CN103131859A - Comprehensive recycling method for metals in superalloy scrap - Google Patents
Comprehensive recycling method for metals in superalloy scrap Download PDFInfo
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- CN103131859A CN103131859A CN2013100700678A CN201310070067A CN103131859A CN 103131859 A CN103131859 A CN 103131859A CN 2013100700678 A CN2013100700678 A CN 2013100700678A CN 201310070067 A CN201310070067 A CN 201310070067A CN 103131859 A CN103131859 A CN 103131859A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title abstract description 8
- 150000002739 metals Chemical class 0.000 title abstract 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000843 powder Substances 0.000 claims abstract description 52
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 24
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 239000011733 molybdenum Substances 0.000 claims abstract description 20
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 31
- 239000000460 chlorine Substances 0.000 claims description 31
- 229910052801 chlorine Inorganic materials 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 239000002699 waste material Substances 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 239000010937 tungsten Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000889 atomisation Methods 0.000 claims description 8
- 238000007796 conventional method Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000012387 aerosolization Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 15
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 239000002253 acid Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a comprehensive recycling method for metals in superalloy scrap. The method comprises the following steps of: melting and atomizing nickel-based superalloy scrap into metal powder in certain particle size distribution by adopting a melting and atomizing process, constructing a metal powder bed layer by placing the metal powder in a fixed fluidized bed, placing the fixed fluidized bed in a tubular furnace, controlling the tubular furnace to be at a certain temperature, and enabling reactant gas with a certain pressure to pass through the metal powder bed layer from bottom to top, so that the reactant gas and nickel-based superalloy powder react at a certain reaction temperature to generate metallic oxides and metal chlorides; and separating different metals by utilizing that saturated vapor pressures of different metallic chlorides are different, then respectively treating the metals in a known manner, and recycling rare and precious metals, especially the metals such as rhenium, molybdenum and ruthenium. By adopting the comprehensive recycling method provided by the invention, the aim of comprehensively recycling valuable metals can be achieved, and the recycling efficiency of rare metals can be greatly improved; and the process is concise, the cost is low, and no pollution is produced.
Description
Technical field
The present invention relates to nickel base superalloy, particularly contain the comprehensive recovering process of the nickel base superalloy waste material of rare precious metal rhenium, ruthenium, tungsten, molybdenum, tantalum etc.
Background technology
Nickel base superalloy refers to take the austenitic alloy of nickel as base (nickeliferous more than 50%).There are higher-strength, better over-all propertieies such as anti-oxidant and corrosion resistance nature, good fatigue property, fracture toughness property 650～1100 ℃ of scopes.
Nickel-base alloy contains more than ten kind of alloying element, and wherein Cr mainly plays anti-oxidant and anticorrosive effect, and other elements mainly play strengthening effect.According to their strengthening effect mode, can be divided into: the solution strengthening element, as tungsten, molybdenum, cobalt, chromium and vanadium etc.; The precipitation strength element, as aluminium, titanium, niobium and tantalum; The grain-boundary strengthening element, as boron, zirconium, magnesium and yttrium etc.
Nickel base superalloy is used for manufacturing aero-jet engine, the hot-end component of various industry gas turbine widely.Also can be used as the high-temperature component of rocket engine, nuclear reactor, petrochemical complex and Energy conversion equipment etc.At present, on advanced engine, nickelalloy has accounted for half of gross weight, not only turbine blade and combustion chamber, and the turbine disk even after what compressor blade also bring into use nickelalloy.In the present generation aircraft engine, turbine blade almost all adopts the nickel-base alloy manufacture.Nickelalloy can become the leading of superalloy, its major cause, and the one, more alloying element can be dissolved in nickel-base alloy, and structure stability preferably can be kept; The 2nd, can form compound g'[Ni3 (Al, Ti) between the orderly A3B shaped metal of coherence] as strengthening phase, alloy is effectively strengthened, obtain than iron-base superalloy and the higher hot strength of cobalt base superalloy; The 3rd, the nickel-base alloy that contains chromium has than the better anti-oxidant and resistance to combustion gas corrosion ability of iron-base superalloy.
Because the alloying element in nickel base superalloy is numerous, carry out recycle applications more difficult after its finishes service hours, but its alloying element contained is the few strategic raw metal of nature reserves.Resource national conditions based on China, the scarcity of resources such as nickel, cobalt, rhenium, tantalum, tungsten, molybdenum, no matter from environmental benefit and economic benefit, be all very significant to the recycling of nickel base superalloy waste material.
The recovery of nickel base superalloy waste material mainly contains two kinds of pyrogenic process and hydrometallurgys, but, due to multiple considerations such as the complex characteristics of its technique and economic evaluation, environmental evaluations, not yet has a kind of economically viable recovery process to be put into practice.The current characteristics for nickel base superalloy, as, complex chemical composition is changeable, and main flow process using wet processing carries out comprehensive reutilization, and its technique generally comprises the technological processs such as leaching, the pre-removal of impurities of chemistry, abstraction impurity removal, Separation of nickel and cobalt, but this technical process is long, energy consumption is high, acid consumption is large, and the environmental protection treatment cost is high, and the rare metal direct yield is low, easily loss on stream, economic benefit is not obvious.
Summary of the invention
For above problem, the object of the present invention is to provide a kind of economy, high-temperature alloy waste material metal efficient, environmental protection comprehensively to reclaim novel process, with simplification of flowsheet, reduce the energy consumption of whole operation, and the consumption that reduces mineral acid, reduce in environmental requirement, especially improve the rare metal direct yield, reclaim to greatest extent the high price rare metal, improve the economic benefit of whole technique.
The present invention realizes by following technical proposal: a kind of comprehensive method reclaimed of high-temperature alloy waste material metal, and following each step of process:
Nickel base superalloy waste material cutting particle is become to 1～2cm, carry out again melting, and to take the aerosolization mode be the alloyed metal powder by its atomization, the silicon oxide powder that is 100～150 μ m with particle diameter by alloyed metal powder 1:1 by volume mixes, build the metal-powder bed, then with the heat-up rate of 2～5 ℃/minute, the metal-powder bed is warming up to 400～500 ℃, pass into from bottom to up oxygen or pressurized air simultaneously, be incubated 1～3 hour, be cooled to subsequently 300～400 ℃, and stop passing into oxygen or pressurized air, then pass into from bottom to up nitrogen and chlorine, be incubated 1～3 hour under 300～400 ℃, be warming up to 500～600 ℃ with 5～10 ℃/minute again, be incubated 1～3 hour, be cooled to subsequently below 200 ℃, stop passing into nitrogen and chlorine, gas (the ReCl produced during this time
5, WCl
6, MoCl
5, TaCl
5and RuCl
3) by water, collect and obtain solution A and (contain the high rhenium acid group ion, tungstate ion, molybdenum acid ion and TaCl
5and RuCl
3the aqueous solution), and obtain rhenium, tungsten, molybdenum, tantalum, ruthenium through conventional method separating-purifying, reaction residue B on the metal-powder bed obtains solution C and filter residue D through washing, filter residue D being placed at 35～45 ℃ of temperature to the hydrochloric acid soln that mass concentration is 10～30% soaks 1～3 hour, obtain after filtration again solution E and filter residue F, filter residue F is given up, and solution C and solution E merging are obtained to nickel, cobalt, copper by the ordinary method separating-purifying.
Described alloyed metal powder is the alloyed metal powder that atomization is 10～50 μ m.
The thickness of described metal-powder bed is 2～10cm.
Describedly pass into oxygen or compressed-air actuated pressure is 1.5～2 normal atmosphere, air flow rate is 200～2000ml/ minute.
The described pressure that passes into nitrogen and chlorine is 1.2～2 normal atmosphere, and the flow of nitrogen is 200～2000ml/ minute, and the flow of chlorine is 100～1000ml/ minute, and nitrogen is controlled at 2～4:1 with the chlorine flowrate ratio.
Describedly through conventional method separating-purifying, obtaining rhenium, tungsten, molybdenum, tantalum, ruthenium, is to add ammoniacal liquor in solution A, obtains the ammonium perrhenate precipitation, carries out solid-liquid separation, solid-state ammonium perrhenate again after repeatedly dissolving the purification drying logical hydrogen reduction can obtain rhenium metal; Other are the separation of purifying respectively of ripe and known road technology as the rare precious metals such as tungsten, molybdenum, tantalum, ruthenium all can adopt.
Describedly through conventional method separating-purifying, obtain nickel, cobalt, copper, the solution of nickelous chloride, cobalt chloride and cupric chloride is separated through extraction process, and the solution after separating is entered to electrolyzer, utilize known electrolysis process can obtain high-purity metallic nickel, cobalt, copper.
Know-why of the present invention is for adopting the metal-powder that atomized molten technique is certain grain size distribution by nickel base superalloy waste material atomized molten, and by metal-powder in the certain thickness metal-powder bed of fixed fluidized bed middle structure, the fixed fluidized bed tube furnace that is placed in, tube furnace is controlled to certain temperature, the reactant gases that simultaneously will have a certain pressure is as oxygen, chlorine, from bottom to top by the metal-powder bed, reactant gases and Ni-base Superalloy Powder are reacted under certain temperature of reaction, generate metal oxide and muriate, and utilize the muriatic saturated vapor pressure difference of different metal, different metal is separated, and will process respectively in known manner subsequently, reclaim rare precious metal, rhenium metal particularly, molybdenum, ruthenium.Adopt above processing step, the nickel base superalloy waste material is obtained to the larger powdered alloy of specific surface area through atomized molten technique, be conducive to the contact area of augmenting response gas and alloy, improve speed of response and efficiency.At high temperature pass into oxygen or pressurized air, be conducive to the reactions such as reactive metal aluminium, titanium and first generate oxide compound, reduce the chlorine consumption, reduce the subsequent technique content of reactive metal at a low price as far as possible, simple flow, enhance productivity, and increases economic efficiency simultaneously.
Advantage and effect that the present invention possesses are:
Utilize the different metal element reaction temperature of controlling in chlorine and nickel base superalloy, generate metal chloride, especially rare metal rhenium, molybdenum, ruthenium with different saturation vapour pressures, its muriate is gaseous state, utilizes gas solid separation that metallic element is separated.Adopt this technique, with other method, compare, strong oxidizer chlorine is easy to react with metallic element the generation metal chloride under hot conditions, do not need to expend a large amount of mineral acids, utilize the different saturation vapour pressure characteristics of metal chloride simultaneously, make the different metal element, especially yttrium just carries out effective gas solid separation with other metallic elements in reaction process, greatly shortened on the one hand technical process, simplified production process, do not need a large amount of mineral acids to carry out oxide treatment simultaneously, under environmental protection pressure, while rare metal rhenium, molybdenum, the metal chloride saturated vapo(u)r of ruthenium forces down, be easy to volatilization, so at first the rare technology in the nickel base superalloy waste material is separated in chloridization process from metallic matrix, reach the preliminary purpose of separating-purifying.The different mechanism at reactant aqueous solution according to the different metal muriate are processed by known technique in subsequent technique simultaneously, reach the comprehensive purpose reclaimed of high-valency metal, can greatly improve the direct yield of rare metal simultaneously.Obtain larger economic benefit.Unreacted chlorine tail gas can adopt known maturation process to carry out harmless treatment, so this technique is that a kind of technique is terse, cost is low, free of contamination comprehensive recycling process, there is not yet relevant report both at home and abroad.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
Adopting certain model nickel base superalloy is raw material, and composition is as following table:
The above-mentioned nickel base superalloy waste material cutting of 10kg particle is become to 1cm, carry out again melting in the intermediate frequency (IF) smelting crucible, and take the aerosolization mode by its atomization the alloyed metal powder as 23 μ m, the silicon oxide powder (purity is greater than 99%) that is 100 μ m with particle diameter by alloyed metal powder 1:1 by volume mixes, be placed on the quartz sand sandwich layer, the metal-powder bed that structure thickness is 2cm, then with the heat-up rate of 2 ℃/minute, the metal-powder bed in tube furnace is warming up to 400 ℃, pass into from bottom to up pressure is 1.5 normal atmosphere simultaneously, the oxygen that air flow rate is 200ml/ minute, be incubated 3 hours, be cooled to subsequently 300 ℃, and stop passing into oxygen, then passing into from bottom to up pressure is 1.2 atmospheric nitrogen and chlorine, wherein the flow of nitrogen is 200ml/ minute, the flow of chlorine is 100ml/ minute (nitrogen is controlled at 2:1 with the chlorine flowrate ratio), under 300 ℃, insulation is 3 hours, be warming up to 500 ℃ with 5 ℃/minute again, be incubated 3 hours, be cooled to subsequently below 200 ℃, stop passing into nitrogen and chlorine, gas (the ReCl produced during this time
5, WCl
6, MoCl
5, TaCl
5and RuCl
3) by water, collect and obtain solution A and (contain the high rhenium acid group ion, tungstate ion, molybdenum acid ion and TaCl
5and RuCl
3the aqueous solution), and obtain rhenium, tungsten, molybdenum, tantalum, ruthenium through conventional method separating-purifying, reaction residue B on the metal-powder bed obtains solution C and filter residue D through washing, filter residue D being placed at 35 ℃ of temperature to the hydrochloric acid soln that mass concentration is 30% soaks 1 hour, obtain after filtration again solution E and filter residue F, filter residue F is given up, and solution C and solution E merging are obtained to nickel, cobalt, copper by the ordinary method separating-purifying.Finally obtain molybdenum powder 156g, cobalt powder 922g, electrolytic nickel 5122g.
Embodiment 2
Adopting certain model nickel base superalloy is raw material, and composition is as following table:
The above nickel base superalloy waste material cutting of 15kg particle is become to 1.5cm, carry out again melting in the intermediate frequency (IF) smelting crucible, and take the aerosolization mode by its atomization the alloyed metal powder as 10 μ m, the silicon oxide powder (purity is greater than 99%) that is 150 μ m with particle diameter by alloyed metal powder 1:1 by volume mixes, be placed on the quartz sand sandwich layer, the metal-powder bed that structure thickness is 6cm, then with the heat-up rate of 5 ℃/minute, the metal-powder bed in tube furnace is warming up to 500 ℃, pass into from bottom to up pressure is 2 normal atmosphere simultaneously, the oxygen that air flow rate is 2000ml/ minute, be incubated 2 hours, be cooled to subsequently 400 ℃, and stop passing into oxygen, then passing into from bottom to up pressure is 2 atmospheric nitrogen and chlorine, wherein the flow of nitrogen is 2000ml/ minute, the flow of chlorine is 500ml/ minute (nitrogen is controlled at 4:1 with the chlorine flowrate ratio), under 400 ℃, insulation is 1 hour, be warming up to 600 ℃ with 10 ℃/minute again, be incubated 1 hour, be cooled to subsequently below 200 ℃, stop passing into nitrogen and chlorine, gas (the ReCl produced during this time
5, WCl
6, MoCl
5, TaCl
5and RuCl
3) by water, collect and obtain solution A and (contain the high rhenium acid group ion, tungstate ion, molybdenum acid ion and TaCl
5and RuCl
3the aqueous solution), and obtain rhenium, tungsten, molybdenum, tantalum, ruthenium through conventional method separating-purifying, reaction residue B on the metal-powder bed obtains solution C and filter residue D through washing, filter residue D being placed at 40 ℃ of temperature to the hydrochloric acid soln that mass concentration is 20% soaks 2 hours, obtain after filtration again solution E and filter residue F, filter residue F is given up, and solution C and solution E merging are obtained to nickel, cobalt, copper by the ordinary method separating-purifying.Finally obtain rhenium powder 401g, molybdenum powder 202g, cobalt powder 1057g, tantalum powder 932g, tungsten powder 667g, hafnium powder 19g, electrolytic nickel 8231g.
Embodiment 3
Adopting certain model nickel base superalloy is raw material, and composition is as following table:
The above nickel base superalloy waste material cutting of 12kg particle is become to 2cm, carry out again melting in the intermediate frequency (IF) smelting crucible, and take the aerosolization mode by its atomization the alloyed metal powder as 50 μ m, the silicon oxide powder that is 110 μ m with particle diameter by alloyed metal powder 1:1 by volume mixes, be placed on the quartz sand sandwich layer, the metal-powder bed that structure thickness is 10cm, then with the heat-up rate of 2.5 ℃/minute, the metal-powder bed in tube furnace is warming up to 450 ℃, pass into from bottom to up pressure is 1.8 normal atmosphere simultaneously, the pressurized air that air flow rate is 1500ml/ minute, be incubated 1 hour, be cooled to subsequently 350 ℃, and stop passing into pressurized air, then passing into from bottom to up pressure is 1.5 atmospheric nitrogen and chlorine, wherein the flow of nitrogen is 1500ml/ minute, the flow of chlorine is 500ml/ minute (nitrogen is controlled at 3:1 with the chlorine flowrate ratio), under 350 ℃, insulation is 2 hours, be warming up to 550 ℃ with 8 ℃/minute again, be incubated 2 hours, be cooled to subsequently below 200 ℃, stop passing into nitrogen and chlorine, gas (the ReCl produced during this time
5, WCl
6, MoCl
5, TaCl
5and RuCl
3) by water, collect and obtain solution A and (contain the high rhenium acid group ion, tungstate ion, molybdenum acid ion and TaCl
5and RuCl
3the aqueous solution), and obtain rhenium, tungsten, molybdenum, tantalum, ruthenium through conventional method separating-purifying, reaction residue B on the metal-powder bed obtains solution C and filter residue D through washing, filter residue D being placed under temperature 45 C to the hydrochloric acid soln that mass concentration is 10% soaks 3 hours, obtain after filtration again solution E and filter residue F, filter residue F is given up, and solution C and solution E merging are obtained to nickel, cobalt, copper by the ordinary method separating-purifying.Finally obtain molybdenum powder 192g, cobalt powder 1021g, tungsten powder 1058g, electrolytic nickel 9622g.
Embodiment 4
Adopting certain model nickel base superalloy is raw material, and composition is as following table:
The above nickel base superalloy waste material cutting of 15kg particle is become to 1.5cm, carry out again melting in the intermediate frequency (IF) smelting crucible, and take the aerosolization mode by its atomization the alloyed metal powder as 10 μ m, the silicon oxide powder (purity is greater than 99%) that is 150 μ m with particle diameter by alloyed metal powder 1:1 by volume mixes, be placed on the quartz sand sandwich layer, the metal-powder bed that structure thickness is 6cm, then with the heat-up rate of 5 ℃/minute, the metal-powder bed in tube furnace is warming up to 500 ℃, pass into from bottom to up pressure is 2 normal atmosphere simultaneously, the oxygen that air flow rate is 2000ml/ minute, be incubated 2 hours, be cooled to subsequently 400 ℃, and stop passing into oxygen, then passing into from bottom to up pressure is 2 atmospheric nitrogen and chlorine, wherein the flow of nitrogen is 2000ml/ minute, the flow of chlorine is 1000ml/ minute (nitrogen is controlled at 2:1 with the chlorine flowrate ratio), under 400 ℃, insulation is 1 hour, be warming up to 600 ℃ with 10 ℃/minute again, be incubated 1 hour, be cooled to subsequently below 200 ℃, stop passing into nitrogen and chlorine, gas (the ReCl produced during this time
5, WCl
6, MoCl
5, TaCl
5and RuCl
3) by water, collect and obtain solution A and (contain the high rhenium acid group ion, tungstate ion, molybdenum acid ion and TaCl
5and RuCl
3the aqueous solution), and obtain rhenium, tungsten, molybdenum, tantalum, ruthenium through conventional method separating-purifying, reaction residue B on the metal-powder bed obtains solution C and filter residue D through washing, filter residue D being placed at 40 ℃ of temperature to the hydrochloric acid soln that mass concentration is 20% soaks 2 hours, obtain after filtration again solution E and filter residue F, filter residue F is given up, and solution C and solution E merging are obtained to nickel, cobalt, copper by the ordinary method separating-purifying.Finally obtain rhenium powder 401g, molybdenum powder 202g, cobalt powder 1057g, tantalum powder 932g, tungsten powder 667g, hafnium powder 19g, electrolytic nickel 8231g.
Claims (5)
1. the comprehensive method reclaimed of a high-temperature alloy waste material metal is characterized in that through following each step:
Nickel base superalloy waste material cutting particle is become to 1～2cm, carry out again melting, and to take the aerosolization mode be the alloyed metal powder by its atomization, the silicon oxide powder that is 100～150 μ m with particle diameter by alloyed metal powder 1:1 by volume mixes, build the metal-powder bed, then with the heat-up rate of 2～5 ℃/minute, the metal-powder bed is warming up to 400～500 ℃, pass into from bottom to up oxygen or pressurized air simultaneously, be incubated 1～3 hour, be cooled to subsequently 300～400 ℃, and stop passing into oxygen or pressurized air, then pass into from bottom to up nitrogen and chlorine, be incubated 1～3 hour under 300～400 ℃, be warming up to 500～600 ℃ with 5～10 ℃/minute again, be incubated 1～3 hour, be cooled to subsequently below 200 ℃, stop passing into nitrogen and chlorine, the gas produced is during this time collected and is obtained solution A by water, and obtain rhenium, tungsten, molybdenum, tantalum, ruthenium through conventional method separating-purifying, reaction residue B on the metal-powder bed obtains solution C and filter residue D through washing, filter residue D being placed at 35～45 ℃ of temperature to the hydrochloric acid soln that mass concentration is 10～30% soaks 1～3 hour, obtain after filtration again solution E and filter residue F, filter residue F is given up, and solution C and solution E merging are obtained to nickel, cobalt, copper by the ordinary method separating-purifying.
2. the method that high-temperature alloy waste material metal according to claim 1 comprehensively reclaims, it is characterized in that: described alloyed metal powder is the alloyed metal powder that atomization is 10～50 μ m.
3. the method that high-temperature alloy waste material metal according to claim 1 comprehensively reclaims, it is characterized in that: the thickness of described metal-powder bed is 2～10cm.
4. the comprehensive method reclaimed of high-temperature alloy waste material metal according to claim 1 is characterized in that: describedly pass into oxygen or compressed-air actuated pressure is 1.5～2 normal atmosphere, air flow rate is 200～2000ml/ minute.
5. the method that high-temperature alloy waste material metal according to claim 1 comprehensively reclaims, it is characterized in that: the described pressure that passes into nitrogen and chlorine is 1.2～2 normal atmosphere, the flow of nitrogen is 200～2000ml/ minute, the flow of chlorine is 100～1000ml/ minute, and nitrogen is controlled at 2～4:1 with the chlorine flowrate ratio.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104651620A (en) * | 2015-03-20 | 2015-05-27 | 西安瑞鑫科金属材料有限责任公司 | Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material |
| CN108726581A (en) * | 2018-06-06 | 2018-11-02 | 江西理工大学 | The method for preparing iron-doped nickel oxide using Ni-Fe alloy melts |
| CN110129572A (en) * | 2019-06-18 | 2019-08-16 | 中国科学院兰州化学物理研究所 | A method of high-purity rehenic acid ammonium is prepared using waste and old nickel base superalloy |
| CN110846502A (en) * | 2019-10-28 | 2020-02-28 | 中南大学 | Method for recovering waste high-temperature alloy through melt extraction |
| CN113337717A (en) * | 2021-06-11 | 2021-09-03 | 南昌航空大学 | Method for separating and recovering valuable metals in electroplating sludge by adopting combined chlorinating agent |
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| CN104651620A (en) * | 2015-03-20 | 2015-05-27 | 西安瑞鑫科金属材料有限责任公司 | Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material |
| CN108726581A (en) * | 2018-06-06 | 2018-11-02 | 江西理工大学 | The method for preparing iron-doped nickel oxide using Ni-Fe alloy melts |
| CN108726581B (en) * | 2018-06-06 | 2020-05-19 | 江西理工大学 | Method for preparing nickel-iron oxide by using Ni-Fe alloy melt |
| CN110129572A (en) * | 2019-06-18 | 2019-08-16 | 中国科学院兰州化学物理研究所 | A method of high-purity rehenic acid ammonium is prepared using waste and old nickel base superalloy |
| CN110129572B (en) * | 2019-06-18 | 2021-01-05 | 中国科学院兰州化学物理研究所 | Method for preparing high-purity ammonium rhenate by using waste nickel-based high-temperature alloy |
| CN110846502A (en) * | 2019-10-28 | 2020-02-28 | 中南大学 | Method for recovering waste high-temperature alloy through melt extraction |
| CN113337717A (en) * | 2021-06-11 | 2021-09-03 | 南昌航空大学 | Method for separating and recovering valuable metals in electroplating sludge by adopting combined chlorinating agent |
| CN114196832A (en) * | 2021-12-16 | 2022-03-18 | 合肥工业大学 | Method for preparing rhenium powder by recycling tungsten-rhenium alloy waste |
| CN114196832B (en) * | 2021-12-16 | 2024-06-07 | 合肥工业大学 | Method for preparing rhenium powder by recycling tungsten-rhenium alloy waste |
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