Method for extracting high-purity metal from nickel-based superalloy return scrap
High-purity metals are extracted from nickel-based superalloy recycled materials through chlorination, volatilization separation, and electrodeposition processes, solving the problems of low purity and recovery rate in existing technologies and achieving efficient metal recycling.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ANHUI FENGLU TECHNOLOGY CO LTD
- Filing Date
- 2026-02-09
- Publication Date
- 2026-05-08
AI Technical Summary
Existing technologies for extracting metals from nickel-based superalloy recycled materials have low purity and recovery rates, making it difficult to effectively recycle valuable metals from waste superalloys.
A high-purity metal is obtained by using chlorination reaction, volatilization separation and electrodeposition processes. The chlorination reaction generates a mixed chloride, which is then separated into a single chloride. The mixed chloride is dissolved in pure water and then electrodeposited.
It improves the purity and recovery rate of metals, obtaining high-purity metals with a purity of over 99.995% and a recovery rate of over 90%. The process is simple and has obvious environmental advantages.
Smart Images
Figure CN121992191A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of non-ferrous metal metallurgy technology, specifically relating to a method for extracting high-purity metals from nickel-based superalloy recycled materials. Background Technology
[0002] Nickel-based superalloys are widely used in aerospace, nuclear reactors, and the petroleum industry due to their excellent properties, including high creep strength, fracture strength, good corrosion resistance, fatigue resistance, and high-temperature oxidation resistance. However, the yield of qualified products in the superalloy production process is only 10%, and a large amount of waste superalloys (i.e., nickel-based superalloy recyclables) are generated. These waste superalloys contain valuable metals such as nickel and cobalt, which have high recycling value. From the perspective of resource utilization and environmental protection, it is necessary to recycle and reuse them.
[0003] Currently, the processes for extracting metals from nickel-based superalloy recycled materials can be broadly categorized into pyrometallurgical and hydrometallurgical methods. Due to the high melting point of nickel-based superalloys, traditional pyrometallurgical or hydrometallurgical methods result in low elemental purity and low yields. Therefore, improving the process to increase metal purity and recovery rate has become a pressing technical challenge in this field. Summary of the Invention
[0004] The purpose of this invention is to provide a method for extracting high-purity metals from nickel-based superalloy recycled materials. The method provided by this invention can obtain high-purity metals with a high recovery rate.
[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for extracting high-purity metals from nickel-based superalloy recycled materials, comprising the following steps: (1) Chlorination reaction of nickel-based superalloy recycled material to obtain mixed chloride; (2) Separate the mixed chloride obtained in step (1) to obtain a single chloride; (3) Mix the single chloride obtained in step (2) with pure water to obtain a chloride aqueous solution; (4) Electrodeposit the chloride aqueous solution obtained in step (3) to obtain the metal element.
[0006] Preferably, the particle size of the nickel-based superalloy return material in step (1) is ≤150μm.
[0007] Preferably, the chlorination reagent used in the chlorination reaction in step (1) is Cl2.
[0008] Preferably, the chlorination reaction temperature in step (1) is 150~200℃ and the chlorination reaction time is 3~10h.
[0009] Preferably, the separation in step (2) is volatile separation; the volatile separation time is 3~5h; the tube furnace used for volatile separation is equipped with 3~6 adjustable temperature control zones.
[0010] Preferably, the tubular furnace is provided with four adjustable temperature control zones, the temperatures of which are 1300~1400℃, 1150~1250℃, 950~1050℃ and 850~950℃ respectively.
[0011] Preferably, the concentration of the metal element in the chloride aqueous solution in step (3) is >30 g / L.
[0012] Preferably, the electrodeposition in step (4) is constant voltage electrodeposition.
[0013] Preferably, the electrodeposition process parameters in step (4) are: electrolytic cell temperature > 40℃, current density 100~200A / m 2 Electrode spacing 10~15cm, pH value 3.0~5.0, electrodeposition time ≥12h.
[0014] Preferably, the anode for electrodeposition in step (4) is a titanium plate coated with ruthenium-iridium.
[0015] This invention provides a method for extracting high-purity metals from recycled nickel-based superalloy materials, comprising the following steps: subjecting the recycled nickel-based superalloy materials to a chlorination reaction to obtain a mixed chloride; separating the mixed chloride to obtain a single chloride; mixing the single chloride with pure water to obtain a chloride aqueous solution; and electrodepositing the chloride aqueous solution to obtain the elemental metal. This invention obtains high-purity metals through a chlorination reaction, separation, preparation of the chloride aqueous solution, and electrodeposition for impurity removal, thus shortening the process flow and improving the recovery rate. Results from the embodiments show that the method provided by this invention yields Ni metal with a purity of 99.992~99.994%, Co metal with a purity of 99.991~99.992%, Al metal with a purity of 99.991~99.994%, and Cr metal with a purity of 99.992~99.995%; the recovery rate of Ni is 92~95%, the recovery rate of Co is 93~98%, the recovery rate of Al is 89~92%, and the recovery rate of Cr is 91~92%. Attached Figure Description
[0016] Figure 1 This is a process flow diagram of the present invention for extracting high-purity metals from nickel-based superalloy recycled materials. Detailed Implementation
[0017] This invention provides a method for extracting high-purity metals from nickel-based superalloy recycled materials, comprising the following steps: (1) Chlorination reaction of nickel-based superalloy recycled material to obtain mixed chloride; (2) Separate the mixed chloride obtained in step (1) to obtain a single chloride; (3) Mix the single chloride obtained in step (2) with pure water to obtain a chloride aqueous solution; (4) Electrodeposit the chloride aqueous solution obtained in step (3) to obtain the metal element.
[0018] The method provided by this invention is applicable to nickel-based superalloy recycled materials, and is preferably applicable to nickel-based superalloy recycled materials whose main components are Ni, Co, Al and Cr.
[0019] This invention does not impose any special restrictions on the source of the raw materials; commercially available products familiar to those skilled in the art can be used.
[0020] This invention involves subjecting recycled nickel-based superalloy materials to a chlorination reaction to obtain mixed chlorides. The recycled nickel-based superalloy materials mainly contain Ni, Co, Al, and Cr elements. By introducing Cl2, each element generates its corresponding chloride.
[0021] The present invention does not have any special limitation on the specific composition of the nickel-based superalloy recycled material; any nickel-based superalloy recycled material well known in the art can be used.
[0022] In this invention, the particle size of the nickel-based superalloy recycled material is preferably ≤150μm.
[0023] In this invention, the chlorinating reagent used in the chlorination reaction is preferably Cl2; the amount of Cl2 used is preferably 2 to 3 times the theoretical total molar amount of Ni, Co, Al, and Cr reacting with it. This invention utilizes the principle of gas-solid reaction, where Cl2 diffuses from the outside in, causing the metallic elements in the nickel-based superalloy return material to gradually form corresponding metal chlorides. By limiting the amount of Cl2 within the above range, the recovery rate can be improved, avoiding insufficient Cl2 usage, incomplete conversion of Ni, Co, Al, and Cr, which remain in the form of metallic elements. Since metallic elements have higher boiling points, a large amount of metallic elements remain in the nickel-based superalloy return material, which is not conducive to separation.
[0024] In one implementation, the amount of Cl2 can be 2.1 times, 2.6 times, or 2.8 times the theoretical total molar amount of Ni, Co, Al, and Cr reacting with it.
[0025] In this invention, the equation for the chlorination reaction is as follows: Ni + Cl₂ = NiCl₂ Co + Cl₂ = CoCl₂ 2Al + 3Cl₂ = 2AlCl₃ 2Cr + 3Cl2 = 2CrCl3.
[0026] In this invention, the preferred temperature for the chlorination reaction is 150-200°C; the preferred reaction time is 3-10 hours. As one embodiment, the temperature for the chlorination reaction can be 160°C, 170°C, 180°C, or 190°C; the reaction time can be 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or 9 hours. Limiting the temperature and time of the chlorination reaction within the above ranges improves the degree of chlorination. Too low a temperature is detrimental to the chlorination of metal chlorides, while too high a temperature increases energy consumption and causes AlCl3 to vaporize prematurely, preventing enrichment. Too short a reaction time hinders the complete formation of metal chlorides, while too long a reaction time increases energy consumption and leads to wasted costs.
[0027] After obtaining the mixed chloride, the present invention separates the mixed chloride to obtain a single chloride.
[0028] In this invention, the separation is preferably volatile separation; the volatile separation time is preferably 3-5 hours; the tube furnace used for volatile separation is equipped with 3-6 adjustable temperature control zones. This invention does not have a specific limitation on the model of the tube furnace; any instrument or equipment well-known to those skilled in the art can be used. In this invention, a mixed chloride is placed in a tube furnace, gradually heated to its corresponding boiling point, and condensed and collected in different temperature control zones at the rear end of the tube furnace to obtain a single chloride.
[0029] In one implementation, the evaporation separation time can be 4 hours.
[0030] In this invention, the outlet of the tubular furnace is preferably connected to a collection bottle containing pure water; the tubular furnace is preferably provided with four adjustable temperature control zones; the temperatures of the adjustable temperature control zones are preferably 1300~1400℃, 1150~1250℃, 950~1050℃ and 850~950℃ respectively. This invention involves volatilizing at 1300-1400℃ for 3-5 hours, ensuring that all mixed chlorides (metal chlorides) are vaporized into the gas phase. The temperature selection is based on the boiling points of different metal chlorides. Specifically, CrCl3, with a boiling point of 1300℃, is collected in the 1150-1250℃ range; CoCl2, with a boiling point of 1049℃, is collected in the 950-1050℃ range; NiCl2, with a boiling point of 949℃, is collected in the 850-950℃ range; and AlCl3, with a boiling point of 178℃, is collected in a collection bottle. The mixed chlorides are heated at 1300-1400℃ and then collected in sections at the rear end of the tube furnace to obtain single metal chlorides.
[0031] In one implementation, the temperature of the adjustable temperature control zone can be 1300℃, 1200℃, 1000℃ and 900℃, 1350℃, 1160℃, 960℃ and 860℃, or 1400℃, 1230℃, 1020℃ and 920℃, respectively.
[0032] After obtaining a single chloride, the present invention mixes the single chloride with pure water to obtain an aqueous chloride solution. The chloride collected in different regions of the present invention is in the form of solid particles, which are dissolved in pure water to obtain an aqueous chloride solution.
[0033] In this invention, the concentration of the metal element in the chloride aqueous solution is preferably >30 g / L. As one embodiment, the concentration of the metal element in the chloride aqueous solution can be 40 g / L, 50 g / L, 60 g / L, or 70 g / L. Limiting the concentration of the metal element in the chloride aqueous solution to the above range avoids the problem of excessively low concentrations hindering metal deposition during subsequent electrodeposition, and excessively high concentrations affecting solution flow, which is also detrimental to metal deposition during subsequent electrodeposition.
[0034] After obtaining the chloride aqueous solution, the present invention performs electrodeposition on the chloride aqueous solution to obtain the elemental metal.
[0035] In this invention, the electrodeposition is preferably constant voltage electrodeposition; the preferred process parameters for the electrodeposition are: electrolytic cell temperature > 40°C, current density 100~200 A / m 2 The electrode spacing is 10-15 cm, the pH value is 3.0-5.0, and the electrodeposition time is ≥12 h. As one embodiment, the electrolytic cell temperature can be 50℃, 52℃, 56℃, or 60℃; the current density can be 110 A / m². 2 120A / m 2 130A / m 2 140A / m 2 150A / m 2 160A / m 2 170A / m 2 180A / m 2 Or 190A / m 2 The electrode spacing can be 11cm, 12cm, 13cm or 14cm; the pH value can be 3.5, 3.9, 4.0 or 4.4; the electrodeposition time can be 12h, 13h, 14h or 15h.
[0036] In this invention, the anode for electrodeposition is preferably a titanium plate coated with a ruthenium-iridium coating; the cathode for electrodeposition is a titanium plate. This invention does not impose any particular limitation on the thickness of the ruthenium-iridium coating; any titanium plate well-known to those skilled in the art can be used. This invention also does not impose any particular limitation on the titanium plate used for the cathode; any ordinary titanium plate well-known to those skilled in the art can be used.
[0037] As one implementation method, the pH value can be adjusted to 3.0~5.0 using liquid alkali.
[0038] In one embodiment, the electrodeposition system can consist of a single chamber (20×8×10cm); the working area of the cathode and anode can be 60cm². 2 .
[0039] The process flow diagram for extracting high-purity metals from nickel-based superalloy recycled materials according to this invention is shown below. Figure 1 As shown. From Figure 1 As can be seen, the raw material used in this invention is recycled nickel-based high-temperature alloy. Impurities are removed through processes such as chloride synthesis, volatilization separation, chloride dissolution, and electrodeposition to obtain high-purity metal of grade 4N5. Compared with existing technologies, the steps are simpler, requiring no large amounts of reagents, resulting in significant environmental advantages. The obtained metal has high purity, stable product quality, and a metal recovery rate exceeding 90%. The process is concise and easy to operate, yielding elemental metals with a purity of over 99.995%, without the need for inorganic acids, further demonstrating significant environmental advantages.
[0040] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.
[0041] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.
[0042] Nickel-based superalloy powder was obtained by gas atomization or water atomization. After sieving, a 150μm high-temperature alloy return material was obtained. The composition of the prepared nickel-based superalloy return material is shown in Table 1 (i.e., the composition of the nickel-based superalloy return material used in the examples).
[0043] Table 1. Composition and Content of Nickel-Based Superalloy Returned Material
[0044] Example 1 A method for extracting metal from nickel-based superalloy recycled materials comprises the following steps: (1) The nickel-based high-temperature alloy recycled material is placed in a tube furnace, heated to 150°C, and Cl2 is introduced to carry out a chlorination reaction for 5 hours to obtain a mixed chloride; wherein, the amount of Cl2 used is 2.1 times the theoretical total molar amount of reacting with Ni, Co, Al and Cr; (2) The tubular furnace is equipped with four adjustable temperature control zones. The mixed chloride is heated to 1300°C for volatilization for 3 hours. The temperatures of the other three adjustable temperature control zones are 1200°C, 1000°C and 900°C, respectively, and a single chloride is obtained in each zone. (3) Dissolve the single chloride in pure water to obtain NiCl2 solution with Ni ion concentration of 60 g / L, CoCl2 solution with Co ion concentration of 55 g / L, AlCl3 solution with Al ion concentration of 48 g / L and CrCl3 solution with Cr ion concentration of 46 g / L respectively. (4) Constant voltage electrodeposition was performed on the different chloride solutions obtained in step (3). The anode was a titanium plate coated with ruthenium-iridium, the cathode was an ordinary titanium plate, the electrolytic cell temperature was 52℃, and the current density was 140A / m. 2 With an electrode spacing of 12 cm, the pH value was adjusted to 3.5 using liquid alkali, and the electrodeposition time was 12 h to obtain the elemental metal.
[0045] The purity of Ni metal prepared in Example 1 was 99.992%, the purity of Co metal was 99.991%, the purity of Al metal was 99.994%, and the purity of Cr metal was 99.992%; the recovery rate of Ni was 92%, the recovery rate of Co was 93%, the recovery rate of Al was 89%, and the recovery rate of Cr was 91%.
[0046] Example 2 A method for extracting metal from nickel-based superalloy recycled materials comprises the following steps: (1) The nickel-based high-temperature alloy recycled material is placed in a tube furnace, heated to 180°C, and Cl2 is introduced to carry out a chlorination reaction for 8 hours to obtain a mixed chloride; wherein, the amount of Cl2 used is 2.8 times the theoretical total molar amount of reacting with Ni, Co, Al and Cr; (2) The tubular furnace is equipped with four adjustable temperature control zones. The mixed chloride is heated to 1350°C for volatilization for 5 hours. The temperatures of the other three adjustable temperature control zones are 1160°C, 960°C and 860°C, respectively, and a single chloride is obtained in each zone. (3) Dissolve the single chloride in pure water to obtain NiCl2 solution with Ni ion concentration of 65 g / L, CoCl2 solution with Co ion concentration of 53 g / L, AlCl3 solution with Al ion concentration of 51 g / L and CrCl3 solution with Cr ion concentration of 57 g / L respectively. (4) Constant voltage electrodeposition is performed on the different chloride solutions obtained in step (3). The anode is a titanium plate coated with ruthenium-iridium, the cathode is an ordinary titanium plate, the electrolytic cell temperature is 60℃, and the current density is 200A / m. 2 With an electrode spacing of 15 cm, the pH value was adjusted to 4.4 using liquid alkali, and the electrodeposition time was 18 h to obtain the elemental metal.
[0047] The purity of Ni metal prepared in Example 2 was 99.994%, the purity of Co metal was 99.992%, the purity of Al metal was 99.991%, and the purity of Cr metal was 99.995%; the recovery rate of Ni was 95%, the recovery rate of Co was 98%, the recovery rate of Al was 92%, and the recovery rate of Cr was 92%.
[0048] Example 3 A method for extracting metal from nickel-based superalloy recycled materials comprises the following steps: (1) The nickel-based high-temperature alloy recycled material is placed in a tube furnace, heated to 170°C, and Cl2 is introduced to carry out a chlorination reaction for 7 hours to obtain a mixed chloride; wherein, the amount of Cl2 used is 2.6 times the theoretical total molar amount of reacting with Ni, Co, Al and Cr; (2) The tubular furnace is equipped with four adjustable temperature control zones to heat the mixed chloride to 1400°C for volatilization. The temperatures of the other three adjustable temperature control zones are 1230°C, 1020°C and 920°C respectively, and the control time is 4 hours. Single chloride is obtained in each zone. (3) Dissolve the single chloride in pure water to obtain NiCl2 solution with Ni ion concentration of 57 g / L, CoCl2 solution with Co ion concentration of 59 g / L, AlCl3 solution with Al ion concentration of 43 g / L and CrCl3 solution with Cr ion concentration of 40 g / L respectively. (4) Constant voltage electrodeposition was performed on the different chloride solutions obtained in step (3). The anode was a titanium plate coated with ruthenium-iridium, the cathode was an ordinary titanium plate, the electrolytic cell temperature was 56℃, and the current density was 170A / m. 2 With an electrode spacing of 13 cm, the pH value was adjusted to 3.9 using liquid alkali, and the electrodeposition time was 15 h to obtain the elemental metal.
[0049] The purity of Ni metal prepared in Example 3 was 99.992%, the purity of Co metal was 99.991%, the purity of Al metal was 99.993%, and the purity of Cr metal was 99.993%; the recovery rate of Ni was 94%, the recovery rate of Co was 94%, the recovery rate of Al was 91%, and the recovery rate of Cr was 92%.
[0050] As can be seen from the above embodiments, the method provided by the present invention can obtain high-purity metals with a high recovery rate.
[0051] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for extracting high-purity metals from nickel-based superalloy recycled materials, comprising the following steps: (1) Chlorination reaction of nickel-based superalloy recycled material to obtain mixed chloride; (2) Separate the mixed chloride obtained in step (1) to obtain a single chloride; (3) Mix the single chloride obtained in step (2) with pure water to obtain a chloride aqueous solution; (4) Electrodeposit the chloride aqueous solution obtained in step (3) to obtain the metal element.
2. The method according to claim 1, characterized in that, The particle size of the nickel-based superalloy return material in step (1) is ≤150μm.
3. The method according to claim 1, characterized in that, The chlorination reagent used in step (1) is Cl2.
4. The method according to claim 1, characterized in that, The chlorination reaction in step (1) is carried out at a temperature of 150~200℃ and for a time of 3~10h.
5. The method according to claim 1, characterized in that, The separation in step (2) is a volatile separation; the volatile separation time is 3~5h; the tube furnace used for the volatile separation is equipped with 3~6 adjustable temperature control zones.
6. The method according to claim 5, characterized in that, The tubular furnace is equipped with four adjustable temperature control zones, with temperatures of 1300~1400℃, 1150~1250℃, 950~1050℃ and 850~950℃ respectively.
7. The method according to claim 1, characterized in that, In step (3), the concentration of metal elements in the chloride aqueous solution is >30g / L.
8. The method according to claim 1, characterized in that, The electrodeposition in step (4) is constant voltage electrodeposition.
9. The method according to claim 1, characterized in that, The electrodeposition process parameters in step (4) are: electrolytic cell temperature > 40℃, current density 100~200A / m 2 Electrode spacing 10~15cm, pH value 3.0~5.0, electrodeposition time ≥12h.
10. The method according to claim 1, characterized in that, In step (4), the anode for electrodeposition is a titanium plate coated with ruthenium-iridium.