Recovery and preparation method of tungsten-rhenium or molybdenum-rhenium alloy

Abstract

The invention relates to the technical field of non-ferrous metal hydrometallurgy, in particular to a tungsten-rhenium or molybdenum-rhenium alloy recycling and preparing method which comprises the steps that a hydrogen peroxide solution is used for carrying out a reaction for leaching a second metal element, a peroxy metal acid solution is obtained, and rhenium leaching is achieved through the acidity of the peroxy metal acid solution and excessive hydrogen peroxide; removing impurity cations in the solution by using cationic resin to prepare an alloy powder preform, and reducing to obtain alloy powder; and sintering the alloy powder to obtain the alloy. According to the method, the tungsten-rhenium / molybdenum-rhenium alloy is leached through hydrogen peroxide, a peroxy acid solution is formed, and leaching of rhenium is synchronously achieved; by utilizing the characteristic that tungsten, molybdenum and rhenium all exist in an anion form under a peroxide ion system, metal cation impurities possibly introduced in the leaching process are removed by using cation resin, and the purity of the solution is further improved; the problems that in the prior art, the recovery process of tungsten-rhenium and molybdenum-rhenium alloy is complex, element distribution is uneven due to doping in the preparation process, cost is high, and the alloy preparation process is complex are solved.

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metal hydrometallurgical technology, and in particular to a method for the recovery and preparation of tungsten-rhenium or molybdenum-rhenium alloys. Background Technology

[0002] Molybdenum-rhenium alloys are widely used due to their excellent high-temperature performance, which eliminates low-temperature brittleness in metals and improves thermal conductivity. They are mainly used in aerospace and defense industries, electronics, semiconductors, nuclear industry, and medical fields. Tungsten-rhenium alloys, on the other hand, have even higher heat resistance and greater density. Rhenium can effectively modify the brittleness of tungsten, and they are mainly used in high-temperature applications such as high-temperature thermocouples. Both tungsten-rhenium and molybdenum-rhenium alloys play irreplaceable roles in their respective fields.

[0003] Currently, the main recycling methods for molybdenum-rhenium alloys / tungsten-rhenium alloys are pyrometallurgical and hydrometallurgical processes. The pyrometallurgical process utilizes the volatility of rhenium heptoxide to volatilize the rhenium element, achieving separation of rhenium from the secondary metal. Hydrometallurgical processes dissolve the alloy using strong oxidants or electrochemical dissolution, then separate it from the solution. Existing recycling methods are costly, complex, and environmentally damaging. Alloy preparation methods include activated sintering, mechanical alloying, or oxide co-reduction. Activated sintering significantly reduces the material's electrical and thermal conductivity, while oxide co-reduction for powder preparation is cumbersome, inefficient, and difficult to mass-produce. Summary of the Invention

[0004] Based on the above analysis, the present invention aims to provide a method for recycling and preparing tungsten-rhenium or molybdenum-rhenium alloys, which solves at least one of the problems existing in the prior art, such as complex recycling processes for tungsten-rhenium and molybdenum-rhenium alloys, uneven element distribution due to doping during the preparation process, high cost, and complex alloy preparation processes.

[0005] The objective of this invention is mainly achieved through the following technical solutions: A method for recovering and preparing tungsten-rhenium or molybdenum-rhenium alloys, comprising: Step (1): Clean and crush the waste binary rhenium alloy, use hydrogen peroxide solution to leach the second metal element to obtain a peroxy metal acid solution of the second metal element, use the acidity of the peroxy metal acid and excess hydrogen peroxide to leach rhenium, and obtain a peroxy metal acid solution containing rhenium. Step (2): After leaching, a mixed solution of peroxy metal acid and rhenium is obtained. The ratio of rhenium to the second metal element in the mixed solution of peroxy metal acid and rhenium is adjusted, and then cation exchange resin is used to remove impurity cations in the solution. Step (3) The mixed solution of the purified peroxy metal acid and rhenium is heated to decompose and crystallize, and alloy precursor powder is obtained. Step (4): Reduce the alloy precursor powder with hydrogen to obtain alloy powder; Step (5): Sinter the alloy powder at 1800℃ ~ 2100℃ to obtain a binary alloy of rhenium and a second metallic element.

[0006] Preferably, the second metallic element in step (1) is tungsten or molybdenum.

[0007] Preferably, in step (1), the mass fraction of rhenium in the binary rhenium alloy is 0.5% to 30%.

[0008] Preferably, the cation resin in step (2) is one or more of commercially available 001, D001, and chelated cation resin.

[0009] Preferably, in step (2), the resin column height is 50cm~200cm, and / or the flow rate is 0.5Bv / h~2Bv / h, and / or the treatment temperature is 15℃~30℃.

[0010] Preferably, in step (3), the crystallization is performed at a temperature of 95°C to 110°C.

[0011] Preferably, in step (4), a hydrogen reduction furnace is used to reduce both the second metal element and rhenium to their elemental form, thereby obtaining molybdenum-rhenium or tungsten-rhenium metal powder.

[0012] A binary rhenium alloy is prepared by the above-mentioned recycling and preparation method of tungsten-rhenium or molybdenum-rhenium alloy. The alloy has a density >98%, rhenium and the second metal element are uniformly distributed, the grains are fine and uniform, the rhenium content deviation in the alloy is ≤0.1%, and the impurity content is ≤0.005%.

[0013] A tungsten-rhenium or molybdenum-rhenium alloy is prepared by the above-mentioned method for recycling and preparing tungsten-rhenium or molybdenum-rhenium alloys. The alloy has a density >98%, rhenium and the second metal element are uniformly distributed, the grains are fine and uniform, and the rhenium content deviation in the alloy is ≤0.1%.

[0014] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects: (1) In this invention, hydrogen peroxide is used to leach tungsten-rhenium / molybdenum-rhenium alloy. The oxidizing property of hydrogen peroxide is combined with the peroxy acid solution formed by tungsten / molybdenum to simultaneously leach rhenium. Then, taking advantage of the fact that tungsten, molybdenum and rhenium all exist in anionic form under the peroxy ion system, cationic resin is used to remove metal cation impurities that may be introduced during the leaching process, thereby further improving the purity of the solution. The sintered alloy blank has a density >99%, rhenium and the second metal element are evenly distributed, and the grains are fine and uniform. The impurity content is ≤0.005%, and the rhenium content deviation in the alloy is ≤0.1%.

[0015] (2) This invention utilizes the property that hydrogen peroxide can react with molybdenum / tungsten. The alloy does not need to be roasted or oxidized under pressure to allow tungsten / molybdenum to enter the solution. Because peroxytungstic acid and peroxymolybdic acid solutions are inherently highly acidic, coupled with the oxidizing properties of hydrogen peroxide, conditions are provided for the leaching of rhenium. Therefore, only the addition of hydrogen peroxide is needed to achieve the leaching of tungsten / molybdenum and rhenium, which greatly simplifies the process and reduces pollution.

[0016] (3) This invention uses waste materials directly as raw materials for alloy production, which greatly shortens the process from alloy recycling to reprocessing. It utilizes the characteristics of tungsten, molybdenum and rhenium in the form of anions in the oxygen system to separate them from impurity metals in the waste materials without introducing other impurities, thus achieving a clever combination of leaching, impurity removal and crystallization decomposition processes.

[0017] Other features and advantages of the invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained from the embodiments described and the accompanying drawings. Attached Figure Description

[0018] Figure 1 This is a process flow diagram of one embodiment of the present invention. Detailed Implementation

[0019] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not intended to limit the present invention.

[0020] On one hand, this invention discloses a method for the recovery and preparation of tungsten-rhenium or molybdenum-rhenium alloys, such as... Figure 1 As shown, it includes: Step (1): Clean and crush the waste binary rhenium alloy, use hydrogen peroxide solution to leach the second metal element to obtain a peroxy metal acid solution of the second metal element, use the acidity of the peroxy metal acid and excess hydrogen peroxide to leach rhenium, and obtain a peroxy metal acid solution containing rhenium. Step (2): Adjust the ratio of rhenium to the second metal element in the peroxy metal acid solution containing rhenium, and then use cation exchange resin to remove impurity cations from the solution; Step (3) involves heating and crystallizing to decompose the resin and preparing the precursor powder from the resin post-treatment solution. Step (4): Reduce the alloy precursor powder with hydrogen to obtain alloy powder; Step (5): Sinter the alloy powder to obtain a binary alloy of rhenium and a second metallic element.

[0021] In practice, this invention employs hydrogen peroxide to leach the tungsten-rhenium / molybdenum-rhenium alloy. The oxidizing properties of hydrogen peroxide, combined with the peroxy metal acid solution formed by tungsten and molybdenum, simultaneously leach rhenium. Furthermore, utilizing the characteristic that the second metal, tungsten, molybdenum, and rhenium all exist in anionic form under the peroxy ion system, a cationic resin is used to remove metal cation impurities that may be introduced during the leaching process, further improving the purity of the solution. Homogeneous precipitation of molybdenum-rhenium oxide is achieved through heating and dissociation of peroxide ions, resulting in a precursor with finer particle size and more uniform elemental distribution. The precursor powder is then reduced with hydrogen to obtain alloy powder.

[0022] Compared with the prior art, the present invention uses hydrogen peroxide to leach tungsten-rhenium / molybdenum-rhenium alloys. The oxidizing property of hydrogen peroxide, combined with the peroxyacid solution formed by tungsten or molybdenum, simultaneously achieves the leaching of rhenium. Furthermore, taking advantage of the characteristic that tungsten, molybdenum, and rhenium all exist in anionic form under the peroxy ion system, a cationic resin is used to remove metal cation impurities that may be introduced during the leaching process, thereby further improving the purity of the solution.

[0023] Specifically, in step (1), the second metal element can be tungsten or molybdenum, and the corresponding peroxy metal acid is peroxytungstic acid or peroxymolybdic acid.

[0024] Specifically, step (1) includes the following steps: Metallic rhenium in waste binary rhenium alloys was dissolved using a peroxymetallic acid solution.

[0025] Specifically, step (2) includes the following steps: A mixed solution is prepared by adding a peroxy metal acid or a rhenium source to a peroxy metal acid solution containing rhenium.

[0026] In practice, the strong acidity of the peroxy metal acid solution and the oxidizing properties of hydrogen peroxide are used to dissolve rhenium-containing materials and prepare a rhenium-containing peroxy metal acid solution, which allows tungsten or molybdenum and rhenium to be mixed in situ, resulting in a more uniform mixture. Then, the mixed solution is heated to decompose and crystallize to obtain an alloy powder precursor. During the solidification process of the precursor solution containing peroxy metal acid ions, a large amount of gas is released, and the bubble rupture process further refines the powder particle size, resulting in the precursor powder obtained from the mixed solution.

[0027] Compared with existing technologies, this invention utilizes the property that hydrogen peroxide can react with molybdenum and / or tungsten. The alloy can be leached into the solution without calcination or pressurized oxidation. Because peroxytungstic acid and peroxymolybdic acid solutions are inherently highly acidic, coupled with the oxidizing properties of hydrogen peroxide, conditions are created for rhenium leaching. Therefore, only the addition of hydrogen peroxide is needed to achieve the leaching of tungsten / molybdenum and rhenium, greatly simplifying the process and reducing pollution.

[0028] Specifically, in step S101, hydrogen peroxide should be in excess. The amount of excess hydrogen should be 5 to 8 times the molar amount of the introduced metal element, for example, it can be 5 times, 5.2 times, 5.4 times, 5.6 times, 5.8 times, 6 times, 6.2 times, 6.4 times, 6.6 times, 6.8 times, 7 times, 7.2 times, 7.4 times, 7.6 times, 7.8 times, or 8 times.

[0029] Specifically, the liquid-to-solid ratio of the excess hydrogen solution to the waste binary rhenium alloy is 5:1 to 20:1, for example, it can be 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 or 20:1.

[0030] It should be noted that the molybdenum concentration in the peroxymetallic acid solution should ideally be controlled between 100 g / L and 250 g / L. This avoids premature molybdenum precipitation due to excessively high concentrations, ensuring the stability of the mixed solution. Excessively high molybdenum concentrations in the peroxymetallic acid solution lead to decreased solution stability.

[0031] Specifically, in step (1), the mass fraction of rhenium in the binary rhenium alloy is 0.5% to 30%, which can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%.

[0032] It should be noted that the rhenium content in the binary rhenium alloy should not be too high, to avoid insufficient production of peroxy metal acid to dissolve the rhenium. Peroxy metal acid helps dissolve rhenium and ensures the stability of the mixed solution.

[0033] Specifically, in step (2), after leaching, a mixed solution of peroxy metal acid and rhenium is obtained. The ratio of rhenium to the second metal element in the mixed solution of peroxy metal acid and rhenium is adjusted, and then cation exchange resin is used to remove impurity cations from the solution. Specifically, adjusting the ratio of rhenium to the second metal element in the mixed solution of peroxy metal acid and rhenium includes: adding a rhenium source or peroxy metal acid according to the mass ratio of the second metal element to rhenium in the finished alloy so that the ratio of rhenium to the second metal element in the mixed solution of peroxy metal acid and rhenium is equal to the mass ratio of the second metal element to rhenium in the finished alloy.

[0034] Specifically, in step (2), the cation resin is one or more of the commercially available 001, D001, and chelated cation resins.

[0035] Specifically, in step (2), the resin column height is 50cm~200cm, which can be 50cm, 60cm, 70cm, 100cm, 180cm or 200cm; the flow rate is 0.5Bv / h~2Bv / h, which can be 0.5Bv / h, 0.6Bv / h, 0.7Bv / h, 0.9Bv / h, 1.2Bv / h, 1.2Bv / h, 1.3Bv / h, 1.5Bv / h, 1.6Bv / h, 1.7Bv / h, 1.9Bv / h or 2Bv / h; and the treatment temperature is 15℃~30℃, which can be 15℃, 18℃, 20℃, 22℃, 25℃, 28℃ or 30℃.

[0036] Specifically, in step (3), the crystallization is carried out by heating and decomposition, and the crystallization temperature is 90℃ ~ 120℃, which can be 90℃, 100℃, 110℃ or 120℃.

[0037] Preferably, in step (4), hydrogen reduction is carried out using a hydrogen reduction furnace, with the hydrogen reduction temperature controlled at 400-950℃ and the reduction time at 3-6 hours, so that both the second metal element and rhenium element are reduced to elemental form, and a homogeneous mixed metal powder is obtained.

[0038] The hydrogen reduction temperature is 400℃ ~ 950℃, which can be 400℃, 420℃, 430℃, 450℃, 460℃, 470℃, 480℃, 490℃, 500℃, 520℃, 530℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, 620℃, 630℃, 650℃, 660℃, 670℃, 680℃, 690℃, 720℃, 730℃, 750℃, 760℃, 770℃, 780℃, 790℃, 820℃, 830℃, 850℃, 860℃, 880℃, 920℃, or 950℃. The restoration time is 3h to 6h; it can be 3h, 3.2h, 3.4h, 3.5h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h, 5.4h, 5.5h, 5.6h, 5.8h or 6h.

[0039] Specifically, the median particle size of the rhenium and second metal element alloy powder prepared in step (4) is ≤1 micrometer, preferably 0.1 ~ 0.9 micrometers.

[0040] Specifically, in step (5), the sintering temperature is 1800℃ ~ 2100℃, which can be 1800℃, 1850℃, 1900℃, 1950℃, 2000℃, 2050℃ or 2100℃.

[0041] The applicant's research has found that fine powders (especially nano / submicron powders) can significantly reduce the sintering temperature of alloy billets (down to below the solidus line), achieving a highly dense and fine-grained microstructure. Compared to conventional sintering, this invention requires a lower sintering temperature, reducing energy consumption; it avoids the heating and cooling process, enabling efficient production and improving production efficiency; low-temperature sintering also contributes to achieving a highly dense and fine-grained microstructure.

[0042] Compared with the prior art, the powder prepared by the present invention through the peroxide system has a finer particle size, which can realize the low-temperature sintering of molybdenum and rhenium, reduce the energy consumption and time cost in the alloy production process, and achieve high-efficiency production. Because rhenium and the second metal element are evenly distributed, the product quality is more stable, the grains are fine and uniform, the density is >98%, and the impurity content is ≤0.005%.

[0043] On the other hand, the present invention discloses an alloy of rhenium and a second metallic element, prepared by the above-described preparation method.

[0044] Specifically, the sintered alloy billet has a density >98%, rhenium and the second metallic element are evenly distributed, the grains are fine and uniform, the rhenium content deviation in the alloy is ≤0.1%, and the impurity content is ≤0.005%.

[0045] To further illustrate the technical solution of the present invention, the following embodiments and comparative examples are provided:

[0046] Example 1 This embodiment provides a method for the recovery and preparation of a molybdenum-rhenium alloy, the preparation method comprising: Step (1): Clean and crush the waste molybdenum-rhenium alloy (rhenium content 10%), and then use hydrogen peroxide solution to carry out the leaching reaction of the alloy. The amount of hydrogen peroxide is 8 times the total molar amount of molybdenum and rhenium, the liquid-solid ratio is 5:1, the temperature is 45℃, and the time is 6h. Step (2): After leaching, a mixed solution of peroxymolybdic acid and rhenium is obtained. Molybdenum is added according to the molybdenum-rhenium ratio required for the alloy to be prepared. The mass fraction of rhenium in the alloy precursor powder is 25%. Then, cation 001×7 resin is used to remove impurity cations in the solution. The resin column height is 200cm, the flow rate is 2Bv / h, and the temperature is 30℃. Step (3) Prepare a precursor from the resin post-solution by heating decomposition crystallization at a decomposition temperature of 100°C to obtain mixed oxide precursor powder; Step (4): The alloy precursor powder is calcined at 500℃ for 5 hours. After calcination, the powder is subjected to hydrogen reduction, with the reduction starting temperature controlled at 400℃ and the ending temperature at 950℃. The hydrogen flow rate is 15m³ / h. 3 / h, reduction time 8 hours, to obtain homogeneous mixed metal powder; Step (5): Press and sinter the alloy powder to obtain molybdenum-rhenium alloy. The alloy powder is pressed into a blank at 250 MPa and then sintered at a temperature of 2000℃. The high-temperature section is held for 4 hours and the sintering atmosphere is vacuum, high-purity hydrogen or Ar.

[0047] The rhenium-molybdenum alloy prepared above was tested by the bulk density method and the sintered alloy billet had a density >98%, with uniform distribution of rhenium and molybdenum elements, fine and uniform grains, and impurity content ≤0.002% as determined by ICP-MS method, and the rhenium content deviation in the alloy was <0.1%.

[0048] Example 2 On the one hand, this embodiment discloses a method for the recovery and preparation of tungsten-rhenium alloy, including the following steps: Step (1): Clean and crush the waste tungsten-rhenium alloy (rhenium content 20%), and then use hydrogen peroxide solution to carry out the leaching reaction of the alloy. The amount of hydrogen peroxide is 5 times the total molar amount of tungsten and rhenium, the liquid-solid ratio is 5:1, the temperature is 15℃, and the time is 2h. Step (2): After leaching, a mixed solution of peroxytungstic acid and rhenium is obtained. Tungsten is added according to the tungsten-rhenium ratio required for the alloy to be prepared. The mass fraction of rhenium in the alloy precursor powder is 20%. Then, cationic D001 resin is used to remove impurity cations in the solution. The resin column height is 50cm, the flow rate is 0.5Bv / h, and the temperature is 15℃. Step (3) Prepare precursor powder from the impurity-removed mixed solution. The preparation method is heating and decomposing crystallization at a decomposition temperature of 80°C to obtain mixed precursor powder. Step (4): The alloy precursor powder is calcined at 550℃ for 4 hours. After calcination, the powder is subjected to hydrogen reduction, with the reduction starting temperature controlled at 500℃ and the ending temperature at 950℃. The hydrogen flow rate is 18m³ / h. 3 / h, reduction time 4 hours, to obtain homogeneous mixed metal powder; Step (5): The alloy powder is pressed and sintered to obtain tungsten rhenium alloy. The alloy powder is pressed into a blank at 250 MPa and then sintered at 1800℃ for 4 hours. The sintering atmosphere is vacuum, high-purity hydrogen or Ar.

[0049] The rhenium-tungsten alloy prepared above was tested by the bulk density method, and the sintered alloy billet showed a density >98%, uniform distribution of rhenium and tungsten elements, fine and uniform grains, and an impurity content ≤0.004% as determined by ICP-MS. The rhenium content deviation in the alloy was <0.1%. The rhenium and second metal element alloy powder prepared during the process had a median particle size of 0.3 micrometers.

[0050] Example 3 On the one hand, this embodiment discloses a method for the recovery and preparation of molybdenum-rhenium alloy, including the following steps: This embodiment provides a method for preparing a tungsten-rhenium alloy, the method comprising: Step (1): Clean and crush the waste molybdenum-rhenium alloy (rhenium content 30%), and then use hydrogen peroxide solution to carry out the alloy leaching reaction, with a liquid-to-solid ratio of 10:1, a temperature of 35℃, and a time of 4h. Step (2): After leaching, a mixed solution of peroxymolybdenum / molybdic acid and rhenium is obtained. Molybdenum / tungsten / rhenium is added according to the molybdenum-rhenium or molybdenum-rhenium ratio required for the alloy to be prepared. The mass fraction of rhenium in the alloy precursor powder is 20%. Then, cationic D001 resin is used to remove impurity cations in the solution. The resin column height is 80cm, the flow rate is 1Bv / h, and the temperature is 20℃. Step (3) Prepare precursor powder from the impurity-removed mixed solution. The preparation method is thermal decomposition and crystallization at a temperature of 120°C. Step (4): The alloy precursor powder is calcined at 500℃ for 5 hours. After calcination, the powder is reduced with hydrogen, with the reduction starting temperature controlled at 400℃ and the ending temperature at 900℃. The hydrogen flow rate is 20 m³ / h. 3 / h, reduction time 6h, to obtain homogeneous mixed metal powder; Step (5): Press and sinter the alloy powder to obtain molybdenum-rhenium alloy. The alloy powder is pressed into a blank at 200 MPa and then sintered at 2100℃ for 2 hours. The sintering atmosphere is vacuum, high-purity hydrogen or Ar.

[0051] The prepared molybdenum-rhenium alloy was tested by the bulk density method, and the sintered alloy billet showed a density >99%. Rhenium and the second metal element were evenly distributed, and the grains were fine and uniform. The impurity content was ≤0.003% by ICP-MS, and the rhenium content deviation in the alloy was <0.1%. The rhenium and second metal element alloy powder prepared in the process had a median particle size of 0.4 micrometers.

[0052] Comparative Example 1 Compared to Example 1, the amount of hydrogen peroxide used does not meet the protection requirements of this invention. The total molar ratio of hydrogen peroxide to elemental metal is 1:1, and the rest is the same as in Example 1.

[0053] Insufficient hydrogen peroxide dosage will result in the ineffective dissolution and recovery of elemental metals, leaving undissolved waste alloys and reducing the recovery rate of molybdenum and rhenium to <90%.

[0054] Comparative Example 2 Compared to Example 1, the leaching temperature does not meet the protection requirements of this invention. The leaching temperature is 65°C, and the rest is the same as in Example 1.

[0055] The leaching temperature affects the decomposition of peroxide ions, reducing the recovery rate of molybdenum and rhenium. Molybdenum will precipitate prematurely, leading to poorer powder refinement during precursor preparation. The median particle size of the powder is 5.2 micrometers, and the uniformity of rhenium and the second metal element distribution is poor. Due to the influence of powder particle size, low-temperature sintering cannot be achieved, and the required temperature and time for sintering are increased.

[0056] Comparative Example 3 Compared to Example 1, the amount of rhenium used does not meet the protection requirements of this invention. The mass of rhenium required to achieve a rhenium mass fraction of 50% is calculated, and a rhenium source is added to the mixed solution. The rest is the same as in Example 1.

[0057] Adding too much rhenium source will prevent rhenium from dissolving completely and entering the solution, resulting in a rhenium content deviation of >3%, which will degrade the quality of the directly prepared precursor.

[0058] In the molybdenum-rhenium alloy prepared above, the uniformity of rhenium and the second metallic element molybdenum distribution deteriorates, and the grains increase in size and become less uniform.

[0059] Comparative Example 4 Compared to Example 1, the cation removal method does not meet the protection requirements of this invention. The resin column height is 30cm, the operating temperature is 40℃, and the rest is the same as in Example 1.

[0060] Insufficient column height, excessive flow rate, and high temperature leading to bubble generation during the process can all result in poor removal of impurity metal cations, significantly increasing the impurity content. According to ICP-MS, the impurity content is >0.005%, affecting the purity of the obtained alloy.

[0061] Comparative Example 5 Compared to Example 1, the heating decomposition temperature does not meet the protection requirements of this invention. Specifically, the heating decomposition temperature is 40°C, and the rest is the same as in Example 1.

[0062] Because low temperatures cannot effectively decompose peroxy acid ions, molybdenum and rhenium do not precipitate completely during the crystallization process, which cannot effectively guarantee the proportion of molybdenum and rhenium in the precursor, thus reducing the effect of further refining the precursor particle size.

[0063] The molybdenum-rhenium alloy prepared above exhibits poor uniformity in the distribution of rhenium and the second metallic element, with increased grain size and reduced uniformity, and a rhenium content deviation of >2% in the alloy.

[0064] The results show: In Examples 1-3, the sintered alloy billet has a density >99%, rhenium and the second metal element are evenly distributed, the grains are fine and uniform, the impurity content is ≤0.005%, the rhenium content deviation in the alloy is ≤0.1%, and the median particle size of the alloy powder used for the sintered alloy billet is ≤1 micrometer.

[0065] Comparing Example 1 and Comparative Examples 1-5, it can be seen that when the mass ratio of rhenium to the second metal element, the amount of hydrogen peroxide, the leaching temperature, the heating decomposition temperature are outside the protection range, or the conditions for using the cationic purification resin change, one or more of the following problems may occur: the particle size of the rhenium-second metal element alloy powder is too large, the purity decreases, the mass ratio of rhenium to the second metal element in the alloy deviates significantly from the theoretical value, the density and grain size grade decrease significantly, and the sintering temperature increases.

[0066] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method of recovery and preparation of a tungsten-rhenium or molybdenum-rhenium alloy, characterized in that, The application relates to a method for recycling and preparing a rhenium-tungsten or rhenium-molybdenum alloy. Step (1): waste binary rhenium alloy is cleaned and crushed, a second metal element is leached by using a hydrogen peroxide solution to carry out a reaction, a peroxometallic acid solution of the second metal element is obtained, rhenium is leached by using the acidity of the peroxometallic acid and excess hydrogen peroxide, and a peroxometallic acid solution containing rhenium is obtained; Step (2): a mixed solution of peroxometallic acid and rhenium is obtained after leaching, the proportion of rhenium and the second metal element in the mixed solution of peroxometallic acid and rhenium is adjusted, and then cation resin is used to remove impurity cations in the solution; Step (3): the mixed solution of peroxometallic acid and rhenium after impurity removal is heated and decomposed to crystallize, and an alloy precursor powder is obtained; Step (4): the alloy precursor powder is hydrogen-reduced to obtain an alloy powder; Step (5): the alloy powder is sintered at 1800 DEG C. to 2100 DEG C. to obtain a binary rhenium-tungsten or rhenium-molybdenum alloy.

2. The method of claim 1, wherein the tungsten-rhenium or molybdenum-rhenium alloy is recovered and prepared by the steps of: In step (1), the second metal element is tungsten or molybdenum.

3. The method of claim 2, wherein the tungsten-rhenium or molybdenum-rhenium alloy is recovered and prepared by the steps of: In step (1), the mass fraction of rhenium in the binary rhenium alloy is 0.5% to 30%.

4. The method of claim 1, wherein the tungsten-rhenium or molybdenum-rhenium alloy is recovered and prepared by the steps of: In step (2), the cation resin is one or more of commercially available 001, D001 and chelate cation resin.

5. The method of claim 4, wherein the tungsten-rhenium or molybdenum-rhenium alloy is recovered and prepared by the steps of: In step (2), the resin column height is 50 cm to 200 cm, and / or the flow rate is 0.5 Bv / h to 2 Bv / h, and / or the treatment temperature is 15 DEG C. to 30 DEG C. ​ 6. The method of claim 1, wherein the tungsten-rhenium or molybdenum-rhenium alloy is recovered and prepared by the steps of: In step (3), the heating and decomposition crystallization is carried out at a crystallization temperature of 90 DEG C. to 120 DEG C.

7. The tungsten-rhenium or molybdenum-rhenium alloy recovery and production method according to claim 6, wherein In step (4), hydrogen reduction is carried out by using a hydrogen reduction furnace, the second metal element and the rhenium element are both reduced to simple substances, and molybdenum-rhenium or tungsten-rhenium metal powder is obtained.

8. The method of claim 1, wherein the tungsten-rhenium or molybdenum-rhenium alloy is recovered and prepared by the steps of: The sintering temperature is 1800 DEG C. to 2100 DEG C. ​ 9. A binary alloy of rhenium, characterized in that, The tungsten-rhenium or molybdenum-rhenium alloy prepared by the method for recycling and preparing the alloy according to any one of claims 1 to 8 has a density of more than 98%, uniform distribution of rhenium and the second metal element, fine and uniform crystal grains, a rhenium content deviation of less than or equal to 0.1%, and an impurity content of less than or equal to 0.005%.

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