
In titanium crucible, industrial calcium bits are filled in the gap location of titanium crucible and stainless steel crucible, then that stainless steel crucible is close using high temperature
Seal washer sealing is intact, specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.3Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 800 DEG C, and keeps the temperature 100h at 800 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, washs removal residual metal calcium with clear water, potassium chloride calcium chloride takes out Titanium.Metal
Deionized water, ethyl alcohol, acetone rinsing surface 8 times are being used in mixing acid elution 8 times of the hydrofluoric acid of titanium surface 4M, nitric acid respectively,
Titanium then obtained by drying to oxygen content 56ppm.
Embodiment 10
Titanium silk 1, quality 20g, oxygen content 830ppm is taken, (CaCl is pressed2): m (Ti)=30:1 weighs anhydrous chlorination
Calcium 600g (is dehydrated 16h at 500 DEG C using preceding), and is incorporated the potassium chloride of 90% anhydrous calcium chloride quality, weighs industrial calcium 48g
(at 700 DEG C, 5 times of calcium saturation solubility in anhydrous calcium chloride fused salt), Titanium, anhydrous calcium chloride and potassium chloride are filled in
In titanium crucible, industrial calcium bits are filled in the gap location of titanium crucible and stainless steel crucible, then stainless steel crucible will be utilized high temperature
Seal washer sealing is intact, specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.4Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 700 DEG C, and keeps the temperature 120h at 700 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, washs removal residual metal calcium with clear water, potassium chloride calcium chloride takes out Titanium.Metal
Deionized water, ethyl alcohol, acetone rinsing surface 10 are being used in mixing acid elution 9 times of the hydrofluoric acid of titanium surface 5M, hydrochloric acid respectively
Time, the Titanium then obtained by drying to oxygen content 46ppm.
Embodiment 11
Titanium dioxide powder 30g is weighed, (CaCl is pressed2): m (TiO2)=30:1 weigh anhydrous calcium chloride 900g (using it is preceding
Be dehydrated 12h at 600 DEG C), and be incorporated the potassium chloride of 60% anhydrous calcium chloride quality, weigh industrial calcium bits 109g (at 950 DEG C, nothing
2 times of calcium saturation solubility in water calcium chloride fused salt), titanium oxide, anhydrous calcium chloride and potassium chloride are filled in titanium crucible, work
Industry calcium considers the gap location for being filled in titanium crucible and stainless steel crucible to be worth doing, then that stainless steel crucible is complete using elevated-temperature seal washer sealing
It is good, it is specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.4Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 950 DEG C, and keeps the temperature 48h at 950 DEG C, after heat preservation, is furnace-cooled to
Room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium, calcium chloride, potassium chloride is washed with clear water and obtains metallic titanium powder.Metal
Deionized water, ethyl alcohol, acetone rinsing surface 4 times are being used in mixing acid elution 3 times of the hydrofluoric acid of titanium valve 0.5M, hydrochloric acid respectively,
Metallic titanium powder then obtained by drying to oxygen content 0.076wt%.
Claims (10)
1. a kind of method that calcium original position distillation-deoxidation prepares high purity titanium, which is characterized in that separate material system A, calcium reduction agent
It is placed in closed reaction vessel, heats in an inert atmosphere, calcium is dissolved in calcium reduction agent with high-purity calcium gas form enters original
In Material system A in fused salt, realizes to titanium material deoxidation, the high purity titanium of oxygen content≤0.10wt% is made；
The material system A is the mixture of titanium material and anhydrous calcium chloride, contains or not contain alkali metal halogen in material system A
One or both of compound, alkaline-earth halide, the titanium material are Titanium or titanium oxide；The calcium reduction agent is gold
Belong to calcium or calcium alloy；
The separated region placed that separates is mutually isolated simultaneously gas phase connection.
2. the oxygen that high purity titanium is made contains the method according to claim 1, wherein the titanium material is Titanium
Measure < 100ppm.
3. the method according to claim 1, wherein the closed reaction vessel include Titanium crucible, it is stainless
Steel crucible, the Titanium crucible are located in stainless steel crucible, by the way that material system A is placed in Titanium crucible, calcium reduction
Agent, which is placed in the gap between Titanium crucible and stainless steel crucible, realizes that separation is placed.
4. the method according to claim 1, wherein the alkali halide is potassium chloride.
5. the method according to claim 1, wherein the titanium material is bulk, plate, silk material, tubing, stick
Material, band or powder；The calcium metal is high-purity calcium, distillation calcium, industrial calcium, and the calcium alloy is calcium silicon, calloy.
6. the method according to claim 1, wherein titanium material and anhydrous calcium chloride in the material system A
Mass ratio be 1:5~1:40, the calcium reduction agent additional amount using the quality of calcium in calcium reduction agent as reaction temperature under anhydrous chlorination
In calcium fused salt subject to 0.5~5 times of calcium saturation solubility.
7. the method according to claim 1, wherein the alkali halide or alkaline-earth halide plus
Enter 50%~90% that amount is anhydrous calcium chloride quality.
8. the reaction time is the method according to claim 1, wherein the reaction temperature is 700~1300 DEG C
12~120h.
9. the method according to claim 1, wherein cleaning after the completion of the deoxidation to raw material titanium: first washing is gone
Except kish calcium, salt, reuse mixed acid surface clean 1~15 time of 0.5~10M, then respectively with deionized water, ethyl alcohol and
Acetone surface clean 1~15 time；Wherein mixed acid is by the mixed acid formed two or more in hydrofluoric acid, nitric acid, hydrochloric acid.
10. -9 described in any item methods according to claim 1, which comprises the following steps:
(1) material filling: material system A, calcium reduction agent separation are placed in reaction vessel, sealed reaction vessel；
(2) it distills deoxidation: sealing reactor is packed into stainless-steel vacuum tank, vacuumize, logical inert gas, heat reaction vessel
Enter calcium in calcium reduction agent in material system A in fused salt with the dissolution of high-purity calcium gas form, realizes to titanium material deoxidation；Reaction
After, cooled to room temperature；
(3) disassembly, cleaning: the titanium material after taking out deoxidation, washing removal kish calcium, salt, and surface clean, drying are carried out,
The high purity titanium of oxygen content≤0.10wt% is made.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110093515A (en) * | 2019-04-16 | 2019-08-06 | 北京科技大学 | A method of the brilliant directly distillation-melting of folder salt titanium prepares hypoxemia high purity titanium ingot |
| CN111118308A (en) * | 2019-12-24 | 2020-05-08 | 中南大学 | Method for directly preparing titanium alloy powder by using high-titanium slag |
| CN111558713A (en) * | 2020-06-24 | 2020-08-21 | 郑州大学 | Oxygen reduction method for small-particle-size titanium powder |
| CN111644610A (en) * | 2020-05-13 | 2020-09-11 | 西南科技大学 | Method for reducing oxygen content in titanium powder |
| CN112030008A (en) * | 2020-07-13 | 2020-12-04 | 昆明理工大学 | Method for preparing metallic titanium by reducing titanium dioxide |
| CN112095021A (en) * | 2020-01-21 | 2020-12-18 | 有研工程技术研究院有限公司 | Method for deeply removing oxygen in metal titanium by using super-oxophilic metal-calcium synergistic method |
| CN112828279A (en) * | 2020-12-31 | 2021-05-25 | 昆明理工大学 | Metal powder gas phase deoxidation method |
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| WO2022114377A1 (en) * | 2020-11-25 | 2022-06-02 | 주식회사 엘오티아이 | Titanium deoxidation method and deoxidation apparatus |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628337A (en) * | 2009-08-06 | 2010-01-20 | 昆明理工大学 | Method for preparing metallic titanium powder by reducing titanium dioxide with magnesium |
| CN101648275A (en) * | 2009-08-06 | 2010-02-17 | 昆明理工大学 | Method for preparing metal titanium powder by using calcium to reduce titanium dioxide |
| US20130125706A1 (en) * | 2011-11-18 | 2013-05-23 | Jae-Won Lim | Method for preparing titanium powder with low oxygen concentration |
| CN105316495A (en) * | 2014-07-15 | 2016-02-10 | 大连洲际新材料有限公司 | Novel technology for extracting titanium from titanium alloy for producing airplane |
-
2018
- 2018-12-21 CN CN201811569164.0A patent/CN109439902A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628337A (en) * | 2009-08-06 | 2010-01-20 | 昆明理工大学 | Method for preparing metallic titanium powder by reducing titanium dioxide with magnesium |
| CN101648275A (en) * | 2009-08-06 | 2010-02-17 | 昆明理工大学 | Method for preparing metal titanium powder by using calcium to reduce titanium dioxide |
| US20130125706A1 (en) * | 2011-11-18 | 2013-05-23 | Jae-Won Lim | Method for preparing titanium powder with low oxygen concentration |
| CN105316495A (en) * | 2014-07-15 | 2016-02-10 | 大连洲际新材料有限公司 | Novel technology for extracting titanium from titanium alloy for producing airplane |
Non-Patent Citations (1)
| Title |
|---|
| 万贺利等: ""钙蒸气还原二氧化钛制备金属钛粉扩大实验研究"", 《功能材料》 * |
Cited By (12)
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|---|---|---|---|---|
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| CN111118308A (en) * | 2019-12-24 | 2020-05-08 | 中南大学 | Method for directly preparing titanium alloy powder by using high-titanium slag |
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| CN111644610A (en) * | 2020-05-13 | 2020-09-11 | 西南科技大学 | Method for reducing oxygen content in titanium powder |
| CN111558713A (en) * | 2020-06-24 | 2020-08-21 | 郑州大学 | Oxygen reduction method for small-particle-size titanium powder |
| CN111558713B (en) * | 2020-06-24 | 2022-05-10 | 郑州大学 | Oxygen reduction method for small-particle-size titanium powder |
| CN112030008A (en) * | 2020-07-13 | 2020-12-04 | 昆明理工大学 | Method for preparing metallic titanium by reducing titanium dioxide |
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| WO2022114377A1 (en) * | 2020-11-25 | 2022-06-02 | 주식회사 엘오티아이 | Titanium deoxidation method and deoxidation apparatus |
| CN112828279A (en) * | 2020-12-31 | 2021-05-25 | 昆明理工大学 | Metal powder gas phase deoxidation method |
| CN112828279B (en) * | 2020-12-31 | 2022-08-12 | 昆明理工大学 | Metal powder gas phase deoxidation method |
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