Recycling Device and Recycling Method for Recycling Scrap Superalloy by Melt Extraction

Abstract

The present invention discloses a recovery device for recycling waste high-temperature alloys by melt extraction, comprising a reaction chamber, the interior of the reaction chamber being divided into a product collection lower chamber and a slag collection upper chamber by a perforated separation partition, a distillation gas overflow pipe being provided on the top of the reaction chamber; a pair of reaction chambers being symmetrically provided in the upper and lower parts, and the pair of reaction chambers being connected by the distillation gas overflow pipe. The present invention also provides a recovery method for recycling waste high-temperature alloys using the above-mentioned recovery device for recycling waste high-temperature alloys by melt extraction. The recovery device and recovery method of the present invention efficiently realize the separation and recycling of magnesium, ensure the recovery rate of magnesium, and solve the safety problem of active metal magnesium being easily oxidized and combustible during separation operations in industrial production. When separating magnesium, the automatic separation of alloy residue and extract nickel is realized, without the need for additional separation steps, thereby achieving the purpose of short-process continuous operation production.

Description

Technical Field

[0001] The present invention belongs to the field of metal recovery, and in particular relates to a device and method for recovering waste high-temperature alloys. Background Art

[0002] Nickel-based single-crystal superalloys are currently a key material for manufacturing high-pressure turbine blades in engines. To further improve the material properties of nickel-based single-crystal superalloys, the content of refractory metals such as tungsten, molybdenum, tantalum, hafnium, and rhenium in these alloys is continuously increasing (to over 30%). With the development of aerospace, marine propulsion, and other fields, the demand for nickel-based single-crystal superalloys continues to grow. Consequently, the production, processing, and application of these alloys generate a significant amount of superalloy waste, which urgently needs to be recycled.

[0003] Nickel-based single-crystal high-temperature alloys are difficult to process using traditional wet and pyrometallurgical smelting and recovery processes due to their high strength, high-temperature resistance, and strong oxidation resistance. In recent years, treatment processes that combine pyrometallurgy and wet metallurgy have been studied. The combined pyrometallurgical and wet metallurgical methods mainly use pyrometallurgy to pretreat the high-temperature alloy, and then use wet metallurgy to dissolve some valuable metals. For example, CN110846502A proposes a method for recovering waste high-temperature alloys by melt extraction, which includes extracting crushed nickel-based high-temperature alloy waste using an extraction medium to obtain a low-melting point eutectic and extraction residue after extraction; the extraction medium is a metallic magnesium or zinc melt, or a binary or multi-component metal melt containing magnesium and zinc; the low-melting point eutectic after extraction is vacuum distilled to obtain a distillation product of nickel metal or nickel-cobalt alloy, and a condensed extraction medium; the extraction residue can be recovered by wet treatment. This method can effectively achieve the recovery of waste high-temperature alloys. However, the low-melting-point eutectic after melt extraction must be cooled, mechanically cut to separate the low-melting-point eutectic from the raffinate, and then heated again for vacuum distillation. Reactive metals such as magnesium and zinc pose safety risks during mechanical cutting and separation, are easily oxidized, and are not conducive to recycling. Repeated heating wastes significant time and energy. Furthermore, this method requires long melt extraction times and high energy consumption for heat preservation. These drawbacks make this method difficult to implement in industrial production. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings and defects mentioned in the above background technology and provide a recovery device and recovery method for waste high-temperature alloys by melt extraction. This method has the advantages of convenient magnesium recycling and fast melt extraction dealloying speed. In order to solve the above technical problems, the technical solution proposed by the present invention is as follows:

[0005] A recovery device for melt extraction and recovery of waste high-temperature alloys includes a reaction chamber, the interior of which is divided into a product collection lower chamber and a slag collection upper chamber by a perforated separation partition, and a distilled gas overflow pipe is provided on the top of the reaction chamber; a pair of reaction chambers are symmetrically provided above and below, and the pair of reaction chambers are connected by the distilled gas overflow pipe.

[0006] In the above-mentioned recovery device, preferably, the outer wall of the lower reaction chamber is further provided with a heating component for heating the reaction chamber, and the heating component is an electromagnetic induction heating coil, and the electromagnetic induction heating coil is arranged around the outer wall of the lower reaction chamber. The interior of the above-mentioned electromagnetic induction heating coil may be hollow, which can be used to pass cooling water. The electromagnetic induction heating coil is made of copper material, and the hollow interior is used to place a cooling water pipe for cooling the induction coil, thereby quickly and accurately achieving the cooling process.

[0007] In the above recovery device, preferably, both ends of the distillation gas overflow pipe can be configured as bell mouths, so that the gas can flow upward into the reaction chamber above during subsequent distillation.

[0008] In the above-mentioned recovery device, preferably, the recovery device also includes a sealable outer shell, the reaction chamber is arranged in the outer shell, and the outer shell is provided with an air pressure safety valve, an air charging and discharging port for charging and discharging inert gas into the sealed outer shell, and a vacuum pump for controlling the vacuum degree in the sealed outer shell; a cooling device is provided above the outer shell near the upper reaction chamber, and the upper and lower reaction chambers are provided with temperature measuring devices for measuring the temperature in the reaction chamber, and the cooling device, temperature measuring device and heating assembly are interlocked with each other to control the temperature in the upper and lower reaction chambers.

[0009] The above-mentioned outer shell, cooling device, air pressure safety valve, etc. can ensure the safety of the recovery device of the present invention. In order to ensure that the outer shell has excellent airtightness, a sealing groove is designed for each connection port, and an "O"-shaped rubber ring is placed in the groove. In order to prevent the rubber ring from aging due to excessive temperature, a cooling device, such as a water cooling device, is provided. The water cooling device adopts independent circulation cooling, and the refrigerant is R22 environmentally friendly refrigerant with a circulation flow rate of 3t / h. Since the inert gas argon contains trace amounts of oxygen, in order to ensure the purity of metallic magnesium, the argon entering the reaction chamber is deoxidized and can be deoxidized through a deoxidation catalyst tube. The deoxidizer in the deoxidation tube uses manganese oxide and aluminum oxide, and Mn2O3 is loaded on the surface of γ-Al2O3. It relies on the low-valent manganese oxide on the solid surface of the deoxidizer to react with the trace oxygen in the gas to deoxidize. The exhaust gas inside the reaction chamber drawn out by the vacuum pump needs to be collected and purified, and the vacuum pump must pump no less than 0.9m per minute. 3 / min. A vacuum pressure sensor and a McFadden vacuum gauge are used to display the vacuum level. The temperatures within the upper and lower reaction chambers can be controlled by interlocking the cooling device, temperature measuring device, and heating assembly, allowing for more accurate control of the temperatures during melt extraction and vacuum distillation within the reaction chambers. The specific interlocking method is not limited.

[0010] The temperature measuring device can be an infrared temperature measuring device or a thermocouple temperature measuring device installed on the reaction chamber, including a high-precision laser infrared thermometer, an S-type platinum-rhodium thermocouple, and a K-type thermocouple. Due to the large temperature difference between the inside and outside of the electromagnetic induction heating crucible, a high-precision laser infrared thermometer and an S-type platinum-rhodium thermocouple are used for temperature calibration. When measuring the temperature inside the reaction chamber, the bottom of the upper reaction chamber can be replaced with a perforated graphite cover to connect a temperature-measuring graphite tube. The intersection of the two laser aiming points of the infrared thermometer is marked from the visual window at the top of the outer shell along the temperature-measuring graphite tube to the bottom of the reaction chamber, allowing direct temperature measurement of the bottom reaction chamber. The S-type platinum-rhodium thermocouple is used to measure the temperature of the outer wall of the lower reaction chamber, and the K-type thermocouple is used to measure the temperature of the upper reaction chamber. By setting a temperature control program, heating, constant temperature, and cooling can be accurately controlled, and the actual temperature of the dealloying reaction deviates from the set temperature by no more than ±5°C.

[0011] To prevent high-temperature corrosion from magnesium metal, the reaction chamber can be made of graphite and have a cylindrical appearance. A pair of reaction chambers can be freely removable and separable, connected by mortise and tenon joints. Within each reaction chamber, the product collection lower chamber and the slag collection upper chamber are separated into two interconnected but independent chambers by a perforated separator (e.g., a graphite separator). During the melt extraction dealloying reaction, electromagnetic induction heating coils are used. Based on the principle of electromagnetic stirring, the middle layer of liquid magnesium metal forms an upward and downward vortex flow, while the upper and lower layers generate a left-right circulation, driving the flow of the magnesium liquid. The waste high-temperature alloy material and magnesium metal dealloy above the graphite separator. During the vacuum distillation process, the magnesium in the upper layer continuously evaporates, and the nickel dissolved in the magnesium liquid is continuously carried into the lower layer of the magnesium liquid by the upward and downward vortex flow. After the vacuum distillation is completed, the alloy residue is located in the slag collection upper chamber above the graphite separator, while the nickel extracted by dealloying is separated by the graphite separator into the product collection lower chamber at the bottom of the reaction chamber. This method effectively separates the alloy residue from the nickel metal. Under the influence of electromagnetic stirring, the swirl and circulation of the liquid metal effectively promotes the diffusion and dissolution rate of the target metal within, achieving uniform temperature distribution and thus enhancing the dealloying (melt extraction) effect. To better collect the magnesium metal, a distilled gas overflow tube is designed to extend to the upper reaction chamber. The vaporized magnesium rises along the distilled gas overflow tube into the upper reaction chamber and condenses in the upper reaction chamber. When the reaction is complete, the nickel metal is stored in the lower reaction chamber, and the magnesium metal is collected in the upper reaction chamber. Then, by simply rotating the lower reaction chamber up and down, it can continue to be used as the melt extraction chamber, eliminating the need for further magnesium addition. This achieves efficient and convenient recycling of the magnesium metal and avoids oxidation and safety issues during magnesium collection and transportation. The recovery device can be reused multiple times, reducing its operating costs.

[0012] The recovery device of the present invention has the significant advantages of strong adaptability to raw materials, no dust, no exhaust gas, good working environment, good sealing performance, no vibration, low noise, low investment cost, and low energy consumption. It can effectively solve many problems existing in the process of recovering valuable metals from waste nickel-based single crystal high-temperature alloys.

[0013] As a general technical concept, the present invention also provides a method for recovering waste high-temperature alloys using the above-mentioned melt extraction recovery device, which includes the following steps:

[0014] S1: Add waste nickel-based superalloy and magnesium metal into the lower reaction chamber (placed on a perforated separation plate), use a heating component to heat the lower reaction chamber, melt the magnesium metal into liquid, and then melt extract the nickel in the waste nickel-based superalloy;

[0015] S2: After melt extraction is complete, the nickel in the scrap nickel-based superalloy is removed and transferred to liquid magnesium metal, which is then distilled to separate the magnesium metal from the nickel. The magnesium metal enters the upper reaction chamber, while the alloy residue obtained after nickel removal from the scrap nickel-based superalloy is collected in the upper slag chamber of the lower reaction chamber. The nickel in the scrap nickel-based superalloy is collected in the lower product chamber of the lower reaction chamber. This method for separating the nickel metal and the alloy residue can achieve complete separation in the reaction chamber without the need for additional screening, air separation, or other steps.

[0016] In the above recycling method, preferably, the waste nickel-based high-temperature alloy is pretreated as follows: the refractory coating on the surface of the waste nickel-based high-temperature alloy is removed, and then the waste nickel-based high-temperature alloy is cleaned and dried.

[0017] In the above-mentioned recovery method, preferably, the waste nickel-based superalloy and metallic magnesium are added in layers and batches, and the mass ratio of the waste nickel-based superalloy to the metallic magnesium is controlled to be 1:(5-10). When using the layered and batched addition method, a layer of metallic magnesium is first added to the upper slag collection chamber, followed by a layer of waste nickel-based superalloy, and so on, until the added material accounts for four-fifths of the volume of the upper slag collection chamber. The amount of magnesium added directly affects the diffusion rate of nickel, and thus the time required for the reaction to be complete. Under certain time and temperature conditions, the higher the mass ratio, the higher the nickel recovery rate. However, adding too much magnesium will increase the time required for vacuum distillation. Taking all factors into consideration, controlling the mass ratio within the above-mentioned range is more effective.

[0018] In the above-mentioned recovery method, preferably, during heating in step S1, the heating temperature in the reaction chamber below is controlled to be 800-900°C, the holding time is 1-5h, and the heating atmosphere is controlled to be an inert atmosphere. The heating temperature should not be too low, as too low a temperature results in a slower rate of the dealloying reaction and a longer holding time. The heating temperature should not be too high either, as too high a temperature causes the liquid metal magnesium to volatilize. At the same time, due to the use of electromagnetic induction heating, eddy currents are generated inside the liquid metal magnesium under the induction action of the alternating electromagnetic field. The eddy currents cause the atoms of the liquid metal magnesium to move at high speed and irregularly, and the atoms collide and rub against each other to generate heat energy, so that the internal temperature of the metal magnesium is higher than the program set temperature and is more volatile. In order to prevent the oxidation of the metal magnesium from affecting the reaction effect, the dealloying reaction process is carried out in a protective gas, and preferably, the protective gas is argon.

[0019] In the above recovery method, preferably, the distillation process is carried out under a vacuum environment, the internal pressure in the reaction chamber is controlled to be below 10Pa, the temperature of the reaction chamber below is controlled to be 900-1000°C during the distillation process, the temperature of the reaction chamber above is controlled to be 400-550°C, and the treatment time is 0.5-3h. More preferably, the temperature of the reaction chamber above is first controlled to be 550-580°C during the distillation process, and the treatment time is 1-1.5h, and then the temperature of the reaction chamber above is controlled to be 400-450°C, and the treatment time is 0.5-1.5h, so that the metallic magnesium in the reaction chamber above is partially dripped onto the alloy residue in the reaction chamber below. By the above temperature control method, in the early stage of distillation, some magnesium will still drip downwards in the reaction chamber above onto the alloy residue, and the nickel that may remain on the alloy residue will be eluted into the magnesium liquid in the lower layer, which can maximize the reduction of the nickel remaining on the alloy residue, and the nickel recovery rate is higher. The effect will be better if the distillation gas overflow pipe with a bell mouth is used. During the above distillation, the temperature of the upper reaction chamber is controlled to be higher for at least until the liquid level of the liquid metal magnesium is slightly lower than the perforated separation partition, that is, to ensure that the metal droplets dripping from the upper side can elute the residue within a certain period of time.

[0020] In the above recovery method, preferably, the alloy residue is ball-milled to obtain a powder, and then the valuable metals in the powder are leached using an oxidative acid leaching method. The leaching agents in the oxidative acid leaching are concentrated hydrochloric acid and hydrogen peroxide. The leaching temperature is controlled at 40-90°C, the leaching time is controlled at 0.5-5 hours, the volume concentration of concentrated hydrochloric acid is controlled at a ratio of V hydrochloric acid:V water = 1:(2-5), and the volume concentration of hydrogen peroxide is controlled at a ratio of V hydrogen peroxide:V water = 1:(1-10). Magnetic stirring is used during leaching, and the stirring speed is controlled between 100-1000 rpm. The dealloyed alloy residue obtained by melt extraction has a porous structure and is easily broken into powder. After ball milling, the residue powder is obtained, and then the high-value metals in the powder are leached using an oxidative acid leaching method, such as obtaining a rhenium-containing leachate and tungsten- and tantalum-rich leach residues. The ball milling time can be 5-30 minutes, and the rotation speed can be 300-1300 rpm.

[0021] In the above recycling method, preferably, in step S2, the metallic magnesium collected in the upper reaction chamber is used for the next recycling process, and the upper and lower reaction chambers are swapped. The above operation method can directly utilize magnesium, making the recycling of magnesium more convenient.

[0022] The raw nickel-based single-crystal superalloy recovered by the present invention has excellent high-temperature and corrosion resistance, high hardness, and high strength, because it eliminates weak grain boundaries at high temperatures. This makes the waste material difficult to crush and dissolve. Conventional methods have difficulty efficiently recovering valuable metals from waste nickel-based single-crystal superalloys. The recovery method and recovery device of the present invention can efficiently recover valuable metals from nickel-based single-crystal superalloys.

[0023] The recovery device and recovery method of the present invention use metallic magnesium to dealloy the waste nickel-based single crystal high-temperature alloy. Liquid metallic magnesium selectively dissolves the main metallic nickel in the nickel-based single crystal high-temperature alloy, and then realizes the recycling of metallic magnesium and the separation between magnesium and nickel through vacuum distillation, and cleverly separates the alloy residue and the extracted metallic nickel through a graphite separation partition. In a more preferred embodiment, under the action of electromagnetic stirring, the diffusion rate of metallic nickel in liquid metallic magnesium is enhanced, which greatly improves the efficiency of dealloying and recovering nickel. After the dealloying reaction of the nickel-based single crystal high-temperature alloy, the large loss of metallic nickel leads to a certain degree of enrichment of other elements and the formation of an alloy residue with a porous structure. Compared with the waste nickel-based single crystal high-temperature alloy, the mechanical properties of the alloy residue are greatly reduced, and it can be easily crushed, which provides a larger reaction interface for the subsequent processing and recovery of rare and precious metals therein. A large amount of high-value metals such as rhenium, tungsten, molybdenum, cobalt, and tantalum enriched in the alloy residue can be recovered by simple oxidative acid leaching. Process production results show that after dealloying waste nickel-based single-crystal superalloys with liquid magnesium, the nickel recovery rate can reach up to 96%, and a crude nickel product with a purity of 90-92% can be obtained. Leaching the alloy residue produces cobalt- and rhenium-rich solutions, as well as tantalum- and tungsten-rich slags.

[0024] The recovery device of the present invention is developed based on the mechanism of metallurgical technology, thermodynamic analysis of the dealloying process in the early stage, and kinetic strengthening theory analysis, combined with mechanical manufacturing and electronic information control. The graphite separation partition designed in the recovery device effectively solves the problem of separating alloy residues from nickel. The distilled gas overflow pipe designed in the recovery device effectively solves the problem of condensation and collection of metallic magnesium. The upper and lower reaction chambers are symmetrically designed. After simply switching the upper and lower reaction chambers, the recycling of the upper and lower reaction chambers avoids the oxidation and safety problems of metallic magnesium during collection and transportation. A cooling water pipe is designed in the hollow copper tube of the electromagnetic induction coil. After the reaction is completed, the cooling process can be quickly achieved, effectively improving production efficiency. The temperature is accurately controlled by infrared temperature measurement and thermocouple temperature measurement, while effectively saving energy consumption. The circulating water cooling device, gas treatment device and vacuum equipment effectively avoid the problems of oxidation, combustion and explosion of metallic magnesium, and solve the production and safety problems such as air pressure, tail gas and cooling water inside the recovery device.

[0025] The recovery device and method of the present invention utilize electromagnetic induction heating, which accelerates the melting of metallic magnesium and improves thermal energy utilization, thereby saving electricity. Furthermore, electromagnetic stirring of the liquid magnesium significantly enhances the dealloying rate, resolving the issues of prolonged pyrometallurgical processing and high temperatures associated with recycling waste high-temperature alloys.

[0026] Compared with the prior art, the advantages of the present invention are:

[0027] 1. The recovery device and method of the present invention efficiently separate and recycle magnesium, ensuring magnesium recovery and resolving the safety issues associated with the susceptibility to oxidation and flammability of active magnesium metal during separation operations in industrial production. Furthermore, dealloying occurs simultaneously with the distillation separation of the magnesium metal, further improving dealloying efficiency. Furthermore, the separation of the magnesium metal automatically separates the alloy residue and nickel extract without requiring additional separation steps, achieving a short-process, continuous production process and avoiding the problem of magnesium metal or nickel-based single crystal high-temperature alloys forming nodules within the furnace.

[0028] 2. The recovery method of the present invention has low requirements on the grade of nickel-based high-temperature alloys and is suitable for the recovery of valuable metals in most waste nickel-based high-temperature alloys. It can recover all components of high-value metals such as nickel, rhenium, cobalt, tungsten and tantalum in waste nickel-based high-temperature alloys. It has the advantages of high metal recovery rate, low recovery temperature and no output of any polluting gas. It effectively solves the problems of high energy consumption of existing pyrometallurgical process, high loss of valuable metals and complex recovery process of wet process, high loss rate of metals such as nickel and cobalt, and single recovered alloy grade. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 This is a schematic structural diagram of a recovery device for waste high-temperature alloys by melt extraction based on electromagnetic induction heating according to the present invention.

[0031] Figure 2 for Figure 1 Schematic diagram of the structure of the middle reaction chamber (cross-section view, product collection lower chamber and perforated separation partition have been decomposed).

[0032] Figure 3 This is another structural schematic diagram of the distillation gas overflow pipe in Example 4.

[0033] Legend:

[0034] 1. Reaction chamber; 101. Product collection lower chamber; 102. Slag collection upper chamber; 2. Perforated separation baffle; 3. Distillation gas overflow pipe; 4. Electromagnetic induction heating coil; 5. Outer shell; 6. Gas charging and discharging port; 7. Vacuum pump; 8. Cooling device; 9. Temperature measuring device. DETAILED DESCRIPTION

[0035] To facilitate understanding of the present invention, the present invention will be described in more comprehensive and detailed form below in conjunction with the accompanying drawings and preferred embodiments. However, the protection scope of the present invention is not limited to the following specific embodiments.

[0036] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0037] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0038] The grade of the waste nickel-based single crystal high-temperature alloy used in the following examples and comparative examples is DD5, and the main components are shown in Table 1 below.

[0039] Table 1: Element content of scrap nickel-based superalloy (DD5)

[0040]

[0041] Note: The alloy element contents in the table are the results of ICP testing.

[0042] Before use, the surface of the waste nickel-based single crystal high-temperature alloy is treated to remove the refractory coating on the surface of the waste nickel-based single crystal high-temperature alloy, and the waste nickel-based single crystal high-temperature alloy is cleaned and dried with a detergent.

[0043] Example 1:

[0044] like Figure 1 and Figure 2 As shown, the recovery device for waste high-temperature alloys by melt extraction of this embodiment includes a reaction chamber 1. The interior of the reaction chamber 1 is divided into a product collection lower chamber 101 and a slag collection upper chamber 102 by a perforated separation partition 2. A distilled gas overflow pipe 3 is provided on the top of the reaction chamber 1; a pair of reaction chambers 1 are symmetrically provided above and below, and the pair of reaction chambers 1 are connected through the distilled gas overflow pipe 3.

[0045] In this embodiment, the outer wall of the lower reaction chamber 1 is further provided with a heating component for heating the reaction chamber 1 , and the heating component is an electromagnetic induction heating coil 4 , which is arranged around the outer wall of the lower reaction chamber 1 .

[0046] In this embodiment, the recovery device also includes a sealable outer shell 5, the reaction chamber 1 is arranged in the outer shell 5, and the outer shell 5 is provided with a charging and discharging port 6 for charging and discharging inert gas into the sealed outer shell 5 and a vacuum pump 7 for controlling the vacuum degree in the sealed outer shell 5; a cooling device 8 is provided above the outer shell 5 near the upper reaction chamber 1, and the upper and lower reaction chambers 1 are both provided with a temperature measuring device 9 for measuring the temperature in the reaction chamber 1. The cooling device 8, the temperature measuring device 9 and the heating assembly are interlocked with each other to control the temperature in the upper and lower reaction chambers 1.

[0047] In this embodiment, the components in contact with metal, such as the reaction chamber 1 , the perforated separation baffle 2 , and the distilled gas overflow pipe 3 , may be made of graphite.

[0048] The method for recovering waste high-temperature alloys using the above-mentioned melt extraction recovery device of this embodiment includes the following steps:

[0049] S1: adding waste nickel-based high-temperature alloy and metal magnesium into the lower reaction chamber 1, heating the lower reaction chamber 1 by using a heating component to melt the metal magnesium into liquid state, and then melt extracting nickel from the waste nickel-based high-temperature alloy;

[0050] S2: After the melt extraction is completed, the nickel in the waste nickel-based high-temperature alloy is removed into liquid metal magnesium, and then distillation treatment is performed to separate the metal magnesium from the nickel. The metal magnesium enters the upper reaction chamber 1, and the alloy residue obtained after the nickel is removed from the waste nickel-based high-temperature alloy is located in the slag collection upper chamber 102 of the lower reaction chamber 1, and the nickel in the waste nickel-based high-temperature alloy is located in the product collection lower chamber 101 of the lower reaction chamber 1.

[0051] In order to better understand the above-mentioned recycling method, the present invention provides a more specific recycling device for recycling waste high-temperature alloys by melt extraction based on electromagnetic induction heating, which is used for recycling waste high-temperature alloys, comprising the following steps:

[0052] (1) After cleaning and drying, waste DD5 nickel-based single crystal high-temperature alloy was weighed to 1.07g, and magnesium metal was weighed to 10.7g. They were added together in layers and batches into the lower reaction chamber 1. Argon was introduced as a protective gas, and the mixture was heated to 850℃ by electromagnetic induction and kept warm for 4h. After the insulation was completed, the temperature was raised to 900℃, and the introduction of argon was stopped. The vacuum pump 7 was used to evacuate the outer shell 5 to a pressure below 10Pa. The temperature of the upper reaction chamber 1 was controlled to 450℃, and vacuum distillation was maintained for 2h. The magnesium entered the upper reaction chamber 1 and was circulated for the next recycling process. After the materials cooled to room temperature, the product of the lower reaction chamber 1 was collected in the lower chamber 101 to obtain an extract of 0.67g, and the slag of the lower reaction chamber 1 was collected in the upper chamber 102 to obtain an alloy residue of 0.40g.

[0053] Analysis of the 0.67g extract revealed 94.05% nickel, 1.71% aluminum, 1.65% chromium, and 2.17% cobalt. The recovered magnesium metal had a purity of 99.99%. The calculated nickel recovery was 98.07%.

[0054] (2) The alloy residue was ground and crushed, and the average particle size of the crushed powder was 20 μm. The powder was placed in a three-necked flask and dissolved and leached with concentrated hydrochloric acid and hydrogen peroxide in a constant temperature water bath. A magnetic stirrer was used for stirring, wherein the stirring speed was 500 r / min and the stirring bar length was 10 mm. Tantalum-rich and tungsten-rich slags were obtained by filtration through a Buchner funnel under the action of a pump. The filtrate contained rhenium, cobalt, aluminum and chromium. The leaching temperature was 50 ° C, the leaching time was 3 h, and the amount of concentrated hydrochloric acid with a mass fraction of 36.5% was V 盐酸 :V 水 =1:2, the amount of hydrogen peroxide is V 双氧水 :V 水 =1:2.

[0055] Analysis and testing showed that the tantalum content in the filter residue was 54.52wt.%, the tungsten content was 42.17wt.%, and the leaching rates of metal rhenium, cobalt, aluminum and chromium were all above 95%.

[0056] When the recovery device of this embodiment is used to process the next batch of high-temperature alloy materials, the high-temperature alloy materials can be directly added after the upper and lower reaction chambers 1 are simply switched up and down.

[0057] Example 2:

[0058] The recovery device in this embodiment is the same as that in embodiment 1.

[0059] A recycling device for recycling waste high-temperature alloys by melt extraction based on electromagnetic induction heating is used to recover waste high-temperature alloys, comprising the following steps:

[0060] (1) Cut, clean, and dry the waste DD5 nickel-based single crystal high-temperature alloy, weigh 1.07g, and weigh 5.35g of magnesium metal, and add them together in layers and batches into the lower reaction chamber 1. Argon is introduced as a protective gas, and the mixture is heated to 800℃ by electromagnetic induction and kept warm for 3 hours. After the insulation is completed, the temperature is raised to 900℃, and the introduction of argon is stopped. The vacuum pump 7 is used to evacuate the outer shell 5 to a pressure below 10Pa. The temperature of the upper reaction chamber 1 is controlled to 450℃, and the vacuum distillation is maintained for 1.5 hours. The magnesium enters the upper reaction chamber 1 and is circulated for the next recycling process. After the materials are cooled to room temperature, the product of the lower reaction chamber 1 is collected in the lower chamber 101 to obtain 0.65g of granular or flaky extract, and the slag of the lower reaction chamber 1 is collected in the upper chamber 102 to obtain 0.42g of block alloy residue.

[0061] Analysis of the 0.65g extract revealed 92.10% nickel, 3.43% aluminum, 2.55% chromium, and 1.11% cobalt. The recovered magnesium metal had a purity of 99.99%. The calculated nickel recovery was 93.17%.

[0062] (2) The alloy residue was ground and crushed, and the average particle size of the crushed powder was 20 μm. The powder was placed in a three-necked flask and dissolved and leached with concentrated hydrochloric acid and hydrogen peroxide in a constant temperature water bath. A magnetic stirrer was used for stirring, wherein the stirring speed was 500 r / min and the stirring bar length was 10 mm. Tantalum-rich and tungsten-rich slags were obtained by filtration through a Buchner funnel under the action of a pump. The filtrate contained rhenium, cobalt, aluminum and chromium. The leaching temperature was 50 ° C, the leaching time was 3 h, and the amount of concentrated hydrochloric acid with a mass fraction of 36.5% was V 盐酸 :V 水 =1:5, the amount of hydrogen peroxide is V 双氧水 :V 水 =1:5.

[0063] Analysis and testing showed that the tantalum content in the filter residue was 34.17wt.%, the tungsten content was 26.36wt.%, the metal rhenium leaching rate was 52.24%, the metal cobalt leaching rate was 66.71%, the metal chromium leaching rate was 62.17%, and the metal aluminum leaching rate was 96.31%.

[0064] Example 3:

[0065] The recovery device in this embodiment is the same as that in embodiment 1.

[0066] A recycling device for recycling waste high-temperature alloys by melt extraction based on electromagnetic induction heating is used to recover waste high-temperature alloys, comprising the following steps:

[0067] (1) Cut, clean, and dry the waste DD5 nickel-based single crystal high-temperature alloy, weigh 1.05g, and weigh 15.75g of magnesium metal. These are then added in layers and batches into the lower reaction chamber 1. Argon is introduced as a protective gas, and the mixture is heated to 900°C by electromagnetic induction and kept warm for 5 hours. After the end of the heat preservation, the introduction of argon is stopped, and the pressure in the outer shell 5 is evacuated by a vacuum pump 7 to be lower than 10Pa. The temperature of the upper reaction chamber 1 is controlled to 450°C, and vacuum distillation is maintained for 3 hours. The magnesium enters the upper reaction chamber 1 and is circulated for the next recycling process. After the materials are cooled to room temperature, the product of the lower reaction chamber 1 is collected in the lower chamber 101 to obtain 0.60g of granular or flaky extract, and the slag of the lower reaction chamber 1 is collected in the upper chamber 102 to obtain 0.45g of block alloy residue.

[0068] Analysis of the extract (0.60 g) revealed 93.73% nickel, 3.13% aluminum, 1.65% chromium, and 1.17% cobalt. The recovered magnesium metal had a purity of 99.99%. The calculated nickel recovery was 89.19%.

[0069] (2) The alloy residue was ground and crushed, and the average particle size of the crushed powder was 20 μm. The powder was placed in a three-necked flask and dissolved and leached with concentrated hydrochloric acid and hydrogen peroxide in a constant temperature water bath. A magnetic stirrer was used for stirring, wherein the stirring speed was 500 r / min and the stirring bar length was 10 mm. Tantalum-rich and tungsten-rich slags were obtained by filtration through a Buchner funnel under the action of a pump. The filtrate contained rhenium, cobalt, aluminum and chromium. The leaching temperature was 80 ° C, the leaching time was 3 h, and the amount of concentrated hydrochloric acid with a mass fraction of 36.5% was V 盐酸 :V 水 =1:2, the amount of hydrogen peroxide is V 双氧水 :V 水 =1:2.

[0070] Analysis and testing showed that the tantalum content in the filter residue was 39.46wt.%, the tungsten content was 22.34wt.%, the metal rhenium leaching rate was 80.42%, the metal cobalt leaching rate was 86.97%, the metal chromium leaching rate was 82.34%, and the metal aluminum leaching rate was 97.15%.

[0071] Example 4:

[0072] The difference between the recovery device in this embodiment and that in embodiment 1 is that: Figure 3 As shown, in this embodiment, both ends of the distilled gas overflow pipe 3 may also be provided with bell mouths.

[0073] Use Figure 3The distillation gas overflow pipe 3 shown in FIG. 1 is based on Example 2. During the distillation process, the temperature of the upper reaction chamber 1 was first controlled at 550°C for 1.5 hours. The metallic magnesium in the upper reaction chamber 1 was then allowed to drip onto the alloy residue in the lower reaction chamber 1. The temperature was then lowered to 450°C and the process continued for 1.5 hours. After the material cooled to room temperature, the product from the lower reaction chamber 1 was collected in the lower chamber 101 to obtain 0.66g of granular or flaky extract. The slag from the lower reaction chamber 1 was collected in the upper chamber 102 to obtain 0.41g of bulk alloy residue.

[0074] Analysis of the 0.66g extract revealed 93.12% nickel, 3.17% aluminum, 2.21% chromium, and 1.07% cobalt. The recovered magnesium metal had a purity of 99.99%. The calculated nickel recovery was 95.65%.

[0075] Comparative Example 1:

[0076] Compared with Example 1, resistance heating is adopted. Specifically, a recovery device for recovering waste high-temperature alloys by melt extraction based on resistance heating is used to recover waste high-temperature alloys, and the recovery method includes the following steps:

[0077] (1) After cleaning and drying, the waste DD5 nickel-based single crystal high-temperature alloy was weighed to 1.07 g, and the metal magnesium was weighed to 10.7 g. Argon was introduced as a protective gas, and the mixture was heated to 850°C by resistance heating and kept warm for 4 h. After the insulation was completed, the temperature was raised to 900°C, the introduction of argon was stopped, and the outer shell 5 was evacuated by vacuum pump 7 to reduce the pressure below 10 Pa. The vacuum distillation was maintained for 2 h, and 0.49 g of extract and 0.58 g of alloy residue were separated and collected.

[0078] Analysis of the 0.49g extract revealed 89.91% nickel, 3.35% aluminum, 3.61% chromium, and 2.58% cobalt. The recovered magnesium metal had a purity of 99.99%. The calculated nickel recovery was 68.57%.

[0079] (2) The alloy residue was ground and crushed, and the average particle size of the crushed powder was 20 μm. The powder was placed in a three-necked flask and dissolved and leached with concentrated hydrochloric acid and hydrogen peroxide in a constant temperature water bath. A magnetic stirrer was used for stirring, wherein the stirring speed was 500 r / min and the stirring bar length was 10 mm. Tantalum-rich and tungsten-rich slags were obtained by filtration through a Buchner funnel under the action of a pump. The filtrate contained rhenium, cobalt, aluminum and chromium. The leaching temperature was 50 ° C, the leaching time was 3 h, and the amount of concentrated hydrochloric acid with a mass fraction of 36.5% was V 盐酸 :V 水 =1:2, the amount of hydrogen peroxide is V 双氧水:V 水 =1:2.

[0080] Analysis and testing showed that the tantalum content in the filter residue was 32.08wt.%, the tungsten content was 23.94wt.%, and the leaching rates of metal rhenium, cobalt, aluminum and chromium were all above 88%.

Claims

1. A device for recovering waste high-temperature alloys by melt extraction, characterized in that: The invention comprises a reaction chamber (1), wherein the interior of the reaction chamber (1) is divided into a product collecting lower chamber (101) and a slag collecting upper chamber (102) by a perforated separation partition (2), and a distilled gas overflow pipe (3) is provided on the top of the reaction chamber (1); a pair of reaction chambers (1) are symmetrically provided in the upper and lower parts, and the pair of reaction chambers (1) are connected via the distilled gas overflow pipe (3); The outer wall of the reaction chamber (1) below is also provided with a heating component for heating the reaction chamber (1), wherein the heating component is an electromagnetic induction heating coil (4), and the electromagnetic induction heating coil (4) is arranged around the outer wall of the reaction chamber (1) below; The recovery device further comprises a sealed outer shell (5), the reaction chamber (1) is arranged in the outer shell (5), the outer shell (5) is provided with a gas filling and discharging port (6) for filling and discharging inert gas into the sealed outer shell (5) and a vacuum pump (7) for controlling the vacuum degree in the sealed outer shell (5); a cooling device (8) is provided above the outer shell (5) near the upper reaction chamber (1), and temperature measuring devices (9) for measuring the temperature in the reaction chamber (1) are provided on the upper and lower reaction chambers (1), and the cooling device (8), the temperature measuring device (9) and the heating assembly are interlocked with each other to control the temperature in the upper and lower reaction chambers (1).

2. A method for recycling waste high-temperature alloys using the melt extraction and recovery device according to claim 1, characterized in that: The following steps are involved: S1: adding waste nickel-based high-temperature alloy and metal magnesium into the lower reaction chamber (1), heating the lower reaction chamber (1) by using a heating component to melt the metal magnesium into a liquid state, and then performing melt extraction on the nickel in the waste nickel-based high-temperature alloy; S2: After the melt extraction is completed, the nickel in the waste nickel-based high-temperature alloy is removed into liquid magnesium metal, and then distillation treatment is performed to separate the magnesium metal from the nickel. The magnesium metal enters the upper reaction chamber (1). The alloy residue obtained after the nickel is removed from the waste nickel-based high-temperature alloy is located in the slag collection upper chamber (102) of the lower reaction chamber (1), and the nickel in the waste nickel-based high-temperature alloy is located in the product collection lower chamber (101) of the lower reaction chamber (1).

3. The recycling method according to claim 2, characterized in that The waste nickel-based high-temperature alloy and metal magnesium are added in layers, and the mass ratio of the waste nickel-based high-temperature alloy to the metal magnesium is controlled to be 1: (5-10).

4. The recycling method according to claim 2, characterized in that During heating in step S1, the heating temperature in the lower reaction chamber (1) is controlled to be 800-900°C, the holding time is 1-5 hours, and the heating atmosphere is controlled to be an inert atmosphere.

5. The recycling method according to claim 2, characterized in that: The distillation treatment is carried out in a vacuum environment, and the internal pressure in the reaction chamber (1) is controlled to be below 10Pa. During the distillation treatment, the temperature of the lower reaction chamber (1) is controlled to be 900-1000°C, and the temperature of the upper reaction chamber (1) is controlled to be 400-600°C. The treatment time is 0.5-3h.

6. The recycling method according to claim 5, characterized in that: During the distillation treatment, the temperature of the upper reaction chamber (1) is first controlled to be 550-580°C for a treatment time of 1-1.5 hours, and then the temperature of the upper reaction chamber (1) is controlled to be 400-450°C for a treatment time of 0.5-1.5 hours, so that the metallic magnesium in the upper reaction chamber (1) drips onto the alloy residue in the lower reaction chamber (1).

7. The recovery method according to any one of claims 2 to 6, characterized in that: The alloy residue is ball-milled to obtain a powder, and then the valuable metals in the powder are leached by oxidative acid leaching. The leaching agents during oxidative acid leaching are concentrated hydrochloric acid and hydrogen peroxide, the leaching temperature is controlled to be 40-90°C, the leaching time is 0.5-5h, and the volume concentration of concentrated hydrochloric acid is controlled to be V 盐酸 :V 水 =1: (2-5), the volume concentration of hydrogen peroxide is controlled to V 双氧水 :V 水 =1: (1-10), magnetic stirring is used during leaching, and the stirring speed is controlled between 100-1000r / min.

8. The recovery method according to any one of claims 2 to 6, characterized in that: In step S2, the metallic magnesium collected in the upper reaction chamber (1) is used for the next recovery process, and the upper and lower reaction chambers (1) are exchanged.

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