CN112522519A - Method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste - Google Patents
Method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste Download PDFInfo
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 136
- 239000002699 waste material Substances 0.000 title claims abstract description 88
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910000691 Re alloy Inorganic materials 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000011084 recovery Methods 0.000 title claims abstract description 53
- 238000000926 separation method Methods 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title abstract description 26
- 239000002184 metal Substances 0.000 title abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000010937 tungsten Substances 0.000 claims abstract description 41
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 39
- 230000009467 reduction Effects 0.000 claims abstract description 33
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 47
- 238000006722 reduction reaction Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000012043 crude product Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 229910019571 Re2O7 Inorganic materials 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- 238000002309 gasification Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 11
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical class [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 abstract description 11
- 229910003449 rhenium oxide Inorganic materials 0.000 abstract description 11
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000009853 pyrometallurgy Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 101800004637 Communis Proteins 0.000 description 1
- 241000235527 Rhizopus Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OKTJSMMVPCPJKN-BJUDXGSMSA-N carbon-11 Chemical compound [11C] OKTJSMMVPCPJKN-BJUDXGSMSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- -1 salt compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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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
- C22B7/001—Dry processes
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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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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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
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
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- 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
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Abstract
The invention discloses a method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste, which has the following basic principle: oxidizing the waste containing tungsten and rhenium in flowing air at a certain temperature, realizing primary separation of tungsten and rhenium by utilizing different volatilization temperatures of tungsten and rhenium oxides, further realizing the purpose of removing tungsten from rhenium oxide gas by selective reduction of tungsten oxide by carbon according to different reduction temperatures of tungsten and rhenium by carbon, and finally carrying out ammonia water absorption and crystallization on the rhenium oxide gas, and drying and reducing hydrogen to obtain high-purity rhenium powder. The method has the advantages of short process flow, low cost, high tungsten-rhenium separation efficiency and rhenium recovery rate and high purity of the obtained rhenium powder, is suitable for tungsten-rhenium alloy waste with low rhenium content and difficult separation of tungsten and rhenium, and can obtain high-purity rhenium powder with the purity of more than or equal to 99.9 percent by batch production.
Description
Technical Field
The invention belongs to the field of scattered metal recovery, and particularly relates to a method for grading separation and recovery of rhenium metal from tungsten-rhenium alloy waste.
Background
Rhenium is a rare metal and is present in the earth's crust in an amount of only 1X 10-9The melting point is about 3180 ℃. Due to high heat resistance and high corrosion resistanceThe characteristics of corrosion, high hardness, mechanical strength and the like, and the rhenium is widely applied to the fields of high-temperature alloy, petroleum catalysis, metallurgy, electronics and the like. Rhenium is not abundant, and has no single independent mineral with mining value, and a part of rhenium exists in other mineral deposits, and a part of rhenium comes from the recovery of rhenium-containing alloy waste. With the shortage of rhenium-containing primary mineral resources, the recovery of rhenium from rhenium-containing alloy waste materials is receiving more and more attention. Rhenium resources in China are scarce, and with the development of the aerospace industry and the progress of scientific technology in the fields of chemical engineering, medical treatment and the like, the demand on rhenium is more and more great, so that the recovery and utilization of rhenium in rhenium-containing alloy waste materials become more important.
The unique physical and chemical properties of rhenium make its recovery process generally complex and difficult. The current technology for recovering rhenium from rhenium-containing alloy scrap mainly comprises pyrometallurgy and hydrometallurgy. Pyrometallurgy is a widely used method for recovering rare metals. Pyrometallurgy is carried out at high temperatures, during which the rhenium in the rhenium-containing waste is readily oxidized to form volatile, readily water-soluble Re2O7Gas, Re2O7And leaching with ammonia water or water, enriching rhenium in the form of ammonium perrhenate or perrhenic acid in the solution, evaporating, concentrating and crystallizing to obtain ammonium perrhenate or perrhenic acid crystal, and finally reducing with hydrogen to obtain metal rhenium. The technological principle of recovering rhenium by wet metallurgy is to leach rhenium from waste material by using oxidizing acid or alkali to make rhenium in solution as ReO4 -Then separating and enriching rhenium from the rhenium-containing solution by adopting a solvent extraction method, an ion exchange method, a chemical precipitation method and the like. Currently, molybdenite, rhenium-containing catalyst scrap, and rhenium-containing alloys are the primary sources of rhenium recovery. The tungsten-rhenium alloy is a solid solution strengthening alloy taking rhenium as a matrix, and because the chemical properties of tungsten and rhenium are very similar, the tungsten and the rhenium exist in the solution in the form of acid radical ions respectively, and the properties of the formed salt compounds are also very similar. Therefore, if the traditional hydrometallurgy is adopted to recover rhenium from the tungsten-rhenium alloy waste, such as a solvent extraction method or an ion exchange method, the aims of thoroughly separating and respectively extracting the two metals are fulfilled, the technology becomes more complicated, and breakthrough progress is difficult to achieve in the process.And the pyrometallurgy utilizes Re2O7Can selectively recover rhenium in the tungsten-rhenium alloy waste material, has good universality, has no requirement on the form of the rhenium-containing waste material, and is suitable for large-scale industrial production. Therefore, the development of a pyrometallurgical method for recovering metallic rhenium from tungsten-rhenium alloy scrap has important use value.
In recent years, researchers at home and abroad use a pyrometallurgical method to recover rhenium metal from rhenium-containing alloy waste, and a great deal of research is carried out, and a lot of results are obtained. Leaf of Rhizopus communis et al (Recovery of Rhinium from tungsten-Rhinium wire by alkali fusion in KOH-K)2CO3binary molten salt, International Journal of reflective Metals and Hard Materials 87(2020)105148) Using an alkaline fusion method from W95Re5The metallic rhenium is effectively recovered from the waste wire. The main steps of recovery include caustic melting, recrystallization, hydrogen reduction and scrubbing. The alkali melting temperature is 800 ℃, the reaction time is 60min, potassium perrhenate crystals are obtained, and finally, Re powder with the purity higher than 99.5 percent is obtained by reduction at 350 ℃, and the granularity is 19.37 mu m. The method is simple and feasible, the purity of the prepared rhenium powder is high, but the tungsten-rhenium separation efficiency is not high, the particle size of the prepared rhenium powder is large, and the recovery rate of rhenium is low. The Su Union cemented carbide factory adopts the method of oxidizing roasting-depositing rhenium to extract rhenium from molybdenite with rhenium content of 0.025%. Oxidizing and roasting at 540-600 deg.c to reach rhenium volatilizing rate of about 95% and Re content2O7The flue gas is collected by a leaching tower and a wet electric dust collector, and Re in the flue gas2O7Dissolving in water to generate perrhenic acid, adding potassium chloride to evaporate and crystallize when the solution is enriched to a certain degree to obtain white potassium perrhenate precipitate, and introducing hydrogen to reduce to prepare rhenium powder, wherein the recovery rate of rhenium is 85%. The method is simple and feasible, but the separation efficiency of tungsten and rhenium is not high, and the final recovery rate and purity of rhenium are low.
In conclusion, the research of recovering rhenium from the tungsten-rhenium alloy waste by adopting pyrometallurgy at present has the problems of low tungsten-rhenium separation efficiency, insufficient rhenium recovery rate and purity and the like. There are also other problems, such as WO during the oxidizing roasting process3Re capable of sublimating and volatilizing2O7The mixing of the gases causes the tungsten element contained in the collected product, resulting in impurities of the finally prepared rhenium powder, and the problems greatly influence the application of the rhenium in various fields. Therefore, the research on a method for recovering metal rhenium from tungsten-rhenium alloy scrap and obtaining high-recovery-rate and high-purity rhenium powder are key to the current research. The invention finds a method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste by researching thermodynamics, kinetics and reaction mechanism of tungsten and rhenium in the recovery process, and aims to provide reference and experience accumulation for future scholars and industries in rhenium recovery.
Disclosure of Invention
The invention aims to provide a method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste, and aims to solve the problems of low tungsten and rhenium separation efficiency, insufficient rhenium recovery rate and purity and the like in the process of recovering rhenium from the tungsten-rhenium alloy waste by adopting pyrometallurgy.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a method for grading separation and recovery of metallic rhenium from tungsten-rhenium alloy waste materials is based on the following basic principle: oxidizing waste containing tungsten and rhenium in flowing air at a certain temperature, realizing primary separation of tungsten and rhenium by utilizing different volatilization temperatures of tungsten and rhenium oxides, further realizing the purpose of removing tungsten from rhenium oxide gas by selective reduction of tungsten oxide by carbon according to different reduction temperatures of tungsten and rhenium by carbon, and finally carrying out ammonia water absorption, crystallization and dry hydrogen reduction on the rhenium oxide gas to obtain high-purity rhenium powder. The method specifically comprises the following steps:
(1) soaking the tungsten-rhenium alloy waste in dilute hydrochloric acid for half an hour to remove impurities on the surface of the waste, and then putting the waste into a blast drying oven for drying; crushing or grinding the dried waste, and fully drying in vacuum until the quality is not changed;
(2) the method comprises the following steps of arranging a double-temperature-zone tubular furnace with a shaft furnace structure, wherein a temperature zone I at the lower part of the double-temperature-zone tubular furnace is an oxidation gasification zone, and a temperature zone II at the upper part of the double-temperature-zone tubular furnace is a porous carbon selective reduction zone; the bottom gas inlet of the double-temperature-zone tube furnace is communicated with an air bottle through a gas valve; a gas outlet at the top of the double-temperature-zone tubular furnace is communicated to a collecting bottle filled with ammonia water through a pipeline;
respectively placing a quartz boat containing tungsten-rhenium alloy waste and porous carbon in a temperature area I and a temperature area II of a double-temperature-area tubular furnace; firstly, starting a heating program of a temperature zone II, heating to 750-900 ℃ and keeping the temperature; starting a heating program of the temperature area I when the temperature area II is heated to a constant temperature, raising the temperature to 600-750 ℃, and keeping the temperature for 2-3 hours; conveying air into the tube furnace in the heat preservation process;
the tungsten-rhenium alloy waste is fully oxidized in a temperature zone I to realize the primary separation of tungsten and rhenium; WO produced3Gas and Re2O7Gas enters a temperature zone II, and porous carbon selective reduction WO is carried out3Allowing the gas to remain in temperature zone II as metallic tungsten for the purpose of removing tungsten from rhenium oxide to obtain high purity Re2O7A gas; re2O7The gas enters a collecting bottle filled with ammonia water;
after the constant temperature is finished, cooling the solution to the room temperature along with the furnace, and collecting the solution in a collecting bottle filled with ammonia water;
(3) putting the collected solution into an oven for evaporation crystallization, and adding rhenium into NH4ReO4Is precipitated in the form of crystals to give NH4ReO4A crude product; to the NH4ReO4Recrystallizing the crude product to obtain pure NH4ReO4Powder;
(4) the obtained pure NH4ReO4And placing the powder in a reduction furnace, and carrying out reduction reaction in a hydrogen atmosphere to obtain the rhenium powder.
Further, in the step (1), the tungsten-rhenium alloy scrap is in the forms of blocks, wires and powder, and the rhenium content is 1 wt% -15 wt%.
Further, in the step (2), the two-temperature zone tube furnace: the temperature zone I is a straight pipe and is connected with a flange with a fixed support for supporting the tungsten-rhenium alloy waste, so that the tungsten-rhenium alloy waste is fully oxidized, and the primary separation of tungsten and rhenium is realized; the temperature zone II is embedded with an S-shaped pipe filled with porous carbon to ensure that the passing gas is fully contacted with the porous carbon,ensure WO3Is completely reduced.
Further, in the step (2), the porous carbon is porous activated carbon, mesoporous carbon or nano carbon particles.
Further, in the step (2), the heating rate of the temperature zone I is 3 ℃/min to 5 ℃/min.
Further, in the step (2), the temperature of the temperature zone II is always kept higher than that of the temperature zone I in the heat preservation stage.
Further, in the step (2), the flow range of the conveying air is 0.1L/min-1.0L/min.
Further, in the step (3), the temperature of the evaporative crystallization is 80 ℃.
Further, in the step (3), the NH is treated4ReO4The method for recrystallizing the crude product comprises the following steps: reacting the NH with4ReO4Dissolving the crude product in deionized water at 100 deg.C, and cooling to below 15 deg.C to obtain NH4ReO4Recrystallizing and repeating for 2-3 times to obtain pure NH4ReO4Powder of
Further, in the step (4), the reduction temperature of the reduction reaction is 450-600 ℃, and the reaction time is 60-120 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the device used by the invention is a double-temperature-zone tubular furnace as shown in figure 1, which is of a shaft furnace structure and comprises an oxidation gasification area (temperature zone I) and a porous carbon selective reduction area (temperature zone II); the temperature zone I is connected with a flange with a fixed support and used for supporting the tungsten-rhenium alloy waste to fully oxidize the tungsten-rhenium alloy waste so as to realize the preliminary separation of tungsten and rhenium; the temperature zone II is embedded with the S-shaped pipe filled with porous carbon, so that the passing gas is fully contacted with the porous carbon, and the WO is ensured3Is completely reduced. Controlling the heating sequence and the heating temperature of the two temperature zones to fully oxidize the tungsten-rhenium alloy waste in the temperature zone I and to oxidize the rhenium oxide Re generated in the temperature zone I2O7Gas and partially volatilized WO3The gas is effectively separated in the temperature zone II, and the recovery rate and the purity of rhenium are improved.
2. The invention passes through the multiple holesThe reduction of tungsten oxide by carbon achieves the purpose of removing tungsten from the rhenium oxide gas. Porous carbon capable of selectively reducing WO3The gas is allowed to remain in the form of metallic tungsten in the porous carbon-filled S-tube in temperature zone II, while Re2O7The gas enters a collecting bottle filled with ammonia water through an S-shaped pipe, and pure rhenium oxide can be obtained in the process. Meanwhile, the thermodynamics and dynamics research on tungsten, rhenium and carbon shows that the carbon, O and oxygen are enabled to be porous by controlling the air flow and the heating temperature in the system2、WO3And Re2O7The reaction between the gases reaches a state of dynamic equilibrium in which the porous carbon and Re are in a state of equilibrium2O7Hardly react with WO3Reduction reaction is carried out, so that the purpose of removing tungsten in rhenium oxide gas is realized, tungsten and rhenium are separated efficiently, and the recovery rate and purity of rhenium powder are improved.
3. The method can realize high-efficiency recovery of blocky, filiform and powdery tungsten-rhenium alloy scraps, does not need specific recovery equipment, has simple equipment requirement, is suitable for tungsten-rhenium alloy scraps which contain less rhenium (3 wt% -10 wt%) and are difficult to separate tungsten and rhenium, and can obtain high-purity rhenium powder with the purity of more than or equal to 99.9% by batch production.
4. Compared with hydrometallurgy, the method has the advantages of short process flow, high tungsten and rhenium separation efficiency, high recovery rate and purity of the obtained rhenium powder, simple operation, simple equipment and suitability for large-scale production.
Drawings
Fig. 1 is a schematic view of the apparatus employed in the present invention, wherein the reference numerals: 1-compressed air cylinder, 2-gas flowmeter, 3-gas inlet pipe, 4-quartz tube, 5-external heat-insulating layer, 6-heating element, 7-mesh support, 8-quartz boat, 9-tungsten-rhenium alloy waste, 10-S type pipe, 11-porous carbon, 12-double temperature zone tube furnace, 13-gas outlet pipe, 14-collecting bottle, 15-ammonia water and 16-gas outlet pipe.
Fig. 2 is an SEM picture of the metal rhenium powder obtained in example 1.
Fig. 3 is a TEM picture of the metal rhenium powder obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The apparatus used in the following examples is shown in FIG. 1 and comprises a shaft furnace structure of a dual-temperature-zone tubular furnace 12, wherein a temperature zone I at the lower part of the dual-temperature-zone tubular furnace is an oxidation gasification zone and a temperature zone II at the upper part of the dual-temperature-zone tubular furnace is a porous carbon selective reduction zone. The temperature zone I is a straight pipe and is connected with a flange with a fixed mesh bracket 7 for supporting a quartz burning boat 8 filled with tungsten-rhenium alloy waste 9; the temperature zone II is embedded with the S-shaped pipe 10 filled with the porous carbon 11, so that the passing gas is fully contacted with the porous carbon, and the WO is ensured3Is completely reduced.
A gas inlet at the bottom of the double-temperature-zone tubular furnace 12 is communicated with a compressed air cylinder 1 through a gas inlet pipe 3, and a gas flowmeter 2 is also arranged on the gas inlet pipe; the top gas outlet of the double-temperature-zone tube furnace 12 is inserted below the ammonia water liquid level of a collecting bottle 14 filled with ammonia water 15 through an air outlet pipe 13, and an exhaust pipe 16 is further arranged in the collecting bottle.
Other structures of the double-temperature-zone tube furnace, such as the quartz tube 4, the outer insulating layer 5 and the heating body 6, are conventional structures, and are not described in detail herein. The double-temperature-zone tube furnace can be any type on the market as long as the requirements of material placement, gas circulation, heating and the like are met.
Example 1
A method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste comprises the following specific steps:
(1) weighing 40g of tungsten-rhenium alloy powder waste with the rhenium content of 5%, soaking the tungsten-rhenium alloy powder waste in dilute hydrochloric acid for half an hour to remove impurities on the surface of the waste, and then putting the waste into a forced air drying oven for drying; the dried powder waste is ground to the granularity of less than 10 mu m and is fully dried in vacuum until the mass is not changed.
(2) As shown in fig. 1, a quartz boat containing tungsten-rhenium alloy powder waste and porous carbon are respectively placed in an oxidation gasification region (temperature region I) and a porous carbon selective reduction region (temperature region II) of a dual-temperature-region tube furnace; firstly, starting a heating program of a temperature zone II, heating to 750 ℃, and keeping the temperature; starting the heating program of the temperature zone I when the temperature zone II is heated to a constant temperature, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 3 h; meanwhile, the gas valve is controlled to convey air to the system, and the flow range is 0.5L/min;
fully oxidizing the tungsten-rhenium alloy powder waste in a temperature zone I to realize primary separation of tungsten and rhenium; WO produced3Gas and Re2O7Gas enters a temperature zone II, and porous carbon selective reduction WO is carried out3The gas is allowed to remain in temperature zone II in the form of metallic tungsten; re2O7The gas enters a collecting bottle filled with ammonia water;
and after the heat preservation is finished, cooling the solution to the room temperature along with the furnace, and collecting the solution in the collection bottle filled with the ammonia water.
(3) Evaporating the collected solution in an oven at 80 ℃ for crystallization, and reacting rhenium with NH4ReO4Is precipitated in the form of crystals to give NH4ReO4A crude product;
reacting NH4ReO4Dissolving the crude product in deionized water at 100 deg.C, and cooling to below 15 deg.C to obtain NH4ReO4Recrystallizing and repeating for 3 times to obtain pure NH4ReO4And (3) powder.
(4) Adding the above pure NH4ReO4And placing the powder in a reduction furnace, heating to 450 ℃ in hydrogen atmosphere for reduction reaction for 90min to obtain the rhenium powder.
NH prepared as described above in this example4ReO4Powder and metal rhenium powder, characterized: NH (NH)4ReO4The purity of the powder was about 99.9959%; the rhenium powder has good crystallinity, the average particle size is about 14.17 mu m, the purity is about 99.9334 percent, and the recovery rate of rhenium reaches 91.43 percent. The method of the invention is adopted to recover rhenium from the tungsten-rhenium alloy powder waste material with the rhenium content of 5 percent, and the final recovery rate and purity of rhenium are higher.
Example 2
A method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste comprises the following specific steps:
(1) weighing 40g of tungsten-rhenium alloy powder waste with the rhenium content of 5%, soaking the tungsten-rhenium alloy powder waste in dilute hydrochloric acid for half an hour to remove impurities on the surface of the waste, and then putting the waste into a forced air drying oven for drying; the dried powder waste is ground to the granularity of less than 10 mu m and is fully dried in vacuum until the mass is not changed.
(2) As shown in fig. 1, a quartz boat containing tungsten-rhenium alloy powder waste and porous carbon are respectively placed in an oxidation gasification region (temperature region I) and a porous carbon selective reduction region (temperature region II) of a dual-temperature-region tube furnace; firstly, starting a heating program of a temperature zone II, heating to 900 ℃ and keeping the temperature; starting a heating program of the temperature area I when the temperature area II is heated to a constant temperature, heating to 750 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 3 h; meanwhile, the gas valve is controlled to convey air to the system, and the flow range is 0.5L/min to 1.0L/min;
fully oxidizing the tungsten-rhenium alloy powder waste in a temperature zone I to realize primary separation of tungsten and rhenium; WO produced3Gas and Re2O7Gas enters a temperature zone II, and porous carbon selective reduction WO is carried out3The gas is allowed to remain in temperature zone II in the form of metallic tungsten; re2O7The gas enters a collecting bottle filled with ammonia water;
and after the heat preservation is finished, cooling the solution to the room temperature along with the furnace, and collecting the solution in the collection bottle filled with the ammonia water.
(3) Evaporating the collected solution in an oven at 80 ℃ for crystallization, and reacting rhenium with NH4ReO4To obtain NH4ReO4A crude product;
reacting NH4ReO4Dissolving the crude product in deionized water at 100 deg.C, and cooling to below 15 deg.C to obtain NH4ReO4Recrystallizing and repeating for 3 times to obtain pure NH4ReO4And (3) powder.
(4) Adding the above pure NH4ReO4And placing the powder in a reduction furnace, heating to 450 ℃ in hydrogen atmosphere for reduction reaction for 90min to obtain the rhenium powder.
NH prepared as described above in this example4ReO4Powder and metal rhenium powder, characterized: NH (NH)4ReO4The purity of the powder was about 99.9981%; the rhenium powder has good crystallinity, the average grain diameter is about 14.11 mu m, the purity is about 99.9467 percent, and the recovery rate of rhenium reaches 92.58 percent. The method of the invention is adopted to recover rhenium from the tungsten-rhenium alloy powder waste material with the rhenium content of 5 percent, and the final recovery rate and purity of rhenium are higher.
Example 3
A method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste comprises the following specific steps:
(1) weighing 40g of tungsten-rhenium alloy powder waste with the rhenium content of 10%, soaking the tungsten-rhenium alloy powder waste in dilute hydrochloric acid for half an hour to remove impurities on the surface of the waste, and then putting the waste into a forced air drying oven for drying; the dried powder waste is ground to the granularity of less than 10 mu m and is fully dried in vacuum until the mass is not changed.
(2) As shown in fig. 1, a quartz boat containing tungsten-rhenium alloy powder waste and porous carbon are respectively placed in an oxidation gasification region (temperature region I) and a porous carbon selective reduction region (temperature region II) of a dual-temperature-region tube furnace; firstly, starting a heating program of a temperature zone II, heating to 900 ℃ and keeping the temperature; starting a heating program of the temperature area I when the temperature area II is heated to a constant temperature, heating to 750 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 3 h; meanwhile, the gas valve is controlled to convey air to the system, and the flow range is 0.5L/min to 1.0L/min;
fully oxidizing the tungsten-rhenium alloy powder waste in a temperature zone I to realize primary separation of tungsten and rhenium; WO produced3Gas and Re2O7Gas enters a temperature zone II, and porous carbon selective reduction WO is carried out3The gas is allowed to remain in temperature zone II in the form of metallic tungsten; re2O7The gas enters a collecting bottle filled with ammonia water;
and after the heat preservation is finished, cooling the solution to the room temperature along with the furnace, and collecting the solution in the collection bottle filled with the ammonia water.
(3) Evaporating the collected solution in an oven at 80 ℃ for crystallization, and reacting rhenium with NH4ReO4To obtain NH4ReO4A crude product;
reacting NH4ReO4Dissolving the crude product in deionized water at 100 deg.C, and cooling to below 15 deg.CBy reaction of NH4ReO4Recrystallizing and repeating for 3 times to obtain pure NH4ReO4And (3) powder.
(4) Adding the above pure NH4ReO4And placing the powder in a reduction furnace, heating to 450 ℃ in hydrogen atmosphere for reduction reaction for 90min to obtain the rhenium powder.
NH prepared as described above in this example4ReO4Powder and metal rhenium powder, characterized: NH (NH)4ReO4The purity of the powder is about 99.9989%; the rhenium powder has good crystallinity, the average grain diameter is about 14.02 mu m, the purity is about 99.9579 percent, and the recovery rate of rhenium reaches 93.71 percent. The method of the invention is adopted to recover rhenium from the tungsten-rhenium alloy powder waste material with 10 percent of rhenium content, and the final recovery rate and purity of rhenium are higher.
Example 4
A method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste comprises the following specific steps:
(1) weighing 40g of tungsten-rhenium alloy wire waste with the rhenium content of 5%, soaking the tungsten-rhenium alloy wire waste in dilute hydrochloric acid for half an hour to remove impurities on the surface of the waste, and then putting the waste into a forced air drying oven for drying; cutting the dried filiform waste material to a length of about 2cm, and fully drying in vacuum until the quality is not changed;
(2) as shown in fig. 1, a quartz boat containing tungsten-rhenium alloy wire waste and porous carbon are respectively placed in an oxidation gasification region (temperature region I) and a porous carbon selective reduction region (temperature region II) of a dual-temperature-region tube furnace; firstly, starting a heating program of a temperature zone II, heating to 900 ℃ and keeping the temperature; starting a heating program of the temperature area I when the temperature area II is heated to a constant temperature, heating to 750 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 3 h; meanwhile, the gas valve is controlled to convey air to the system, and the flow range is 0.5L/min;
fully oxidizing the tungsten-rhenium alloy wire waste in a temperature zone I to realize primary separation of tungsten and rhenium; WO produced3Gas and Re2O7Gas enters a temperature zone II, and porous carbon selective reduction WO is carried out3The gas is allowed to remain in temperature zone II in the form of metallic tungsten; re2O7The gas enters a collecting bottle filled with ammonia water;
and after the heat preservation is finished, cooling the solution to the room temperature along with the furnace, and collecting the solution in the collection bottle filled with the ammonia water.
(3) Evaporating the collected solution in an oven at 80 ℃ for crystallization, and reacting rhenium with NH4ReO4Is precipitated in the form of crystals to give NH4ReO4A crude product;
reacting NH4ReO4Dissolving the crude product in deionized water at 100 deg.C, and cooling to below 15 deg.C to obtain NH4ReO4Recrystallizing and repeating for 3 times to obtain pure NH4ReO4And (3) powder.
(4) Adding the above pure NH4ReO4And placing the powder in a reduction furnace, heating to 450 ℃ in hydrogen atmosphere for reduction reaction for 90min to obtain the rhenium powder.
NH prepared as described above in this example4ReO4Powder and metal rhenium powder, characterized: NH (NH)4ReO4The purity of the powder was about 99.9901%; the rhenium powder has good crystallinity, the average grain diameter is about 14.68 mu m, the purity is about 99.9289 percent, and the recovery rate of rhenium reaches 91.21 percent. The method of the invention is adopted to recover rhenium from the tungsten-rhenium alloy wire waste material with the rhenium content of 5 percent, and the final recovery rate and purity of rhenium are higher.
Example 5
A method for grading separation and recovery of metal rhenium from tungsten-rhenium alloy waste comprises the following specific steps:
(1) weighing 40g of tungsten-rhenium alloy block waste with the rhenium content of 5%, soaking in dilute hydrochloric acid for half an hour to remove impurities on the surface of the waste, and then putting the waste into a blast drying oven for drying; the dried massive waste is crushed and fully dried in vacuum until the quality is not changed.
(2) As shown in fig. 1, a quartz boat containing tungsten-rhenium alloy block waste and porous carbon are respectively placed in an oxidation gasification region (temperature region I) and a porous carbon selective reduction region (temperature region II) of a dual-temperature-region tube furnace; firstly, starting a heating program of a temperature zone II, heating to 900 ℃ and keeping the temperature; starting a heating program of the temperature area I when the temperature area II is heated to a constant temperature, heating to 750 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 3 h; meanwhile, the gas valve is controlled to convey air to the system, and the flow range is 0.5L/min;
fully oxidizing the tungsten-rhenium alloy block waste in a temperature zone I to realize primary separation of tungsten and rhenium; WO produced3Gas and Re2O7Gas enters a temperature zone II, and porous carbon selective reduction WO is carried out3The gas is allowed to remain in temperature zone II in the form of metallic tungsten; re2O7The gas enters a collecting bottle filled with ammonia water;
and after the heat preservation is finished, cooling the solution to the room temperature along with the furnace, and collecting the solution in the collection bottle filled with the ammonia water.
(3) Evaporating the collected solution in an oven at 80 ℃ for crystallization, and reacting rhenium with NH4ReO4Is precipitated in the form of crystals to give NH4ReO4A crude product;
reacting NH4ReO4Dissolving the crude product in deionized water at 100 deg.C, and cooling to below 15 deg.C to obtain NH4ReO4Recrystallizing and repeating for 3 times to obtain pure NH4ReO4And (3) powder.
(4) Adding the above pure NH4ReO4And placing the powder in a reduction furnace, heating to 450 ℃ in hydrogen atmosphere for reduction reaction for 90min to obtain the rhenium powder.
NH prepared as described above in this example4ReO4Powder and metal rhenium powder, characterized: NH (NH)4ReO4The purity of the powder is about 99.9893%, the crystallinity of the rhenium powder is good, the average grain diameter is about 14.97 mu m, the purity is about 99.9216%, and the recovery rate of rhenium reaches 90.84%. The method of the invention is adopted to recover rhenium from the tungsten-rhenium alloy block waste material with the rhenium content of 5 percent, and the final recovery rate and purity of rhenium are higher.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for grading separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap, characterized by comprising the steps of:
(1) soaking the tungsten-rhenium alloy waste in dilute hydrochloric acid for half an hour to remove impurities on the surface of the waste, and then putting the waste into a blast drying oven for drying; crushing or grinding the dried waste, and fully drying in vacuum until the quality is not changed;
(2) the method comprises the following steps of arranging a double-temperature-zone tubular furnace with a shaft furnace structure, wherein a temperature zone I at the lower part of the double-temperature-zone tubular furnace is an oxidation gasification zone, and a temperature zone II at the upper part of the double-temperature-zone tubular furnace is a porous carbon selective reduction zone; the bottom gas inlet of the double-temperature-zone tube furnace is communicated with an air bottle through a gas valve; a gas outlet at the top of the double-temperature-zone tubular furnace is communicated to a collecting bottle filled with ammonia water through a pipeline;
respectively placing a quartz boat containing tungsten-rhenium alloy waste and porous carbon in a temperature area I and a temperature area II of a double-temperature-area tubular furnace; firstly, starting a heating program of a temperature zone II, heating to 750-900 ℃ and keeping the temperature; starting a heating program of the temperature area I when the temperature area II is heated to a constant temperature, raising the temperature to 600-750 ℃, and keeping the temperature for 2-3 hours; conveying air into the tube furnace in the heat preservation process;
the tungsten-rhenium alloy waste is fully oxidized in a temperature zone I to realize the primary separation of tungsten and rhenium; WO produced3Gas and Re2O7Gas enters a temperature zone II, and porous carbon selective reduction WO is carried out3The gas is allowed to remain in temperature zone II in the form of metallic tungsten; re2O7The gas enters a collecting bottle filled with ammonia water;
after the heat preservation is finished, cooling the solution to the room temperature along with the furnace, and collecting the solution in a collecting bottle filled with ammonia water;
(3) putting the collected solution into an oven for evaporation crystallization, and adding rhenium into NH4ReO4Is precipitated in the form of crystals to give NH4ReO4A crude product; to the NH4ReO4Recrystallizing the crude product to obtain pure NH4ReO4Powder;
(4) the obtained pure NH4ReO4And placing the powder in a reduction furnace, and carrying out reduction reaction in a hydrogen atmosphere to obtain the rhenium powder.
2. The method for the fractional separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that: in the step (1), the tungsten-rhenium alloy waste is in the form of blocks, filaments and powder, and the rhenium content of the tungsten-rhenium alloy waste is 1 wt% -15 wt%.
3. The method for grading separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that step (2) is performed in the dual-temperature zone tube furnace: the temperature zone I is a straight pipe and is connected with a flange with a fixed bracket for supporting tungsten-rhenium alloy waste; the temperature zone II is embedded with an S-shaped pipe filled with porous carbon.
4. The method for the fractional separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that: in the step (2), the porous carbon is porous active carbon, mesoporous carbon or nano carbon particles.
5. The method for the fractional separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that: in the step (2), the heating rate of the temperature zone I is 3 ℃/min to 5 ℃/min.
6. The method for the fractional separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that: in the step (2), the temperature of the temperature zone II is always kept higher than that of the temperature zone I in the heat preservation stage.
7. The method for the fractional separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that: in the step (2), the flow range of the conveying air is 0.1L/min-1.0L/min.
8. The method for the fractional separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that: in the step (3), the temperature of the evaporative crystallization is 80 ℃.
9. The method for the fractional separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that: in step (3), the NH is reacted4ReO4The method for recrystallizing the crude product comprises the following steps: reacting the NH with4ReO4Dissolving the crude product in deionized water at 100 deg.C, and cooling to below 15 deg.C to obtain NH4ReO4Recrystallizing and repeating for 2-3 times to obtain pure NH4ReO4And (3) powder.
10. The method for the fractional separation and recovery of metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, characterized in that: in the step (4), the reduction temperature of the reduction reaction is 450-600 ℃, and the reaction time is 60-120 min.
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| 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 |
| CN114561543A (en) * | 2022-03-01 | 2022-05-31 | 合肥工业大学 | Device and method for recovering rhenium powder from tungsten-rhenium alloy scrap |
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| 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 |
| CN114561543A (en) * | 2022-03-01 | 2022-05-31 | 合肥工业大学 | Device and method for recovering rhenium powder from tungsten-rhenium alloy scrap |
| CN114561543B (en) * | 2022-03-01 | 2023-09-29 | 合肥工业大学 | Device and method for recycling rhenium powder from tungsten-rhenium alloy waste |
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