CN115502392A - Method for reducing oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluotitanate - Google Patents
Method for reducing oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluotitanate Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000010936 titanium Substances 0.000 title claims abstract description 102
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 95
- 239000000843 powder Substances 0.000 title claims abstract description 91
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 90
- 239000001301 oxygen Substances 0.000 title claims abstract description 81
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 81
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000002253 acid Substances 0.000 claims abstract description 100
- 238000005406 washing Methods 0.000 claims abstract description 59
- 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 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 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 19
- 238000005554 pickling Methods 0.000 claims abstract description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 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
- 239000007788 liquid Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 230000002829 reductive effect Effects 0.000 claims description 13
- 239000000203 mixture Substances 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
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- 238000009461 vacuum packaging Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 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 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 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 26
- 239000000243 solution Substances 0.000 description 17
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910010038 TiAl Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005530 etching Methods 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
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011020 pilot scale process 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
- 238000012545 processing 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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Abstract
A method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluotitanate belongs to the field of preparation of non-ferrous metal materials. The method adopts mixed acid of reducing organic acid and dilute hydrochloric acid as a mixed acid impurity removing agent to carry out acid washing leaching on titanium or titanium alloy powder prepared by aluminothermic reduction-vacuum distillation of fluorotitanate to obtain low-oxygen titanium or titanium alloy powder, wherein the mass percent of oxygen is lower than 0.2%, and the product quality meets the requirements of industrial 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 large potential safety hazard, high operation and maintenance cost, large environmental pollution and the like in hydrofluoric acid cleaning 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 aluminothermic reduction of fluotitanate, belonging to the field of preparation of non-ferrous metal materials.
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 leading-edge technical fields of aerospace, national defense and military industry and the like. The preparation method of titanium or titanium alloy is a Kroll method, and the method for realizing industrial production is characterized in that titanium tetrachloride is reduced by using metal magnesium at high temperature to obtain titanium sponge, then titanium sponge is smelted by a vacuum consumable arc furnace to obtain titanium ingots, and a series of titanium products are obtained by subsequent processing. The process technology is mature, but the production process of the titanium sponge has long period, large environmental corrosivity and serious pollution. Therefore, optimization or innovation of the titanium or titanium alloy production process is required for the purpose of clean production. Thus, in addition to the Kroll process, the titanium metallurgist has developed TiCl successively 4 Fused salt electrolysis method, tiO 2 Among these methods, the fluorotitanate aluminothermic reduction method is favored by researchers because of its characteristics of simple process flow, short reduction period, etc.
The current aluminothermic fluorotitanate reduction methods are mainly studied as follows, for example, K 2 TiF6、Na 2 TiF 6 A research on the preparation of titanium sponge by using Zn-Al reducing agent to reduce potassium fluotitanate was carried out in 1996 by a method for preparing metallic titanium and a titanium-aluminum alloy (Patent No. 2837426) with the titanium content of 0.1-95%, beijing nonferrous metals research institute Wang Wuyo, but the purity of the obtained metallic titanium is not qualified. Chen Xuemin et al performed on Na 2 TiF 6 The research on preparing metallic titanium by taking aluminum or aluminum zinc and aluminum magnesium zinc as reducing agents as raw materials (CN 12534260A) cannot thoroughly solve the purity problem of metallic titanium and a byproduct cryolite and the full component recycling problem of titanium and aluminum. Method for realizing material recycling by developing Feng Naixiang and the like of northeast university, in particular to titanium fluorideThe method is characterized in that sodium acid is used as a raw material, aluminum is used as a reducing agent to prepare titanium/titanium-aluminum alloy, and a two-stage aluminothermic reduction process (CN 104911376A) of sodium cryolite serving as a byproduct is used for directly preparing titanium/titanium alloy powder in a short process, low cost and zero emission manner. The fluotitanate thermit reduction-vacuum distillation method provides a new path for preparing titanium or titanium alloy powder at low cost.
However, experimental research and pilot-scale research on the process of aluminothermic reduction-vacuum distillation of the fluorotitanate show that the purity of the product titanium or titanium alloy powder is limited by the factors of raw material purity, unstable process operation and the like, and the problems of excessive content of main interstitial element oxygen and the like of partial batches of products can be caused. 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 a later impurity removal means, and the method has important significance for optimizing the technological process and saving energy and creating efficiency of industry.
At present, the removal of titanium or titanium alloy oxide films at home and abroad is mostly focused on the research of plates, and a two-step method is mostly adopted, namely, firstly, melting alkali washing is carried out, and then, acid washing is carried out; however, the temperature of the molten alkali cleaning medium is higher about 450 ℃, and premature aging strengthening of alpha + beta and beta titanium alloy semi-finished products is easily caused; in addition, pickling with nitric acid and hydrofluoric acid after alkaline pickling may also cause corrosion and hydrogen embrittlement of the titanium alloy surface. The university of Zhongnan Wang Xuewen and the like found that the impurities in the titanium sponge are agglomerated and gathered 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% diluted hydrochloric acid and soaking the titanium sponge at room temperature for 24 hours. Shenyang aircraft industry Co Ltd Qiao Yonglian, etc. by using the technological process of first hot alkali washing and then acid washing to research the oxide skin removing process of TC4 titanium alloy after oxidation at different temperatures, hydrofluoric acid and nitric acid (the volume ratio is HF: HNO) 3 ：H 2 O = 1: 3), indicating that the scale on the surface of the TC4 titanium alloy was completely removed.
In addition, in the titanium or titanium alloy treatment, oxalic acid is also used, however, oxalic acid is only used for degreasing and etching of the titanium or titanium alloy workpiece, because when the catalytic layer is thermally coated or electrodeposited on the surface of the titanium substrate, the titanium or titanium alloy substrate is usually subjected to three steps of mechanical polishing, alkali cleaning for degreasing and acid etching, and oxalic acid is often used for treating the titanium or titanium alloy workpiece with a complex shape, and is used for improving the surface roughness of the workpiece, 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 to form a good plating layer.
Therefore, the invention is provided for solving the problem that part of titanium or titanium-aluminum alloy powder prepared by aluminothermic reduction of fluotitanate has high oxygen content.
Disclosure of Invention
The invention provides a method for reducing the oxygen content of titanium or titanium alloy powder prepared by fluorotitanate aluminothermic reduction aiming at partial high oxygen content products in the process of preparing the titanium or titanium alloy powder by the fluorotitanate aluminothermic reduction-vacuum distillation method, the method adopts an acid cleaning impurity removal method, the mass percent of oxygen of the high oxygen content titanium or titanium alloy products obtained by the fluorotitanate aluminothermic reduction-vacuum distillation process can be reduced to be lower than 0.2 percent, and the product quality meets the requirements of the industry standard.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the method for reducing the oxygen content of the titanium or titanium alloy powder prepared by aluminothermic reduction of the fluotitanate comprises the following steps:
(1) Ball mill
Performing ball milling on high-oxygen-content metal titanium or titanium alloy prepared by aluminothermic reduction-vacuum distillation of fluotitanate 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 removing agent
Uniformly mixing reductive organic acid and dilute hydrochloric acid to obtain a mixed acid impurity removing agent;
(3) Acid pickling
Mixing titanium or titanium alloy powder with a mixed acid impurity removing agent, and carrying out acid pickling and leaching, wherein the acid pickling and leaching temperature is 0-40 ℃, and the acid pickling and leaching time is controlled to be 1-12h, so as to obtain a solid-liquid mixture; according to the liquid-solid ratio, mixing an acid impurity removing agent: 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 machine
Washing the solid substance with absolute ethyl alcohol to obtain washed titanium or titanium alloy powder;
(6) Drying
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), the molar ratio of the reducing organic acid: 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 h.
The low-oxygen titanium or titanium alloy powder prepared by the invention has the oxygen mass percentage of 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 aluminothermic reduction of the fluotitanate has the following beneficial effects:
(1) Aiming at partial high oxygen content products of titanium or titanium alloy powder prepared by aluminothermic reduction-vacuum distillation of fluotitanate, the method can reduce the oxygen content of the partial products to be less than 0.2 percent, meet the national standard of titanium alloy and effectively improve the product quality.
(2) At present, the common industrial acid pickling methods for titanium or titanium alloy plates are combinations of hydrochloric acid + hydrofluoric acid, hydrochloric acid + nitric acid + hydrofluoric acid and the like, and the hydrofluoric acid has a strong corrosive effect on skin and respiratory tracts, so that the requirements on equipment safety and environmental-friendly treatment of tail liquid in the use process are high. The invention adopts a combination of hydrochloric acid and reducing organic acid (oxalic acid and/or citric acid). The problems of large potential safety hazard, high operation and maintenance cost, large environmental pollution and the like in hydrofluoric acid cleaning in the conventional method are effectively solved.
Drawings
FIG. 1 is a flow chart of acid washing and impurity removing of high oxygen content metallic titanium or titanium alloy prepared by aluminothermic reduction-vacuum distillation of fluotitanate of the 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 adjusted accordingly after understanding the essence of the present invention, which is also within the scope of the claimed invention.
The acid-washing impurity-removing flow chart of the high-oxygen content metal titanium or titanium-aluminum alloy powder prepared by adopting the fluorotitanate aluminothermic reduction-vacuum distillation in the following examples is shown in figure 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 partial batches of products is found to be 0.37 percent and exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by removing impurities. The method comprises the following specific steps:
(1) Ball-milling the batch of high-oxygen metal titanium and titanium-aluminum alloy to 63-75 μm under the protection of argon atmosphere;
(2) Preparing a mixed acid impurity removing agent: 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% of oxalic acid and 2% of hydrochloric acid, wherein the mixed acid solution is used as a mixed acid impurity removing agent;
(3) Mixing the titanium or titanium alloy powder obtained in the step (1) with an acid impurity removing agent according to a liquid-solid ratio: titanium or titanium alloy powder =10mL: adding 1g of the mixed acid impurity removing agent obtained in the step (2) into acid washing, wherein the acid washing temperature is 30 ℃, and the acid washing time is 6 hours;
(4) After the acid washing 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 at a low temperature (the temperature is lower than 40 ℃) for 3 hours to obtain 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 requirement of the national standard of titanium alloy on the 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 partial batches of products is found to be 0.65 percent and exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by removing impurities. The method comprises the following specific steps:
(1) Ball-milling the batch of high-oxygen metal titanium and titanium-aluminum alloy to 63-75 μm under the protection of argon atmosphere;
(2) Preparing a mixed acid impurity removing agent, pouring 0.5g of 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 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 according to a liquid-solid ratio: titanium or titanium alloy powder =10mL:1g, adding the mixed acid impurity removing agent obtained in the step (2) to carry out acid washing, wherein the acid washing temperature is 30 ℃, and the acid washing time is 9 hours;
(4) After the acid washing 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 at a low temperature (the temperature is lower than 40 ℃) for 3 hours to obtain 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 requirement of the national standard of titanium alloy on the oxygen content.
Example 3
Preparation of Ti by aluminothermic reduction-vacuum distillation of potassium fluotitanate 3 In the process of Al alloy powder, the oxygen content of partial batches of products 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 removing impurities. The method comprises the following specific steps:
(1) Ball-milling the batch of high-oxygen metal titanium and titanium-aluminum alloy to 63-75 μm 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 and 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 according to a liquid-solid ratio: titanium or titanium alloy powder =12mL:1g, adding the mixed acid impurity removing agent obtained in the step (2) to carry out acid washing, wherein the acid washing temperature is 30 ℃, and the acid washing time is 9 hours;
(4) After the acid washing 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 (4) drying the washing product obtained in the step (5) in a vacuum oven at a low temperature (the temperature is lower than 40 ℃) for 3 hours to obtain titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.19 percent by an ONH836 oxygen-nitrogen analyzer. Meets the requirement of the national standard of titanium alloy on the oxygen content.
Example 4
During the process of preparing TiAl alloy powder by potassium fluotitanate aluminothermic reduction-vacuum distillation, the oxygen content of partial batches of products is found to be 0.36 percent, which exceeds the national standard requirement of titanium alloy for 0.2 percent, and the oxygen content needs to be reduced by removing impurities. The method comprises the following specific steps:
(1) Ball-milling the batch of high-oxygen metal titanium and titanium-aluminum alloy to 63-75 μm 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 according to a liquid-solid ratio: titanium or titanium alloy powder =12mL:1g, adding the mixed acid impurity removing agent obtained in the step (2) to carry out acid washing, wherein the acid washing temperature is 30 ℃, and the acid washing time is 6 hours;
(4) After the acid washing 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 at a low temperature (the temperature is lower than 40 ℃) for 3 hours to obtain 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 requirement of the national standard of titanium alloy on the oxygen content.
Example 5
During the process of preparing TiAl alloy powder by potassium fluotitanate aluminothermic reduction and vacuum distillation, the oxygen content of partial batches of products is found to be 0.38 percent and exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by removing impurities. The method comprises the following specific steps:
(1) Ball-milling the batch of high-oxygen metal titanium and titanium-aluminum alloy to 63-75 μm 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 a mixed acid solution of 0.5% of oxalic acid, 0.5% of citric acid and 2% of hydrochloric acid 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 according to a liquid-solid ratio: titanium or titanium alloy powder =10mL:1g, adding the mixed acid impurity removing agent obtained in the step (2) to carry out acid washing, wherein the acid washing temperature is 30 ℃, and the acid washing time is 4 hours;
(4) After the acid washing 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 at a low temperature (the temperature is lower than 40 ℃) for 3 hours to obtain 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 requirement of the national standard of titanium alloy on the oxygen content.
Comparative example 1
The difference from example 1 is that the oxygen content increases dramatically when oxalic acid is replaced by hydrofluoric acid.
Preparation of Ti by aluminothermic reduction-vacuum distillation of sodium fluotitanate 3 In the process of Al alloy powder, the oxygen content of partial batches of products is found to be 0.47 percent and exceeds that of titanium alloyThe requirement of the household standard is 0.2%, and the oxygen content needs to be reduced by removing impurities. The method comprises the following specific steps:
(1) Ball-milling the batch of high-oxygen metal titanium and titanium-aluminum alloy to 63-75 μm 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 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 according to a liquid-solid ratio: titanium or titanium alloy powder =10mL:1g, adding the mixed acid impurity removing agent obtained in the step (2) to carry out acid washing, wherein the acid washing temperature is 30 ℃, and the acid washing time is 6 hours;
(4) After the acid washing 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 at a low temperature (the temperature is lower than 40 ℃) for 3 hours to obtain 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. And does not meet the requirement of the national standard of titanium alloy on the oxygen content.
Comparative example 2
The difference from example 1 is that the oxygen scavenging effect is not significant with 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 partial batches of products is found to be 0.55 percent and exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by removing impurities. The method comprises the following specific steps:
(1) Ball-milling the batch of high-oxygen metal titanium and titanium-aluminum alloy to 63-75 μm 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 up to obtain 4% hydrochloric acid solution serving as the acid impurity removing agent;
(3) Removing impurities from the titanium or titanium alloy powder obtained in the step (1) by using a liquid-solid ratio acid: titanium or titanium alloy powder =10mL:1g, adding the mixed acid impurity removing agent obtained in the step (2) to carry out acid washing, wherein the acid washing temperature is 30 ℃, and the acid washing time is 6 hours;
(4) After the acid washing 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 at a low temperature (the temperature is lower than 40 ℃) for 3 hours to obtain 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. And does not meet the requirement of the national standard of titanium alloy on the oxygen content.
Comparative example 3
The difference from example 1 is that the oxygen scavenging effect is not significant 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 partial batches of products is found to be 0.53 percent and exceeds the national standard requirement of titanium alloy by 0.2 percent, and the oxygen content needs to be reduced by removing impurities. The method comprises the following specific steps:
(1) Ball-milling the batch of high-oxygen metal titanium and titanium-aluminum alloy to 63-75 μm 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 up to obtain a 1% oxalic acid solution serving as the acid impurity removing agent;
(3) Removing impurities from the titanium or titanium alloy powder obtained in the step (1) by using a liquid-solid ratio acid: titanium or titanium alloy powder =10mL: adding 1g of the mixed solution into the acid impurity removing agent obtained in the step (2) for acid washing, wherein the acid washing temperature is 30 ℃, and the acid washing time is 6 hours;
(4) After the acid washing 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 at a low temperature (the temperature is lower than 40 ℃) for 3 hours to obtain titanium-aluminum alloy powder, and detecting the oxygen content of the titanium-aluminum alloy powder to be 0.41 percent by an ONH836 oxygen-nitrogen analyzer. And does not meet the requirement of the national standard of titanium alloy on the oxygen content.
Claims (9)
1. A method for reducing oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluotitanate is characterized in that mixed acid of reducing organic acid and dilute hydrochloric acid is used as a mixed acid impurity removal agent, and acid pickling leaching is carried out on titanium or titanium alloy prepared by aluminothermic reduction of fluotitanate and vacuum distillation to obtain low-oxygen titanium or titanium alloy powder.
2. A method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluotitanate is characterized by comprising the following steps:
(1) Ball mill
Performing ball milling on high-oxygen-content metal titanium or titanium alloy prepared by aluminothermic reduction-vacuum distillation of fluotitanate 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) Mixed acid impurity removing agent
Uniformly mixing reductive organic acid and dilute hydrochloric acid to obtain a mixed acid impurity removing agent;
(3) Acid pickling
Mixing titanium or titanium alloy powder with a mixed acid impurity removing agent, and carrying out acid pickling and leaching, wherein the acid pickling and leaching temperature is 0-40 ℃, and the acid pickling and leaching time is controlled to be 1-12h, so as to obtain a solid-liquid mixture; mixing acid impurity removing agents according to a liquid-solid ratio: titanium or titanium alloy powder = (5-15) mL:1g of a compound;
(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 machine
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.
3. The method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluorotitanate according to claim 2, wherein in said step (2), the reducing organic acid is oxalic acid and/or citric acid.
4. The method for reducing the oxygen content of titanium or titanium alloy powder produced by aluminothermic reduction of fluorotitanate according to claim 2, wherein in said step (2), the molar ratio of reducing organic acid: HCl = (1-2.5): (14.8-30).
5. The method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluorotitanate according to claim 2, wherein the mass percentage concentration of the reducing organic acid in the step (2) is 0.4-1%.
6. The method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluorotitanate according to claim 2, wherein the concentration of dilute hydrochloric acid in step (2) is 2-4% by mass.
7. The method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluorotitanate according to claim 2, wherein in said step (6), the drying time is 3 hours or more.
8. 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 size classification and then vacuum packaging.
9. The method for reducing the oxygen content of titanium or titanium alloy powder prepared by aluminothermic reduction of fluorotitanate according to claim 1 or 2, wherein said titanium or titanium alloy powder having low oxygen content has oxygen content of <0.2% by mass.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101194387A (en) * | 2005-07-28 | 2008-06-04 | 株式会社神户制钢所 | Titanium material for electrode |
| CN102677092A (en) * | 2012-05-30 | 2012-09-19 | 浙江大学 | Preparation method of titanium anode |
| CN102921953A (en) * | 2012-10-31 | 2013-02-13 | 昆明理工大学 | Method of preparing metal titanium powder through TiO2 |
| CN104911376A (en) * | 2015-07-17 | 2015-09-16 | 东北大学 | Method of preparing titanium or titanium-aluminum alloy and additionally producing titanium-free cryolite through two-stage aluminothermic reduction |
| CN104947162A (en) * | 2015-07-22 | 2015-09-30 | 四川华丰企业集团有限公司 | Titanium alloy surface electroplating method |
| CN105658582A (en) * | 2013-08-19 | 2016-06-08 | 犹他大学研究基金会 | Producing a titanium product |
| CN107236869A (en) * | 2017-05-23 | 2017-10-10 | 东北大学 | A kind of method that multistage drastic reduction prepares reduction titanium valve |
| CN108687339A (en) * | 2017-04-06 | 2018-10-23 | 中国科学院福建物质结构研究所 | Titanium or titanium alloy spherical powder of low oxygen content and its preparation method and application |
| CN110666178A (en) * | 2019-08-26 | 2020-01-10 | 中国航天空气动力技术研究院 | Recovery processing method of additive manufacturing waste titanium or titanium alloy powder |
| CN111005045A (en) * | 2019-12-31 | 2020-04-14 | 西安西工大超晶科技发展有限责任公司 | Preparation method of titanium and titanium alloy surface coating |
| KR20200122442A (en) * | 2019-04-17 | 2020-10-28 | 한국생산기술연구원 | Pickling methods of titanium powder of fabricated by self-propagating high temperature synthesis |
| US20210016348A1 (en) * | 2019-07-19 | 2021-01-21 | Global Advanced Metals Usa, Inc. | Spherical Tantalum-Titanium Alloy Powder, Products Containing The Same, And Methods Of Making The Same |
| CN112496326A (en) * | 2020-11-10 | 2021-03-16 | 中南大学 | Oxygen removing process for injection molding titanium alloy and application thereof |
| WO2022046020A1 (en) * | 2020-08-28 | 2022-03-03 | Velta Holding Us Inc | Method for producing alloy powders based on titanium metal |
| CN114672850A (en) * | 2022-05-07 | 2022-06-28 | 华北理工大学 | Method for preparing metal titanium by separating titanium-aluminum alloy through molten salt electrolytic deoxidation |
-
2022
- 2022-10-11 CN CN202211238039.8A patent/CN115502392B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101194387A (en) * | 2005-07-28 | 2008-06-04 | 株式会社神户制钢所 | Titanium material for electrode |
| CN102677092A (en) * | 2012-05-30 | 2012-09-19 | 浙江大学 | Preparation method of titanium anode |
| CN102921953A (en) * | 2012-10-31 | 2013-02-13 | 昆明理工大学 | Method of preparing metal titanium powder through TiO2 |
| CN105658582A (en) * | 2013-08-19 | 2016-06-08 | 犹他大学研究基金会 | Producing a titanium product |
| CN104911376A (en) * | 2015-07-17 | 2015-09-16 | 东北大学 | Method of preparing titanium or titanium-aluminum alloy and additionally producing titanium-free cryolite through two-stage aluminothermic reduction |
| CN104947162A (en) * | 2015-07-22 | 2015-09-30 | 四川华丰企业集团有限公司 | Titanium alloy surface electroplating method |
| CN108687339A (en) * | 2017-04-06 | 2018-10-23 | 中国科学院福建物质结构研究所 | Titanium or titanium alloy spherical powder of low oxygen content and its preparation method and application |
| CN107236869A (en) * | 2017-05-23 | 2017-10-10 | 东北大学 | A kind of method that multistage drastic reduction prepares reduction titanium valve |
| KR20200122442A (en) * | 2019-04-17 | 2020-10-28 | 한국생산기술연구원 | Pickling methods of titanium powder of fabricated by self-propagating high temperature synthesis |
| US20210016348A1 (en) * | 2019-07-19 | 2021-01-21 | Global Advanced Metals Usa, Inc. | Spherical Tantalum-Titanium Alloy Powder, Products Containing The Same, And Methods Of Making The Same |
| CN110666178A (en) * | 2019-08-26 | 2020-01-10 | 中国航天空气动力技术研究院 | Recovery processing method of additive manufacturing waste titanium or titanium alloy powder |
| CN111005045A (en) * | 2019-12-31 | 2020-04-14 | 西安西工大超晶科技发展有限责任公司 | Preparation method of titanium and titanium alloy surface coating |
| WO2022046020A1 (en) * | 2020-08-28 | 2022-03-03 | Velta Holding Us Inc | Method for producing alloy powders based on titanium metal |
| CN112496326A (en) * | 2020-11-10 | 2021-03-16 | 中南大学 | Oxygen removing process for injection molding titanium alloy and application thereof |
| CN114672850A (en) * | 2022-05-07 | 2022-06-28 | 华北理工大学 | Method for preparing metal titanium by separating titanium-aluminum alloy through molten salt electrolytic deoxidation |
Non-Patent Citations (4)
| Title |
|---|
| 万贺利: "钙热还原法制备钛粉过程的研究", 《功能材料》, pages 1 - 7 * |
| 周欣: "金属钛制备的研究现状与进展", 《北方钒钛》, pages 22 - 25 * |
| 赵坤: "真空铝热还原法制备金属钛及钛合金的研究", 《真空科学与技术学报》, pages 1320 - 1324 * |
| 郑锋: "钛及钛合金的酸洗技术", 《稀有金属与硬质合金》, pages 26 - 29 * |
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