CN112095021B - Method for removing oxygen in metal titanium in depth by using super-oxophilic metal-calcium synergy - Google Patents

Method for removing oxygen in metal titanium in depth by using super-oxophilic metal-calcium synergy Download PDF

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CN112095021B
CN112095021B CN202010071472.1A CN202010071472A CN112095021B CN 112095021 B CN112095021 B CN 112095021B CN 202010071472 A CN202010071472 A CN 202010071472A CN 112095021 B CN112095021 B CN 112095021B
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titanium
calcium
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oxygen
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CN112095021A (en
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王力军
马朝辉
闫国庆
张顺利
张建东
吴延科
齐申
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GRIMN Engineering Technology Research Institute Co Ltd
GRINM Resources and Environment Technology Co Ltd
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Abstract

The invention discloses a method for deeply removing oxygen in metal titanium by using an ultra-oxophilic metal-calcium synergistic method. The method comprises the steps of filling materials such as super-oxophilic metal, anhydrous calcium chloride, a titanium raw material, a calcium reducing agent and the like into a specific position of a reactor; by the distillation deoxidation and the disassembly cleaning, the oxygen content in the titanium can be stably reduced to less than 100 ppm. The super-oxygen-philic metal has strong oxygen affinity, and can dissolve oxygen in the calcium chloride molten salt into solid or form oxide so as to create extremely low oxygen potential and solve the thermodynamic problem of deep deoxidation; the calcium chloride molten salt has good fluidity and larger solubility to a calcium reducing agent and calcium oxide, and solves the dynamics problem of deoxidation. The invention realizes deep, efficient and stable removal of oxygen in the metal titanium by organically combining the two. The method is simple and easy to implement, has good oxygen removal effect, does not produce secondary pollution, and the product meets the use requirements in the fields of target material manufacturing, optical coating, electronic element manufacturing and the like.

Description

Method for removing oxygen in metal titanium in depth by using super-oxophilic metal-calcium synergy
Technical Field
The invention belongs to the technical field of metal smelting, and particularly relates to a method for deeply removing oxygen in metal titanium by using an ultra-oxophilic metal-calcium synergistic manner.
Background
Titanium has the advantages of small density, high strength, no magnetism, corrosion resistance, heat resistance, easy processing and molding, and the like, and becomes a 'third metal' rising after iron and aluminum, so that the 21 st century is predicted to be the titanium century. The physicochemical properties of metallic titanium are very sensitive to interstitial atoms in the metal, such as oxygen, carbon, nitrogen, etc. Because the nature of titanium has very strong affinity to these gaseous impurities, especially oxygen, titanium is very easy to deprive external oxygen during smelting and processing, and the purity of titanium is reduced. In particular, oxygen is very easy to enter titanium during cold and hot working and welding processes of titanium, thereby remarkably reducing the physical and chemical properties of the titanium. At present, the sponge titanium prepared by the Kroll method can be used for preparing high-purity titanium with the titanium purity of more than 99.995% and the oxygen content of less than 100ppm by adopting the processes of electrolytic refining, iodination purification, electron beam melting, zone melting and the like, but the processes have the problems of low metal yield, small processing capacity, high energy consumption, incapability of being applied to formed titanium materials and the like, so that the production cost of the high-purity titanium is high, and the application of the titanium is limited. However, the method for simply and effectively solving the problems is rarely reported in the existing patents and documents, so that the method for deeply removing oxygen in the metal titanium is found to be of great significance for improving the production yield of the titanium materials and expanding the application of the titanium and the titanium alloy in the top field.
In recent years, with the continuous exploration and trial in this respect by metallurgy and materials workers, a new method for deoxidizing solid metal titanium by using active metal such as metal Ca is gradually formed, and the progress is made as follows:
chinese patent CN201811569164.0 proposes a Ca-CaCl-based material2The calcium in-situ distillation-deoxidation method of the system. The method organically combines the purification and deoxidation of Ca, reduces the deoxidation cost while ensuring the deoxidation effect, and simultaneously introduces CaCl2The molten salt system reduces the activity of the deoxidation product on one hand and improves the uniformity of the deoxidation reaction on the other hand, so that the oxygen content of the titanium can be reduced to below 100ppm at the minimum. The method has the advantages of low equipment requirement, simple operation, low energy consumption and capability of deoxidizing the processed forming material, but has the defect that CaCl2The solubility of the deoxidized product CaO is limited, and CaCl is generated along with the deoxidation process2The activity of CaO in the molten salt is gradually increased to deoxidizeThe capability is gradually deteriorated, when the dissolution saturation is reached, the thermodynamic activity of CaO reaches a maximum value 1, the change is converted into Ca-CaO equilibrium deoxidation, and the deep deoxidation is not facilitated, so that the deoxidation effect of the method has fluctuation, and the method is suitable for the titanium raw material with lower initial oxygen content.
Through the analysis of the patents, the metal Ca is used for deoxidation, and the key for ensuring the deoxidation depth is to reduce the activity of CaO of a deoxidation product. According to the literature, it is reported that O in molten salt can be introduced by electrolysis technology2-Conversion to COxThereby controlling the activity of oxygen at a low level, but Cl is inevitably generated during electrolysis2And meanwhile, carbon pollution is caused, so that the application of the method is limited.
Therefore, it is desired to provide a method for reducing the activity of calcium oxide without generating other pollution, and realizing deep removal of oxygen.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a method for deeply removing oxygen in metallic titanium by using the cooperation of super-oxophilic metal and calcium, which further perfects the calcium deoxidation technology of the metallic titanium and solves the problems that the activity of calcium oxide is easily increased and the deoxidation effect is easily fluctuated in the existing calcium deoxidation technology.
In order to achieve the aim, the invention provides a method for deeply removing oxygen in metallic titanium by using an ultra-oxophilic metal-calcium synergistic method, which comprises the following steps:
1) filling materials: putting raw materials of super-oxophilic metal, anhydrous calcium chloride and titanium into a titanium crucible of a closed reaction container, adding a calcium reducing agent into a gap between the titanium crucible and a stainless steel crucible of the closed reaction container, and then sealing the closed reaction container;
2) and (3) distillation deoxidation: putting the sealed reaction container into a stainless steel vacuum tank, vacuumizing, introducing inert gas, heating the reaction container to 700-1100 ℃, reacting for 12-120 h, and naturally cooling to room temperature after the reaction is finished;
3) disassembling and cleaning: opening the stainless steel vacuum tank, taking out the sealed reaction container, opening the sealed reaction container, and taking out the titanium crucible; then washing with water to remove residual calcium reducing agent and anhydrous calcium chloride in the titanium crucible, taking out the deoxidized titanium raw material and the residual super-oxophilic metal, carrying out surface cleaning and drying on the deoxidized titanium raw material to obtain low-oxygen high-purity titanium, and carrying out surface cleaning and drying on the residual super-oxophilic metal for recycling;
the closed reaction vessel consists of a titanium crucible, a stainless steel crucible, a high-temperature sealing washer, a stainless steel sealing cover and a plurality of sealing bolts; the titanium crucible is placed in the stainless steel crucible, corresponding flanges are arranged at the edges of the stainless steel crucible and the stainless steel sealing cover, a high-temperature sealing gasket is clamped between the stainless steel crucible and the stainless steel sealing cover, and the sealing bolt penetrates through the stainless steel crucible and the corresponding flange at the edge of the stainless steel sealing cover to seal the closed reaction vessel;
wherein, the adding amount of the super-oxophilic metal is 2-120% of the mass of the titanium raw material; the mass ratio of the titanium raw material to the anhydrous calcium chloride is 1: 5-1: 40; the addition amount of the calcium reducing agent is 0.5-5 times of the saturated dissolution amount of calcium in the calcium chloride molten salt at the reaction temperature.
Preferably, the titanium raw material is metal titanium or titanium oxide, wherein the metal titanium is a block material, a plate material, a wire material, a pipe material, a bar material, a strip material, a powder material or a special-shaped member, and the titanium oxide is powder.
Preferably, the hyperoxophilic metal is a metal that is more oxophilic than calcium, preferably lutetium, holmium, erbium, yttrium, and more preferably yttrium.
Preferably, the form of the super-oxophilic metal is a block, plate, wire or sponge metal.
Preferably, one or two of alkali metal halide and alkaline earth metal halide are further added into the titanium crucible in the step 1); the addition amount of the alkali metal halide and the alkaline earth metal halide is 0 to 90 percent of the mass of the anhydrous calcium chloride, and the alkali metal halide is preferably potassium chloride.
Preferably, the calcium reducing agent is metallic calcium or calcium alloy, and the metallic calcium is high-purity calcium, distilled calcium or industrial calcium; the calcium alloy is calcium silicon alloy or calcium aluminum alloy.
Preferably, the inert gas is argon.
Preferably, the surface cleaning method in step 3) is as follows: washing with mixed acid containing 1M hydrofluoric acid and 1M nitric acid for 5 times, and washing the surface with deionized water, ethanol, and acetone for 5 times.
The anhydrous calcium chloride is obtained by dehydrating calcium chloride at 300-600 ℃ for 12-36 h.
The closed reaction container used in the invention keeps sealed during the reaction period, so that the atmosphere in the reaction container is not influenced by vacuumizing and introducing inert gas in the vacuum tank. The purpose of vacuumizing and introducing inert gas is to ensure that the outer surface of the closed reaction container is not oxidized at high temperature so as to prevent the deoxidation effect from being influenced by sealing failure caused by the oxidation of the outer surface. The internal atmosphere of the closed reaction container is controlled by adding substances such as metallic calcium reducing agent and super-oxophilic metal, which create an atmospheric oxygen partial pressure (up to 10)-40～10-45Pa) is much lower than the level (10) that can be achieved by a vacuum pump-3～10-4Pa) is added. The inside and outside of the closed reaction vessel need to be separated by a seal.
The invention provides a method for deeply removing oxygen in metal titanium by cooperation of oxophilic metal and calcium, which is characterized in that a titanium raw material, a calcium reducing agent, anhydrous calcium chloride and a super-oxophilic metal are coexisted in the same system of a closed container, the calcium reducing agent dissolved in the calcium chloride can firstly deoxidize the titanium raw material to form calcium oxide at a reaction temperature, the calcium oxide can be diffused to the surface of the more oxophilic super-oxophilic metal after being dissolved in the calcium chloride and is reduced to be metal calcium to continuously participate in the deoxidation reaction, and the oxygen is dissolved in solid solution by the super-oxophilic metal or forms an oxide, so that the oxygen activity in molten salt is reduced, and the deep deoxidation of the titanium raw material is realized. The method can obtain the low-oxygen high-purity titanium product with the oxygen content less than 100 ppm.
The super-oxophilic metal is a metal having a stronger oxygen affinity than calcium and can stably coexist with calcium and calcium chloride.
It will be appreciated that the molten salt system of the present invention should be able to completely cover the titanium feedstock after complete melting.
The reaction temperature in the invention is higher than the melting point of the salt in the reaction system, so that the salt is completely melted, and calcium in the reducing agent is sublimated to form high-purity calcium gas.
The invention has the beneficial effects that:
(1) the traditional calcium-calcium chloride system has good mass transfer and diffusion kinetic conditions at the reaction temperature, but because the solubility of calcium chloride to calcium oxide is limited, the deoxidation effect is easy to fluctuate, and the requirement on the initial oxygen content of the raw material is strict; the super-oxophilic metal and the corresponding chloride salt system thereof can create extremely low oxygen potential, but the chloride fused salt of the super-oxophilic metal generally has higher vapor pressure and is unstable at reaction temperature, and the speed of the metal dissolving into the fused salt is slow, which is not beneficial to improving the deoxidation efficiency. The invention organically combines the calcium chloride and the super-oxophilic metal to form a calcium-calcium chloride-super-oxophilic metal system, thereby making up the defects of the respective systems and exerting the respective advantages and advantages. When the super-oxophilic metal, the titanium raw material, the metallic calcium and the calcium chloride coexist in the same system, oxygen in the titanium raw material is transferred from the titanium raw material to the super-oxophilic metal according to the following path: titanium raw material → metallic calcium → calcium oxide → super oxophilic metal. In this process, calcium and calcium chloride actually play a role in oxygen transport and reaction efficiency improvement, while the super-oxophilic metal plays a role in storing oxygen and creating a very low oxygen potential.
(2) The super-oxygen-philic metals such as erbium and yttrium generally have strong nitrogen and carbon affinity and can absorb nitrogen and carbon in the molten salt. Therefore, when the super-oxophilic metal is added into the calcium chloride molten salt, the super-oxophilic metal can remove oxygen and absorb carbon and nitrogen impurities entering the calcium chloride molten salt through various ways (such as the titanium crucible is polluted by carbon and nitrogen), thereby avoiding the pollution of the titanium raw material by carbon and nitrogen to a certain extent.
(3) The method is simple and easy to implement, has good oxygen removal effect, does not generate secondary pollution, can stably control the oxygen content of the deoxidized titanium product to be less than 100ppm, and can meet the use requirements of the fields of target material manufacturing, optical coating, electronic component manufacturing and the like.
Drawings
FIG. 1 is a schematic diagram of a reaction vessel for deeply removing oxygen from metallic titanium by using the cooperation of super-oxophilic metal-calcium.
Reference numerals
1: anhydrous calcium chloride; 2: a super-oxophilic metal; 3: a calcium reducing agent; 4: a high temperature sealing gasket; 5: a titanium raw material; 6: a titanium crucible; 7: stainless steel crucible.
Detailed Description
The invention provides a method for deeply removing oxygen in metal titanium by using a super-oxophilic metal-calcium synergistic method, which is further described by combining the following embodiment and the accompanying drawings.
FIG. 1 is a schematic view of a reaction vessel for deeply removing oxygen from metallic titanium by using a synergistic effect of super-oxophilic metal and calcium, wherein a titanium crucible 6 is disposed inside a stainless steel crucible 7, the inside of the titanium crucible 6 is defined as region A, and the gap between the titanium crucible 6 and the stainless steel crucible 7 is defined as region B. Before reaction, a titanium raw material 5 and a super-oxophilic metal 2 are placed in an area A, anhydrous calcium chloride 1 (alkali metal halide or alkaline earth metal halide can also be added) is filled in the area B, a calcium reducing agent 3 is filled in the area B, a high-temperature sealing washer 4 is clamped between a stainless steel crucible 7 and the edge of a stainless steel sealing cover, and the stainless steel crucible is sealed by adopting a flange and sealing bolt mode to form a closed reaction container.
Example 1
Taking 15g of metal titanium strip, with an initial oxygen content of 1330ppm (CaCl)2): m (Ti) (. 5: 1) is added with 75g of anhydrous calcium chloride (dehydrated at 500 ℃ for 24h before use), 10g of industrial calcium scraps (2 times of the saturated solubility of calcium in the anhydrous calcium chloride molten salt at 900 ℃), 7.5g of high-purity sponge yttrium (50 percent of the mass of the titanium raw material), 22g of potassium chloride (30 percent of the mass of the anhydrous calcium chloride), metallic titanium strips, the anhydrous calcium chloride, potassium chloride and the high-purity sponge yttrium are filled in a titanium crucible, the industrial calcium scraps are filled in a gap between the titanium crucible and a stainless steel crucible, and then the stainless steel crucible is sealed well by a high-temperature sealing washer, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.04Pa, and washing with argon. Heating to 900 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 100 hours at 900 ℃, and cooling to room temperature after heat preservation. Opening the crucible after the crucible is taken out of the furnace, washing the crucible with clear water to remove residual metallic calcium and calcium chloride, and taking out metallic titanium and yttrium; washing the surface of the metal titanium belt for 5 times by using mixed acid of 1M hydrofluoric acid and nitric acid, washing the surface for 5 times by using deionized water, ethanol and acetone respectively, and drying to obtain the metal titanium belt with the oxygen content of 34 ppm.
Example 2
Taking 17g of metallic titanium block, the initial oxygen content is 1610ppm according to (CaCl)2): m (Ti) ═ 8:1, 136g of anhydrous calcium chloride (dehydrated at 500 ℃ for 24 hours before use), 8g of distilled calcium chips (calculated according to 1.5 times of the saturated solubility of calcium in the anhydrous calcium chloride molten salt at 800 ℃), 5g of high-purity yttrium blocks (30% of the mass of the titanium raw material), 81g of potassium chloride (60% of the mass of the anhydrous calcium chloride), metal titanium blocks, anhydrous calcium chloride, potassium chloride and high-purity yttrium blocks are filled in a titanium crucible, the distilled calcium chips are filled in the gap between the titanium crucible and a stainless steel crucible, and then the stainless steel crucible is sealed well by using a high-temperature sealing gasket, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.4Pa, and washing with argon. Heating to 700 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 120h at 700 ℃, and cooling to room temperature after heat preservation. Opening the crucible after the crucible is taken out of the furnace, washing the crucible with clear water to remove residual metallic calcium and calcium chloride, and taking out metallic titanium and yttrium; washing the surface of the metal titanium block for 5 times by using mixed acid of 1M hydrofluoric acid and nitric acid, washing the surface for 5 times by using deionized water, ethanol and acetone respectively, and drying to obtain the metal titanium block with the oxygen content of 34 ppm.
Example 3
32g of a metallic titanium rod was taken, and the initial oxygen content was 2100ppm in terms of (CaCl)2): (Ti): 20:1, 640g of anhydrous calcium chloride (dehydrated at 500 ℃ for 24h before use), 20.48g of high-purity calcium chips (0.5 time of the saturated solubility of calcium in the anhydrous calcium chloride molten salt at 1000 ℃), 0.6g of high-purity erbium plate (2 percent of the mass of the titanium raw material), and metal in the absence of potassium chlorideThe titanium rod, the anhydrous calcium chloride and the high-purity erbium plate are filled in the titanium crucible, the high-purity calcium chips are filled in the gap between the titanium crucible and the stainless steel crucible, and then the stainless steel crucible is well sealed by the high-temperature sealing washer, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.1Pa, and washing with argon. Heating to 1000 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 40h at 1000 ℃, and cooling to room temperature after heat preservation. Opening the crucible after the crucible is taken out of the furnace, washing the crucible with clear water to remove residual metallic calcium and calcium chloride, and taking out metallic titanium and erbium; washing the surface of the metal titanium rod for 5 times by using mixed acid of 1M hydrofluoric acid and nitric acid, washing the surface for 5 times by using deionized water, ethanol and acetone respectively, and drying to obtain the metal titanium rod with the oxygen content of 66 ppm.
Example 4
Taking 18g of a metal titanium plate, wherein the initial oxygen content is 1050ppm according to (CaCl)2): 720g of anhydrous calcium chloride (dehydrated at 500 ℃ for 24 hours before use), 648g of calcium-silicon alloy (3 times of the saturated solubility of calcium in the anhydrous calcium chloride molten salt at 1100 ℃), 18g of high-purity sponge erbium (100 percent of the mass of the titanium raw material), 144g of potassium chloride (20 percent of the mass of the anhydrous calcium chloride), metal titanium plates, the anhydrous calcium chloride, the potassium chloride and the high-purity sponge erbium are filled in a titanium crucible, the calcium-silicon alloy is filled in a gap between the titanium crucible and a stainless steel crucible, and the stainless steel crucible is well sealed by a high-temperature sealing washer, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.2Pa, and washing with argon. Heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat at 1100 ℃ for 12h, and cooling to room temperature after heat preservation. Opening the crucible after the crucible is taken out of the furnace, washing the crucible with clear water to remove residual calcium-silicon alloy and calcium chloride, and taking out metal titanium and erbium; washing the surface of the metal titanium plate with 1M hydrofluoric acid and nitric acid mixed acid for 5 times, washing the surface with deionized water, ethanol and acetone for 5 times respectively, and drying to obtain the metal titanium plate with the oxygen content of 85 ppm.
Example 5
Taking 10g of a metal titanium tube, wherein the initial oxygen content is 2500ppm (CaCl)2): m (Ti): 35:1, 350g of anhydrous calcium chloride (dehydrated at 500 ℃ for 24h before use), 61g of calcium-aluminum alloy (3.5 times of the saturated solubility of calcium in the anhydrous calcium chloride molten salt at 800 ℃), 8g of high-purity holmium wire (80 percent of the mass of the titanium raw material), 140g of potassium chloride (40 percent of the mass of the anhydrous calcium chloride), metal titanium tube, anhydrous calcium chloride, potassium chloride and high-purity holmium wire are filled in the titanium crucible, the calcium-aluminum alloy is filled in the gap between the titanium crucible and the stainless steel crucible, and then the stainless steel crucible is sealed by using a high-temperature sealing gasket, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.05Pa, and washing with argon. Heating to 800 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 100 hours at 800 ℃, and cooling to room temperature after heat preservation. After the crucible is taken out of the furnace, the crucible is opened, and the residual calcium-aluminum alloy and calcium chloride are removed by washing with clear water, so that the metal titanium and holmium are taken out; washing the surface of the metal titanium tube for 5 times by using mixed acid of 1M hydrofluoric acid and nitric acid, washing the surface for 5 times by using deionized water, ethanol and acetone respectively, and drying to obtain the metal titanium tube with the oxygen content of 82 ppm.
Example 6
Taking 11g of metal titanium wire, wherein the initial oxygen content is 2700ppm according to (CaCl)2): m (Ti) ═ 28:1, 308g of anhydrous calcium chloride (dehydrated at 500 ℃ for 24h before use), 125g of calcium-aluminum alloy (5 times of the saturated solubility of calcium in the anhydrous calcium chloride molten salt at 900 ℃), 13g of high-purity holmium sponge (120 percent of the mass of the titanium raw material), 231g of potassium chloride (75 percent of the mass of the anhydrous calcium chloride), metal titanium wires, the anhydrous calcium chloride, the potassium chloride and the pure holmium sponge are filled in a titanium crucible, the calcium-aluminum alloy is filled in the gap between the titanium crucible and a stainless steel crucible, and then the stainless steel crucible is sealed well by using a high-temperature sealing gasket, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.2Pa, and washing with argon. Heating to 900 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 80h at 900 ℃, and cooling to room temperature after heat preservation. After the crucible is taken out of the furnace, the crucible is opened, and the residual calcium-aluminum alloy and calcium chloride are removed by washing with clear water, so that the metal titanium and holmium are taken out; washing the surface of the metal titanium wire for 5 times by using mixed acid of 1M hydrofluoric acid and nitric acid, washing the surface for 5 times by using deionized water, ethanol and acetone respectively, and drying to obtain the metal titanium wire with the oxygen content of 34 ppm.
Example 7
Taking 15g of metal titanium powder, wherein the initial oxygen content is 4200ppm according to (CaCl)2): m (Ti): 16:1, 240g of anhydrous calcium chloride (dehydrated at 500 ℃ for 24h before use), 230g of calcium-silicon alloy (at 1000 ℃, 4.5 times of the saturated solubility of calcium in the anhydrous calcium chloride molten salt), 9g of high-purity lutetium plate (60 percent of the mass of the titanium raw material), 216g of potassium chloride (90 percent of the mass of the anhydrous calcium chloride), metal titanium powder, the anhydrous calcium chloride, the potassium chloride and the high-purity lutetium plate are filled in a titanium crucible, the calcium-silicon alloy is filled in a gap between the titanium crucible and a stainless steel crucible, and then the stainless steel crucible is sealed by a high-temperature sealing washer, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.8Pa, and washing with argon. Heating to 1000 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat at 1000 ℃ for 12h, and cooling to room temperature after heat preservation. Opening the crucible after the crucible is taken out of the furnace, washing the crucible with clear water to remove residual metal calcium and calcium chloride, and taking out metal titanium and lutetium; washing the surface of the metal titanium powder for 5 times by using mixed acid of 1M hydrofluoric acid and nitric acid, washing the surface for 5 times by using deionized water, ethanol and acetone respectively, and drying to obtain the metal titanium powder with the oxygen content of 88 ppm.
Example 8
Taking 15g of special-shaped metal titanium, wherein the initial oxygen content is 950ppm according to (CaCl)2): m (Ti) 26:1 is added with 390g of anhydrous calcium chloride (dehydrated for 24h at 500 ℃ before use), 100g of industrial calcium scrap (4 times of the saturated solubility of calcium in the anhydrous calcium chloride molten salt at 1000 ℃) is added, 10g of high-purity lutetium sponge (70 percent of the mass of the titanium raw material) is added, the titanium crucible is filled with the special-shaped metal titanium, the anhydrous calcium chloride and the high-purity lutetium sponge without potassium chloride, and the titanium crucible is filled with the industrial calcium scrapAnd a stainless steel crucible, and then the stainless steel crucible is well sealed by a high-temperature sealing washer, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.4Pa, and washing with argon. Heating to 1000 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 60 hours at 1000 ℃, and cooling to room temperature after heat preservation. Opening the crucible after the crucible is taken out of the furnace, washing the crucible with clear water to remove residual metal calcium and calcium chloride, and taking out metal titanium and lutetium; washing the surface of the special-shaped metal titanium for 5 times by using mixed acid of 1M hydrofluoric acid and nitric acid, washing the surface for 5 times by using deionized water, ethanol and acetone respectively, and drying to obtain the special-shaped metal titanium with the oxygen content of 56 ppm.
Example 9
Taking 20g of titanium oxide according to the formula (CaCl)2): m (Ti) ═ 30:1, 600g of anhydrous calcium chloride (dehydrated at 500 ℃ for 24 hours before use), 97g of distilled calcium chips (2.5 times of the saturated solubility of calcium in the anhydrous calcium chloride molten salt at 900 ℃), 18g of high-purity yttrium sponge (90% of the mass of the titanium raw material), 30g of potassium chloride (5% of the mass of the anhydrous calcium chloride), titanium oxide, anhydrous calcium chloride, potassium chloride and high-purity yttrium sponge are filled in a titanium crucible, the distilled calcium chips are filled in the gap between the titanium crucible and a stainless steel crucible, and then the stainless steel crucible is well sealed by a high-temperature sealing gasket, as shown in figure 1.
And (3) putting the sealed crucible into a vacuum tank heated by a resistance furnace, covering a furnace cover, vacuumizing to 0.1Pa, and washing with argon. Heating to 900 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 48 hours at 900 ℃, and cooling to room temperature after heat preservation. Opening the crucible after the crucible is taken out of the furnace, washing the crucible with clear water to remove residual metallic calcium and calcium chloride, and taking out metallic titanium and yttrium; washing the surface of the metal titanium powder for 5 times by using mixed acid of 1M hydrofluoric acid and nitric acid, washing the surface for 5 times by using deionized water, ethanol and acetone respectively, and drying to obtain the metal titanium powder with the oxygen content of 72 ppm.
As can be seen from the above examples, the method provided by the present invention can not only reduce the oxygen content in the metallic titanium to less than 100ppm, but also reduce the titanium oxide to the metallic titanium with the oxygen content less than 100 ppm. This demonstrates that the present invention is not only suitable for deoxidizing metallic titanium at a variety of starting oxygen contents, but also for reducing titanium oxide to metallic titanium and removing its oxygen to less than 100 ppm. Therefore, the method provided by the invention can be suitable for deep deoxidation of metal titanium (including titanium oxide) with any oxygen content, and the use amount of the super-oxophilic metal is only required to be increased at the initial reaction of the titanium raw material with high oxygen content, so that the application range of the titanium raw material is widened, and the deoxidized high-purity titanium can better meet the requirements of electronic components and optical coating industries requiring the oxygen content to be less than 100 ppm.
The method for deeply removing oxygen in metal titanium by using the super-oxophilic metal-calcium synergistic effect provided by the invention utilizes the extremely strong oxygen affinity of the super-oxophilic metals such as lutetium, holmium, erbium and yttrium and the good diffusion and mass transfer conditions of a metal calcium-calcium chloride molten salt system in synergistic effect, thereby realizing deep, efficient and stable removal of oxygen in metal titanium. When a titanium raw material to be deoxidized, a super-oxophilic metal, metallic calcium and anhydrous calcium chloride coexist in the same system, an oxygen diffusion channel is formed according to the direction of oxygen potential reduction: titanium raw material → metallic calcium → calcium oxide → super oxophilic metal. In the process, because the calcium chloride molten salt has good fluidity and larger solubility to calcium and calcium oxide, the calcium and the calcium chloride actually play a role of a transmission medium of oxygen, and the dynamics problem of deoxidation is solved; the super-oxophilic metal can capture and reduce calcium oxide in the molten salt, and oxygen is dissolved or formed into oxide, so that an extremely low oxygen potential is created, and the thermodynamic problem of deoxidation is solved. By organically combining the two, the problem that the deoxidation effect of the traditional calcium-calcium chloride system is unstable when the initial oxygen content of the titanium raw material is higher is solved, and the problems of high vapor pressure, slow dissolution rate and the like of a chloride salt system corresponding to the super-oxophilic metal are solved, so that the oxygen content in the titanium can be stably reduced to less than 100 ppm. The method provided by the invention is simple and easy to implement, has good oxygen removal effect, does not generate secondary pollution, and the product meets the use requirements in the fields of target material manufacturing, optical coating, electronic element manufacturing and the like.

Claims (6)

1. A method for removing oxygen in metal titanium in a synergistic and deep manner by using super-oxophilic metal-calcium is characterized by comprising the following steps:
1) filling materials: putting raw materials of super-oxophilic metal, anhydrous calcium chloride and titanium into a titanium crucible of a closed reaction container, adding a calcium reducing agent into a gap between the titanium crucible and a stainless steel crucible of the closed reaction container, and then sealing the closed reaction container;
2) and (3) distillation deoxidation: putting the sealed reaction container into a stainless steel vacuum tank, vacuumizing, introducing inert gas, heating the reaction container to 700-1100 ℃, reacting for 12-120 h, and naturally cooling to room temperature after the reaction is finished;
3) disassembling and cleaning: opening the stainless steel vacuum tank, taking out the sealed reaction container, opening the sealed reaction container, and taking out the titanium crucible; then washing with water to remove residual calcium reducing agent and anhydrous calcium chloride in the titanium crucible, taking out the deoxidized titanium raw material and the residual super-oxophilic metal, carrying out surface cleaning and drying on the deoxidized titanium raw material to obtain low-oxygen high-purity titanium, and carrying out surface cleaning and drying on the residual super-oxophilic metal for recycling;
the closed reaction vessel consists of a titanium crucible, a stainless steel crucible, a high-temperature sealing washer, a stainless steel sealing cover and a plurality of sealing bolts; the titanium crucible is placed in the stainless steel crucible, corresponding flanges are arranged at the edges of the stainless steel crucible and the stainless steel sealing cover, a high-temperature sealing gasket is clamped between the stainless steel crucible and the stainless steel sealing cover, and the sealing bolt penetrates through the stainless steel crucible and the corresponding flange at the edge of the stainless steel sealing cover to seal the closed reaction vessel;
wherein, the adding amount of the super-oxophilic metal is 2-120% of the mass of the titanium raw material; the mass ratio of the titanium raw material to the anhydrous calcium chloride is 1: 5-1: 40; the addition amount of the calcium reducing agent is 0.5-5 times of the saturated dissolution amount of calcium in the calcium chloride molten salt at the reaction temperature;
the titanium raw material is metal titanium or titanium oxide, wherein the metal titanium is a block material, a plate material, a wire material, a pipe material, a bar material, a strip material, a powder material or a special-shaped member, and the titanium oxide is powder;
the super-oxophilic metal is a metal more oxophilic than calcium, specifically lutetium, holmium, erbium and yttrium;
the calcium reducing agent is metal calcium or calcium alloy, and the metal calcium is high-purity calcium, distilled calcium or industrial calcium; the calcium alloy is calcium silicon alloy or calcium aluminum alloy.
2. The method for the synergistic deep removal of oxygen from metallic titanium of claim 1, wherein said hyperoxophilic metal is in the form of a block, plate, wire or sponge metal.
3. The method for the synergistic deep removal of oxygen in metallic titanium by the use of the hyperoxophilic metal-calcium according to claim 1, wherein in step 1), one or both of an alkali metal halide and an alkaline earth metal halide is further added into the titanium crucible; the addition amount of the alkali metal halide and the alkaline earth metal halide is 0 to 90 percent of the mass of the anhydrous calcium chloride.
4. The method for the synergistic deep removal of oxygen from metallic titanium of claim 3, wherein said alkali metal halide is potassium chloride.
5. The method for the cooperative deep removal of oxygen from titanium metal with an oxophilic metal-calcium in accordance with claim 1, in which the inert gas is argon.
6. The method for removing oxygen in metallic titanium in a synergistic and deep manner by using the hyperoxophilic metal-calcium according to claim 1, wherein the surface cleaning method in step 3) comprises the following steps: washing with mixed acid containing 1M hydrofluoric acid and 1M nitric acid for 5 times, and washing the surface with deionized water, ethanol, and acetone for 5 times.
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