CN116219171A - Method for recovering Mg from cobalt-nickel intermediate product - Google Patents

Method for recovering Mg from cobalt-nickel intermediate product Download PDF

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CN116219171A
CN116219171A CN202211575120.5A CN202211575120A CN116219171A CN 116219171 A CN116219171 A CN 116219171A CN 202211575120 A CN202211575120 A CN 202211575120A CN 116219171 A CN116219171 A CN 116219171A
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cobalt
nickel intermediate
solution
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washed
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张颖
秦汝勇
王健安
钟晖
黄亚祥
郑江峰
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute Co Ltd
Jiangxi Jiana Energy Technology Co Ltd
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute Co Ltd
Jiangxi Jiana Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention relates to the technical field of metal recovery, in particular to a method for recovering Mg from cobalt-nickel intermediate products. The method for recovering Mg from cobalt-nickel intermediate product comprises the following steps: (A) Washing the cobalt-nickel intermediate product to obtain a washed liquid and a washed cobalt-nickel intermediate product; (B) Separating the washed cobalt-nickel intermediate by a decomposition method, a chemical method impurity removal method and an extraction method in sequence to obtain a solution containing nickel sulfate and/or cobalt sulfate and raffinate; (C) Sequentially removing oil, exchanging ions and crystallizing by dissolving out to obtain a mixed crystal of magnesium sulfate and sodium sulfate; (D) After the mixed crystal of magnesium sulfate and sodium sulfate is dissolved, adding sodium hydroxide solution for reaction to obtain magnesium hydroxide and sodium sulfate solution. The method can recycle Mg in the nickel cobalt intermediate product to obtain magnesium hydroxide, the recovery rate of Mg is more than or equal to 95 percent, and all byproducts in the method can be recycled in the system, thereby reducing the generation of hazardous waste.

Description

Method for recovering Mg from cobalt-nickel intermediate product
Technical Field
The invention relates to the technical field of metal recovery, in particular to a method for recovering Mg from cobalt-nickel intermediate products.
Background
Along with the rapid increase of global electric automobile yield, the consumption of battery metal is gradually increased, the demand for nickel and cobalt raw materials is gradually increased, and most of the nickel and cobalt raw materials are nickel and cobalt intermediate products.
The intermediate product of cobalt and nickel is a primary hydroxide product with higher cobalt and nickel content obtained by taking minerals containing cobalt and nickel as raw materials and carrying out processes such as leaching, precipitation and the like. The intermediate class of nickel and cobalt includes nickel hydroxide (Ni (OH) 2 ) Cobalt hydroxide (Co (OH) 2 ) And cobalt nickel hydroxide (MHP).
The common intermediate products of nickel and cobalt are mostly precipitated by magnesium oxide, so that the intermediate products are inevitably entrained with part of Mg metal ions. The nickel cobalt intermediate product is used as a raw material, a wet smelting process is adopted to prepare a nickel cobalt sulfate product, and as the raw material contains a plurality of metal elements such as nickel, cobalt, copper, manganese, magnesium and the like, the recovery of magnesium in the actual production of recovered metal is mainly to prepare low-added-value products such as industrial magnesium carbonate or magnesium sulfate and the like.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for recovering Mg from a cobalt-nickel intermediate product, which can recover metal Mg in the process of hydrometallurgy of the nickel-cobalt intermediate product to obtain magnesium hydroxide, wherein the recovery rate of Mg is more than or equal to 95 percent, and all byproducts in the method can be recycled in a system, so that the generation of dangerous waste is reduced.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a method for recovering Mg from cobalt-nickel intermediate products, which comprises the following steps:
(A) Washing the cobalt-nickel intermediate product to obtain a washed liquid and a washed cobalt-nickel intermediate product;
(B) Separating the washed cobalt-nickel intermediate by a decomposition method, a chemical method impurity removal method and an extraction method in sequence to obtain a solution containing nickel sulfate and/or cobalt sulfate and raffinate;
(C) The washed liquid is subjected to oil removal, ion exchange and elution crystallization in sequence to obtain a mixed crystal of magnesium sulfate and sodium sulfate;
(D) And after the mixed crystal of magnesium sulfate and sodium sulfate is dissolved, adding a sodium hydroxide solution to react, so as to obtain a magnesium hydroxide and sodium sulfate solution.
Further, in the step (A), the pH of the washed detergent is 5.0 to 6.0.
Preferably, the washed detergent comprises the raffinate in step (B).
Further, in the step (A), the washing temperature is 45-60 ℃; the liquid-solid ratio of the washing is 3-5 mL/g, and the washing time is 1-3 h.
Further, in the step (A), the pH of the washing liquid is 7.5-8.5, and the total concentration of Ni and Co in the washing liquid is 0.3-0.5 g/L.
Further, in step (B), the decomposing comprises mixing the washed cobalt nickel intermediate, an acid solution, and a reducing agent.
Preferably, sulfuric acid is included in the acid solution.
Preferably, the reducing agent comprises at least one of sodium sulfite, sodium metabisulfite and sulfur dioxide.
Further, in the step (C), the degreasing includes subjecting the post-washing liquid to an adsorption treatment with an adsorption resin.
Further, in the step (C), the adsorption resin includes one or more of a styrene-based polymeric adsorption resin, a styrene-divinylbenzene copolymer gel type resin, a nonpolar macroporous adsorption resin, a medium-sized macroporous adsorption resin, and a weak-sized macroporous adsorption resin.
Further, in the step (C), the ion-exchanged ion-exchange resin includes one or more of a styrene-based chelate resin, a free amine-based resin, an epoxy-based chelate resin, and an iminodiacetic acid-based chelate resin.
Preferably, the Co content in the washing liquid after ion exchange is less than or equal to 0.001g/L, and the Ni content is less than or equal to 0.0005g/L.
Preferably, the cation in the post-ion-exchange washing liquid comprises Na + And Mg (magnesium) 2+ 。
Further, in step (C), the elution crystallization includes adding the post-ion-exchanged washed liquid to an ethanol solution.
Further, in the step (D), bipolar membrane electrodialysis treatment is carried out on the sodium sulfate solution to obtain sodium hydroxide solution and sulfuric acid solution.
Compared with the prior art, the invention has the beneficial effects that:
the method for recycling Mg in the cobalt-nickel intermediate product can comprehensively recycle metal Mg in the nickel-cobalt intermediate product to obtain magnesium hydroxide, and the recovery rate of the Mg is more than or equal to 95%; meanwhile, the method has excellent yield of metal Mg in the nickel cobalt intermediate product, and simultaneously ensures the yields of metal Co and Ni.
The method for recycling Mg from the cobalt-nickel intermediate product considers the whole slag and water circulation, has low cost and high circulation rate in the process design process, can recycle all byproducts in the system, and reduces the generation of dangerous waste.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for recovering Mg from a cobalt nickel intermediate product of example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Referring to fig. 1, a method for recovering Mg from a cobalt nickel intermediate product according to an embodiment of the present invention will be specifically described.
In some embodiments of the invention, a method for recovering Mg from a cobalt nickel intermediate is provided, comprising the steps of:
(A) Washing the cobalt-nickel intermediate product to obtain a washed liquid and a washed cobalt-nickel intermediate product;
(B) Separating the washed cobalt-nickel intermediate by a decomposition method, a chemical method impurity removal method and an extraction method in sequence to obtain a solution containing nickel sulfate and/or cobalt sulfate and raffinate;
(C) Sequentially removing oil, exchanging ions and crystallizing by dissolving out to obtain a mixed crystal of magnesium sulfate and sodium sulfate;
(D) After the mixed crystal of magnesium sulfate and sodium sulfate is dissolved, adding sodium hydroxide solution for reaction to obtain magnesium hydroxide and sodium sulfate solution.
The method for recycling Mg in the cobalt-nickel intermediate product can comprehensively recycle metal Mg in the nickel-cobalt intermediate product to obtain magnesium hydroxide, and the recovery rate of the Mg is more than or equal to 95%; meanwhile, the yields of the metal Co and Ni are also ensured.
The method for recycling Mg from the cobalt-nickel intermediate product considers the whole slag and water circulation, has low cost and high circulation rate in the process design process, can recycle all byproducts in the system, and reduces the generation of dangerous waste.
The method provided by the invention can separate and recover magnesium from the raw material section, more than 30% of Mg can be washed in the raw material washing process, the impurity removal cost in the extraction impurity removal process can be reduced in the process, and meanwhile, high-content Co and Ni in the feed liquid can be subjected to precipitation recovery in the washing process.
In some embodiments of the invention, the cobalt nickel intermediate comprises a cobalt intermediate, a nickel intermediate, or a mixture of a cobalt intermediate and a nickel intermediate.
In some embodiments of the invention, in step (a), the pH of the detergent employed in the washing process is from 5.0 to 6.0.
In some embodiments of the invention, in step (a), the detergent employed in the washing process comprises the raffinate of step (B).
In some embodiments of the invention, the pH of the raffinate is from 5.0 to 6.0; in the raffinate, the total concentration of Co and Ni is 3-5 g/L, the concentration of Mg is 5-10 g/L, and the concentration of Na is 45-60 g/L.
In some embodiments of the invention, in step (a), the temperature of the wash is 45-60 ℃; the liquid-solid ratio of the washing is 3-5 mL/g, and the washing time is 1-3 h; typical but non-limiting, for example, the temperature of the wash is 45 ℃, 50 ℃, 55 ℃, or 60 ℃, etc.; the liquid-solid ratio of the washing is 3mL/g, 4mL/g or 5mL/g, etc.; the washing time is 1h, 1.5h, 2h, 2.5h or 3h, etc.
In some embodiments of the invention, in step (A), the pH of the post-wash liquor is from 7.5 to 8.5 and the total concentration of Ni and Co in the post-wash liquor is from 0.3 to 0.5g/L.
In the step (A) of the invention, the content of Mg in the washed cobalt-nickel intermediate product can be reduced by 30-40% compared with the content of Mg in the cobalt-nickel intermediate product.
In some embodiments of the invention, in step (B), decomposing comprises mixing the washed cobalt nickel intermediate, the acid solution, and the reducing agent.
In some embodiments of the invention, in step (B), the acid solution comprises sulfuric acid.
In some embodiments of the invention, in step (B), the reducing agent comprises at least one of sodium sulfite, sodium metabisulfite, and sulfur dioxide.
In some embodiments of the invention, in step (B), the chemical process comprises precipitation and/or displacement.
In some embodiments of the invention, in step (B), the separation by extraction comprises extraction, washing and stripping processes; preferably, liquid alkali soap is used for extraction; preferably, the extractant employed in the separation process of the extraction method comprises at least one of P204, P507 and C272. P204 minus Fe, al, zn, mn, cr, cd, ca, etc.; p507 or C272 separates Co, ni and Mg.
In the step (B), most Fe, al, cr, cd and other elements of the washed cobalt-nickel intermediate product can be removed by a decomposition and chemical impurity removal method; the solution after the chemical impurity removal method is extracted, and trace Fe, al, cr, cd and Ca, zn, mn, cu can be removed to obtain pure cobalt and nickel salt solution (i.e. solution containing nickel sulfate and/or cobalt sulfate).
In the method for recovering Mg from the cobalt-nickel intermediate product, the raffinate after Co and Ni metal extraction is used as a detergent in the washing process, and most of heavy metals Co and Ni in the raffinate are precipitated and returned to the raw slag while residual acid existing in the raffinate is consumed, so that the yield of the metal Co and Ni is ensured.
In some embodiments of the invention, in step (C), degreasing comprises subjecting the post-wash liquor to an adsorption treatment with an adsorption resin.
In some embodiments of the invention, in step (C), the adsorbent resin comprises one or more of a styrenic polymeric adsorbent resin, a styrene-divinylbenzene copolymer gel resin, a nonpolar macroporous adsorbent resin, a medium-sized macroporous adsorbent resin, and a low-sized macroporous adsorbent resin.
In some embodiments of the invention, in step (C), the ion exchange resin employed in the ion exchange process comprises one or more of a styrenic chelating resin, a free amine type resin, an epoxy type chelating resin, and an iminodiacetic acid type chelating resin.
In some embodiments of the invention, in step (C), the Co content in the post-ion-exchange wash solution is less than or equal to 0.001g/L and the Ni content is less than or equal to 0.0005g/L.
In some embodiments of the invention, in step (C), the cation in the post-ion exchanged post-wash liquor comprises Na + And Mg (magnesium) 2+ 。
The ion exchange is adopted to remove the weight of the solution, the ion exchange resin can separate most of Co, ni and Mg in the solution, the enrichment effect is good, the Co and Ni mixed solution with higher purity and concentration is obtained, the operation of the ion exchange is simple, the safety is good, the running cost is relatively low, and the yield of Co and Ni is further improved in the step.
In some specific embodiments of the present invention, in the step (C), the ion-exchanged ion exchange resin is resolved by using a sulfuric acid solution to obtain a resolved solution; then washing is carried out to obtain a washing liquid.
In some embodiments of the invention, the total concentration of Co and Ni in the analytical solution is 20-40 g/L, the concentration of Mg is less than or equal to 0.1g/L, H + The concentration of (C) is 1.0-2.0 mol/L.
The analysis liquid and the washing liquid in the step (B) are used for the dissolution step in the step (B), so that closed loop recycling is realized.
In some embodiments of the invention, in step (C), the dialysis crystallization comprises adding the post-ion-exchanged wash solution to an ethanol solution.
Evaporating mother liquor after the solvent-out crystallization by using distillation equipment to obtain volatile component ethanol, wherein the ethanol can be returned to the solvent-out crystallization step for recycling; the components which are difficult to volatilize can be discharged after being directly treated.
The washed solution after ion exchange is added into high-purity ethanol solution (for preventing ethanol from volatilizing) in a closed container by utilizing the property that sodium sulfate and magnesium sulfate are insoluble in ethanol, and sodium sulfate crystals and magnesium sulfate crystals are separated out. The magnesium sulfate and the sodium sulfate are purified and concentrated by utilizing the property of small solubility in ethanol.
Ethanol is adopted as a solvent-out crystallization reagent, and because the ethanol can be basically regarded as non-toxic, the safety of the ethanol is higher than that of other organic solvents, the boiling point of the ethanol is not high (78.3 ℃), the ethanol is easy to distill and remove, the recovery rate is high, the ethanol can be recycled, and the cost is low.
In some embodiments of the invention, in step (C), drying the mixed crystals of magnesium sulfate and sodium sulfate is further included.
In some embodiments of the present invention, in the step (D), after the dried mixed crystal of magnesium sulfate and sodium sulfate is dissolved, sodium hydroxide is added to react, mg in the solution is precipitated, pure magnesium hydroxide precipitate is obtained, and the magnesium hydroxide product is obtained after drying.
In some embodiments of the invention, in step (D), the sodium sulfate solution is subjected to bipolar membrane electrodialysis to obtain sodium hydroxide solution and sulfuric acid solution.
The sodium sulfate solution is treated by bipolar membrane electrodialysis, and the obtained sulfuric acid solution can be returned to the decomposition step in the step (B), and the obtained sodium hydroxide solution is used for mixing with mixed crystals of magnesium sulfate and sodium sulfate to precipitate magnesium hydroxide.
In some embodiments of the present invention, in the step (B), the source of the acid solution is divided into three parts, the first part is the resolving solution and the washing solution, the second part is the sulfuric acid obtained in the bipolar membrane electrodialysis process, and the third part is the concentrated sulfuric acid used when the recovered acid is insufficient.
Example 1
Referring to fig. 1, the method for recovering Mg from cobalt-nickel intermediate product provided in this embodiment includes the following steps:
1. washing the cobalt-nickel intermediate by adopting a detergent to obtain 480mL of washed liquid and 97.7g of washed cobalt-nickel intermediate;
the detergent is raffinate obtained in the step 4; the temperature is controlled to be 60 ℃ in the washing process, and the liquid-solid ratio of the detergent to the cobalt-nickel intermediate product is 5mL:1g, washing time is 2h.
2. Mixing the washed cobalt-nickel intermediate in the step 1, 500mL of acid solution and 7g of reducing agent, and reacting to obtain a mixed solution;
the sources of the acid solution are the resolving fluid and the washing fluid obtained in the step 5, the sulfuric acid solution obtained in the bipolar membrane electrodialysis process in the step 7 and the concentrated sulfuric acid which is used when the consumption of the acid is insufficient; the reducing agent is sodium metabisulfite.
3. Removing impurities from the mixed solution in the step 2 by adopting a chemical method to remove most Fe, al, cr, cd and other elements;
the chemical method for removing impurities comprises an oxidation precipitation method.
4. Separating and removing trace Fe, al, cr, cd and Ca, zn, mn, cu from the mixed solution subjected to impurity removal by a chemical method by using an extraction method to obtain pure nickel and cobalt sulfate solution;
the extraction agents adopted in the separation process of the extraction method are P204, P507 and C272; the extraction separation comprises extraction, washing and back extraction processes.
5. Removing oil from the washed liquid in the step 1 by using styrene-divinylbenzene copolymerized gel resin, then performing ion exchange by using styrene chelating resin ion exchange resin to remove heavy metals, adsorbing Co and Ni, wherein the Co content in the solution after ion exchange treatment is less than or equal to 0.001g/L, and the Ni content is less than or equal to 0.0005g/L; in the solution after ion exchange, the cation mainly comprises Na + And Mg (magnesium) 2+ ；
And (3) analyzing the resin adsorbed with the metal ions by utilizing sulfuric acid solution, and then washing to obtain analysis liquid and washing liquid, wherein the analysis liquid and the washing liquid in the step return to the step (2) and serve as a part of an acid solution source, so that closed-loop recycling is realized.
6. Adding 200mL of the solution obtained after ion exchange into 400mL of absolute ethanol solution in a closed container (the reactor is required to be the closed container for preventing ethanol from volatilizing), so as to obtain mixed crystals and mother liquor of magnesium sulfate and sodium sulfate; placing the mixed crystal of magnesium sulfate and sodium sulfate in a closed dryer for drying; evaporating the crystallized mother liquor by using distillation equipment to obtain volatile component ethanol for recycling; the components which are difficult to volatilize can be discharged after being directly treated.
7. Adding the dried magnesium sulfate and sodium sulfate mixed crystal into pure water, dissolving to obtain a mixed solution, controlling the concentration of sulfate radical in the mixed solution to be 2mol/L, then adding a sodium hydroxide solution at 40 ℃, adjusting the pH to be 11-12, precipitating Mg in the solution, and filtering to obtain pure magnesium hydroxide and sodium sulfate solution; treating the sodium sulfate solution by bipolar membrane electrodialysis to obtain about 2mol/L sulfuric acid solution and about 4mol/L sodium hydroxide solution; the sulfuric acid solution can be returned to step 2 for use and the sodium hydroxide solution is used to precipitate magnesium hydroxide.
Example 2
The method for recovering Mg from the cobalt-nickel intermediate product provided by the embodiment comprises the following steps:
1. washing the cobalt-nickel intermediate by adopting a detergent to obtain 380mL of washed liquid and 98.4g of washed cobalt-nickel intermediate;
the detergent is raffinate obtained in the step 4; the temperature is controlled to be 70 ℃ in the washing process, and the liquid-solid ratio of the detergent to the cobalt-nickel intermediate product is 4mL:1g, washing time is 2h.
2. Mixing the washed cobalt-nickel intermediate in the step 1, 400mL of acid solution and 8g of reducing agent, and reacting to obtain a mixed solution;
the sources of the acid solution are the resolving fluid and the washing fluid obtained in the step 5, the sulfuric acid solution obtained in the bipolar membrane electrodialysis process in the step 7 and the concentrated sulfuric acid which is used when the consumption of the acid is insufficient; the reducing agent is sodium metabisulfite.
3. Removing impurities from the mixed solution in the step 2 by adopting a chemical method to remove most Fe, al, cr, cd and other elements;
the chemical method for removing impurities comprises an oxidation precipitation method.
4. Separating and removing trace Fe, al, cr, cd and Ca, zn, mn, cu from the mixed solution subjected to impurity removal by a chemical method by using an extraction method to obtain pure nickel and cobalt sulfate solution;
the extraction agents adopted in the separation process of the extraction method are P204, P507 and C272; the separation of the extraction method comprises extraction, washing and back extraction processes.
5. Removing oil from the washed liquid in the step 1 by using styrene-divinylbenzene copolymerized gel resin, then performing ion exchange by using styrene chelating resin ion exchange resin to remove heavy metals, adsorbing Co and Ni, wherein the Co content in the solution after ion exchange treatment is less than or equal to 0.001g/L, and the Ni content is less than or equal to 0.0005g/L; in the solution after ion exchange, the cation mainly comprises Na + And Mg (magnesium) 2+ ；
And (3) analyzing the resin adsorbed with the metal ions by utilizing sulfuric acid solution, and then washing to obtain analysis liquid and washing liquid, wherein the analysis liquid and the washing liquid in the step return to the step (2) and serve as a part of an acid solution source, so that closed-loop recycling is realized.
6. Adding 300mL of the solution obtained after ion exchange into 400mL of absolute ethanol solution (a reactor is needed to be a closed container for preventing ethanol from volatilizing) in a closed container to obtain mixed crystals and mother liquor of magnesium sulfate and sodium sulfate; placing the mixed crystal of magnesium sulfate and sodium sulfate in a closed dryer for drying; evaporating the crystallized mother liquor by using distillation equipment to obtain volatile component ethanol for recycling; the components which are difficult to volatilize can be discharged after being directly treated.
7. Adding the dried magnesium sulfate and sodium sulfate mixed crystal into pure water, dissolving to obtain a mixed solution, controlling the concentration of sulfate radical in the mixed solution to be 2.2mol/L, then adding a sodium hydroxide solution at 50 ℃, adjusting the pH to be 11-12, precipitating Mg in the solution, and filtering to obtain pure magnesium hydroxide and sodium sulfate solution; treating the sodium sulfate solution by bipolar membrane electrodialysis to obtain about 2mol/L sulfuric acid solution and about 4mol/L sodium hydroxide solution; the sulfuric acid solution can be returned to step 2 for use and the sodium hydroxide solution is used to precipitate magnesium hydroxide.
Test example 1
The components and the contents thereof in each solution in each step of example 1 were tested, and the results are shown in tables 1, 2, 3 and 4.
The recovery rate of each step of example 1 was measured, and the results are shown in table 5. The recovery rate after ion exchange refers to the recovery rate of each metal in the liquid after washing after ion exchange. The recovery rate after Mg precipitation refers to the yield of Mg from the cobalt nickel intermediate.
TABLE 1
Figure BDA0003989077000000121
TABLE 2
Figure BDA0003989077000000122
TABLE 3 Table 3
Figure BDA0003989077000000123
TABLE 4 Table 4
Figure BDA0003989077000000124
TABLE 5
Figure BDA0003989077000000125
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. A method for recovering Mg from cobalt-nickel intermediate products, which is characterized by comprising the following steps:
(A) Washing the cobalt-nickel intermediate product to obtain a washed liquid and a washed cobalt-nickel intermediate product;
(B) Separating the washed cobalt-nickel intermediate by a decomposition method, a chemical method impurity removal method and an extraction method in sequence to obtain a solution containing nickel sulfate and/or cobalt sulfate and raffinate;
(C) The washed liquid is subjected to oil removal, ion exchange and elution crystallization in sequence to obtain a mixed crystal of magnesium sulfate and sodium sulfate;
(D) And after the mixed crystal of magnesium sulfate and sodium sulfate is dissolved, adding a sodium hydroxide solution to react, so as to obtain a magnesium hydroxide and sodium sulfate solution.
2. The method for recovering Mg from cobalt nickel intermediate according to claim 1, wherein in step (a), the pH of the washed detergent is 5.0 to 6.0;
preferably, the washed detergent comprises the raffinate in step (B).
3. The method for recovering Mg from cobalt nickel intermediate according to claim 1, wherein in step (a), the washing temperature is 45 to 60 ℃; the liquid-solid ratio of the washing is 3-5 mL/g, and the washing time is 1-3 h.
4. The method for recovering Mg from a cobalt nickel intermediate according to claim 1, wherein in step (a), the pH of the post-washing liquid is 7.5 to 8.5, and the total concentration of Ni and Co in the post-washing liquid is 0.3 to 0.5g/L.
5. The method of recovering Mg from a cobalt nickel intermediate according to claim 1, wherein in step (B), said decomposing comprises mixing said washed cobalt nickel intermediate, an acid solution and a reducing agent;
preferably, the acid solution comprises sulfuric acid;
preferably, the reducing agent comprises at least one of sodium sulfite, sodium metabisulfite and sulfur dioxide.
6. The method for recovering Mg from a cobalt nickel intermediate according to claim 1, wherein in step (C), said degreasing includes subjecting said post-washing liquid to an adsorption treatment with an adsorption resin.
7. The method for recovering Mg from cobalt nickel intermediate according to claim 6, wherein in step (C), said adsorbent resin comprises one or more of a styrene-based polymeric adsorbent resin, a styrene-divinylbenzene copolymer gel-type resin, a nonpolar macroporous adsorbent resin, a medium-sized macroporous adsorbent resin, and a weakly polar macroporous adsorbent resin.
8. The method for recovering Mg from cobalt nickel intermediate according to claim 1, wherein in step (C), the ion-exchanged ion exchange resin comprises one or more of a styrene-based chelating resin, a free amine-based resin, an epoxy-based chelating resin, and an iminodiacetic acid-based chelating resin;
preferably, the Co content in the washing liquid after ion exchange is less than or equal to 0.001g/L, and the Ni content is less than or equal to 0.0005g/L;
preferably, the cation in the post-ion-exchange washing liquid comprises Na + And Mg (magnesium) 2+ 。
9. The method for recovering Mg from a cobalt nickel intermediate according to claim 1, wherein in step (C), said elution crystallization comprises adding said post-ion-exchanged washed liquid to an ethanol solution.
10. The method for recovering Mg from cobalt nickel intermediate according to claim 1, wherein in step (D), the sodium sulfate solution is subjected to bipolar membrane electrodialysis to obtain a sodium hydroxide solution and a sulfuric acid solution.
CN202211575120.5A 2022-12-08 2022-12-08 Method for recovering Mg from cobalt-nickel intermediate product Pending CN116219171A (en)

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