CN112522519B - Method for grading and recycling metal rhenium from tungsten-rhenium alloy scrap - Google Patents
Method for grading and recycling metal rhenium from tungsten-rhenium alloy scrap Download PDFInfo
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 136
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910000691 Re alloy Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title abstract description 15
- 239000002184 metal Substances 0.000 title abstract description 15
- 238000004064 recycling Methods 0.000 title abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 62
- 239000002699 waste material Substances 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010937 tungsten Substances 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 40
- 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 22
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 44
- 238000006722 reduction reaction Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000012043 crude product Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002309 gasification Methods 0.000 claims description 9
- 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
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 31
- 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
- 230000001590 oxidative effect Effects 0.000 abstract description 10
- 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 17
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 238000009853 pyrometallurgy Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000004927 fusion Effects 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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000126 substance Substances 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
- 238000001354 calcination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 238000009825 accumulation Methods 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
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 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
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- -1 salt compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a method for grading and recycling metal rhenium from tungsten-rhenium alloy scraps, which has the following basic principle: and oxidizing the waste containing tungsten and rhenium in flowing air at a certain temperature, realizing preliminary separation of tungsten and rhenium by utilizing the difference of volatilization temperatures of tungsten and rhenium oxides, further realizing the purpose of removing tungsten from rhenium oxide gas by selectively reducing tungsten oxide through carbon according to the difference of reduction temperatures of tungsten and rhenium, and finally carrying out ammonia water absorption and crystallization on the rhenium oxide gas, and drying hydrogen reduction to obtain the high-purity rhenium powder. The method has the advantages of short process flow, low cost, high separation efficiency of tungsten and rhenium, high recovery rate of rhenium, high purity of the obtained rhenium powder, suitability for tungsten-rhenium alloy waste with less rhenium content and difficult separation of tungsten and rhenium, and capability of obtaining high-purity rhenium powder with purity more than or equal to 99.9 percent in batch production.
Description
Technical Field
The invention belongs to the field of recovery of scattered metals, and particularly relates to a method for grading and recovering metal rhenium from tungsten-rhenium alloy scraps.
Background
Rhenium is a rare earth metal and is present in the crust in an amount of only 1X 10 -9 The melting point is about 3180 ℃. Because of the characteristics of high heat resistance, high corrosion resistance, high hardness, mechanical strength and the like, rhenium is widely applied to the fields of high-temperature alloy, petroleum catalysis, metallurgy, electronics and the like. However, rhenium resources are not abundant, there is no single, separate mineral of mining value, some of which are present in other deposits, and some of which are derived from the recovery of rhenium-containing alloy scrap. With the lack of primary mineral resources containing rhenium, there is increasing interest in recovering rhenium from rhenium-containing alloy scrap. The 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 industry, medical treatment and the like, the demand for rhenium is more and more great, so that the recycling of rhenium in rhenium-containing alloy waste materials is particularly important.
The unique physical and chemical properties of rhenium make its recovery process generally complex and difficult. Current techniques for recovering rhenium from rhenium-containing alloy scrap mainly include pyrometallurgy and hydrometallurgy. Pyrometallurgy is a widely used rare metal recovery process. Pyrometallurgy is carried out at high temperatures and during calcination, rhenium in the rhenium-containing waste is prone to oxygenIs converted into Re which is easy to volatilize and dissolve in water 2 O 7 Gas Re 2 O 7 And leaching out the rhenium by ammonia water or water, enriching the rhenium in a solution in the form of ammonium perrhenate or perrhenic acid, evaporating, concentrating and crystallizing to obtain ammonium perrhenate or perrhenic acid crystals, and finally reducing the rhenium by hydrogen to obtain the metal rhenium. The principle of the hydrometallurgical recovery of rhenium is to use the rhenium in the oxidizing acid or alkali leaching waste to make the rhenium in solution as ReO 4 - And 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-rhenium alloy exists in the form of acid radical ions in solution, and the properties of formed salt compounds are very similar. Therefore, if the conventional hydrometallurgy is adopted to recover rhenium from the tungsten-rhenium alloy waste material, such as a solvent extraction method or an ion exchange method, so as to achieve the purpose of thoroughly separating and respectively extracting the two metals, the technology becomes more complicated, and the breakthrough progress is difficult to achieve in the process. While pyrometallurgy utilizes Re 2 O 7 The characteristic of the method can selectively recycle rhenium in the tungsten-rhenium alloy scrap, has good universality, has no requirement on the form of the rhenium-containing scrap, and is suitable for mass industrial production. Therefore, development of a pyrometallurgical process for recovering metallic rhenium from tungsten-rhenium alloy scrap has significant utility.
In recent years, researchers at home and abroad have conducted a great deal of research on recovering metallic rhenium from rhenium-containing alloy scrap by a pyrometallurgical method, and have achieved a number of results. She Longgang et al (Recovery of rhenium from tungsten-rhenium wire by alkali fusion in KOH-K) 2 CO 3 binary molten salt, international Journal of Refractory Metals and Hard Materials 87 (2020) 105148) are prepared from W by alkali fusion 95 Re 5 The metal rhenium is effectively recovered from the scrap wire. The main steps of recovery include alkali fusion, recrystallization, hydrogen reduction and washing. The alkali fusion temperature is 800 ℃, the reaction time is 60min, the potassium perrhenate crystal is obtained, and finally the reaction is carried out at the temperature ofReducing at 350 deg.c to obtain Re powder with purity over 99.5% and granularity of 19.37 microns. The method is simple and feasible, the prepared rhenium powder has higher purity, but the separation efficiency of tungsten and rhenium is not high, the prepared rhenium powder has larger granularity, and the recovery rate of rhenium is lower. The oxidation roasting-rhenium precipitation method is adopted by a Subi cemented carbide factory to extract rhenium from molybdenite with the rhenium content of 0.025 percent. Oxidizing and roasting at 540-600 deg.c to reach rhenium volatilizing rate of 95% and Re content 2 O 7 The flue gas in the flue gas is collected by a leaching tower and a wet electric dust collector, re in the flue gas 2 O 7 Dissolving in water to generate perrhenic acid, adding potassium chloride for evaporating and crystallizing when the solution is enriched to a certain degree to obtain white potassium perrhenate precipitate, and introducing hydrogen for reduction to prepare rhenium powder, wherein the recovery rate of rhenium is up to 85%. The method is simple and feasible, but has low tungsten-rhenium separation efficiency, and the recovery rate and purity of the final rhenium are low.
In summary, the current research of recovering rhenium from tungsten-rhenium alloy scraps by adopting pyrometallurgy has the problems of low separation efficiency of tungsten and rhenium, insufficient recovery rate and purity of rhenium and the like. There are also other problems, such as WO during the oxidative calcination 3 Re capable of sublimation and volatilization 2 O 7 The gas mixing, which causes the tungsten element in the collected product, results in the impurity of the rhenium powder finally produced, which greatly affects the application of rhenium in various fields. Therefore, it is a key to the current research to explore a method for recovering metallic rhenium from tungsten-rhenium alloy scraps to obtain high-recovery-rate high-purity rhenium powder. The invention provides a method for grading and recovering metal rhenium from tungsten-rhenium alloy waste materials through researching thermodynamics, dynamics and reaction mechanism of tungsten and rhenium in the recovery process, and aims to provide reference and experience accumulation for future scholars and industry in the recovery of rhenium.
Disclosure of Invention
The invention aims to provide a method for grading and recovering metal rhenium from tungsten-rhenium alloy scraps, which aims to solve the problems of low separation efficiency of tungsten and rhenium, insufficient recovery rate and purity of rhenium and the like in the process of recovering rhenium from tungsten-rhenium alloy scraps by adopting pyrometallurgy.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for separating and recovering metal rhenium from tungsten-rhenium alloy scraps in a grading manner is based on the following basic principles: and oxidizing the waste containing tungsten and rhenium in flowing air at a certain temperature, realizing preliminary separation of tungsten and rhenium by utilizing the difference of volatilization temperatures of tungsten and rhenium oxides, further realizing the purpose of removing tungsten from rhenium oxide gas by selectively reducing tungsten oxide by carbon according to the difference of reduction temperatures of tungsten and rhenium, and finally carrying out ammonia water absorption, crystallization and dry hydrogen reduction on the rhenium oxide gas to obtain the high-purity rhenium powder. The method specifically comprises the following steps:
(1) Soaking tungsten-rhenium alloy scraps in dilute hydrochloric acid for half an hour, removing impurities on the surfaces of the scraps, and then putting the scraps into a blast drying oven for drying; crushing or grinding the dried waste, and fully drying in vacuum until the quality is unchanged;
(2) A double-temperature-zone tube furnace with a shaft furnace structure is arranged, wherein a temperature zone I at the lower part of the double-temperature-zone tube furnace is an oxidation gasification zone, and a temperature zone II at the upper part of the double-temperature-zone tube 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; the top gas outlet of the double-temperature-zone tubular furnace is communicated to a collecting bottle containing ammonia water through a pipeline;
respectively placing a quartz boat and porous carbon containing tungsten-rhenium alloy waste in a temperature zone I and a temperature zone II of a double-temperature zone tube furnace; firstly, starting a heating program in a temperature zone II, heating to 750-900 ℃ and keeping the temperature constant; when the temperature zone II is heated to constant temperature, the heating program of the temperature zone I is started, the temperature is raised to 600-750 ℃, and the heat preservation time is 2-3 hours; air is conveyed into the tube furnace in the heat preservation process;
the tungsten-rhenium alloy waste is fully oxidized in a temperature zone I, so that preliminary separation of tungsten and rhenium is realized; WO produced 3 Gas and Re 2 O 7 Gas enters a temperature zone II, and porous carbon selectively reduces WO 3 The gas is remained in the temperature zone II in the form of metallic tungsten, thereby achieving the purpose of removing tungsten from rhenium oxide and obtaining high-purity Re 2 O 7 A gas; re (Re) 2 O 7 The gas enters ammonia water for collectionA bottle;
after the constant temperature is finished, cooling to room temperature along with the furnace, and collecting the solution in the collecting bottle containing ammonia water;
(3) The collected solution is put into an oven for evaporative crystallization, and rhenium is treated with NH 4 ReO 4 Is precipitated in the form of crystals to obtain NH 4 ReO 4 Crude products; for the NH 4 ReO 4 Recrystallizing the crude product to obtain pure NH 4 ReO 4 A powder;
(4) Pure NH obtained 4 ReO 4 And placing the powder into a reducing furnace, and carrying out reduction reaction under the hydrogen atmosphere to obtain rhenium powder.
Further, in the step (1), the tungsten-rhenium alloy scrap is in a form of a block, a wire or a powder, and the rhenium content of the tungsten-rhenium alloy scrap is 1-15 wt%.
Further, in the double-temperature zone tube furnace of step (2): the temperature zone I is a straight pipe, and is connected with a flange with a fixed bracket, so as to support the tungsten-rhenium alloy waste, fully oxidize the tungsten-rhenium alloy waste and realize the primary separation of tungsten and rhenium; the temperature zone II is embedded with an S-shaped tube filled with porous carbon, so that the passing gas is ensured to be fully contacted with the porous carbon, and WO is ensured 3 Is 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 the temperature of the temperature zone I in the heat preservation stage.
Further, in the step (2), the flow rate of the conveying air is in the range of 0.1L/min to 1.0L/min.
Further, in the step (3), the temperature of the evaporative crystallization is 80 ℃.
Further, in step (3), the NH is reacted with 4 ReO 4 The method for recrystallizing the crude product comprises the following steps: NH is subjected to 4 ReO 4 Dissolving the crude product in deionized water at 100deg.C, and cooling to below 15deg.C to obtain NH 4 ReO 4 Recrystallizing, repeating for 2-3 times,obtaining pure NH 4 ReO 4 Powder
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 in the invention is a double-temperature zone tube furnace shown in figure 1, is of a shaft furnace structure and comprises an oxidation gasification zone (temperature zone I) and a porous carbon selective reduction zone (temperature zone II); the temperature zone I is connected with a flange with a fixed bracket and is used for supporting tungsten-rhenium alloy scraps, so that the tungsten-rhenium alloy scraps are fully oxidized, and primary separation of tungsten and rhenium is realized; the temperature zone II is embedded with an S-shaped tube filled with porous carbon, so that the passing gas is ensured to be fully contacted with the porous carbon, and WO is ensured 3 Is completely reduced. The heating sequence and the heating temperature of the double temperature areas are controlled, so that the tungsten-rhenium alloy waste material in the temperature area I is fully oxidized, and rhenium oxide Re generated by oxidation in the temperature area I is formed 2 O 7 Gas and partially volatilized WO 3 The gas is effectively separated in a temperature zone II, and the recovery rate and purity of rhenium are improved.
2. The invention realizes the purpose of removing tungsten from rhenium oxide gas through the reduction of the porous carbon to tungsten oxide. Porous carbon can selectively reduce WO 3 The gas is retained in the form of tungsten metal in the S-shaped tube filled with porous carbon in temperature zone II, while Re 2 O 7 The gas enters a collecting bottle containing ammonia water through an S-shaped pipe, and pure rhenium oxide can be obtained in the process. Meanwhile, thermodynamic and kinetic studies on tungsten, rhenium and carbon show that the air flow and heating temperature in the system are controlled to enable the porous carbon and O to be formed 2 、WO 3 Re and Re 2 O 7 The reaction between the gases reaches a state of dynamic equilibrium in which the porous carbon is in contact with Re 2 O 7 Hardly reacts with WO 3 The reduction reaction is carried out, so that the purpose of removing tungsten from rhenium oxide gas is realized, tungsten and rhenium are separated efficiently, and the recovery rate and purity of rhenium powder are improved.
3. The invention can realize high-efficiency recovery of massive, filiform and powdery tungsten-rhenium alloy scraps, does not need specific recovery equipment, has simple equipment requirement, is suitable for tungsten-rhenium alloy scraps with less rhenium content (3-10wt%) 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 in batch production.
4. Compared with hydrometallurgy, the method has the advantages of short process flow, high separation efficiency of tungsten and rhenium, 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 diagram of an apparatus used in the present invention, wherein reference numerals are used to designate: 1-compressed air cylinder, 2-gas flowmeter, 3-intake pipe, 4-quartz tube, 5-outer insulating layer, 6-heat-generating body, 7-mesh support, 8-quartz boat, 9-tungsten-rhenium alloy waste, 10-S type pipe, 11-porous carbon, 12-double temperature zone tubular furnace, 13-outlet duct, 14-collecting bottle, 15-ammonia water, 16-blast pipe.
Fig. 2 is an SEM image of the metal rhenium powder obtained in example 1.
Fig. 3 is a TEM photograph 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 given as detailed embodiments and specific operation procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
The apparatus used in the examples described below is shown in FIG. 1 and comprises a double-temperature zone tube furnace 12 of shaft furnace construction, with a lower temperature zone I being the oxidation gasification zone and an upper temperature zone II being the 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 burner 8 filled with tungsten-rhenium alloy scraps 9; the temperature zone II is embedded with an S-shaped pipe 10 filled with porous carbon 11, so that the passing gas is ensured to be fully contacted with the porous carbon, and WO is ensured 3 Is completely reduced.
The bottom gas inlet of the double-temperature-zone tube furnace 12 is communicated with a compressed air cylinder 1 through an air inlet tube 3, and a gas flowmeter 2 is also arranged on the air inlet tube; 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 containing ammonia water 15 through a gas outlet pipe 13, and an exhaust pipe 16 is arranged in the collecting bottle.
Other structures of the double-temperature-zone tube furnace, such as the outer heat-insulating layer 5 of the quartz tube 4 and the heating element 6, are conventional structures, and will not be described here. The double-temperature-zone tube furnace can be of 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 and recovering metallic rhenium from tungsten-rhenium alloy scraps, which comprises the following specific steps:
(1) Weighing 40g of tungsten-rhenium alloy powder waste with rhenium content of 5%, soaking in dilute hydrochloric acid for half an hour, removing impurities on the surface of the waste, and then putting into a blast drying box for drying; grinding the dried powder waste until the granularity is below 10 mu m, and fully drying in vacuum until the quality is unchanged.
(2) As shown in fig. 1, a quartz boat and porous carbon containing tungsten-rhenium alloy powder waste are respectively placed in an oxidation gasification area (temperature area I) and a porous carbon selective reduction area (temperature area II) of a double-temperature-area tube furnace; firstly, starting a heating program in a temperature zone II, heating to 750 ℃ and keeping the temperature constant; when the temperature zone II is heated to constant temperature, a heating program of the temperature zone I is started, the temperature is raised to 600 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 3 hours; simultaneously controlling a gas valve to convey air to the system, wherein the flow range is 0.5L/min;
fully oxidizing the tungsten-rhenium alloy powder waste in a temperature zone I to realize preliminary separation of tungsten and rhenium; WO produced 3 Gas and Re 2 O 7 Gas enters a temperature zone II, and porous carbon selectively reduces WO 3 The gas is allowed to remain in the form of metallic tungsten in the temperature zone II; re (Re) 2 O 7 The gas enters a collecting bottle containing ammonia water;
after the heat preservation is finished, cooling to room temperature along with the furnace, and collecting the solution in the collecting bottle containing ammonia water.
(3) Evaporating and crystallizing the collected solution at 80 ℃ in an oven, and taking rhenium as NH 4 ReO 4 Is precipitated in the form of crystals to obtain NH 4 ReO 4 Crude products;
NH is added to 4 ReO 4 Dissolving the crude product in deionized water at 100deg.C, and cooling to below 15deg.C to obtain NH 4 ReO 4 Recrystallizing and repeating for 3 times to obtain pure NH 4 ReO 4 And (3) powder.
(4) Pure NH as described above 4 ReO 4 And (3) placing the powder in a reducing furnace, heating to 450 ℃ in a hydrogen atmosphere for reduction reaction for 90min to obtain rhenium powder.
NH produced by the method of this example 4 ReO 4 Powder and metallic rhenium powder, characterized: NH (NH) 4 ReO 4 The powder purity was about 99.9959%; the crystallinity of the rhenium powder is good, the average grain diameter 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 used for recovering rhenium from tungsten-rhenium alloy powder waste with the rhenium content of 5 percent, and the recovery rate and purity of the final rhenium are higher.
Example 2
A method for grading and recovering metallic rhenium from tungsten-rhenium alloy scraps, which comprises the following specific steps:
(1) Weighing 40g of tungsten-rhenium alloy powder waste with rhenium content of 5%, soaking in dilute hydrochloric acid for half an hour, removing impurities on the surface of the waste, and then putting into a blast drying box for drying; grinding the dried powder waste until the granularity is below 10 mu m, and fully drying in vacuum until the quality is unchanged.
(2) As shown in fig. 1, a quartz boat and porous carbon containing tungsten-rhenium alloy powder waste are respectively placed in an oxidation gasification area (temperature area I) and a porous carbon selective reduction area (temperature area II) of a double-temperature-area tube furnace; firstly, starting a heating program in a temperature zone II, heating to 900 ℃ and keeping the temperature constant; when the temperature zone II is heated to constant temperature, a heating program of the temperature zone I is started, the temperature is raised to 750 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 3 hours; simultaneously controlling a gas valve to convey air to the system, wherein the flow range is 0.5L/min-1.0L/min;
fully oxidizing the tungsten-rhenium alloy powder waste in a temperature zone I to realize preliminary separation of tungsten and rhenium; WO produced 3 Gas and Re 2 O 7 Gas entryTemperature zone II, porous carbon Selective reduction WO 3 The gas is allowed to remain in the form of metallic tungsten in the temperature zone II; re (Re) 2 O 7 The gas enters a collecting bottle containing ammonia water;
after the heat preservation is finished, cooling to room temperature along with the furnace, and collecting the solution in the collecting bottle containing ammonia water.
(3) Evaporating and crystallizing the collected solution at 80 ℃ in an oven, and taking rhenium as NH 4 ReO 4 Is precipitated to obtain NH 4 ReO 4 Crude products;
NH is added to 4 ReO 4 Dissolving the crude product in deionized water at 100deg.C, and cooling to below 15deg.C to obtain NH 4 ReO 4 Recrystallizing and repeating for 3 times to obtain pure NH 4 ReO 4 And (3) powder.
(4) Pure NH as described above 4 ReO 4 And (3) placing the powder in a reducing furnace, heating to 450 ℃ in a hydrogen atmosphere for reduction reaction for 90min to obtain rhenium powder.
NH produced by the method of this example 4 ReO 4 Powder and metallic rhenium powder, characterized: NH (NH) 4 ReO 4 The powder purity was about 99.9981%; the crystallinity of the rhenium powder is good, 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 used for recovering rhenium from tungsten-rhenium alloy powder waste with the rhenium content of 5 percent, and the recovery rate and purity of the final rhenium are higher.
Example 3
A method for grading and recovering metallic rhenium from tungsten-rhenium alloy scraps, which comprises the following specific steps:
(1) Weighing 40g of tungsten-rhenium alloy powder waste with 10% of rhenium content, soaking in dilute hydrochloric acid for half an hour, removing impurities on the surface of the waste, and then putting into a blast drying box for drying; grinding the dried powder waste until the granularity is below 10 mu m, and fully drying in vacuum until the quality is unchanged.
(2) As shown in fig. 1, a quartz boat and porous carbon containing tungsten-rhenium alloy powder waste are respectively placed in an oxidation gasification area (temperature area I) and a porous carbon selective reduction area (temperature area II) of a double-temperature-area tube furnace; firstly, starting a heating program in a temperature zone II, heating to 900 ℃ and keeping the temperature constant; when the temperature zone II is heated to constant temperature, a heating program of the temperature zone I is started, the temperature is raised to 750 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 3 hours; simultaneously controlling a gas valve to convey air to the system, wherein the flow range is 0.5L/min-1.0L/min;
fully oxidizing the tungsten-rhenium alloy powder waste in a temperature zone I to realize preliminary separation of tungsten and rhenium; WO produced 3 Gas and Re 2 O 7 Gas enters a temperature zone II, and porous carbon selectively reduces WO 3 The gas is allowed to remain in the form of metallic tungsten in the temperature zone II; re (Re) 2 O 7 The gas enters a collecting bottle containing ammonia water;
after the heat preservation is finished, cooling to room temperature along with the furnace, and collecting the solution in the collecting bottle containing ammonia water.
(3) Evaporating and crystallizing the collected solution at 80 ℃ in an oven, and taking rhenium as NH 4 ReO 4 Is precipitated to obtain NH 4 ReO 4 Crude products;
NH is added to 4 ReO 4 Dissolving the crude product in deionized water at 100deg.C, and cooling to below 15deg.C to obtain NH 4 ReO 4 Recrystallizing and repeating for 3 times to obtain pure NH 4 ReO 4 And (3) powder.
(4) Pure NH as described above 4 ReO 4 And (3) placing the powder in a reducing furnace, heating to 450 ℃ in a hydrogen atmosphere for reduction reaction for 90min to obtain rhenium powder.
NH produced by the method of this example 4 ReO 4 Powder and metallic rhenium powder, characterized: NH (NH) 4 ReO 4 The purity of the powder was about 99.9989%; the crystallinity of the rhenium powder is good, 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 used for recovering rhenium from the tungsten-rhenium alloy powder waste material with the rhenium content of 10 percent, and the recovery rate and purity of the final rhenium are higher.
Example 4
A method for grading and recovering metallic rhenium from tungsten-rhenium alloy scraps, which comprises the following specific steps:
(1) Weighing 40g of tungsten-rhenium alloy wire waste with rhenium content of 5%, soaking in dilute hydrochloric acid for half an hour, removing impurities on the surface of the waste, and then putting into a blast drying box for drying; cutting the dried filiform waste to a length of about 2cm, and fully drying in vacuum until the quality is unchanged;
(2) As shown in fig. 1, a quartz boat and porous carbon containing tungsten-rhenium alloy wire waste are respectively placed in an oxidation gasification area (temperature area I) and a porous carbon selective reduction area (temperature area II) of a double-temperature-area tube furnace; firstly, starting a heating program in a temperature zone II, heating to 900 ℃ and keeping the temperature constant; when the temperature zone II is heated to constant temperature, a heating program of the temperature zone I is started, the temperature is raised to 750 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 3 hours; simultaneously controlling a gas valve to convey air to the system, wherein the flow range is 0.5L/min;
fully oxidizing the tungsten-rhenium alloy wire scraps in a temperature zone I to realize preliminary separation of tungsten and rhenium; WO produced 3 Gas and Re 2 O 7 Gas enters a temperature zone II, and porous carbon selectively reduces WO 3 The gas is allowed to remain in the form of metallic tungsten in the temperature zone II; re (Re) 2 O 7 The gas enters a collecting bottle containing ammonia water;
after the heat preservation is finished, cooling to room temperature along with the furnace, and collecting the solution in the collecting bottle containing ammonia water.
(3) Evaporating and crystallizing the collected solution at 80 ℃ in an oven, and taking rhenium as NH 4 ReO 4 Is precipitated in the form of crystals to obtain NH 4 ReO 4 Crude products;
NH is added to 4 ReO 4 Dissolving the crude product in deionized water at 100deg.C, and cooling to below 15deg.C to obtain NH 4 ReO 4 Recrystallizing and repeating for 3 times to obtain pure NH 4 ReO 4 And (3) powder.
(4) Pure NH as described above 4 ReO 4 And (3) placing the powder in a reducing furnace, heating to 450 ℃ in a hydrogen atmosphere for reduction reaction for 90min to obtain rhenium powder.
NH produced by the method of this example 4 ReO 4 Powder and metallic rhenium powder, characterized: NH (NH) 4 ReO 4 The powder purity was about 99.9901%; the crystallinity of the rhenium powder is good, 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 used for recovering rhenium from the tungsten-rhenium alloy wire scrap with the rhenium content of 5 percent, and the recovery rate and purity of the final rhenium are higher.
Example 5
A method for grading and recovering metallic rhenium from tungsten-rhenium alloy scraps, which comprises the following specific steps:
(1) Weighing 40g of tungsten-rhenium alloy block waste with rhenium content of 5%, soaking in dilute hydrochloric acid for half an hour, removing impurities on the surface of the waste, and then putting into a blast drying box for drying; crushing the dried massive waste, and fully drying in vacuum until the quality is unchanged.
(2) As shown in fig. 1, a quartz boat and porous carbon containing tungsten-rhenium alloy block waste are respectively placed in an oxidation gasification area (temperature area I) and a porous carbon selective reduction area (temperature area II) of a double-temperature-area tubular furnace; firstly, starting a heating program in a temperature zone II, heating to 900 ℃ and keeping the temperature constant; when the temperature zone II is heated to constant temperature, a heating program of the temperature zone I is started, the temperature is raised to 750 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 3 hours; simultaneously controlling a gas valve to convey air to the system, wherein the flow range is 0.5L/min;
fully oxidizing the tungsten-rhenium alloy block waste in a temperature zone I to realize preliminary separation of tungsten and rhenium; WO produced 3 Gas and Re 2 O 7 Gas enters a temperature zone II, and porous carbon selectively reduces WO 3 The gas is allowed to remain in the form of metallic tungsten in the temperature zone II; re (Re) 2 O 7 The gas enters a collecting bottle containing ammonia water;
after the heat preservation is finished, cooling to room temperature along with the furnace, and collecting the solution in the collecting bottle containing ammonia water.
(3) Evaporating and crystallizing the collected solution at 80 ℃ in an oven, and taking rhenium as NH 4 ReO 4 Is precipitated in the form of crystals to obtain NH 4 ReO 4 Crude products;
NH is added to 4 ReO 4 Dissolving the crude product in deionized water at 100deg.C, and cooling to below 15deg.C to obtain NH 4 ReO 4 Recrystallizing and repeating for 3 times to obtain pure NH 4 ReO 4 And (3) powder.
(4) Pure NH as described above 4 ReO 4 And (3) placing the powder in a reducing furnace, heating to 450 ℃ in a hydrogen atmosphere for reduction reaction for 90min to obtain rhenium powder.
NH produced by the method of this example 4 ReO 4 Powder and metallic rhenium powder, characterized: NH (NH) 4 ReO 4 The powder has the purity of about 99.9893 percent, the crystallinity of the rhenium powder is good, the average particle size is about 14.97 mu m, the purity is about 99.9216 percent, and the recovery rate of rhenium reaches 90.84 percent. The method of the invention is used for recovering rhenium from the tungsten-rhenium alloy block waste with the rhenium content of 5 percent, and the recovery rate and purity of the final rhenium are higher.
The foregoing is illustrative only and is not intended to limit the present invention, and any modifications, equivalents, improvements and modifications falling within the spirit and principles of the invention are intended to be included within the scope of the present invention.
Claims (6)
1. A method for fractionating and recovering metallic rhenium from tungsten-rhenium alloy scrap, comprising the steps of:
(1) Soaking tungsten-rhenium alloy scraps in dilute hydrochloric acid for half an hour, removing impurities on the surfaces of the scraps, and then putting the scraps into a blast drying oven for drying; crushing or grinding the dried waste, and fully drying in vacuum until the quality is unchanged; the tungsten-rhenium alloy waste is in a block, thread and powder form, and the rhenium content is 1-15 wt%;
(2) A double-temperature-zone tube furnace with a shaft furnace structure is arranged, wherein a temperature zone I at the lower part of the double-temperature-zone tube furnace is an oxidation gasification zone, and a temperature zone II at the upper part of the double-temperature-zone tube 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; the top gas outlet of the double-temperature-zone tubular furnace is communicated to a collecting bottle containing ammonia water through a pipeline;
the temperature zone I is a straight pipe and is connected with a flange with a fixed bracket for supporting tungsten-rhenium alloy scraps; the temperature zone II is embedded with an S-shaped pipe filled with porous carbon;
respectively placing a quartz boat and porous carbon containing tungsten-rhenium alloy waste in a temperature zone I and a temperature zone II of a double-temperature zone tube furnace; firstly, starting a heating program in a temperature zone II, heating to 750-900 ℃ and keeping the temperature constant; when the temperature zone II is heated to a constant temperature, starting a heating program of the temperature zone I, heating to 600-750 ℃, and keeping the temperature for 2-3 hours; air is conveyed into the tube furnace in the heat preservation process, and the flow rate of the conveyed air ranges from 0.1L/min to 1.0L/min; the temperature of the temperature zone II is always kept higher than that of the temperature zone I in the heat preservation stage;
the tungsten-rhenium alloy waste is fully oxidized in a temperature zone I, so that preliminary separation of tungsten and rhenium is realized; WO produced 3 Gas and Re 2 O 7 Gas enters a temperature zone II, and porous carbon selectively reduces WO 3 The gas is allowed to remain in the form of metallic tungsten in the temperature zone II; re (Re) 2 O 7 The gas enters a collecting bottle containing ammonia water;
after the heat preservation is finished, cooling to room temperature along with a furnace, and collecting the solution in a collecting bottle containing ammonia water;
(3) The collected solution is put into an oven for evaporative crystallization, and rhenium is treated with NH 4 ReO 4 Is precipitated in the form of crystals to obtain NH 4 ReO 4 Crude products; for the NH 4 ReO 4 Recrystallizing the crude product to obtain pure NH 4 ReO 4 A powder;
(4) Pure NH obtained 4 ReO 4 And placing the powder into a reducing furnace, and carrying out reduction reaction under the hydrogen atmosphere to obtain rhenium powder.
2. A method for fractionating and recovering metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, wherein: in the step (2), the porous carbon is porous activated carbon, mesoporous carbon or nano carbon particles.
3. A method for fractionating and recovering metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, wherein: in the step (2), the heating rate of the temperature zone I is 3-5 ℃ per minute.
4. A method for fractionating and recovering metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, wherein: in the step (3), the temperature of the evaporative crystallization is 80 ℃.
5. A method for fractionating and recovering metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, wherein: in step (3), the NH is reacted with 4 ReO 4 The method for recrystallizing the crude product comprises the following steps: NH is subjected to 4 ReO 4 Dissolving the crude product in deionized water at 100deg.C, and cooling to below 15deg.C to obtain NH 4 ReO 4 Recrystallizing and repeating for 2-3 times to obtain pure NH 4 ReO 4 And (3) powder.
6. A method for fractionating and recovering metallic rhenium from tungsten-rhenium alloy scrap according to claim 1, wherein: 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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| US3399981A (en) * | 1967-04-25 | 1968-09-03 | Allied Chem | Tungsten-rhenium alloys |
| CN101148709A (en) * | 2007-11-09 | 2008-03-26 | 清华大学 | Method and device for extracting high-purity rhenium from tungsten-rhenium alloy |
| CN103725885A (en) * | 2012-10-10 | 2014-04-16 | 长沙欧泰稀有金属有限公司 | New method for recycling tungsten-rhenium alloy leftover materials and waste materials |
| CN105219980A (en) * | 2015-10-30 | 2016-01-06 | 嵩县开拓者钼业有限公司 | A kind of method extracting rhenium |
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| US3399981A (en) * | 1967-04-25 | 1968-09-03 | Allied Chem | Tungsten-rhenium alloys |
| CN101148709A (en) * | 2007-11-09 | 2008-03-26 | 清华大学 | Method and device for extracting high-purity rhenium from tungsten-rhenium alloy |
| CN103725885A (en) * | 2012-10-10 | 2014-04-16 | 长沙欧泰稀有金属有限公司 | New method for recycling tungsten-rhenium alloy leftover materials and waste materials |
| CN105219980A (en) * | 2015-10-30 | 2016-01-06 | 嵩县开拓者钼业有限公司 | A kind of method extracting rhenium |
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