CN115502392B - Method for reducing oxygen content of titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction - Google Patents
Method for reducing oxygen content of titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 97
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 90
- 239000000843 powder Substances 0.000 title claims abstract description 86
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 85
- 239000001301 oxygen Substances 0.000 title claims abstract description 74
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 74
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 66
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000012535 impurity Substances 0.000 claims abstract description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 238000005554 pickling Methods 0.000 claims abstract description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 19
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 18
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 46
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000003832 thermite Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000009461 vacuum packaging Methods 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000004140 cleaning Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- 239000011734 sodium Substances 0.000 description 9
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910010038 TiAl Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001040 Beta-titanium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100396546 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) tif-6 gene Proteins 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 aluminum magnesium zinc Chemical compound 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A method for reducing oxygen content of titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction belongs to the field of nonferrous metal material preparation. According to the method, mixed acid of reducing organic acid and dilute hydrochloric acid is used as a mixed acid impurity removing agent, titanium or titanium alloy powder prepared by aluminothermic reduction-vacuum distillation of fluotitanate is subjected to pickling leaching, so that low-oxygen titanium or titanium alloy powder is obtained, the mass percentage of oxygen is lower than 0.2%, and the product quality meets the requirements of industry standards. Compared with other common pickling methods, the method adopts the combination of hydrochloric acid and reducing organic acid (oxalic acid and/or citric acid), and effectively solves the problems of high potential safety hazard of hydrofluoric acid cleaning, high operation and maintenance cost, high environmental pollution and the like in the existing method.
Description
Technical Field
The invention relates to a method for reducing the oxygen content of titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction, belonging to the field of nonferrous metal material preparation.
Background
Titanium and titanium alloy have the characteristics of small density, high specific strength, good high-temperature performance, strong corrosion resistance and the like, and are applied to the front technical fields of aerospace, national defense, military industry and the like. The preparation method of titanium or titanium alloy is many, the method for realizing industrial production is a Kroll method, the method is to reduce titanium tetrachloride by magnesium metal at high temperature to obtain titanium sponge, then the titanium sponge is smelted by a vacuum consumable arc furnace to obtain a titanium ingot, and the titanium ingot is processed to obtain a series of titanium products. The process technology is mature, but the production process of the titanium sponge has long period, large environmental corrosiveness and serious pollution. Therefore, optimization or innovation of titanium or titanium alloy production process is required for the purpose of clean production. Thus, titanium metallurgists developed TiCl in succession, in addition to the Kroll process 4 Molten salt electrolysis process, tiO 2 The cathode deoxidation method, the fluorotitanate aluminothermic reduction method and the like are favored by researchers because of the characteristics of simple process flow, short reduction period and the like.
The current research on aluminothermic reduction of fluorotitanates is mainly as follows, for example, K 2 TiF6、Na 2 TiF 6 A method for preparing titanium and titanium-aluminum alloy (Patent No. 2837426) with 0.1-95% of titanium content is carried out in Wang Wuyo of Beijing nonferrous metals research institute in 1996, the research of preparing sponge titanium by reducing potassium fluotitanate by Zn-Al reducer is carried out, but the purity of the obtained product titanium is not qualified. Chen Xuemin et al performed with Na 2 TiF 6 The research of preparing metallic titanium by taking aluminum or aluminum zinc and aluminum magnesium zinc as reducing agents (CN 12534260A) is carried out, but the purity problem of metallic titanium and byproduct cryolite and the recycling problem of the whole components of titanium and aluminum cannot be thoroughly solved. University of northeast, feng Naixiang et alThe method for realizing the recycling of materials is a two-stage aluminothermic reduction process (CN 104911376A) for preparing titanium/titanium aluminum alloy and byproduct sodium cryolite by taking sodium fluotitanate as a raw material and aluminum as a reducing agent, so as to realize the direct preparation of titanium/titanium alloy powder with short flow, low cost and zero emission. The fluorotitanate aluminothermic reduction-vacuum distillation method provides a new path for preparing titanium or titanium alloy powder at low cost.
However, experimental researches and pilot plant researches are carried out on the fluorotitanate aluminothermic reduction-vacuum distillation process, and the problems that the main interstitial element oxygen content exceeds standard and the like can occur in partial batches of products due to the fact that the purity of the product titanium or titanium alloy powder is limited by factors such as raw material purity, unstable process operation and the like. The titanium-aluminum alloy product with high oxygen content is converted into titanium or titanium-aluminum alloy with oxygen content lower than 0.2% by means of post impurity removal, and the method has important significance for optimizing the process, saving energy and creating effect in industry.
At present, the removal of titanium or titanium alloy oxide films at home and abroad is mostly concentrated on the research of plates, and a two-step method is mostly adopted, namely, firstly melting and alkaline washing and then acid washing; however, the temperature of the molten alkaline cleaning medium is about 450 ℃, and the early aging strengthening of the alpha+beta and beta titanium alloy semi-finished products is easy to cause; in addition, acid washing with nitric acid and hydrofluoric acid after alkali washing may also lead to corrosion and hydrogen embrittlement of the titanium alloy surface. The university of south China Wang Xuewen and the like find that impurities in the titanium sponge are clustered and accumulated on the surface of titanium sponge particles, and the oxygen content can be reduced from 0.705% to 0.072% by adding the titanium sponge into 2% dilute hydrochloric acid and soaking for 24 hours at room temperature. The oxide skin removing process of TC4 titanium alloy oxidized at different temperatures is researched by adopting the technical processes of hot alkali washing and acid washing, namely Qiao Yonglian of Shenyang aircraft industry Co., ltd, hydrofluoric acid and nitric acid (the volume ratio is HF: HNO) 3 ：H 2 O=1:1:3), indicating that the oxide skin on the surface of TC4 titanium alloy can be completely removed.
In addition, oxalic acid is also used in the treatment of titanium or titanium alloy, but oxalic acid is only used for degreasing and etching of titanium or titanium alloy workpieces, because when a catalytic layer is thermally coated or electrodeposited on the surface of a titanium substrate, three steps of mechanical polishing, alkaline cleaning degreasing and acid etching are usually carried out on the titanium or titanium alloy substrate, oxalic acid is often used for treating titanium or titanium alloy workpieces with complex shapes, is used for improving the surface roughness of the workpieces, increasing the surface area, reducing the current density and improving the electrochemical performance so as to plate on the surface of the titanium or titanium alloy, and a good plating layer is formed.
Therefore, the invention is provided for solving the problem that the oxygen content of partial titanium or titanium-aluminum alloy powder prepared by aluminothermic reduction of fluorotitanate is high.
Disclosure of Invention
Aiming at partial high-oxygen-content products in the process of preparing titanium or titanium alloy powder by using a fluorotitanate aluminothermic reduction-vacuum distillation method, the invention provides a method for reducing the oxygen content of the titanium or titanium alloy powder prepared by using the fluorotitanate aluminothermic reduction method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention discloses a method for reducing the oxygen content of titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction, which comprises the following steps:
(1) Ball milling
Ball milling high oxygen content metal titanium or titanium alloy prepared by fluorotitanate aluminothermic reduction-vacuum distillation under the protection of argon atmosphere to obtain titanium or titanium alloy powder, wherein the granularity of the titanium or titanium alloy powder is 180-48 mu m;
(2) Preparing mixed acid impurity remover
Uniformly mixing the reducing organic acid with dilute hydrochloric acid to obtain a mixed acid impurity remover;
(3) Acid washing
Mixing titanium or titanium alloy powder with a mixed acid impurity removing agent, and carrying out pickling and leaching at the pickling and leaching temperature of 0-40 ℃ for 1-12h to obtain a solid-liquid mixture; mixing the acid impurity removing agent according to the liquid-solid ratio: titanium or titanium alloy powder= (5-15) mL:1g;
(4) Solid-liquid separation
Carrying out solid-liquid separation on the solid-liquid mixture to obtain a solid substance and a liquid substance;
(5) Washing
Washing the solid substance with absolute ethyl alcohol to obtain washed titanium or titanium alloy powder;
(6) Drying
And drying the washed titanium or titanium-aluminum alloy powder in a vacuum oven at the temperature of less than 40 ℃ to obtain low-oxygen titanium or titanium alloy powder, and carrying out vacuum packaging after grading the granularity.
In the step (2), the reducing organic acid is preferably oxalic acid and/or citric acid.
In the step (2), reducing organic acid according to the mole ratio: hcl= (1-2.5): (14.8-30).
In the step (2), the mass percentage concentration of the reducing organic acid is preferably 0.4-1%.
In the step (2), the mass percentage concentration of the dilute hydrochloric acid is preferably 2-4%.
In the step (6), the drying time is more than 3 hours.
The mass percentage of oxygen of the low-oxygen titanium or titanium alloy powder prepared by the invention is less than 0.2%.
Compared with the prior art, the method for reducing the oxygen content of the titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction has at least the following beneficial effects:
(1) Aiming at partial high-oxygen-content products of titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction-vacuum distillation, the oxygen content of the partial products can be reduced to below 0.2 percent by the method, the national standard of titanium alloy is met, and the quality of the products can be effectively improved.
(2) The current common acid washing method for titanium or titanium alloy plates in industry is a combination of hydrochloric acid, hydrofluoric acid, hydrochloric acid, nitric acid, hydrofluoric acid and the like, and the hydrofluoric acid has strong corrosion effect on skin and respiratory tract, so that the use process has high requirements on equipment safety and environmental protection treatment of tail liquid. The invention adopts a combination of hydrochloric acid and reducing organic acid (oxalic acid and/or citric acid). The problems of high potential safety hazard in hydrofluoric acid cleaning, high operation and maintenance cost, high environmental pollution and the like in the existing method are effectively solved.
Drawings
FIG. 1 is a flow chart of the acid washing and impurity removal of high oxygen content metallic titanium or titanium alloy prepared by aluminothermic reduction-vacuum distillation of fluorotitanate according to the present invention.
Detailed Description
The invention is further illustrated by the following specific examples.
The steps described in the present invention are not limited to the preparation sequence, and the sequence can be correspondingly adjusted after understanding the essence of the present invention, and the steps are also within the scope of the present invention.
In the following examples, the flow chart of the pickling impurity removal of the high oxygen content metallic titanium or titanium-aluminum alloy powder prepared by fluorotitanate thermite reduction-vacuum distillation is shown in fig. 1.
Example 1
Preparation of Ti by aluminothermic reduction-vacuum distillation of sodium fluotitanate 3 In the process of Al alloy powder, the oxygen content of the product of partial batch is found to be 0.37 percent, which exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by impurity removal. The method comprises the following specific steps:
(1) Ball milling the batch of high-oxygen content metallic titanium and titanium-aluminum alloy to 63-75 mu m under the protection of argon atmosphere;
(2) Preparing a mixed acid impurity remover: pouring 0.2g of oxalic acid and 10mL of 10% hydrochloric acid solution into the same beaker, adding distilled water to 50mL, and uniformly mixing to obtain a mixed acid solution of 0.4% oxalic acid and 2% hydrochloric acid, wherein the mixed acid solution is used as a mixed acid impurity remover;
(3) Mixing the titanium or titanium alloy powder obtained in the step (1) with an acid impurity removing agent in a liquid-solid ratio: titanium or titanium alloy powder = 10mL:1g of the mixed acid impurity removing agent obtained in the step (2) is added for acid washing, the acid washing temperature is 30 ℃, and the acid washing time is 6 hours;
(4) After the pickling is finished, filtering and separating the solid-liquid mixture obtained in the step (3);
(5) Washing the filter residue titanium-aluminum alloy powder obtained in the step (4) with absolute ethyl alcohol;
(6) And (3) drying the washing product obtained in the step (5) in a vacuum oven for 3 hours at a low temperature (the temperature is less than 40 ℃) to obtain the titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.18% by an ONH836 oxygen-nitrogen analyzer. Meets the requirements of the national standard of titanium alloy on oxygen content.
Example 2
Preparation of Ti by aluminothermic reduction-vacuum distillation of sodium fluotitanate 3 In the process of Al alloy powder, the oxygen content of the product of partial batch is found to be 0.65 percent, which exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by impurity removal. The method comprises the following specific steps:
(1) Ball milling the batch of high-oxygen content metallic titanium and titanium-aluminum alloy to 63-75 mu m under the protection of argon atmosphere;
(2) Preparing a mixed acid impurity removing agent, pouring 0.5g oxalic acid and 10mL of 10% hydrochloric acid solution into the same beaker, adding distilled water to 50mL, and uniformly mixing to obtain 1% oxalic acid+2% hydrochloric acid mixed acid solution serving as the mixed acid impurity removing agent;
(3) Mixing the titanium or titanium alloy powder obtained in the step (1) with an acid impurity removing agent in a liquid-solid ratio: titanium or titanium alloy powder = 10mL:1g, adding the mixture into the mixed acid impurity removing agent obtained in the step (2) for pickling, wherein the pickling temperature is 30 ℃, and the pickling time is 9 hours;
(4) After the pickling is finished, filtering and separating the solid-liquid mixture obtained in the step (3);
(5) Washing the filter residue titanium-aluminum alloy powder obtained in the step (4) with absolute ethyl alcohol;
(6) And (3) drying the washing product obtained in the step (5) in a vacuum oven for 3 hours at a low temperature (the temperature is less than 40 ℃) to obtain the titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.17% by an ONH836 oxygen-nitrogen analyzer. Meets the requirements of the national standard of titanium alloy on oxygen content.
Example 3
Preparation of Ti by thermite reduction-vacuum distillation of potassium fluotitanate 3 In the process of Al alloy powder, the oxygen content of the product of partial batch is found to be 0.45 percent, which exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by impurity removal. The method comprises the following specific steps:
(1) Ball milling the batch of high-oxygen content metallic titanium and titanium-aluminum alloy to 63-75 mu m under the protection of argon atmosphere;
(2) Preparing a mixed acid impurity removing agent, pouring 0.25g of oxalic acid and 15mL of 10% hydrochloric acid solution into the same beaker, adding distilled water to 50mL, and uniformly mixing to obtain 0.5% oxalic acid+3% hydrochloric acid mixed acid solution serving as the mixed acid impurity removing agent;
(3) Mixing the titanium or titanium alloy powder obtained in the step (1) with an acid impurity removing agent in a liquid-solid ratio: titanium or titanium alloy powder = 12mL:1g, adding the mixture into the mixed acid impurity removing agent obtained in the step (2) for pickling, wherein the pickling temperature is 30 ℃, and the pickling time is 9 hours;
(4) After the pickling is finished, filtering and separating the solid-liquid mixture obtained in the step (3);
(5) Washing the filter residue titanium-aluminum alloy powder obtained in the step (4) with absolute ethyl alcohol;
(6) And (3) drying the washing product obtained in the step (5) in a vacuum oven for 3 hours at a low temperature (the temperature is less than 40 ℃) to obtain the titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.19% by an ONH836 oxygen-nitrogen analyzer. Meets the requirements of the national standard of titanium alloy on oxygen content.
Example 4
In the process of preparing TiAl alloy powder by fluorotitanate thermite-vacuum distillation, the oxygen content of partial batches is found to be 0.36 percent, which exceeds the national standard requirement of 0.2 percent of titanium alloy, and the oxygen content needs to be reduced by impurity removal. The method comprises the following specific steps:
(1) Ball milling the batch of high-oxygen content metallic titanium and titanium-aluminum alloy to 63-75 mu m under the protection of argon atmosphere;
(2) Preparing a mixed acid impurity removing agent, pouring 0.25g of citric acid and 20mL of 10% hydrochloric acid solution into the same beaker, adding distilled water to 50mL, and uniformly mixing to obtain 0.5% citric acid and 4% hydrochloric acid mixed acid solution serving as the mixed acid impurity removing agent;
(3) Mixing the titanium or titanium alloy powder obtained in the step (1) with an acid impurity removing agent in a liquid-solid ratio: titanium or titanium alloy powder = 12mL:1g, adding the mixture into the mixed acid impurity removing agent obtained in the step (2) for pickling, wherein the pickling temperature is 30 ℃, and the pickling time is 6 hours;
(4) After the pickling is finished, filtering and separating the solid-liquid mixture obtained in the step (3);
(5) Washing the filter residue titanium-aluminum alloy powder obtained in the step (4) with absolute ethyl alcohol;
(6) And (3) drying the washing product obtained in the step (5) in a vacuum oven for 3 hours at a low temperature (the temperature is less than 40 ℃) to obtain the titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.17% by an ONH836 oxygen-nitrogen analyzer. Meets the requirements of the national standard of titanium alloy on oxygen content.
Example 5
In the process of preparing TiAl alloy powder by fluorotitanate thermite-vacuum distillation, the oxygen content of partial batches is found to be 0.38 percent, which exceeds the national standard requirement of 0.2 percent of titanium alloy, and the oxygen content needs to be reduced by impurity removal. The method comprises the following specific steps:
(1) Ball milling the batch of high-oxygen content metallic titanium and titanium-aluminum alloy to 63-75 mu m under the protection of argon atmosphere;
(2) Preparing a mixed acid impurity removing agent, pouring 0.25g of oxalic acid, 0.25g of citric acid and 10mL of 10% hydrochloric acid solution into the same beaker, adding distilled water to 50mL, and uniformly mixing to obtain 0.5% oxalic acid, 0.5% citric acid and 2% hydrochloric acid mixed acid solution serving as the mixed acid impurity removing agent;
(3) Mixing the titanium or titanium alloy powder obtained in the step (1) with an acid impurity removing agent in a liquid-solid ratio: titanium or titanium alloy powder = 10mL:1g, adding the mixture into the mixed acid impurity removing agent obtained in the step (2) for pickling, wherein the pickling temperature is 30 ℃, and the pickling time is 4 hours;
(4) After the pickling is finished, filtering and separating the solid-liquid mixture obtained in the step (3);
(5) Washing the filter residue titanium-aluminum alloy powder obtained in the step (4) with absolute ethyl alcohol;
(6) And (3) drying the washing product obtained in the step (5) in a vacuum oven for 3 hours at a low temperature (the temperature is less than 40 ℃) to obtain the titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.18% by an ONH836 oxygen-nitrogen analyzer. Meets the requirements of the national standard of titanium alloy on oxygen content.
Comparative example 1
The difference from example 1 is that the oxygen content increases dramatically by using hydrofluoric acid instead of oxalic acid.
Preparation of Ti by aluminothermic reduction-vacuum distillation of sodium fluotitanate 3 During the Al alloy powder process, it was found thatThe oxygen content of the partial batch product is 0.47%, which exceeds the national standard requirement of titanium alloy by 0.2%, and the oxygen content needs to be reduced by impurity removal. The method comprises the following specific steps:
(1) Ball milling the batch of high-oxygen content metallic titanium and titanium-aluminum alloy to 63-75 mu m under the protection of argon atmosphere;
(2) Preparing a mixed acid impurity removing agent, pouring 1mL of 40% hydrofluoric acid solution and 10mL of 10% hydrochloric acid solution into the same beaker, adding distilled water to 50mL, and uniformly mixing to obtain 0.8% hydrofluoric acid+2% hydrochloric acid mixed acid solution serving as the mixed acid impurity removing agent;
(3) Mixing the titanium or titanium alloy powder obtained in the step (1) with an acid impurity removing agent in a liquid-solid ratio: titanium or titanium alloy powder = 10mL:1g, adding the mixture into the mixed acid impurity removing agent obtained in the step (2) for pickling, wherein the pickling temperature is 30 ℃, and the pickling time is 6 hours;
(4) After the pickling is finished, filtering and separating the solid-liquid mixture obtained in the step (3);
(5) Washing the filter residue titanium-aluminum alloy powder obtained in the step (4) with absolute ethyl alcohol;
(6) And (3) drying the washing product obtained in the step (5) in a vacuum oven for 3 hours at a low temperature (the temperature is less than 40 ℃) to obtain the titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 2.49% by an ONH836 oxygen-nitrogen analyzer. The requirement of the national standard of titanium alloy on the oxygen content is not met.
Comparative example 2
The difference from example 1 is that the oxygen scavenging effect is not evident by using a single dilute hydrochloric acid.
Preparation of Ti by aluminothermic reduction-vacuum distillation of sodium fluotitanate 3 In the process of Al alloy powder, the oxygen content of the product of partial batch is found to be 0.55 percent, which exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by impurity removal. The method comprises the following specific steps:
(1) Ball milling the batch of high-oxygen content metallic titanium and titanium-aluminum alloy to 63-75 mu m under the protection of argon atmosphere;
(2) Preparing an acid impurity removing agent, pouring 20mL of 10% hydrochloric acid solution into a beaker, adding distilled water, and shaking uniformly to obtain 4% hydrochloric acid solution serving as the acid impurity removing agent;
(3) And (3) mixing the titanium or titanium alloy powder obtained in the step (1) with a liquid-solid ratio acid impurity removing agent: titanium or titanium alloy powder = 10mL:1g, adding the mixture into the mixed acid impurity removing agent obtained in the step (2) for pickling, wherein the pickling temperature is 30 ℃, and the pickling time is 6 hours;
(4) After the pickling is finished, filtering and separating the solid-liquid mixture obtained in the step (3);
(5) Washing the filter residue titanium-aluminum alloy powder obtained in the step (4) with absolute ethyl alcohol;
(6) And (3) drying the washing product obtained in the step (5) in a vacuum oven for 3 hours at a low temperature (the temperature is less than 40 ℃) to obtain the titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.34% by an ONH836 oxygen-nitrogen analyzer. The requirement of the national standard of titanium alloy on the oxygen content is not met.
Comparative example 3
The difference from example 1 is that the oxygen scavenging effect is not evident with oxalic acid alone.
Preparation of Ti by aluminothermic reduction-vacuum distillation of sodium fluotitanate 3 In the process of Al alloy powder, the oxygen content of the product of partial batch is found to be 0.53 percent, which exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by impurity removal. The method comprises the following specific steps:
(1) Ball milling the batch of high-oxygen content metallic titanium and titanium-aluminum alloy to 63-75 mu m under the protection of argon atmosphere;
(2) Preparing an acid impurity removing agent, pouring 0.5g of oxalic acid into a beaker, adding distilled water to 50mL, and shaking uniformly to obtain a 1% oxalic acid solution serving as the acid impurity removing agent;
(3) And (3) mixing the titanium or titanium alloy powder obtained in the step (1) with a liquid-solid ratio acid impurity removing agent: titanium or titanium alloy powder = 10mL:1g of the acid impurity removing agent is added into the acid impurity removing agent obtained in the step (2) for acid washing, the acid washing temperature is 30 ℃, and the acid washing time is 6 hours;
(4) After the pickling is finished, filtering and separating the solid-liquid mixture obtained in the step (3);
(5) Washing the filter residue titanium-aluminum alloy powder obtained in the step (4) with absolute ethyl alcohol;
(6) And (3) drying the washing product obtained in the step (5) in a vacuum oven for 3 hours at a low temperature (the temperature is less than 40 ℃) to obtain the titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.41% by an ONH836 oxygen-nitrogen analyzer. The requirement of the national standard of titanium alloy on the oxygen content is not met.
Claims (4)
1. A method for reducing the oxygen content of titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction is characterized in that mixed acid of reducing organic acid and dilute hydrochloric acid is used as a mixed acid impurity removing agent, and the titanium or titanium alloy prepared by fluorotitanate aluminothermic reduction-vacuum distillation is subjected to pickling leaching to obtain low-oxygen titanium or titanium alloy powder;
the method specifically comprises the following steps:
(1) Ball milling
Ball milling high oxygen content metal titanium or titanium alloy prepared by fluorotitanate aluminothermic reduction-vacuum distillation under the protection of argon atmosphere to obtain titanium or titanium alloy powder, wherein the granularity of the titanium or titanium alloy powder is 180-48 mu m;
(2) Preparing mixed acid impurity remover
Uniformly mixing the reducing organic acid with dilute hydrochloric acid to obtain a mixed acid impurity remover;
the reducing organic acid is oxalic acid and/or citric acid; reducing organic acid according to the mole ratio: hcl= (1-2.5): (14.8-30); the mass percentage concentration of the reducing organic acid is 0.4-1%, and the mass percentage concentration of the dilute hydrochloric acid is 2-4%;
(3) Acid washing
Mixing titanium or titanium alloy powder with a mixed acid impurity removing agent, and carrying out pickling and leaching at the pickling and leaching temperature of 0-40 ℃ for 1-12h to obtain a solid-liquid mixture; mixing the acid impurity removing agent according to the liquid-solid ratio: titanium or titanium alloy powder= (5-15) mL:1g;
(4) Solid-liquid separation
Carrying out solid-liquid separation on the solid-liquid mixture to obtain a solid substance and a liquid substance;
(5) Washing
Washing the solid substance with absolute ethyl alcohol to obtain washed titanium or titanium alloy powder;
(6) Drying
And drying the washed titanium or titanium-aluminum alloy powder in a vacuum oven at the temperature of less than 40 ℃ to obtain the low-oxygen titanium or titanium alloy powder.
2. The method for reducing the oxygen content of titanium or titanium alloy powder prepared by thermite reduction of fluorotitanate according to claim 1, wherein in the step (6), the drying time is more than 3 hours.
3. The method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluorotitanate according to claim 1, wherein the obtained low-oxygen titanium or titanium alloy powder is subjected to particle size classification and then vacuum packaging.
4. The method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluorotitanate according to claim 1, wherein the weight percentage of oxygen in the low-oxygen titanium or titanium alloy powder is less than 0.2%.
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