CN111410240A - Method for preparing nickel-cobalt hydroxide battery grade raw material by using high-temperature alloy waste - Google Patents
Method for preparing nickel-cobalt hydroxide battery grade raw material by using high-temperature alloy waste Download PDFInfo
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Abstract
The invention discloses a method for preparing nickel-cobalt hydroxide battery grade raw materials by using high-temperature alloy waste, and belongs to the technical field of comprehensive recycling of high-temperature alloy waste. Firstly, high-temperature alloy waste is mixed with dilute acid and reacts under the action of ultrasonic reinforcement, easily soluble elements such as nickel, cobalt, aluminum, chromium and the like in the alloy waste are directionally leached out, a solution containing nickel and cobalt is obtained through solid-liquid separation, a pure nickel-cobalt solution is obtained after the nickel-cobalt solution is subjected to synergistic extraction and back extraction, and the pure nickel-cobalt solution is subjected to controllable coupling coprecipitation treatment and solid-liquid separation to obtain a nickel-cobalt hydroxide battery grade raw material. The method has high leaching efficiency of the soluble elements, simultaneously prepares nickel-cobalt hydroxide battery grade raw materials, improves the added value of products, can enrich rare and precious metal elements such as rhenium and tungsten, reduces the waste treatment capacity of the subsequent separation and extraction working section, and has great social benefit and economic benefit.
Description
Technical Field
The invention relates to the technical field of comprehensive recycling of high-temperature alloy waste, in particular to a method for preparing nickel-cobalt hydroxide battery grade raw materials by using high-temperature alloy waste.
Background
The high-temperature alloy is an indispensable important material for aerospace engines, electric power, metallurgy, chemical engineering and the like in China, and is also a key material for ensuring the service performance of weaponry and important civil equipment. In recent years, with the continuous expansion of the application field of the high-temperature alloy, the domestic demand is compositely increased by more than 20 percent in years, and particularly, the development of the aviation industry has more remarkable increasing demand on the high-temperature alloy. The high-temperature alloy contains multiple rare and precious metal elements such as rhenium, ruthenium, cobalt, nickel, tungsten, molybdenum, niobium, tantalum, hafnium and the like, and is an important rare and precious metal secondary resource. However, high temperature alloy parts are mainly finished through multiple processes of alloy smelting, thermal deformation, machining, thermal treatment and the like, the product yield is in a descending trend along with the increase of complexity and quality requirements of parts, and a large amount of alloy flows out in solid waste forms such as pouring channels, risers, waste parts, lathing scraps, defective products, blank holders and the like. Based on this estimate: at least 70% of the material in the whole production process of the high-temperature alloy part flows out in the form of waste.
However, so far, the recovery rate of the high-temperature alloy is low, which causes waste of rare and precious metal resources. Most of the alloy is not efficiently utilized, and is mainly used as a low-value alloy additive material at present, and the real utility and value utilization of the alloy additive material are not fully utilized. The valuable elements in the high-temperature alloy are recycled, so that the method has important significance for relieving the demand of strategic scarce resources in China, reducing the cost of the noble metal alloy and promoting the upgrading and updating of the high-temperature alloy.
In order to meet the use conditions at high temperature, the high-temperature alloy generally has good corrosion resistance and oxidation resistance, and elements such as Re, Ru, Ta, W, Mo, Co and the like added in the alloy also have low chemical activity and are difficult to dissolve in the hydrometallurgy process. The traditional high-temperature alloy electrolyte is an acidic system containing oxidizing media such as hydrochloric acid, nitric acid, sulfuric acid, hydrogen peroxide and the like, wherein the oxidizing media promote easily passivated elements Cr, and hydrogen peroxide in the high-temperature alloy,Passivation of Al to form Cr on the alloy surface2O3/Al2O3And (5) passivating the film. Due to Cr2O3With Al2O3The passive film has good compactness and greatly reduces the dissolution speed. Although these dissolution systems can achieve dissolution of high temperature alloys, the dissolution rate is not ideal, a long dissolution time is often required, the acid consumption in the dissolution process is large, the corrosion of equipment is severe, and the dissolution cost is huge. At present, however, a passivation film is easily formed on the surface of the alloy in the chemical dissolution process, the dissolution of the alloy is hindered by the formation of the passivation film, the dissolution speed of the alloy waste in the wet recovery process of the high-temperature alloy waste is low, the high-temperature alloy dissolution process becomes a bottleneck of the comprehensive utilization of the high-temperature alloy waste, the bottleneck becomes a difficult point of a neck, and the development of the green comprehensive utilization of the secondary resources of the high-temperature alloy is severely restricted.
Some patents disclose comprehensive utilization of high temperature alloys. Patent 201811286512.3 discloses a new leaching and separating method for nickel-cobalt alloy material containing molybdenum and vanadium, which comprises: the method comprises four steps of raw material preparation, ingredient slurrying reaction, pressure leaching for removing iron and valuable metal recovery. According to the method, iron in the alloy material is preferentially converted into a stable goethite form for fixed precipitation through the optimal control of reaction parameters in the batching slurrying reaction and the pressure leaching iron removal treatment, so that the problem that the recovery rate of molybdenum and vanadium is low due to the fact that the 3-valent iron is easy to react with molybdenum and vanadium in a solution after oxidation in the oxidation iron removal process in the prior art is effectively solved, valuable metals such as molybdenum, vanadium, cobalt and nickel in the alloy material can fully enter a filtrate for subsequent separation, recovery and utilization, and the full recovery and utilization of valuable metal resources in the alloy material are realized. The invention mainly aims to put valuable metals such as molybdenum, vanadium, cobalt and nickel in the alloy material into solution, and meanwhile, the invention has the advantages of long process flow, high requirement on equipment, complicated operation of pressurization and high recovery cost, but the raw material has no characteristics of high-temperature alloy, so the problems encountered when the high-temperature alloy waste is treated are completely different.
Patent 106893859B relates to a method for processing nickel-cobalt alloy waste, which comprises the steps of placing dilute sulphuric acid system nickel-cobalt alloy waste slurry into a slurry tank, arranging a mechanical stirring paddle in the slurry tank, keeping the slurry in a uniformly mixed state, feeding the slurry into a rotational flow electrolysis system through a pneumatic pump at a certain speed, discharging the slurry from an electrolysis device after electrolysis, continuously feeding the slurry into the slurry tank, circulating the process, and efficiently extracting nickel and cobalt in the minerals after a certain time.
Patent 108622943B discloses a method for producing battery grade nickel sulfate and cobalt sulfate from waste nickel cobalt alloy, comprising the steps of: the method comprises the steps of pretreating nickel-cobalt alloy waste, then electrochemically dissolving, removing impurities such as iron, chromium, aluminum and the like from the obtained solution step by using a chemical method and an extraction method, extracting cobalt from the solution after impurity removal, then extracting nickel to obtain cobalt-containing extract liquor and nickel-containing extract liquor respectively, obtaining nickel sulfate solution and cobalt sulfate solution after back extraction, and then evaporating, cooling, crystallizing and centrifugally dehydrating the solutions respectively to obtain the battery-grade nickel sulfate and cobalt sulfate products. The method adopts an electrochemical mode to recover nickel and cobalt, has high energy consumption of electrolysis, long process flow and huge recovery cost after multiple extraction processes, and has no characteristics of high-temperature alloy in raw materials, thereby having no practical significance for the method.
Patent 106947877B relates to a method for separating and recovering cobalt and nickel from waste iron-nickel-cobalt alloy, the process comprises the following steps: 1) leaching waste iron-nickel-cobalt alloys containing 54% of Fe, 18% of Co and 28% of Ni by sulfuric acid to obtain leachate of which the main metals are iron, nickel and cobalt; 2) by using the compounding agent of OH-NH3、C2N2H8One or more of the precipitating agents is CO32-forming a "complexing-precipitating" system to act on the nickel-cobalt-iron leach liquor, separating iron and cobalt by fractional precipitation to obtain a cobalt compound; 3) nickel is mixed in the solution, and metal nickel is obtained by further electrolysis. The method mainly treats the iron-based nickel-cobalt alloy,in the process of adopting the matching-precipitation, the separation efficiency of valuable elements is low, the process flow is long, a large amount of waste acid is generated in the process, and the equipment is seriously corroded.
Patent 201610116168.8 discloses a method of leaching nickel cobalt from alloy scrap. Firstly, the bulk alloy waste containing nickel and cobalt is put into an electrolytic bath for electrolytic dissolution, after nickel ions in an electrolytic solution reach a proper concentration, a solid-liquid mixture formed by anode mud and the electrolytic solution in the electrolytic bath is subjected to solid-liquid separation to obtain a nickel and cobalt concentrated solution for recycling nickel and cobalt, and more than 80% of nickel and cobalt can be transferred into the electrolytic solution through the electrolytic dissolution. And (3) performing acid leaching on the anode mud under normal pressure, completely leaching the residual nickel and cobalt, preparing a leaching solution to be used as an electro-solution for next electro-dissolution, and using filter residues as raw materials for recovering rare metals, wherein the content of nickel and cobalt in the filter residues is less than 0.5% (mass percentage). The method adopts an electrochemical mode to recover nickel and cobalt, has high electrolysis energy consumption, long process flow and huge recovery cost, and the raw materials do not have the characteristics of high-temperature alloy.
The patent 201910428948.X relates to a method for extracting vanadium by roasting vanadium titano-magnetite concentrate and ultrasonically leaching, which comprises the following steps of preparing the vanadium titano-magnetite concentrate into pellets, roasting to obtain roasted clinker, placing the roasted clinker in acid liquor with the pH of 2.0-3.0, performing ultrasonic leaching, performing solid-liquid separation to obtain leachate and leached tailings, performing cyclic leaching on the leachate and the vanadium titano-magnetite concentrate until the vanadium concentration in the leachate is 10-20 g/L, precipitating vanadium, and calcining to obtain vanadium pentoxide.
In summary, in the recycling of the high-temperature alloy waste materials, the alloy solution has low efficiency, high energy consumption, severe equipment corrosion and high cost, so that the valuable metal elements in the high-temperature alloy waste materials are difficult to be effectively recycled. Therefore, a new method for comprehensively recycling secondary resources of the high-temperature alloy is urgently needed to be developed, the bottleneck problem that valuable metal elements in the high-temperature alloy waste are difficult to effectively recycle is solved, and the efficient separation and extraction of the elements in the high-temperature alloy are realized.
Disclosure of Invention
Aiming at the technical problems of low alloy dissolution efficiency, high energy consumption and high cost in the existing high-temperature alloy waste electrochemical dissolution technology, the invention provides a method for preparing nickel-cobalt hydroxide battery grade raw materials by utilizing high-temperature alloy waste.
The technical scheme adopted by the invention is as follows:
a method for preparing nickel-cobalt hydroxide battery grade raw materials by utilizing high-temperature alloy waste materials specifically comprises the following steps:
(1) a leaching section: mixing the high-temperature alloy waste with dilute acid, reacting under the conditions of ultrasonic strengthening and stirring, leaching out soluble elements (nickel, cobalt, aluminum, chromium and the like) in the high-temperature alloy waste, and then carrying out solid-liquid separation to obtain a solution containing nickel and cobalt and leaching slag I;
(2) adjusting the pH value of the nickel-cobalt-containing solution obtained in the step (1) to 4-6, and then performing synergistic extraction and back extraction to obtain a pure nickel-cobalt solution and raffinate; wherein the synergistic extraction agent is one or more of P204, P507, N235 and Cyanex 272;
(3) adding a precipitator (OH) into the pure nickel-cobalt solution obtained in the step (2)-) And carrying out controllable coupling coprecipitation treatment, wherein the controllable coupling coprecipitation treatment process specifically comprises the steps of adopting a step-by-step adding measure, dropwise adding a sodium hydroxide solution with the concentration of 8-25 g/L into a pure nickel-cobalt solution, controlling the pH value to be 13.5-14, stirring at the speed of 200rpm, and carrying out solid-liquid separation on a reaction product to obtain the nickel-cobalt hydroxide battery grade raw material.
The high-temperature alloy waste is produced after the high-temperature alloy is produced, cast, processed, inspected and scrapped; such as: K417G alloy, DZ40M alloy, DD5 alloy, DD6 alloy, and the like.
In the step (1), the dilute acid is one or a mixture of more of dilute hydrochloric acid, dilute nitric acid and dilute sulfuric acid, the concentration of the dilute hydrochloric acid is 5-36 wt.%, and the concentration of the dilute sulfuric acid is 1-10 mol/L.
In the step (1), in the directional leaching reaction process of the high-temperature alloy waste and the dilute acid, the liquid-solid ratio of the high-temperature alloy waste to the dilute acid is (4-20) m L: 1 g.
The reaction in the step (1) is carried out in a reaction kettle, wherein the ultrasonic wave is generated by an ultrasonic generator, and the range of the ultrasonic wave is 400-1200W; the stirring rate was 200 and 1000 rpm.
In the step (2), the raffinate returns to the leaching section in the step (1), so that the recycling of the dilute acid is realized, and no waste acid solution is discharged.
The leaching residue I obtained in the step (1) mainly contains insoluble elements such as tantalum, niobium and the like, and can be directly recycled as rare and precious metal raw materials.
In the nickel hydroxide cobalt battery grade raw material obtained in the step (3), the impurity content is less than 1 wt%.
Compared with the prior art, the invention has the advantages that:
(1) aiming at the problems of serious equipment corrosion and high equipment cost in a high-temperature alloy dissolving section caused by the use of a large amount of strong oxidizing media and strong acid in order to realize the one-time dissolution of all elements in the high-temperature alloy in the existing high-temperature alloy dissolving process, the invention adopts a directional leaching mode and utilizes the difference of the chemical activity of valuable elements in alloy waste to realize the directional leaching of nickel and cobalt in the alloy waste.
(2) In the directional leaching process, dilute acid leaching is adopted, under the ultrasonic strengthening effect, easily soluble elements such as nickel, cobalt, aluminum, chromium and the like (mainly nickel and cobalt) in the high-temperature alloy enter a liquid phase, and trace elements such as rare and precious metals such as rhenium, tungsten, molybdenum, tantalum, niobium and the like in the high-temperature alloy are enriched in leaching residues in the primary leaching process, so that the use of a large amount of strong oxidizing acid in the leaching process is avoided, and the defect of the use of Cr in the leaching process is overcome2O3/Al2O3The production of the passive film has high leaching efficiency of valuable metals, and simultaneously, the corrosion of equipment is reduced, and the production cost is reduced.
(3) In the directional leaching process, the acidity and the oxidability of a leaching system are strictly controlled, so that nickel and cobalt are leached while other elements are prevented from being leached.
(4) The invention adopts ultrasonic wave to assist electrolysis, and greatly enhances the diffusion speed of the liquid-solid system carrier layer through the cavitation action of the ultrasonic wave, thereby improving the dissolution rate of the electro-dissolved high-temperature alloy waste.
(5) By adopting a directional leaching mode, elements such as rhenium, tungsten, molybdenum, tantalum, niobium and the like are enriched in leaching slag in the directional leaching process, so that the solution circulation amount is reduced for the subsequent working section, and the production cost is reduced; the enriched leaching residue can be used as a raw material for extracting rare and noble metals in the next stage.
(6) Extracting the nickel-cobalt-containing solution obtained after leaching the high-temperature alloy waste material by synergism, back-extracting to obtain a pure nickel-cobalt solution, and precipitating the pure nickel-cobalt solution by using a precipitator (OH)-) Step-by-step addition, controllable coupling coprecipitation treatment is carried out, the pH value is controlled to be 13.5-14, solid-liquid separation is carried out to obtain a nickel-cobalt hydroxide battery grade raw material, and the residual solution returns to a precipitation stage to realize the recycling of alkali; the raffinate returns to the leaching section, so that the recycling of the dilute acid is realized, and no waste acid or waste alkali solution is discharged in the whole production process.
(7) The invention adopts the controllable coupling coprecipitation technology to prepare the nickel-cobalt hydroxide battery grade raw material, thereby improving the added value of the product.
(8) The invention realizes the recycling of acid and alkali in the production process; no waste acid or waste alkali solution is discharged in the whole production process.
Drawings
Fig. 1 is a process flow diagram for preparing nickel-cobalt hydroxide battery grade raw materials by using high-temperature alloy waste.
Detailed Description
The following example is a process for preparing nickel-cobalt hydroxide battery grade raw material from high temperature alloy scrap, the process flow is shown in fig. 1.
Example 1
The method comprises the steps of reacting high-temperature alloy waste with 2.5 mol/L dilute sulfuric acid in a normal-pressure reaction kettle, carrying out the reaction under stirring conditions and ultrasonic strengthening, wherein the reaction time is 30min, the reaction temperature is 50 ℃, the liquid-solid ratio is 8m L: 1g, the stirring speed is 300rpm, the ultrasonic power is 400W, directionally leaching out readily soluble elements such as nickel, cobalt, aluminum, chromium and the like in the alloy waste, filtering to obtain leaching liquid containing nickel and cobalt and leaching residues rich in rare and noble metal elements such as rhenium, tungsten, molybdenum, tantalum, niobium and the like, collecting the leaching residues which can be used as raw materials for extracting the rare and noble metals at the next stage, wherein the leaching rate of nickel in the high-temperature alloy waste reaches 99.03%, and the leaching rate of cobalt is 98.58%.
Firstly, regulating the pH value of the solution containing nickel and cobalt to be 4.5, and obtaining pure nickel and cobalt solution after P204-P507 synergistic extraction and back extraction.
Adding a precipitator (OH-) into the pure nickel-cobalt solution, and performing controllable coupling coprecipitation treatment to obtain a nickel-cobalt hydroxide battery-grade raw material, wherein the controllable coupling coprecipitation treatment specifically comprises the steps of adopting a step-by-step adding measure, dropwise adding 10 g/L of sodium hydroxide solution into the pure nickel-cobalt solution, controlling the pH value to be 13.5-14, stirring at the speed of 100rpm, and performing solid-liquid separation on the reacted material to obtain the nickel-cobalt hydroxide battery-grade raw material, wherein the content of nickel hydroxide is 92.12%, the content of cobalt hydroxide is 4.32%, and the content of other impurities is less than 0.5%.
The residual solution after controllable coupling coprecipitation treatment and solid-liquid separation returns to the precipitation stage, so that the recycling of alkali is realized; the raffinate of the solution containing nickel and cobalt after synergistic extraction and back extraction returns to the leaching section, so that the recycling of the dilute acid is realized, and no waste acid or waste alkali solution is discharged in the whole production process.
Example 2
The method comprises the steps of reacting high-temperature alloy waste with dilute hydrochloric acid with the mass fraction of 10% in a normal-pressure reaction kettle, wherein the reaction is carried out under the stirring condition and the ultrasonic strengthening effect, the reaction time is 60min, the reaction temperature is 60 ℃, the liquid-solid ratio is 12m L: 1g, the stirring speed is 200rpm, the ultrasonic power is 600W, soluble elements such as nickel, cobalt, aluminum and chromium in the alloy waste are directionally leached, leaching solution containing nickel and cobalt and rare and noble metal element enriched slag such as rhenium, tungsten, molybdenum, tantalum, niobium and the like are obtained by filtering, the enriched leaching slag can be used as a raw material for extracting the rare and noble metals at the next stage, the leaching rate of nickel in the high-temperature alloy waste reaches 99.56%, and the leaching rate of cobalt is 97.37%;
firstly, regulating the pH value of the solution containing nickel and cobalt to 5.5, and obtaining pure nickel and cobalt solution after P204-P507 synergistic extraction and back extraction.
Adding a precipitator (OH-) into the pure nickel-cobalt solution, and performing controllable coupling coprecipitation treatment to obtain a nickel-cobalt hydroxide battery grade raw material, wherein the controllable coupling coprecipitation treatment comprises the specific steps of adopting a step-by-step adding measure, dropwise adding 20 g/L of sodium hydroxide solution into the pure nickel-cobalt solution, controlling the pH value to be 14, stirring at the speed of 100rpm, and performing solid-liquid separation on the reacted material to obtain the nickel-cobalt hydroxide battery grade raw material, wherein the content of nickel hydroxide is 93.15%, the content of cobalt hydroxide is 3.82%, and the content of other impurities is less than 0.4%;
the residual solution after controllable coupling coprecipitation treatment and solid-liquid separation returns to the precipitation stage, so that the recycling of alkali is realized; the raffinate of the solution containing nickel and cobalt after synergistic extraction and back extraction returns to the leaching section, so that the recycling of the dilute acid is realized, and no waste acid or waste alkali solution is discharged in the whole production process.
Example 3
The method comprises the steps of reacting high-temperature alloy waste with 4 mol/L dilute sulfuric acid in a normal-pressure reaction kettle, wherein the reaction is carried out under the stirring condition and the ultrasonic strengthening effect, the reaction time is 60min, the reaction temperature is 40 ℃, the liquid-solid ratio is 10m L: 1g, the stirring speed is 400rpm, the ultrasonic power is 600W, soluble elements such as nickel, cobalt, aluminum, chromium and the like in the alloy waste are directionally leached, leaching solution containing nickel and cobalt and enriched slag of rare and noble metal elements such as rhenium, tungsten, molybdenum, tantalum, niobium and the like are obtained by filtering, the enriched leaching slag can be used as a raw material for extracting the rare and noble metals at the next stage, the leaching rate of nickel in the high-temperature alloy waste reaches 99.13%, and the leaching rate of cobalt is 98.68%;
firstly, the pH value of the solution containing nickel and cobalt is adjusted to 4.5, and the pure nickel and cobalt solution is obtained after N235-P507 synergistic extraction and back extraction.
Adding a precipitator (OH-) into the pure nickel-cobalt solution, and performing controllable coupling coprecipitation treatment to obtain a nickel-cobalt hydroxide battery grade raw material, wherein the controllable coupling coprecipitation treatment comprises the steps of adopting a step-by-step adding measure, dropwise adding 15 g/L of sodium hydroxide solution into the pure nickel-cobalt solution, controlling the pH value to be 14, stirring at the speed of 150rpm, and performing solid-liquid separation on the reacted material to obtain the nickel-cobalt hydroxide battery grade raw material, wherein the content of nickel hydroxide is 95.37%, the content of cobalt hydroxide is 3.12%, and the content of other impurities is less than 0.2%.
The residual solution after controllable coupling coprecipitation treatment and solid-liquid separation returns to the precipitation stage, so that the recycling of alkali is realized; the raffinate of the solution containing nickel and cobalt after synergistic extraction and back extraction returns to the leaching section, so that the recycling of the dilute acid is realized, and no waste acid or waste alkali solution is discharged in the whole production process.
Example 4
The method comprises the steps of reacting high-temperature alloy waste with a mixed solution of 2 mol/L dilute sulfuric acid and 8% dilute hydrochloric acid in a normal-pressure reaction kettle, wherein the reaction is carried out under stirring conditions and ultrasonic strengthening, the reaction time is 30min, the reaction temperature is 50 ℃, the liquid-solid ratio is 10m L: 1g, the stirring speed is 100rpm, the ultrasonic power is 700W, soluble elements such as nickel, cobalt, aluminum and chromium in the alloy waste are directionally leached, leaching solution containing nickel and cobalt and enriched slag of rare and noble metal elements such as rhenium, tungsten, molybdenum, tantalum and niobium are obtained through filtration, and the enriched leaching slag can be used as a raw material for extracting the rare and noble metal at the next stage, wherein the leaching rate of nickel reaches 99.43%, and the leaching rate of cobalt is 98.78%;
firstly, regulating the pH value of the solution containing nickel and cobalt to be 4.5, and obtaining pure nickel and cobalt solution after P204-N235 synergistic extraction and back extraction.
Adding a precipitator (OH-) into a solution containing nickel and cobalt, and performing controllable coupling coprecipitation treatment to obtain a nickel and cobalt hydroxide battery grade raw material, wherein the controllable coupling coprecipitation treatment specifically comprises the steps of adopting a step-by-step adding measure, dropwise adding 10 g/L of sodium hydroxide solution into the pure nickel and cobalt solution, controlling the pH value to be 13.5-14, stirring at the speed of 100rpm, and performing solid-liquid separation on the reacted material to obtain the nickel and cobalt hydroxide battery grade raw material, wherein the content of nickel hydroxide is 94.34%, the content of cobalt hydroxide is 4.17%, and the content of other impurities is less than 0.2%.
The residual solution after controllable coupling coprecipitation treatment and solid-liquid separation returns to the precipitation stage, so that the recycling of alkali is realized; the raffinate of the solution containing nickel and cobalt after synergistic extraction and back extraction returns to the leaching section, so that the recycling of the dilute acid is realized, and no waste acid or waste alkali solution is discharged in the whole production process.
Claims (8)
1. A method for preparing nickel-cobalt hydroxide battery grade raw materials by utilizing high-temperature alloy waste is characterized by comprising the following steps of: the method specifically comprises the following steps:
(1) a leaching section: mixing the high-temperature alloy waste with dilute acid, reacting under the conditions of ultrasonic strengthening and stirring, leaching out soluble elements (nickel, cobalt, aluminum, chromium and the like) in the high-temperature alloy waste, and performing solid-liquid separation to obtain a solution containing nickel and cobalt and leaching slag I;
(2) adjusting the pH value of the solution containing nickel and cobalt obtained in the step (1) to 4-6, and then obtaining pure nickel and cobalt solution and raffinate after synergistic extraction and back extraction; wherein the synergistic extraction agent is one or more of P204, P507, N235 and Cyanex 272;
(3) adding a precipitator (OH) into the pure nickel-cobalt solution obtained in the step (2)-) And carrying out controllable coupling coprecipitation treatment, wherein the controllable coupling coprecipitation treatment process specifically comprises the steps of adopting a step-by-step adding measure, dropwise adding a sodium hydroxide solution with the concentration of 8-25 g/L into a pure nickel-cobalt solution, controlling the pH value to be 13.5-14, stirring at the speed of 200rpm, and carrying out solid-liquid separation on a reaction product to obtain the nickel-cobalt hydroxide battery grade raw material.
2. The method of utilizing superalloy scrap for making nickel-cobalt hydroxide battery grade feedstock as claimed in claim 1, wherein: the high-temperature alloy waste is produced after the high-temperature alloy is produced, cast, processed, inspected and scrapped; such as: one or more of K417G alloy, DZ40M alloy, DD5 alloy, DD6 alloy and the like.
3. The method for preparing nickel cobalt hydroxide battery grade raw material by using high-temperature alloy scrap according to claim 1, wherein in the step (1), the dilute acid is one or a mixture of dilute hydrochloric acid, dilute nitric acid and dilute sulfuric acid, the concentration of the dilute hydrochloric acid is 5-36 wt.%, and the concentration of the dilute sulfuric acid is 1-10 mol/L.
4. The method for preparing the nickel-cobalt hydroxide battery grade raw material by using the high-temperature alloy waste material is characterized in that in the step (1), the liquid-solid ratio of the high-temperature alloy waste material to the dilute acid is (4-20) m L: 1g in the directional leaching reaction process of the high-temperature alloy waste material and the dilute acid.
5. The method of utilizing superalloy scrap for making nickel-cobalt hydroxide battery grade feedstock as claimed in claim 1, wherein: the reaction in the step (1) is carried out in a reaction kettle, the ultrasonic wave is generated by an ultrasonic generator, the ultrasonic generator is arranged at the bottom of the reaction kettle, and the range of the ultrasonic wave is 400-1200W; the stirring rate was 200 and 1000 rpm.
6. The method of utilizing superalloy scrap for making nickel-cobalt hydroxide battery grade feedstock as claimed in claim 1, wherein: in the step (2), the raffinate returns to the leaching section in the step (1), so that the recycling of the dilute acid is realized, and no waste acid solution is discharged.
7. The method of utilizing superalloy scrap for making nickel-cobalt hydroxide battery grade feedstock as claimed in claim 1, wherein: the leaching residue I obtained in the step (1) mainly contains insoluble elements such as tantalum, niobium and the like, and can be directly recycled as rare and precious metal raw materials.
8. The method of utilizing superalloy scrap for making nickel-cobalt hydroxide battery grade feedstock as claimed in claim 1, wherein: and (4) in the nickel-cobalt hydroxide battery grade raw material obtained in the step (3), the impurity content is less than 1 wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010192A (en) * | 2022-07-28 | 2022-09-06 | 郑州中科新兴产业技术研究院 | Method for regenerating element gradient manganese-rich ternary precursor by using ternary precursor waste |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925695A (en) * | 2012-10-20 | 2013-02-13 | 贵研铂业股份有限公司 | Method for leaching nickel (Ni) and cobalt (Co) from waste high-temperature alloy material |
| CN103233125A (en) * | 2013-04-22 | 2013-08-07 | 贵研铂业股份有限公司 | Method for extracting tungsten, molybdenum and rhenium from waste high-temperature alloy |
| JP5326610B2 (en) * | 2009-02-02 | 2013-10-30 | 住友金属鉱山株式会社 | Method for recovering metals from used nickel metal hydride batteries |
| CN106935923A (en) * | 2017-03-31 | 2017-07-07 | 山东理工大学 | The method that valuable metal is reclaimed from waste nickel hydrogen battery |
| CN109735709A (en) * | 2018-12-13 | 2019-05-10 | 江西赣锋循环科技有限公司 | A kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material |
-
2020
- 2020-03-31 CN CN202010244663.3A patent/CN111410240A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5326610B2 (en) * | 2009-02-02 | 2013-10-30 | 住友金属鉱山株式会社 | Method for recovering metals from used nickel metal hydride batteries |
| CN102925695A (en) * | 2012-10-20 | 2013-02-13 | 贵研铂业股份有限公司 | Method for leaching nickel (Ni) and cobalt (Co) from waste high-temperature alloy material |
| CN103233125A (en) * | 2013-04-22 | 2013-08-07 | 贵研铂业股份有限公司 | Method for extracting tungsten, molybdenum and rhenium from waste high-temperature alloy |
| CN106935923A (en) * | 2017-03-31 | 2017-07-07 | 山东理工大学 | The method that valuable metal is reclaimed from waste nickel hydrogen battery |
| CN109735709A (en) * | 2018-12-13 | 2019-05-10 | 江西赣锋循环科技有限公司 | A kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material |
Non-Patent Citations (2)
| Title |
|---|
| 孙传尧: "《选矿工程师手册 第1册 上 选矿通论》", 31 March 2015, 冶金工业出版社 * |
| 张深根等: "《典型废旧金属循环利用技术》", 28 February 2017, 冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010192A (en) * | 2022-07-28 | 2022-09-06 | 郑州中科新兴产业技术研究院 | Method for regenerating element gradient manganese-rich ternary precursor by using ternary precursor waste |
| CN115010192B (en) * | 2022-07-28 | 2024-03-26 | 郑州中科新兴产业技术研究院 | Method for regenerating element gradient manganese-rich ternary precursor by utilizing ternary precursor waste |
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