CN116463568A - Titanium waste recycling method - Google Patents
Titanium waste recycling method Download PDFInfo
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- CN116463568A CN116463568A CN202310366572.0A CN202310366572A CN116463568A CN 116463568 A CN116463568 A CN 116463568A CN 202310366572 A CN202310366572 A CN 202310366572A CN 116463568 A CN116463568 A CN 116463568A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000010936 titanium Substances 0.000 title claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 55
- -1 wherein A Substances 0.000 claims abstract description 46
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 239000012459 cleaning agent Substances 0.000 claims abstract description 15
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 11
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 239000011362 coarse particle Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000280 densification Methods 0.000 claims abstract description 3
- 239000007921 spray Substances 0.000 claims abstract description 3
- 238000005550 wet granulation Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005238 degreasing Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000007670 refining Methods 0.000 abstract description 11
- 238000001694 spray drying Methods 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a titanium waste recycling method, which relates to recycling of titanium waste, wherein A, titanium or titanium alloy waste is washed by a cleaning agent; b, vacuum drying the cleaned titanium waste, adding the titanium waste into a vacuum hydrogenation furnace for hydrogenation, and crushing the hydrogenated material C to obtain micro powder; pulping the micro powder, and performing wet granulation on the micro powder slurry by using a fluidized bed or a spray dryer to obtain titanium hydride ball coarse particles; carrying out densification sintering on the titanium hydride coarse particles in a vacuum sintering furnace, and carrying out secondary crushing on the densified titanium particles to obtain titanium hydride powder; g, adding calcium powder or magnesium powder to remove impurities and deoxidize; and H, finally, carrying out vacuum dehydrogenation treatment on the titanium hydride powder after impurity removal and deoxidation. Compared with the prior art, the method has the advantages that through the steps of hydrogenation, crushing, pulping, granulating, coarsening and re-refining, the spray drying or the fluidized bed method is adopted for carrying out wet pulping and granulating, the large-particle titanium powder with controllable morphology is obtained, and then deoxidation treatment is carried out.
Description
Technical Field
The invention relates to recycling of titanium waste, in particular to a method for preparing high-added-value titanium powder from titanium waste.
Background
Titanium and titanium alloy have the advantages of low density, high strength, high corrosion resistance and the like, and are widely applied to the fields of aerospace, military sea, medical chemical industry and the like. However, the titanium has poor hot working performance, so that the yield of titanium is less than 50% in the traditional processing technology process, a large amount of titanium scraps, waste titanium, residual titanium scraps and the like are generated, and a large amount of titanium resources are wasted. Therefore, recovery of waste titanium materials to produce high value titanium products is urgent.
The traditional titanium waste recovery process generally has two kinds, and firstly, a remelting ingot is produced by adopting a proper proportion and a titanium raw material, wherein the titanium waste accounts for about 20 percent, and impurities can be out of standard when the titanium waste accounts for a larger proportion. The second process is to prepare titanium powder by the traditional hydrogenation method, and the titanium material obtained by the method has high impurity content and oxygen content and can only be degraded to be used as an additive or a firework and firecracker fuel. For this reason, there is a need for an efficient and high-value titanium material recovery method.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a titanium waste recycling method, wherein the titanium waste has complex morphology, the titanium waste is subjected to granulation coarsening and refining after hydrogenation crushing slurrying, wet slurrying granulation is carried out by adopting a spray drying or fluidized bed method, so as to obtain large-particle titanium powder with controllable morphology, and then deoxidation treatment is carried out. Compared with the prior art, the method has low cost, and the obtained titanium powder has high quality and oxygen content lower than 0.15 percent.
In order to solve the technical problems, the invention is solved by the following technical scheme: a titanium waste recycling method comprises the following steps: step A: washing titanium or titanium alloy waste with a cleaning agent to remove oil stains on the surface of the waste, and activating the surface of the waste; and (B) step (B): vacuum drying the cleaned waste, adding into a vacuum hydrogenation furnace for hydrogenation, wherein the vacuum degree is less than 10 -4 Pa, and a hydrogenation temperature of not less than 300 ℃; step C: carrying out crushing treatment on the hydrogenated waste material to obtain irregular titanium hydride micro powder with the particle size of less than 2 um; step D: pulping the micro powder, wherein the solid content of the micro powder slurry is less than 50% by mass, and then carrying out wet granulation on the micro powder slurry by using a fluidized bed or a spray dryer to obtain titanium hydride ball coarse particles with the particle size less than 2 mm; step by stepStep E: carrying out densification degreasing sintering on titanium hydride coarse particles in a vacuum sintering furnace, wherein the sintering temperature is less than 1100 ℃; step F: secondarily crushing the densified titanium particles to obtain titanium hydride powder with the particle size smaller than 100 microns; step G: removing impurities and deoxidizing the titanium hydride powder; step H: and carrying out vacuum dehydrogenation treatment on the titanium hydride powder after impurity removal and deoxidation, wherein the dehydrogenation temperature is 300-900 ℃, and obtaining the spherical-like titanium or titanium alloy powder after dehydrogenation.
Preferably, in the above technical solution, in step C or step F, the crushing method is one or a combination of coarse crushing, fine crushing and ball milling.
Preferably, in the above technical scheme, in the step a, the cleaning agent is an organic cleaning agent, and the organic cleaning agent includes hydrocarbons, chlorinated hydrocarbons, fluorinated hydrocarbons, alcohols, alcohol ethers, ketones, and benzenes.
Preferably, in the above technical scheme, in the step D, the slurry agent is water, ethanol or a mixture of both.
Preferably, in the above technical solution, in step D, a binder is further added during pulping.
Preferably, in the above technical solution, in step D, the binder is paraffin wax.
Preferably, in the above technical solution, in the step G, the deoxidizer is calcium powder or magnesium powder, and one or more of magnesium chloride, calcium chloride, and rare earth chloride compounds are further added as auxiliary deoxidizers.
Preferably, in the above technical scheme, in step B, the hydrogenation temperature is 300 ℃ to 900 ℃.
The difference between the present application and the conventional hydrogenation method is that granulation is performed after hydrogenation. Sintering and removing impurities and deoxidizing the granulated titanium hydride. Firstly, compared with the titanium powder prepared by the traditional hydrogenation method, the titanium powder density index is greatly improved, and the titanium powder density is 4.4-4.49 g/cm 3 Apparent density of 2.45-2.6 g/cm 3 Tap density is 2.8-2.9 g/cm 3 Compared with the titanium powder prepared by the traditional method, the titanium powder has the density improvement rate of 5% -10%; secondly, the invention prepares the titanium powder with the granularity controllable range of 5 mu m to 100 mu m and the powder yield of more than 70 percent by a secondary shaping technology, and compared with the traditional methodThe powder rate is improved by 30% -50%, the fluidity is 20-25 s/50g, and the fluidity index is improved by 15% -30%; thirdly, the invention adopts special process equipment to remove impurities from the titanium powder, and the content of Fe, C, N and H in the obtained titanium powder impurities can reach Fe<0.01%，C<0.03%，N<0.01%，H<0.003%，O<0.15% by weight of impurity content, improvement of quality>20%。
Compared with the prior art, the method has the advantages that through the steps of hydrogenation, crushing, pulping, granulating, coarsening and re-refining, the spray drying or the fluidized bed method is adopted for carrying out wet pulping and granulating, the large-particle titanium powder with controllable morphology is obtained, and then deoxidation treatment is carried out. Compared with the prior art, the method has low cost, and the obtained titanium powder has high quality and oxygen content lower than 0.15 percent.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
As shown in fig. 1.
Example 1: weighing 5 kg of waste titanium scraps, and preparing 10l of special organic cleaning agent which is chlorinated hydrocarbon. Placing into oven after stirring and cleaning, oven drying at 100deg.C, adding into hydrogenation furnace, and vacuumizing to vacuum degree of 7×10 -4 Pa, heating to 900 ℃, slowly introducing hydrogen and beginning to cool, after 8 hours, taking out materials, crushing to 1 micron, uniformly stirring with 5L of ethanol, 2L of water and 100 g of paraffin, adding into a fluidized bed reactor for granulating to obtain coarse titanium hydride particles with the particle size of 1mm, degreasing, compacting and sintering at the temperature of 950 ℃, crushing and refining the sintered particles for the second time, shaping the materials in the refining process to obtain spheroidal titanium hydride powder with the particle size of less than 100 microns, and mixing the titanium hydride powder with deoxidizer calcium powder and calcium chloride according to the weight ratio of 1:9, mixing uniformly, placing into a deoxidizing furnace, vacuumizing to a vacuum degree of 5 multiplied by 10 -4 Carrying out deoxidization treatment at Pa and 900 ℃ for 8h, cooling, fully washing and filtering the deoxidized titanium hydride powder in a reaction kettle under the condition of 50% acetic acid solution with the volume mass liquid-solid ratio of 1/2, vacuum drying at 80 ℃ to obtain deoxidized titanium hydride powder, finally, putting the deoxidized titanium hydride powder after impurity removal in a dehydrogenation furnace, and vacuumizing to the vacuum degree of 5 multiplied by 10 in the furnace -4 Pa, dehydrogenation treatment is carried out at the temperature of 950 ℃, after reaction of 10h, the furnace is cooled down to normal temperature, and high-quality titanium or titanium alloy powder can be obtained, wherein the indexes of the titanium powder are as follows: density 4.44g/cm 3 Apparent density 2.51g/cm 3 Tap density 2.84g/cm 3 Particle size D50 is 35 μm, powder yield is 73%, fluidity is 23s/50g, impurity iron content is 0.006%, carbon content is 0.017%, nitrogen content is 0.0074%, hydrogen content is 0.0024%, oxygen content is 0.1%.
Example 2: 10 kg of waste titanium scraps are weighed, and 30L of special organic cleaning agent is prepared, wherein the cleaning agent is fluorocarbon. Placing into oven after stirring and cleaning, oven drying at 100deg.C, adding into hydrogenation furnace, and vacuumizing to vacuum degree of 6×10 -4 Pa, heating to 900 ℃, slowly introducing hydrogen and beginning to cool, after 10 hours, taking out materials, crushing to 2 microns, uniformly stirring with 10L of ethanol, 5L of water and 200 g of paraffin, adding into a fluidized bed reactor for granulating to obtain coarse titanium hydride particles with the particle size of 0.8mm, degreasing and closely sintering at the temperature of 900 ℃, secondarily crushing and refining the sintered particles, shaping the materials in the refining process to obtain spheroidal titanium hydride powder with the particle size of 40 microns, and mixing the titanium hydride powder with deoxidizer calcium powder and calcium chloride according to the weight ratio of 1:8, mixing uniformly, placing into a deoxidizing furnace, vacuumizing to a vacuum degree of 6×10 in the furnace -4 Carrying out deoxidation treatment at Pa and 900 ℃ to 9 h, cooling, fully washing and filtering the cooled deoxidized titanium hydride powder in a reaction kettle under the condition of 60% acetic acid solution with the volume mass liquid-solid ratio of 1/3, vacuum drying at 85 ℃ to obtain deoxidized titanium hydride powder, finally, putting the deoxidized titanium hydride powder after impurity removal in a dehydrogenation furnace, and vacuumizing to the vacuum degree of 5 multiplied by 10 in the furnace -4 Pa, carrying out dehydrogenation treatment at 900 ℃, reacting 12h, and cooling the furnace to normal temperature to obtain high-quality titanium or titanium alloy powder. Titanium powder index: density 4.45g/cm 3 Apparent density 2.52g/cm 3 Tap density 2.83g/cm 3 Particle size D50 was 52 μm, powder yield 75%, flowability 25s/50g, impurity iron content 0.007%, carbon content 0.018%, nitrogen content 0.0071%, hydrogen content 0.0026% and oxygen content 0.09%.
Example 3: weighing scale5 kg of waste titanium scraps are taken to prepare 10L of special organic cleaning agent which is chlorinated hydrocarbon. Placing into oven after stirring and cleaning, oven drying at 100deg.C, adding into hydrogenation furnace, and vacuumizing to vacuum degree of 7×10 -4 Pa, heating to 300 ℃, slowly introducing hydrogen and beginning to cool, after 12 hours, taking out materials, crushing to 1 micron, uniformly stirring with 5L of ethanol, 2L of water and 100 g of paraffin, adding into a fluidized bed reactor for granulating to obtain coarse titanium hydride particles with the particle size of 1mm, degreasing, compacting and sintering at the temperature of 1100 ℃, carrying out secondary crushing and refining on the sintered particles, carrying out shaping treatment on the materials in the refining process to obtain spheroidal titanium hydride powder with the particle size of less than 100 microns, and mixing the titanium hydride powder with deoxidizer calcium powder and chlorinated rare earth compound according to the weight ratio of 1:9, mixing uniformly, placing into a deoxidizing furnace, vacuumizing to a vacuum degree of 5 multiplied by 10 -4 Deoxidizing at 300 deg.c for 15 hr, cooling, washing in a reactor with acetic acid solution of 50% concentration and volume-to-solid ratio of 1/2, filtering, vacuum drying at 80 deg.c to obtain deoxidized titanium hydride powder, final eliminating impurity, vacuum pumping to vacuum degree of 5×10 -4 Pa, dehydrogenation treatment is carried out at 950 ℃, after reaction is carried out for 10h, the furnace is cooled down to normal temperature, and high-quality titanium or titanium alloy powder can be obtained. Titanium powder index: density 4.43g/cm 3 Apparent density 2.5g/cm 3 Tap density 2.81g/cm 3 Particle size D50 is 64 μm, powder yield is 77%, fluidity is 24s/50g, impurity iron content is 0.008%, carbon content is 0.011%, nitrogen content is 0.0077%, hydrogen content is 0.0021%, oxygen content is 0.11%.
Example 4: 10 kg of waste titanium scraps are weighed, 30L of special organic cleaning agent is prepared, and the cleaning agent is ketone. Placing into oven after stirring and cleaning, oven drying at 100deg.C, adding into hydrogenation furnace, and vacuumizing to vacuum degree of 2×10 -4 Pa, heating to 900 ℃, slowly introducing hydrogen and beginning to cool, after 10 hours, taking out the materials, crushing to 2 microns, uniformly stirring with 10L of ethanol, 5L of water and 200 g of paraffin, adding into a fluidized bed reactor, granulating, and obtainingCoarse titanium hydride particles with the particle size of 1mm are subjected to degreasing compact sintering at the temperature of 800 ℃, the sintered particles are subjected to secondary crushing and refining, and the materials are subjected to shaping treatment in the refining process to obtain spherical titanium hydride powder with the particle size of 40 microns, and the titanium hydride powder, deoxidizer magnesium powder and rare earth chloride compound are mixed according to the proportion of 1:8, mixing uniformly, placing into a deoxidizing furnace, vacuumizing to a vacuum degree of 4 multiplied by 10 in the furnace -4 Carrying out deoxidation treatment at Pa and 600 ℃ to 9 h, cooling, fully washing and filtering the cooled deoxidized titanium hydride powder in a reaction kettle under the condition of 60% acetic acid solution with the volume mass liquid-solid ratio of 1/3, vacuum drying at 85 ℃ to obtain deoxidized titanium hydride powder, finally, putting the deoxidized titanium hydride powder after impurity removal in a dehydrogenation furnace, and vacuumizing to the vacuum degree of 5 multiplied by 10 in the furnace -4 Pa, dehydrogenating at 600 ℃, reacting 12h, and cooling the furnace to normal temperature to obtain high-quality titanium or titanium alloy powder. Titanium powder index: density 4.46g/cm 3 Apparent density 2.55g/cm 3 Tap density 2.85g/cm 3 Particle size D50 was 25 μm, powder yield 71%, flowability 22s/50g, impurity iron content 0.009%, carbon content 0.019%, nitrogen content 0.0078%, hydrogen content 0.0029% and oxygen content 0.12%.
Claims (8)
1. The titanium waste recycling method is characterized by comprising the following steps of:
step A: washing titanium or titanium alloy waste with a cleaning agent to remove oil stains on the surface of the waste, and activating the surface of the waste;
and (B) step (B): vacuum drying the cleaned waste, adding into a vacuum hydrogenation furnace for hydrogenation, wherein the vacuum degree is less than 10 -4 Pa, and a hydrogenation temperature of not less than 300 ℃;
step C: carrying out crushing treatment on the hydrogenated waste material to obtain irregular titanium hydride micro powder with the particle size of less than 2 um;
step D: pulping the micro powder, wherein the solid content of the micro powder slurry is less than 50% by mass, and then carrying out wet granulation on the micro powder slurry by using a fluidized bed or a spray dryer to obtain titanium hydride ball coarse particles with the particle size less than 2 mm;
step E: carrying out densification degreasing sintering on titanium hydride coarse particles in a vacuum sintering furnace, wherein the sintering temperature is less than 1100 ℃;
step F: secondarily crushing the densified titanium particles to obtain titanium hydride powder with the particle size smaller than 100 microns;
step G: removing impurities and deoxidizing the titanium hydride powder;
step H: and carrying out vacuum dehydrogenation treatment on the titanium hydride powder after impurity removal and deoxidation, wherein the dehydrogenation temperature is 300-900 ℃, and obtaining the spherical-like titanium or titanium alloy powder after dehydrogenation.
2. The method for recycling titanium scraps according to claim 1, wherein in the step C or the step F, the crushing method is one or a combination of coarse crushing, fine crushing and ball milling.
3. The method for recycling titanium waste according to claim 1, wherein in the step a, the cleaning agent is an organic cleaning agent, and the organic cleaning agent includes hydrocarbons, chlorinated hydrocarbons, fluorinated hydrocarbons, alcohols, alcohol ethers, ketones, and benzenes.
4. The method for recycling titanium waste according to claim 1, wherein in the step D, the slurrying agent is water, ethanol or a mixture of both.
5. The method for recycling titanium scraps according to claim 4, wherein in the step D, a binder is further added during the slurrying.
6. The method for recycling titanium scraps according to claim 5, wherein in the step D, the binder is paraffin wax.
7. The method for recycling titanium scraps according to claim 4, wherein in the step G, the deoxidizer is calcium powder or magnesium powder, and one or more of magnesium chloride, calcium chloride, rare earth chloride compounds are further added as auxiliary deoxidizers.
8. The method for recycling titanium scrap according to claim 1, wherein in the step B, the hydrogenation temperature is 300 ℃ to 900 ℃.
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| CN202310366572.0A CN116463568A (en) | 2023-04-07 | 2023-04-07 | Titanium waste recycling method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117161388A (en) * | 2023-11-04 | 2023-12-05 | 天钛隆（天津）金属材料有限公司 | Low-oxygen-content titanium alloy powder and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117161388A (en) * | 2023-11-04 | 2023-12-05 | 天钛隆（天津）金属材料有限公司 | Low-oxygen-content titanium alloy powder and preparation method thereof |
| CN117161388B (en) * | 2023-11-04 | 2024-01-12 | 天钛隆（天津）金属材料有限公司 | Low-oxygen-content titanium alloy powder and preparation method thereof |
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