Recycling method of tungsten-rhenium alloy waste

Abstract

The invention belongs to the technical field of scattered metal recovery, and particularly relates to a recycling method of tungsten-rhenium alloy waste. The tungsten-rhenium alloy is a solid solution strengthened alloy which takes tungsten element as a matrix and consists of the tungsten element and rhenium element, and has the characteristics of high melting point, high strength and high hardness. As the price is high, it is very necessary to comprehensively utilize the tungsten-rhenium alloy waste. The invention discloses a recycling method of tungsten-rhenium alloy waste. Firstly, tungsten-rhenium alloy waste is cleaned, dried and smashed, and waste powder is formed; then dispersing the waste material powder into water dissolved with ammonium metatungstate and a surfactant; then, carrying out spray drying to form mixed powder; and finally, the mixed powder is subjected to roasting and hydrogen reduction, and tungsten-rhenium alloy powder with the metal rhenium content lower than the metal rhenium content in the tungsten-rhenium alloy waste is formed. Compared with an existing tungsten-rhenium alloy waste recycling method, the recycling method has the advantages of being simple in process, low in energy consumption, small in loss and good in uniformity.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of scattered metal recycling, and particularly relates to a recycling method of tungsten-rhenium alloy waste. BACKGROUND

[0002] Tungsten-rhenium alloy is a solid solution strengthened alloy with tungsten as a matrix and rhenium as a component, and has the characteristics of high melting point, high strength and high hardness. Therefore, the tungsten-rhenium alloy is widely used in the fields of electronic technology, thermal control, modern nuclear technology, space technology, temperature measurement, instruments and meters, and other cutting-edge scientific and technological fields. Due to the high price, it is necessary to recycle the tungsten-rhenium alloy waste.

[0003] There are three schemes for recycling the tungsten-rhenium alloy waste in the prior art: 1. The tungsten-rhenium alloy waste is oxidized, separated, purified and reduced by hydrogen to obtain reusable metal rhenium; 2. The tungsten-rhenium alloy waste is dissolved by acid, separated, purified, evaporated, crystallized and reduced by hydrogen to obtain reusable metal rhenium; and 3. The tungsten-rhenium alloy waste is cleaned and dried, crushed and ground, and reduced by hydrogen to obtain tungsten-rhenium alloy powder. The above three recycling methods have advantages and disadvantages.

[0004] A new method for recycling tungsten-rhenium alloy scraps and waste products is disclosed in CN103725885A published in 2014. The method comprises the following steps: first, washing the tungsten-rhenium alloy scraps and waste products with a dilute alkali and a dilute acid solution, then dissolving them in a chemical reagent, and then adding ammonia water to form a mixed salt solution of ammonium tungstate and ammonium rhenium acid, controlling the PH value range and temperature of the solution to make it stable and not precipitate any crystals. The solution is input into a spray dryer for spray drying to obtain a mixed crystal powder of ammonium tungstate and ammonium rhenium acid with uniform composition. The mixed crystal powder is placed in a reduction furnace for hydrogen reduction to obtain tungsten-rhenium alloy powder with uniform composition. After analyzing and determining the rhenium content of the alloy powder, it can be re-entered into the main process flow of tungsten-rhenium alloy and synchronized with normal production. The preparation method has the problems of high energy consumption of spray drying, uneven precipitation of crystals in the spray drying process, and poor uniformity of the tungsten-rhenium alloy powder.

[0005] CN107604166A disclosed a method for recovering tungsten and rhenium from waste tungsten-rhenium thermocouple wire in 2018. Specifically, it includes the following steps: a, the waste tungsten-rhenium thermocouple wire is taken out from the waste tungsten-rhenium thermocouple, and the surface is cleaned with alkali and acid respectively, and then the waste tungsten-rhenium thermocouple wire is put into a strong oxidizing agent for overall leaching; b, the leaching solution obtained in step a is dried and then calcined; c, the calcined material obtained in step b is washed and filtered with pure water to obtain filter residue and filtrate; d, the filtrate obtained in step c is added with ammonia water for recrystallization and precipitation, and ammonium rhenate powder is obtained after filtration and drying. The preparation method only recovers the metal rhenium in the tungsten-rhenium thermocouple wire, and the metal tungsten is not recovered, which has the problem of low resource utilization rate.

[0006] CN114196832A disclosed a method for recovering and preparing rhenium powder from tungsten-rhenium alloy waste in 2022. Specifically, it includes the following steps: 1) chlorination of tungsten-rhenium alloy waste in flowing chlorine gas; 2) pass the volatilized WCl6 and ReCl5 steam into hydrogen peroxide for condensation and absorption, and separate HReO4 solution and WCl6 precipitate by filtration; 3) add ammonia water to the separated HReO4 solution, evaporate and crystallize the obtained solution to obtain NH4ReO4 powder, and then reduce the powder in a hydrogen atmosphere to obtain rhenium powder. The preparation method uses chlorine gas to treat tungsten-rhenium alloy waste, which has the problems of high danger and non-comprehensive utilization of metal tungsten.

[0007] In summary, the existing recovery and utilization methods of tungsten-rhenium alloy waste generally have the problems of complex process, high recovery cost, and insufficient utilization of metal tungsten in the alloy. SUMMARY

[0008] In view of the above technical problems, the present application aims to provide a method for recovering and utilizing tungsten-rhenium alloy waste, which specifically includes the following steps:

[0009] (1) The tungsten-rhenium alloy waste is washed with alkali, acid, water, dried and crushed to form waste powder;

[0010] (2) Ammonium metatungstate is added to water and dissolved by heating to form an ammonium metatungstate solution;

[0011] (3) The waste powder and a surfactant are added to the ammonium metatungstate solution and mixed uniformly by high-speed shearing to form a suspension;

[0012] (4) The suspension is spray dried to form a mixed powder;

[0013] (5) The mixed powder is calcined and reduced by hydrogen to form a tungsten-rhenium alloy powder;

[0014] In the tungsten-rhenium alloy powder of step (5), the content of metal rhenium is less than that in the tungsten-rhenium alloy waste of step (1).

[0015] The most important reason for the decrease of the comprehensive performance of tungsten-rhenium alloy is oxidation. In order to fully utilize the metal tungsten and the metal rhenium in the tungsten-rhenium alloy waste, most of the existing technologies are to prepare the corresponding salt by completely dissolving the tungsten-rhenium alloy waste, and then to prepare the tungsten-rhenium alloy. Different from the existing technologies, the tungsten-rhenium alloy waste is first washed by alkali, washed by acid, washed by water, dried, and crushed to form a waste powder. At this time, the waste powder needs to be crushed very uniformly, so as to facilitate the subsequent hydrogen reduction to obtain the tungsten-rhenium alloy powder with uniform rhenium content. Then, ammonium metatungstate is dissolved in water to form an ammonium metatungstate solution. The waste powder and a surfactant are added into the ammonium metatungstate solution, and are uniformly mixed by high-speed shearing to form a suspension. The present application prepares the uniform waste powder and the uniform system of ammonium metatungstate by dispersing the tungsten-rhenium alloy waste powder into the solution of ammonium metatungstate and the surfactant. It is equivalent to wrapping a layer of ammonium metatungstate on the outer surface of the tungsten-rhenium alloy waste powder. As long as the particle size distribution of the tungsten-rhenium alloy waste powder is uniform, the uniform distribution of ammonium metatungstate can be ensured. By adding the surfactant, the present application weakens the sedimentation of the tungsten-rhenium alloy waste powder, so that the tungsten-rhenium alloy waste powder is better suspended in the ammonium metatungstate solution. Then, the suspension is spray dried to form a mixed powder. At this time, the mixed powder is a sandwich structure with the waste powder as the core and the surfactant and the ammonium metatungstate wrapped thereon. In the macroscopic and microscopic ranges, the element tungsten and the element rhenium maintain the same proportion. Finally, the mixed powder is calcined and reduced by hydrogen in a tube furnace to form a tungsten-rhenium alloy powder. The content of the metal rhenium in the tungsten-rhenium alloy powder recovered by the recycling method is lower than that in the tungsten-rhenium alloy waste. In this way, the loss rate of the metal rhenium in the recycling process can be reduced, and the recovery rate of the metal rhenium in the recycling process can be improved. Since the tungsten-rhenium alloy waste is not completely dissolved in the acid, the present application has the characteristics of less waste and low energy consumption.

[0016] In some specific implementations, the particle size D(50) of the waste powder in step (1) is ≤ 20 μm. When the tungsten-rhenium alloy waste is ground finer or the particle size D(50) of the waste powder is smaller, the uniformity of the tungsten-rhenium alloy powder prepared by recycling is better. However, the finer the tungsten-rhenium alloy waste is ground, the greater the time cost is. The present application controls the particle size D(50) of the waste powder to be ≤ 20 μm, so that the tungsten-rhenium alloy powder with good uniformity can be recovered.

[0017] In some specific implementations, the mass ratio of water to the ammonium metatungstate in step (2) is 6-15:1. The larger the ratio of water to ammonium metatungstate, the less favorable it is to uniformly suspend the waste powder into the ammonium metatungstate solution. A large ratio is only suitable when more tungsten-rhenium alloy waste powder needs to be added under the condition of the same amount of ammonium metatungstate. The smaller the ratio of water to ammonium metatungstate, the more favorable it is to uniformly suspend the waste powder into the ammonium metatungstate solution. A small ratio is only suitable when less tungsten-rhenium alloy waste powder needs to be added under the condition of the same amount of ammonium metatungstate.

[0018] In some specific implementations, the temperature of the heating and dissolving process in step (2) is 45-65℃. The temperature of the heating and dissolving process is set by considering three factors: 1, the temperature range in which the surfactant is most active; 2, the relatively flat region of the ammonium metatungstate solubility curve; and 3, the lowest possible heating energy consumption. By considering these factors, a temperature range of 45-65℃ is adopted to avoid trade-offs.

[0019] In some specific implementations, the mass ratio of the surfactant to the waste powder in step (3) is 0.02-0.15:1, and the surfactant is selected from at least one of polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 6000, and polyethylene glycol 8000. The surfactant reduces the surface tension between the waste powder and the ammonium metatungstate solution, increases the sedimentation resistance of the waste powder, and makes it easier for the waste powder to be uniformly dispersed into the ammonium metatungstate solution. The present application uses at least one surfactant selected from polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 6000, and polyethylene glycol 8000, which has no elements other than C, H, and O in its structure and can be converted into a gaseous substance during subsequent baking and hydrogen reduction, without remaining in the tungsten-rhenium alloy powder to affect the quality of the tungsten-rhenium alloy powder. The mass ratio of the surfactant to the waste powder is 0.02-0.15:1, which balances the mutual contradiction between the sufficient dispersion of the waste powder in the ammonium metatungstate solution and the minimum amount of surfactant.

[0020] In some specific embodiments, the high-speed shearing mixing process in step (3) is carried out under the action of a shearing disc. The present application uniformly disperses the waste powder into the ammonium metatungstate aqueous solution under the action of the shearing disc and improves the stability of the dispersion liquid under the action of the surfactant. Commonly used high-speed shearing devices include a shearing disc, a fixed-rotor shearing device and an emulsifying pump, wherein the mechanical structure and principle of the emulsifying pump are similar to those of the fixed-rotor shearing device. Compared with the fixed-rotor shearing device, the shearing disc not only provides high-efficiency shearing action but also can provide a flow field for macroscopic mixing, thereby ensuring that the waste powder is uniformly dispersed into the ammonium metatungstate solution in both microcosmic and macroscopic aspects. The fixed-rotor shearing device and the emulsifying pump focus on providing high-efficiency shearing mixing effect, and the macroscopic mixing effect depends on the internal structure of the mixing container, and the problem of uneven distribution of the waste powder in the ammonium metatungstate solution is prone to occur.

[0021] In some specific embodiments, the spray drying process in step (4) is carried out in a spray dryer equipped with a two-fluid atomizer. The structure of the atomizer in the spray drying process has a great influence on the stability of the suspension in the spray drying process. When a common pressure atomizer is used, the flow rate of the suspension sprayed from the atomizer nozzle under the action of high pressure of the spray pump is high, the centrifugal force of the atomized droplets of the suspension when rotating in the spray dryer is large, and the problem of centrifugal sedimentation of the waste powder particles in the droplets is prone to occur, and finally the problem of uneven distribution of the waste powder in the ammonium metatungstate solution occurs, thereby reducing the uniformity of the final tungsten-rhenium alloy powder. The present application uses a two-fluid atomizer to carry out the atomization process of the suspension, the pressure of the power airflow is low, and the spraying speed of the atomized droplets is low, so that the above-mentioned problem of uneven distribution of the waste powder in the ammonium metatungstate solution does not occur.

[0022] In some specific embodiments, the pressure of the airflow supplied to the two-fluid atomizer is 0.3-0.35 MPa. Due to the reasons as described above, the pressure of the power airflow of the atomizer is as low as possible under the condition of fully atomizing the suspension. The present application uses an airflow pressure of 0.3-0.35 MPa, which can meet the requirement of preparing a uniformly dispersed mixed powder.

[0023] In some specific embodiments, the temperature of the calcination process in step (5) is 400-500°C. The surfactant in the mixed powder is vaporized and thermally decomposed by calcination, and the surfactant calcination residue is removed from the tubular furnace. The calcination process needs to be thorough, and the surfactant calcination residue will be brought into the final tungsten-rhenium alloy powder if the calcination is not thorough.

[0024] In some specific implementations, the hydrogen reduction process in step (5) is performed at a temperature of 600-1200°C. The hydrogen reduction process is performed at a temperature of 600-1200°C, which can fully reduce the tungsten and rhenium oxides into tungsten-rhenium alloy powder. The hydrogen flow rate and the hydrogen reduction time are adjusted according to different reduction equipment, and the paratungstate or tungsten oxide or rhenium oxide needs to be completely reduced into tungsten-rhenium alloy powder.

[0025] The tungsten-rhenium alloy waste recycling method provided by the application does not need to completely dissolve the tungsten-rhenium alloy waste to recover the metal tungsten and the metal rhenium therein, thereby reducing the energy consumption of the recovery; the tungsten-rhenium alloy waste powder is dispersed into the ammonium paratungstate solution, thereby reducing the loss of the metal rhenium in the recovery process; and the surfactant is added when the suspension is prepared, thereby improving the dispersion effect. The tungsten-rhenium alloy powder that can be comprehensively utilized is recovered from the tungsten-rhenium alloy waste through a simple process. DETAILED DESCRIPTION

[0026] The application will be specifically described below through examples, but the application is not limited to these examples.

[0027] Example 1

[0028] (1) Pretreatment:

[0029] Take tungsten-rhenium alloy waste (tungsten-rhenium alloy wire): 180.0 g (metal rhenium content: 5.052%), and immerse the tungsten-rhenium alloy wire in a 5.5% sodium hydroxide aqueous solution at room temperature for 2.0 h. After the sodium hydroxide aqueous solution immersion is completed, immerse the tungsten-rhenium alloy wire in a 12.5% dilute hydrochloric acid aqueous solution for 2.0 h. After the dilute hydrochloric acid aqueous solution immersion is completed, wash the tungsten-rhenium alloy wire with deionized water to remove the residual hydrochloric acid on the surface of the tungsten-rhenium alloy wire. Put the tungsten-rhenium alloy wire into an oven, set the oven temperature to 120°C, and dry for 4 hours. Cut the dried tungsten-rhenium alloy wire into short sections, and then ball mill in a ball mill to D(50)=13.241 μm to obtain waste powder.

[0030] (2) Preparation of suspension:

[0031] Add ammonium paratungstate (four crystal waters): 25.000 g (content: 99.163%) into an 800 ml beaker, add deionized water: 220 g, polyethylene glycol (4000): 16.50 g, and waste powder: 165.000 g. Put the beaker into a constant-temperature water bath, and set the water bath temperature to 50°C. Immerse the dispersion disc of a high-speed shearing device below the liquid surface, turn on the high-speed shearing device, and set the rotation speed of the dispersion disc (dispersion disc diameter: 4.2 cm) to 1000 r / min. High-speed shearing for 5 min. After high-speed shearing is completed, a suspension is obtained.

[0032] (3) Spray drying:

[0033] The dispersing disc rotation speed was set to 500 r / min, and hot air was pre- introduced into the spray drying tower, with a hot air temperature of 180°C. The two-fluid compressed air inlet valve was opened, and the compressed air flow rate was set to 1.0 L / min, and the pressure was set to 0.32 MPa. The inlet pipe of the peristaltic pump was inserted into the bottom of the beaker, and the peristaltic pump was turned on, and the peristaltic pump flow rate was set to 0.06 L / min, and the spray drying was carried out. After the spray drying was completed, the mixed powder was obtained.

[0034] (4) Calcination:

[0035] The mixed powder was placed in a tube furnace, and the air flow rate was controlled to 0.2 L / min, and the tube furnace temperature was set to 450°C, and the calcination was carried out for 3.0 hours.

[0036] (4) Hydrogen reduction:

[0037] After the calcination was completed, high-purity nitrogen was first introduced into the tube furnace, and the high-purity nitrogen flow rate was controlled to 1.0 L / min for 10 minutes. After the replacement was completed, hydrogen was introduced into the tube furnace, and the hydrogen flow rate was controlled to 0.2 L / min, and the tube furnace temperature was increased to 1050°C, and the hydrogen reduction was carried out for 8.0 hours. After the hydrogen reduction was completed, the hydrogen flow rate was set to 0.05 L / min, and the natural cooling was carried out. After the natural cooling was completed to room temperature, the tungsten-rhenium-molybdenum alloy powder of about 180.3 g was obtained.

[0038] Uniformity evaluation: After the tungsten-rhenium-molybdenum alloy powder was mixed uniformly, 20.0 g of the sample was taken, and a rectangular thin layer of 5*3 cm was laid (the long side was horizontally arranged), and the sample was taken from the upper left, upper middle, upper right, lower left, lower middle, lower right, and the diagonal midpoint of the rectangular tungsten-rhenium-molybdenum alloy thin layer in order. The rhenium content of the molybdenum-rhenium alloy powder was detected by ICP-OES, and the detection contents were 4.5689%, 4.5321%, 4.5621%, 4.5596%, 4.5795%, 4.5256%, and 4.5689%, respectively, and the average content was 4.5567%, the standard deviation (SD) was 0.0201%, and the relative standard deviation (RSD) was 0.4414%.

[0039] Example 2

[0040] The preparation process and process parameters of Example 2 were basically the same as those of Example 1, except that the waste powder was ball milled in the ball mill to D(50)=8.126 μm.

[0041] Uniformity evaluation: After the tungsten-rhenium alloy powder was mixed uniformly, 20g of sample was taken and laid into a 5*3cm rectangular thin layer (the long side was horizontally arranged), and samples were taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder was detected by ICP-OES, and the detection contents were 4.5623%, 4.5701%, 4.5747%, 4.5389%, 4.5378%, 4.5498%, and 4.5404% in turn, the average content was 4.5534%, the standard deviation (SD) was 0.0155%, and the relative standard deviation (RSD) was 0.3411%.

[0042] Example 3

[0043] The preparation process and process parameters of Example 3 were basically the same as those of Example 1, except that the waste powder was ball milled in a ball mill to D(50)=19.475μm.

[0044] Uniformity evaluation: After the tungsten-rhenium alloy powder was mixed uniformly, 20g of sample was taken and laid into a 5*3cm rectangular thin layer (the long side was horizontally arranged), and samples were taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder was detected by ICP-OES, and the detection contents were 4.5717%, 4.5744%, 4.5281%, 4.5369%, 4.5374%, 4.5311%, and 4.5873% in turn, the average content was 4.5524%, the standard deviation (SD) was 0.0244%, and the relative standard deviation (RSD) was 0.5369%.

[0045] Example 4

[0046] The preparation process and process parameters of Example 4 were basically the same as those of Example 1, except that the amount of polyethylene glycol (4000) was reduced to 3.30g.

[0047] Uniformity evaluation: After the tungsten-rhenium alloy powder was mixed uniformly, 20g of sample was taken and laid into a 5*3cm rectangular thin layer (the long side was horizontally arranged), and samples were taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder was detected by ICP-OES, and the detection contents were 4.5823%, 4.5709%, 4.5669%, 4.5317%, 4.5735%, 4.5305%, and 4.5214% in turn, the average content was 4.5539%, the standard deviation (SD) was 0.0250%, and the relative standard deviation (RSD) was 0.5486%.

[0048] Example 5

[0049] The preparation process and process parameters of Example 5 are basically the same as those of Example 1, except that the amount of polyethylene glycol (2000) is increased to 24.75 g.

[0050] Uniformity evaluation: After the tungsten-rhenium alloy powder is mixed uniformly, 20 g of sample is taken and laid into a 5*3 cm rectangular thin layer (the long side is horizontally arranged), and the sample is taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder is detected by ICP-OES, and the detection contents are 4.5649%, 4.5376%, 4.5647%, 4.5614%, 4.5709%, 4.5446%, 4.5389% in turn, the average content is 4.5547%, the standard deviation (SD) is 0.0139%, and the relative standard deviation (RSD) is 0.3047%.

[0051] Example 6

[0052] The preparation process and process parameters of Example 6 are basically the same as those of Example 1, except that 16.50 g of polyethylene glycol (2000) is used instead of polyethylene glycol (4000).

[0053] Uniformity evaluation: After the tungsten-rhenium alloy powder is mixed uniformly, 20 g of sample is taken and laid into a 5*3 cm rectangular thin layer (the long side is horizontally arranged), and the sample is taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder is detected by ICP-OES, and the detection contents are 4.5889%, 4.5387%, 4.5339%, 4.5587%, 4.5382%, 4.5732%, 4.5316% in turn, the average content is 4.5519%, the standard deviation (SD) is 0.0222%, and the relative standard deviation (RSD) is 0.4885%.

[0054] Example 7

[0055] The preparation process and process parameters of Example 7 are basically the same as those of Example 1, except that 16.50 g of polyethylene glycol (6000) is used instead of polyethylene glycol (4000).

[0056] Uniformity evaluation: After the tungsten-rhenium alloy powder was mixed uniformly, 20 g of sample was taken and laid into a 5*3 cm rectangular thin layer (the long side was horizontally arranged), and samples were taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder was detected by ICP-OES, and the detection contents were 4.5713%, 4.5428%, 4.5669%, 4.5358%, 4.5614%, 4.5311%, 4.5715% in turn, the average content was 4.5544%, the standard deviation (SD) was 0.0174%, and the relative standard deviation (RSD) was 0.3810%.

[0057] Example 8

[0058] The preparation method and process parameters of Example 8 are basically the same as those of Example 1, except that 16.50 g of polyethylene glycol (8000) is used instead of polyethylene glycol (4000).

[0059] Uniformity evaluation: After the tungsten-rhenium alloy powder was mixed uniformly, 20 g of sample was taken and laid into a 5*3 cm rectangular thin layer (the long side was horizontally arranged), and samples were taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder was detected by ICP-OES, and the detection contents were 4.5713%, 4.5428%, 4.5669%, 4.5358%, 4.5614%, 4.5311%, 4.5715% in turn, the average content was 4.5544%, the standard deviation (SD) was 0.0174%, and the relative standard deviation (RSD) was 0.3810%.

[0060] Comparative Example 1

[0061] The preparation method and process parameters of Comparative Example 1 are basically the same as those of Example 1, except that the waste powder is ball milled to D(50)=23.574 μm in the ball mill.

[0062] Uniformity evaluation: After the tungsten-rhenium alloy powder was mixed uniformly, 20 g of sample was taken and laid into a 5*3 cm rectangular thin layer (the long side was horizontally arranged), and samples were taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder was detected by ICP-OES, and the detection contents were 4.5713%, 4.5428%, 4.5669%, 4.5358%, 4.5614%, 4.5311%, 4.5715% in turn, the average content was 4.5544%, the standard deviation (SD) was 0.0174%, and the relative standard deviation (RSD) was 0.3810%.

[0063] Comparative Example 2

[0064] The preparation method and process parameters of Comparative Example 2 are basically the same as those of Example 1, except that no surfactant polyethylene glycol (4000) is added.

[0065] Uniformity evaluation: After the tungsten-rhenium alloy powder is mixed uniformly, 20g of sample is taken and laid flat into a 5*3cm rectangular thin layer (the long side is arranged horizontally), and samples are taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder is detected by ICP-OES, and the detection contents are 4.6123%, 4.5092%, 4.5056%, 4.5215%, 4.5989%, 4.5975%, and 4.5811%, respectively, the average content is 4.5609%, the standard deviation (SD) is 0.0468%, and the relative standard deviation (RSD) is 1.0252%.

[0066] Comparative Example 3

[0067] The preparation method and process parameters of Comparative Example 3 are basically the same as those of Example 1, except that the compressed air pressure is set to 0.42MPa during spray drying.

[0068] Uniformity evaluation: After the tungsten-rhenium alloy powder is mixed uniformly, 20g of sample is taken and laid flat into a 5*3cm rectangular thin layer (the long side is arranged horizontally), and samples are taken in the order of the upper left, upper middle, upper right, lower left, lower middle, lower right, and diagonal midpoint of the rectangular tungsten-rhenium alloy thin layer). The rhenium content of the molybdenum-rhenium alloy powder is detected by ICP-OES, and the detection contents are 4.5017%, 4.5946%, 4.5904%, 4.5194%, 4.5969%, 4.5046%, and 4.5914%, respectively, the average content is 4.5570%, the standard deviation (SD) is 0.0457%, and the relative standard deviation (RSD) is 1.0025%.

[0069] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for recycling tungsten-rhenium alloy waste, characterized in that, Specifically, the steps include the following: (1) Tungsten-rhenium alloy waste is subjected to alkali washing, acid washing, water washing, drying and crushing to form waste powder; (2) Add ammonium metatungstate to water and heat it to dissolve it, forming an ammonium metatungstate solution; (3) Add waste powder and surfactant to ammonium metatungstate solution, mix evenly by high-speed shearing to form a suspension; (4) The suspension is spray-dried to form a mixed powder; (5) The mixed powder is calcined and reduced with hydrogen to form tungsten-rhenium alloy powder; In step (5), the rhenium content in the tungsten-rhenium alloy powder is less than the rhenium content in the tungsten-rhenium alloy waste in step (1).

2. The recycling method according to claim 1, characterized in that, The particle size D(50) of the waste powder in step (1) is ≤20μm.

3. The recycling method according to claim 1, characterized in that, In step (2), the mass ratio of water to ammonium metatungstate is 6 to 15:

1.

4. The recycling method according to claim 1, characterized in that, The temperature of the heating and dissolving process in step (2) is 45-65℃.

5. The recycling method according to claim 1, characterized in that, In step (3), the mass ratio of the surfactant to the waste powder is 0.02 to 0.15:1; the surfactant is selected from at least one of polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 6000 and polyethylene glycol 8000.

6. The recycling method according to claim 1, characterized in that, The high-speed shearing and mixing process described in step (3) is carried out under the action of the shearing disk.

7. The recycling method according to claim 1, characterized in that, The spray drying process described in step (4) is carried out in a spray dryer equipped with a two-fluid atomizer.

8. The recycling method according to claim 7, characterized in that, The airflow pressure supplied to the two-fluid atomizer is 0.3 to 0.35 MPa.

9. The recycling method according to claim 1, characterized in that, The temperature of the roasting process in step (5) is 400-500℃.

10. The recycling method according to claim 1, characterized in that, The temperature of the hydrogen reduction process in step (5) is 600 to 1200°C.