CN116970812A - Recycling method of molybdenum alloy waste target - Google Patents
Recycling method of molybdenum alloy waste target Download PDFInfo
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- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 137
- 239000000843 powder Substances 0.000 claims abstract description 63
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims description 53
- 239000000956 alloy Substances 0.000 claims description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 21
- 230000001681 protective effect Effects 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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
- B22F9/023—Hydrogen absorption
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- Chemical & Material Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a recycling method of a molybdenum alloy waste target, which comprises the following steps: sequentially carrying out first hydrogenation, second hydrogenation, crushing treatment and dehydrogenation treatment on the molybdenum alloy waste target to obtain molybdenum alloy powder; the temperature of the first hydrogenation is less than the temperature of the second hydrogenation. According to the invention, the molybdenum alloy waste target is prepared into the molybdenum alloy powder with high purity, low hydrogen content and low oxygen content through the first hydrogenation-second hydrogenation-crushing treatment-dehydrogenation treatment procedures, so that the molybdenum alloy powder can be reused in the production of the molybdenum alloy target, the process is simple, the energy consumption is low, and the utilization rate of materials is improved; further, by controlling the temperature of the first hydrogenation to be lower than that of the second hydrogenation, not only can the waste targets of any shape and thickness be ensured to be crushed into powder, but also the oxygen content of the molybdenum alloy powder can be further reduced.
Description
Technical Field
The invention belongs to the technical field of target recycling, and particularly relates to a recycling method of a molybdenum alloy waste target.
Background
With the rapid development of the electronic information industry, the application of film science is increasingly wide. The sputtering method is one of the main techniques for preparing film materials, and the raw material of the sputtering deposited film is the target. The film deposited by sputtering the target material has high density and good adhesiveness. In the 90 s of the 20 th century, new devices and materials in the microelectronics industry have developed rapidly, and electronic, magnetic, optical, photoelectric, superconducting thin films and the like have been widely applied to the fields of high and new technologies and industries, so that the market scale of sputtering targets is promoted to be increasingly enlarged. Today, metal targets have been vigorously developed into a specialized industry. Currently, flat Panel Displays (FPDs), including liquid crystal displays, plasma displays, and touch screens, have become the mainstream of displays, and have been increasingly applied to various aspects of our lives.
The molybdenum alloy target material is widely used in the panel display industry because of the good corrosion resistance and diffusion resistance. However, in the production and manufacturing process of the molybdenum alloy target material and the sputtering process, only a part of the target material is used, and the residual scraps and residual targets still have considerable value.
CN114087875a discloses a molybdenum alloy smelting recovery apparatus, method and vacuum degassing impurity-removing smelting furnace, the molybdenum alloy smelting recovery method comprises four steps of preparing consumable electrode, vacuum degassing impurity-removing, refining and preparing recovered molybdenum alloy block. The method uses a vacuum electron beam melting mode to treat the material, improves the purity of the recovered molybdenum alloy blocks, and improves the melting efficiency.
CN111620367a discloses a method for recovering ITO powder from ITO residual target/waste target, which comprises cleaning and pickling the surface of ITO residual target/waste target, thermal stress crushing treatment, ring roller grinding crushing treatment, air flow crushing treatment and vibration ball milling treatment, and processing ITO residual target/waste target into ITO nano powder with particle size of 100-500 nm.
However, the powder recovered by the method has higher hydrogen content and oxygen content, and further treatment is needed for preparing new targets. Therefore, the development of the method has the advantages of simple process and low energy consumption, and the recovered powder can be directly used in target production, so that the method is a technical problem which needs to be solved by a person skilled in the art.
Disclosure of Invention
The invention aims to provide a recycling method of a molybdenum alloy waste target, which is characterized in that the molybdenum alloy waste target is sequentially subjected to first hydrogenation, second hydrogenation, crushing and dehydrogenation treatment to obtain molybdenum alloy powder with high purity, low hydrogen content and low oxygen content, the method can be reused in the production of the molybdenum alloy target, the process is simple, the energy consumption is low, the material utilization rate is greatly improved, and the product production cost is also saved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a recycling method of a molybdenum alloy waste target, which comprises the following steps: sequentially carrying out first hydrogenation, second hydrogenation, crushing treatment and dehydrogenation treatment on the molybdenum alloy waste target to obtain molybdenum alloy powder;
the temperature of the first hydrogenation is less than the temperature of the second hydrogenation.
According to the recycling method, the molybdenum alloy waste target is prepared into the molybdenum alloy powder with high purity, low hydrogen content and low oxygen content through the first hydrogenation-second hydrogenation-crushing treatment-dehydrogenation treatment procedures, so that the method can be reused in the production of the molybdenum alloy target, is simple in process and low in energy consumption, and improves the utilization rate of materials; meanwhile, only a small amount of acid is used for cleaning in the recycling method, strong alkali and organic reagent are not used, and environmental pollution is reduced.
It is worth noting that the invention further ensures that the waste targets of any shape and thickness are crushed into powder by controlling the temperature of the first hydrogenation to be smaller than the temperature of the second hydrogenation, and can further reduce the oxygen content of the molybdenum alloy powder.
As a preferred embodiment of the present invention, the first hydrogenation includes: and placing the molybdenum alloy waste target in a hydrogenation device, vacuumizing, performing first heating, then introducing hydrogen for first hydrogenation, and then cooling to room temperature to obtain a first hydrogenation material.
In the invention, the surface of the molybdenum alloy waste target is sequentially subjected to acid washing and water washing before the first hydrogenation, and the surface is not required to be crushed into thin slices and then subjected to hydrogenation treatment.
As a preferred embodiment of the present invention, the first heating is performed in a protective atmosphere.
The protective atmosphere comprises high-purity argon or high-purity nitrogen; the purity is more than 99.999%.
The temperature of the first heating is preferably 250 to 300 ℃, and may be 255 ℃, 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃, 285 ℃, 290 ℃, 295 ℃ or the like, for example, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
In the invention, when the preset heating temperature is reached, protective atmosphere is not introduced, and the high-purity hydrogen is introduced.
Preferably, the flow rate of the hydrogen is 3-5m 3 /h, for example, may be 3.2m 3 /h、3.4m 3 /h、3.6m 3 /h、3.8m 3 /h、4m 3 /h、4.2m 3 /h、4.4m 3 /h、4.6m 3 /h or 4.8m 3 And/h, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The hydrogen selected in the invention is high-purity hydrogen, and the purity of the high-purity hydrogen is more than 99.999 percent.
Preferably, the pressure of the hydrogen gas is 0.05-0.08MPa, for example, 0.055MPa, 0.06MPa, 0.065MPa, 0.07MPa or 0.075MPa, etc., but the hydrogen gas is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the temperature rising rate of the first hydrogenation is 3-5 ℃/min, for example, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min or 4.8 ℃/min, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
The temperature of the first hydrogenation is preferably 400 to 600 ℃, and may be 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, or the like, for example, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical range are equally applicable.
Preferably, the first hydrogenation time is 5-8h, for example, 5h, 5.2h, 5.4h, 5.6h, 5.8h, 6h, 6.2h, 6.4h, 6.6h, 6.8h, 7h, 7.2h, 7.4h, 7.6h or 7.8h, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the second hydrogenation includes: and placing the first hydrogenation material in a hydrogenation device, vacuumizing, performing second heating, introducing hydrogen for second hydrogenation, and cooling to room temperature to obtain a second hydrogenation material.
In the invention, in order to ensure that the molybdenum alloy material is fully hydrogenated and absorbed with hydrogen and further reduce the oxygen content, the first hydrogenated material is crushed into blocks and then is put into a hydrogenation device again for secondary hydrogenation.
As a preferred embodiment of the present invention, the second heating is performed in a protective atmosphere.
Preferably, the temperature of the second heating is 250 to 300 ℃, for example, 255 ℃, 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃, 285 ℃, 290 ℃, 295 ℃ or the like, but the second heating is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
In the invention, when the preset heating temperature is reached, protective atmosphere is not introduced, and the high-purity hydrogen is introduced.
Preferably, the flow rate of the hydrogen is 3-5m 3 /h, for example, may be 3.2m 3 /h、3.4m 3 /h、3.6m 3 /h、3.8m 3 /h、4m 3 /h、4.2m 3 /h、4.4m 3 /h、4.6m 3 /h or 4.8m 3 And/h, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the pressure of the hydrogen gas is 0.05-0.08MPa, for example, 0.055MPa, 0.06MPa, 0.065MPa, 0.07MPa or 0.075MPa, etc., but the hydrogen gas is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the temperature rising rate of the second hydrogenation is 3-5 ℃/min, for example, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min or 4.8 ℃/min, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
The temperature of the second hydrogenation is preferably 450 to 700 ℃, and may be 470 ℃, 490 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃, or the like, for example, but the second hydrogenation is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the second hydrogenation time is 6-10h, for example, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h or 9.5h, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the crushing treatment is carried out in a jet mill.
Preferably, the crushing treatment is carried out in a protective atmosphere.
Preferably, the pressure of the protective atmosphere is 0.3-0.5MPa, for example, 0.32MPa, 0.34MPa, 0.36MPa, 0.38MPa, 0.4MPa, 0.42MPa, 0.44MPa, 0.46MPa or 0.48MPa, etc., but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the time of the crushing treatment is 3-5h, for example, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h or 4.8h, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, after the crushing treatment, molybdenum hydride alloy powder with the particle size of <100 μm is obtained.
As a preferred embodiment of the present invention, the dehydrogenation treatment includes: and (3) layering the molybdenum hydride alloy powder in a dehydrogenation device, vacuumizing, performing dehydrogenation treatment, and cooling to room temperature to obtain the molybdenum alloy powder.
As a preferable embodiment of the present invention, the thickness of each layer of the molybdenum hydride alloy powder is not more than 10mm, and for example, it may be 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm or 9mm, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
In the present invention, in order to ensure sufficient dehydrogenation of the molybdenum hydride alloy powder, the hydrogenated powder is layered.
PreferablyVacuum degree of dehydrogenation treatment<10 -2 Pa。
The dehydrogenation treatment is preferably carried out at a temperature of 700 to 900 ℃, and may be carried out at 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 890 ℃ or the like, for example, but the dehydrogenation treatment is not limited to the above-mentioned values, and other values not mentioned in the numerical range are equally applicable.
Preferably, the dehydrogenation treatment is performed for a period of time ranging from 6 to 10 hours, for example, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, or 9.5 hours, etc., but the present invention is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
In a preferred embodiment of the present invention, the molybdenum alloy powder has a hydrogen content of < 200ppm, for example, 20ppm, 40ppm, 60ppm, 80ppm, 100ppm, 120ppm, 150ppm, 170ppm, 180ppm, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the oxygen content of the molybdenum alloy powder is less than 800ppm, for example, 720ppm, 740ppm, 760ppm, 770ppm, 780ppm or 790ppm, etc., but the molybdenum alloy powder is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The preferable technical scheme of the invention is characterized in that the recycling method comprises the following steps:
(1) First hydrogenation: placing a molybdenum alloy waste target in a hydrogenation device, vacuumizing, performing first heating, then introducing hydrogen for first hydrogenation, and then cooling to room temperature to obtain a first hydrogenated material;
the first heating is performed in a protective atmosphere; the temperature of the first heating is 250-300 ℃;
the flow rate of the hydrogen is 3-5m 3 And/h, the pressure is 0.05-0.08MPa;
the heating rate of the first hydrogenation is 3-5 ℃/min, the temperature is 400-600 ℃ and the time is 5-8h;
(2) Second hydrogenation: placing the first hydrogenation material in a hydrogenation device, vacuumizing, performing second heating, then introducing hydrogen to perform second hydrogenation, and cooling to room temperature to obtain a second hydrogenation material;
the second heating is performed in a protective atmosphere; the temperature of the second heating is 250-300 ℃;
the flow rate of the hydrogen is 3-5m 3 And/h, the pressure is 0.05-0.08MPa;
the temperature rising rate of the second hydrogenation is 3-5 ℃/min, the temperature is 450-700 ℃ and the time is 6-10h;
the temperature of the first hydrogenation is less than the temperature of the second hydrogenation;
(3) Crushing: placing the second hydrogenation material in an airflow crusher, introducing protective atmosphere with the pressure of 0.3-0.5MPa, and crushing for 3-5h to obtain molybdenum hydride alloy powder with the particle size of less than 100 mu m;
(4) Dehydrogenation treatment: layering molybdenum hydride alloy powder in a dehydrogenation device, vacuumizing, performing dehydrogenation treatment, and cooling to room temperature to obtain molybdenum alloy powder with hydrogen content less than 200ppm and oxygen content less than 800 ppm;
the thickness of each layer of molybdenum hydride alloy powder is less than or equal to 10mm;
vacuum degree of dehydrogenation treatment<10 -2 Pa, the temperature is 700-900 ℃ and the time is 6-10h.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) The recycling method provided by the invention can prepare the molybdenum alloy waste targets with any shape and thickness into molybdenum alloy powder with purity more than or equal to 99.97%, hydrogen content less than 200ppm and oxygen content less than 800ppm through the control of the first hydrogenation-second hydrogenation-crushing treatment-dehydrogenation treatment process and related process parameters, can be reused in the production of the molybdenum alloy targets, has simple process and low energy consumption, and improves the utilization rate of the materials;
(2) In the recycling method, only a small amount of acid is used for cleaning, no strong alkali or organic reagent is used, and environmental pollution is reduced.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a recycling method of a molybdenum alloy waste target, which comprises the following steps:
(1) First hydrogenation: cleaning a molybdenum alloy waste target, placing the cleaned molybdenum alloy waste target in a hydrogenation device, vacuumizing, performing first heating, introducing high-purity argon, switching to introducing high-purity hydrogen, performing first hydrogenation, and cooling to room temperature to obtain a first hydrogenation material;
the temperature of the first heating is 270 ℃; the flow rate of the high-purity hydrogen is 4m 3 And/h, the pressure is 0.07MPa;
the heating rate of the first hydrogenation is 4 ℃/min, the temperature is 500 ℃ and the time is 6h;
(2) Second hydrogenation: crushing the first hydrogenation material into blocks, placing the blocks in a hydrogenation device, vacuumizing, heating, performing second heating, introducing high-purity argon, switching to introducing high-purity hydrogen, performing second hydrogenation, and cooling to room temperature to obtain a second hydrogenation material;
the second heating temperature is 270 ℃; the flow rate of the high-purity hydrogen is 4m 3 And/h, the pressure is 0.07MPa;
the heating rate of the second hydrogenation is 4 ℃/min, the temperature is 600 ℃ and the time is 7h;
(3) Crushing: placing the second hydrogenation material in an airflow crusher, introducing high-purity argon with the pressure of 0.4MPa, and crushing for 4 hours to obtain molybdenum hydride alloy powder with the particle size of 70-80 mu m;
(4) Dehydrogenation treatment: layering the crushed molybdenum hydride alloy powder in a dehydrogenation device, vacuumizing, performing dehydrogenation treatment, and cooling to room temperature to obtain molybdenum alloy powder;
the thickness of each layer of molybdenum hydride alloy powder is 6mm;
the vacuum degree of the dehydrogenation treatment is 10 -3 Pa, 800 ℃ and 8 hours.
Example 2
The embodiment provides a recycling method of a molybdenum alloy waste target, which comprises the following steps:
(1) First hydrogenation: cleaning a molybdenum alloy waste target, placing the cleaned molybdenum alloy waste target in a hydrogenation device, vacuumizing, performing first heating, introducing high-purity argon, switching to introducing high-purity hydrogen, performing first hydrogenation, and cooling to room temperature to obtain a first hydrogenation material;
the temperature of the first heating is 300 ℃; the flow rate of the high-purity hydrogen is 3m 3 And/h, the pressure is 0.05MPa;
the heating rate of the first hydrogenation is 5 ℃/min, the temperature is 600 ℃ and the time is 5h;
(2) Second hydrogenation: crushing the first hydrogenation material into blocks, placing the blocks in a hydrogenation device, vacuumizing, performing second heating, introducing high-purity argon, switching to introducing high-purity hydrogen, performing second hydrogenation, and cooling to room temperature to obtain a second hydrogenation material;
the temperature of the second heating is 300 ℃; the flow rate of the high-purity hydrogen is 3m 3 And/h, the pressure is 0.05MPa;
the heating rate of the second hydrogenation is 5 ℃/min, the temperature is 700 ℃ and the time is 7 hours;
(3) Crushing: placing the second hydrogenation material in an airflow crusher, introducing high-purity argon with the pressure of 0.3MPa, and crushing for 5 hours to obtain molybdenum hydride alloy powder with the particle size of 60-65 mu m;
(4) Dehydrogenation treatment: layering the crushed molybdenum hydride alloy powder in a dehydrogenation device, vacuumizing, performing dehydrogenation treatment, and cooling to room temperature to obtain molybdenum alloy powder;
the thickness of each layer of molybdenum hydride alloy powder is 8mm;
the vacuum degree of the dehydrogenation treatment is 5 multiplied by 10 -3 Pa, temperature 900 ℃ and time 6h.
Example 3
The embodiment provides a recycling method of a molybdenum alloy waste target, which comprises the following steps:
(1) First hydrogenation: cleaning a molybdenum alloy waste target, placing the cleaned molybdenum alloy waste target in a hydrogenation device, vacuumizing, performing first heating, introducing high-purity argon, switching to introducing high-purity hydrogen, performing first hydrogenation, and cooling to room temperature to obtain a first hydrogenation material;
the temperature of the first heating is 250 ℃; the flow rate of the high-purity hydrogen is 5m 3 And/h, the pressure is 0.08MPa;
the heating rate of the first hydrogenation is 3 ℃/min, the temperature is 450 ℃ and the time is 8 hours;
(2) Second hydrogenation: crushing the first hydrogenation material into blocks, placing the blocks in a hydrogenation device, vacuumizing, performing second heating, introducing high-purity argon, switching to introducing high-purity hydrogen, performing second hydrogenation, and cooling to room temperature to obtain a second hydrogenation material;
the temperature of the second heating is 250 ℃; the flow rate of the high-purity hydrogen is 5m 3 And/h, the pressure is 0.08MPa;
the heating rate of the second hydrogenation is 3 ℃/min, the temperature is 600 ℃ and the time is 9 hours;
(3) Crushing: placing the second hydrogenation material in an airflow crusher, introducing high-purity argon with the pressure of 0.5MPa, and crushing for 3 hours to obtain molybdenum hydride alloy powder with the particle size of 60-65 mu m;
(4) Dehydrogenation treatment: layering the crushed molybdenum hydride alloy powder in a dehydrogenation device, vacuumizing, performing dehydrogenation treatment, and cooling to room temperature to obtain molybdenum alloy powder;
the thickness of each layer of molybdenum hydride alloy powder is 5mm;
the vacuum degree of the dehydrogenation treatment is 8 multiplied by 10 -3 Pa, 800 ℃ and 9 hours.
Example 4
This embodiment differs from embodiment 1 only in that: the temperature of the first hydrogenation was 350℃and the other conditions were the same as in example 1.
Example 5
This embodiment differs from embodiment 1 only in that: the first hydrogenation was performed directly with high purity hydrogen without first heating after the first hydrogenation was evacuated, and the other conditions were the same as in example 1.
Example 6
This embodiment differs from embodiment 1 only in that: the temperature of the second hydrogenation was 750℃and the other conditions were the same as in example 1.
Example 7
This embodiment differs from embodiment 1 only in that: the second hydrogenation was performed under the same conditions as in example 1, except that the second hydrogenation was performed under vacuum without performing the second heating, but directly introducing high purity hydrogen gas to perform the first hydrogenation.
Example 8
This embodiment differs from embodiment 1 only in that: the thickness of each layer of the molybdenum hydride alloy powder was 30mm, and the other conditions were the same as in example 1.
Example 9
This embodiment differs from embodiment 1 only in that: the dehydrogenation treatment was carried out at 600℃under the same conditions as in example 1.
Example 10
This embodiment differs from embodiment 1 only in that: the dehydrogenation treatment was carried out at 1000℃under the same conditions as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that: the temperature of the first hydrogenation was 700℃and the other conditions were the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that: the temperature of the second hydrogenation was 450℃and the other conditions were the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that: the temperature of the second hydrogenation was 400℃and the other conditions were the same as in example 1.
Comparative example 4
This comparative example differs from example 1 only in that: the second hydrogenation was not carried out, and the other conditions were the same as in example 1.
The purity, hydrogen content and oxygen content of the molybdenum alloy powders obtained in the above examples and comparative examples were measured, and the results are shown in table 1.
TABLE 1
From table 1, the following points can be found:
(1) By adopting the recycling method provided by the embodiment 1-3 of the invention, the purity of the obtained molybdenum alloy powder is more than or equal to 99.97%, the hydrogen content is less than 120ppm, and the oxygen content is less than 800ppm, so that the method can be reused in the production of molybdenum alloy targets;
(2) Combining examples 1 and 4, it is known that when the temperature of the first hydrogenation is too low, the crushing of the material is difficult, and the crushing time increases, so that the purity of the molybdenum alloy powder decreases and the oxygen content increases; it is clear from the combination of examples 1 and 5 and 7 that if the first hydrogenation or the second hydrogenation is not heated after being vacuumized, high-purity hydrogen is directly introduced for hydrogenation, and if the heating treatment is not performed, the hydrogen content and the oxygen content in the molybdenum alloy powder are slightly increased, and the air is not fully replaced by inert gas, and a certain danger exists in the process of directly introducing hydrogen for heating hydrogenation, so that the operation is not recommended; when the temperature of the second hydrogenation is too high, the material hydrogenation degree is not high, and the crushing time is increased, so that the purity of the molybdenum alloy powder is reduced, and the oxygen content is increased;
(3) Combining examples 1 and 9-10, it is seen that when the temperature of the dehydrogenation treatment is low, the hydrogen content of the molybdenum alloy powder increases due to insufficient dehydrogenation; when the temperature of the dehydrogenation treatment is higher, the surface activity of the powder is too high, so that the oxygen content of the molybdenum alloy powder is increased;
(4) As can be seen from the combination of example 1 and comparative example 1, if the temperature of the first hydrogenation is too high, the sintering of the material part occurs, the hardness increases, the crushing difficulty increases, and the purity of the molybdenum alloy powder decreases; in comparison of the combination of example 1 and comparative examples 2 to 3, if the second hydrogenation temperature is too low, the degree of hydrogenation of the material is too low, the gas stream is difficult to crush, the crushing time is prolonged, the powder yield is low, and the oxygen content is increased.
(5) It is apparent from the combination of example 1 and comparative example 4 that the molybdenum alloy waste target could not be crushed effectively without the second hydrogenation treatment, the powder yield was severely lowered, and the purity of the molybdenum alloy powder was lowered and the oxygen content was increased due to the prolonged crushing time.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A method for recycling a molybdenum alloy waste target, characterized in that the method comprises the steps of: sequentially carrying out first hydrogenation, second hydrogenation, crushing treatment and dehydrogenation treatment on the molybdenum alloy waste target to obtain molybdenum alloy powder;
the temperature of the first hydrogenation is less than the temperature of the second hydrogenation.
2. The recycling method according to claim 1, wherein the first hydrogenation comprises: and placing the molybdenum alloy waste target in a hydrogenation device, vacuumizing, performing first heating, then introducing hydrogen for first hydrogenation, and then cooling to room temperature to obtain a first hydrogenation material.
3. The recycling method according to claim 2, characterized in that the first heating is performed in a protective atmosphere;
preferably, the temperature of the first heating is 250-300 ℃;
preferably, the flow rate of the hydrogen is 3-5m 3 /h；
Preferably, the pressure of the hydrogen is 0.05-0.08MPa;
preferably, the heating rate of the first hydrogenation is 3-5 ℃/min;
preferably, the temperature of the first hydrogenation is in the range 400-600 ℃;
preferably, the time of the first hydrogenation is from 5 to 8 hours.
4. A recycling method according to any one of claims 1-3, characterized in that the second hydrogenation comprises: and placing the first hydrogenation material in a hydrogenation device, vacuumizing, performing second heating, introducing hydrogen for second hydrogenation, and cooling to room temperature to obtain a second hydrogenation material.
5. The recycling method according to claim 4, wherein the second heating is performed in a protective atmosphere;
preferably, the temperature of the second heating is 250-300 ℃;
preferably, the flow rate of the hydrogen is 3-5m 3 /h；
Preferably, the pressure of the hydrogen is 0.05-0.08MPa;
preferably, the temperature rise rate of the second hydrogenation is 3-5 ℃/min;
preferably, the temperature of the second hydrogenation is from 450 ℃ to 700 ℃;
preferably, the second hydrogenation time is from 6 to 10 hours.
6. The recycling method according to any one of claims 1 to 5, characterized in that the crushing treatment is performed in a jet crusher;
preferably, the crushing treatment is carried out in a protective atmosphere;
preferably, the pressure of the protective atmosphere is 0.3-0.5MPa;
preferably, the time of the crushing treatment is 3-5 hours;
preferably, after the crushing treatment, molybdenum hydride alloy powder with the particle size of <100 μm is obtained.
7. The recycling method according to any one of claims 1 to 6, wherein the dehydrogenation process comprises: and (3) layering the molybdenum hydride alloy powder in a dehydrogenation device, vacuumizing, performing dehydrogenation treatment, and cooling to room temperature to obtain the molybdenum alloy powder.
8. The method of claim 7, wherein the thickness of each layer of molybdenum hydride alloy powder is less than or equal to 10mm;
preferably, the dehydrogenation treatment is carried out under vacuum<10 -2 Pa；
Preferably, the temperature of the dehydrogenation treatment is 700-900 ℃;
preferably, the dehydrogenation treatment is carried out for a period of time ranging from 6 to 10 hours.
9. The recycling method according to any one of claims 1 to 8, characterized in that the hydrogen content of the molybdenum alloy powder is < 200ppm;
preferably, the molybdenum alloy powder has an oxygen content of < 800ppm.
10. The recycling method according to any one of claims 1 to 9, characterized in that the recycling method comprises the steps of:
(1) First hydrogenation: placing a molybdenum alloy waste target in a hydrogenation device, vacuumizing, performing first heating, then introducing hydrogen for first hydrogenation, and then cooling to room temperature to obtain a first hydrogenated material;
the first heating is performed in a protective atmosphere; the temperature of the first heating is 250-300 ℃;
the flow rate of the hydrogen is 3-5m 3 And/h, the pressure is 0.05-0.08MPa;
the heating rate of the first hydrogenation is 3-5 ℃/min, the temperature is 400-600 ℃ and the time is 5-8h;
(2) Second hydrogenation: placing the first hydrogenation material in a hydrogenation device, vacuumizing, performing second heating, then introducing hydrogen to perform second hydrogenation, and cooling to room temperature to obtain a second hydrogenation material;
the second heating is performed in a protective atmosphere; the temperature of the second heating is 250-300 ℃;
the flow rate of the hydrogen is 3-5m 3 And/h, the pressure is 0.05-0.08MPa;
the temperature rising rate of the second hydrogenation is 3-5 ℃/min, the temperature is 450-700 ℃ and the time is 6-10h;
the temperature of the first hydrogenation is less than the temperature of the second hydrogenation;
(3) Crushing: placing the second hydrogenation material in an airflow crusher, introducing protective atmosphere with the pressure of 0.3-0.5MPa, and crushing for 3-5h to obtain molybdenum hydride alloy powder with the particle size of less than 100 mu m;
(4) Dehydrogenation treatment: layering molybdenum hydride alloy powder in a dehydrogenation device, vacuumizing, performing dehydrogenation treatment, and cooling to room temperature to obtain molybdenum alloy powder with hydrogen content less than 200ppm and oxygen content less than 800 ppm;
the thickness of each layer of molybdenum hydride alloy powder is less than or equal to 10mm;
vacuum degree of dehydrogenation treatment<10 -2 Pa, the temperature is 700-900 ℃ and the time is 6-10h.
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