CN113461071A - Method for preparing nickel-zinc ferrite from waste nickel-hydrogen waste battery - Google Patents
Method for preparing nickel-zinc ferrite from waste nickel-hydrogen waste battery Download PDFInfo
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- CN113461071A CN113461071A CN202110649397.7A CN202110649397A CN113461071A CN 113461071 A CN113461071 A CN 113461071A CN 202110649397 A CN202110649397 A CN 202110649397A CN 113461071 A CN113461071 A CN 113461071A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B7/007—Wet processes by acid leaching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries, which comprises the following steps: firstly, weighing three minerals of nickel-hydrogen waste batteries, zinc oxide mineral powder and scrap iron after dealkalization roasting according to the mass ratio of nickel, zinc and iron in the product nickel-zinc ferrite, adding the three raw materials and a sulfuric acid solution with a certain concentration into a leaching tank, and stirring and leaching; and step two, filtering the leached ore pulp in the step one to respectively obtain filter residues and leachate, washing the filter residues and then piling up the filter residues, and returning washing water to the leaching process. The method for directly preparing the nickel-zinc ferrite from the waste nickel-metal hydride batteries has the advantages of advanced process, high leaching rates of valuable metals of nickel, zinc and iron, low cost, high-efficiency utilization of iron and shortened process flow.
Description
Technical Field
The invention relates to the technical field of preparation methods of nickel-zinc ferrite, in particular to a method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries.
Background
The soft magnetic ferrite is a nonmetal magnetic material which is most widely applied in ferrite and has the largest production capacity, and is mainly characterized by high resistivity, lower residual magnetic flux density and coercive force and good high-frequency property. Nickel zinc ferrite is one of soft magnetic ferrites, which has the advantages of excellent high frequency characteristics, good temperature stability, large nonlinearity, and the like, compared with the most commonly used manganese zinc ferrite. The high-frequency resonant transformer is widely applied to medium-frequency transformers, magnetic heads, short-wave antenna rods, tuning inductance reactors and magnetic saturation amplifiers. At present, the mainstream production process of the nickel-zinc ferrite comprises an oxide method (ceramic method) and a chemical coprecipitation method:
1. the oxide method uses metal oxide or easily decomposed metal salt as raw materials, firstly mixes various materials according to a product formula, puts the weighed raw materials into a ball milling tank for ball milling and mixing, presinteres the uniformly mixed powder at a temperature lower than the sintering temperature to generate a preliminary solid phase reaction, and then carries out ball milling mixing, granulation, molding, sintering and grinding on the presintered sample to obtain the nickel-zinc ferrite product. The method is mature, has the advantages of wide raw material source, small equipment investment, simple process and the like, is the method for preparing the soft magnetic ferrite which is developed most mature at the earliest application, and has the following defects: the raw materials are mixed in a granular form, the raw materials are difficult to be mixed uniformly, the granules greatly influence the solid phase reaction,
2. the chemical coprecipitation method is to dissolve pure metal or pure metal compound as raw material in acid or alkali to form nitrate, sulfate or hydroxide solution of metal, after filtering, measure solution according to formula proportion and mix. Adding proper precipitant to coprecipitate metal ions, filtering and roasting to form coprecipitate material, and pre-sintering, ball milling, granulating, molding, sintering and grinding the coprecipitate sample to obtain the nickel-zinc ferrite product. The precipitates obtained by the method are mixed in a molecular or ionic state, are uniform in uniformity and good in activity, and can be used for preparing high-performance soft magnetic ferrite materials. But the method has higher production cost compared with the oxide method;
in conclusion, the oxide method of the nickel-zinc ferrite has the defects of high reaction temperature, difficult uniform mixing of materials, large powder particles, difficult sintering, poor activity, large pollution and the like; the chemical coprecipitation method of nickel-zinc ferrite has the defects of high production cost and the like due to the requirement of pure metal or metal compound as raw materials. Therefore, the research and development of a new method for directly preparing the manganese-zinc ferrite by taking the waste batteries as raw materials have very important significance for overcoming the problems in the existing manganese-zinc ferrite preparation process.
Disclosure of Invention
The invention provides a method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries, which aims to solve the problems in the background art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries comprises the following steps:
firstly, weighing three minerals of nickel-hydrogen waste batteries, zinc oxide mineral powder and scrap iron after dealkalization roasting according to the mass ratio of nickel, zinc and iron in the product nickel-zinc ferrite, adding the three raw materials and a sulfuric acid solution with a certain concentration into a leaching tank, and stirring and leaching;
step two, filtering the leached ore pulp in the step one to respectively obtain filter residues and leachate, washing the filter residues and then piling the filter residues, and returning washing water to the leaching process; leaching rare earth metals in the nickel-metal hydride battery into a solution, firstly recovering the rare earth metals in the solution, and adding ammonium sulfate into filtrate to precipitate rare earth metals;
thirdly, purifying and decontaminating the solution after recovering the rare earth, and obtaining a sulfate double salt precipitate through two steps of primary purification and deep purification in the purification process;
and fourthly, adding a sulfuric acid solution into the double-salt sulfate precipitate for dissolving, simultaneously adding a certain amount of pure nickel sulfate, zinc sulfate and ferrous sulfate solution according to the proportion of nickel, zinc and iron of the nickel-zinc ferrite product, then adding slightly excessive ammonium oxalate for coprecipitation to obtain oxalate precipitates of nickel, zinc and iron, and finally washing and drying the oxalate precipitates of nickel, zinc and iron to obtain the product.
As a further improvement scheme of the technical scheme: in the first step, the leaching conditions are controlled as follows: the liquid-solid ratio is 3-10: 1.
As a further improvement scheme of the technical scheme: in the first step, the leaching conditions are controlled as follows: the initial sulfuric acid concentration is 100g/L to 600 g/L.
As a further improvement scheme of the technical scheme: in the first step, the leaching conditions are controlled as follows: the time is 0.5h-5.0 h.
As a further improvement scheme of the technical scheme: in the first step, the leaching conditions are controlled as follows: the temperature is controlled between 40 ℃ and 100 ℃.
As a further improvement scheme of the technical scheme: in the first step, the leaching conditions are controlled as follows: the stirring speed is 300r/min-700 r/min.
As a further improvement scheme of the technical scheme: in the second step, the control conditions of adding ammonium sulfate into the filtrate to precipitate rare earth are as follows: the temperature is 20-100 ℃, and the time is 0.5-4 h.
As a further improvement scheme of the technical scheme: in the second step, the control conditions of adding ammonium sulfate into the filtrate to precipitate rare earth are as follows: the molar ratio of the rare earth to the ammonium sulfate is 1: 2-10.
As a further improvement scheme of the technical scheme: in the third step, the primary purification is to firstly add lime milk as a neutralizer, neutralize until the pH of the solution is 2.0-6.0, control the temperature to be 30-95 ℃ and time to be 0.5-2 h, add a certain amount of flocculant PMA to remove silicon and aluminum, add a certain amount of ammonium sulfide to remove copper and cadmium, add a certain amount of ammonium fluoride to remove calcium, magnesium and rare earth, and further obtain purified liquid and slag respectively, wherein the slag is used for recovering rare earth.
As a further improvement scheme of the technical scheme: in the third step, the deep purification process is to add a certain amount of ammonium sulfate into the purified liquid, most of nickel, zinc and iron generate double sulfate salt precipitates, impurity elements are left in the solution, and most of impurities in the solution can be removed in the process.
Compared with the prior art, the invention has the beneficial effects that:
(1) the leaching rates of the valuable metals of nickel, zinc and iron are high. Compared with the traditional nickel-zinc ferrite preparation process, the invention takes the dealkalized and roasted waste nickel-hydrogen batteries, zinc oxide ores and scrap iron as raw materials, and takes the sulfuric acid solution as a leaching agent, so that the leaching rate of nickel and zinc is as high as more than 94 percent, the leaching rate of iron is as high as more than 90 percent, and the leaching rate of valuable metals such as nickel, zinc, iron and the like is high;
(2) changing waste into valuable and reducing the cost. Compared with the traditional oxide method and coprecipitation method for producing the nickel-zinc ferrite, the process takes the nickel-metal hydride waste battery as the raw material, belongs to the high-efficiency utilization of waste resources, has cheap and wide sources of the raw material, can simultaneously recover the rare earth metal in the nickel-metal hydride battery, and greatly reduces the production cost;
(3) high utilization of iron and short technological process. In the wet recovery process of the nickel-metal hydride battery, iron is used as a harmful impurity to avoid leaching into a solution as much as possible, the waste nickel-metal hydride battery is used as a raw material to produce nickel-zinc ferrite, and the iron is used as one of the raw materials to change the harmful impurity into a useful metal, so that the iron removal process is reduced, the economic benefit is increased, and the process flow is shortened;
in conclusion, the method for directly preparing the nickel-zinc ferrite from the waste nickel-metal hydride batteries has the advantages of advanced process, high leaching rates of valuable metals of nickel, zinc and iron, low cost, high-efficiency utilization of iron and shortened process flow.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings. The detailed description of the present invention is given in detail by the following examples and the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is a flow chart of a preferred embodiment of a method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries according to the present invention;
FIG. 2 is a process flow chart of a method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The invention is described in more detail in the following paragraphs by way of example with reference to the accompanying drawings. Advantages and features of the present invention will become apparent from the following description and from the claims. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When a component is referred to as being "connected" to another component, it can be directly connected to the other component or intervening components may also be present. When a component is referred to as being "disposed on" another component, it can be directly on the other component or intervening components may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1-2, in an embodiment of the present invention, a method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries is characterized by comprising the following steps:
firstly, weighing three minerals of nickel-hydrogen waste batteries, zinc oxide mineral powder and scrap iron after dealkalization roasting according to the mass ratio of nickel, zinc and iron in the product nickel-zinc ferrite, adding the three raw materials and a sulfuric acid solution with a certain concentration into a leaching tank, and stirring and leaching;
step two, filtering the leached ore pulp in the step one to respectively obtain filter residues and leachate, washing the filter residues and then piling the filter residues, and returning washing water to the leaching process; leaching rare earth metals in the nickel-metal hydride battery into a solution, firstly recovering the rare earth metals in the solution, and adding ammonium sulfate into filtrate to precipitate rare earth metals;
thirdly, purifying and decontaminating the solution after recovering the rare earth, and obtaining a sulfate double salt precipitate through two steps of primary purification and deep purification in the purification process;
and fourthly, adding a sulfuric acid solution into the double-salt sulfate precipitate for dissolving, simultaneously adding a certain amount of pure nickel sulfate, zinc sulfate and ferrous sulfate solution according to the proportion of nickel, zinc and iron of the nickel-zinc ferrite product, then adding slightly excessive ammonium oxalate for coprecipitation to obtain oxalate precipitates of nickel, zinc and iron, and finally washing and drying the oxalate precipitates of nickel, zinc and iron to obtain the product.
Preferably, in the first step, the leaching conditions are controlled as follows: the liquid-solid ratio is 3-10: 1.
Preferably, in the first step, the leaching conditions are controlled as follows: the initial sulfuric acid concentration is 100g/L to 600 g/L.
Preferably, in the first step, the leaching conditions are controlled as follows: the time is 0.5h-5.0 h.
Preferably, in the first step, the leaching conditions are controlled as follows: the temperature is controlled between 40 ℃ and 100 ℃.
Preferably, in the first step, the leaching conditions are controlled as follows: the stirring speed is 300r/min-700 r/min.
Preferably, in the second step, the control conditions of adding ammonium sulfate into the filtrate to precipitate rare earth are as follows: the temperature is 20-100 ℃, and the time is 0.5-4 h.
Preferably, in the second step, the control conditions of adding ammonium sulfate into the filtrate to precipitate rare earth are as follows: the molar ratio of the rare earth to the ammonium sulfate is 1: 2-10.
Preferably, in the third step, the preliminary purification is to firstly add lime milk as a neutralizer, neutralize until the pH of the solution is 2.0-6.0, control the temperature to be 30-95 ℃ and time to be 0.5-2 h, add a certain amount of flocculant PMA to remove silicon and aluminum, add a certain amount of ammonium sulfide to remove copper and cadmium, add a certain amount of ammonium fluoride to remove calcium, magnesium and rare earth, further obtain a purified liquid and slag respectively, and use the slag for recovering rare earth.
Preferably, in the third step, the deep purification process is to add a certain amount of ammonium sulfate into the purified solution, most of nickel, zinc and iron generate double sulfate salt precipitate, and impurity elements remain in the solution, so that most of impurities in the solution can be removed.
The following explains a method for preparing a precursor of a positive electrode material by using a waste ternary lithium battery according to the present invention by using a specific embodiment:
example 1
According to the formula Ni of nickel-zinc ferrite0.6Zn0.4Fe2O4Weighing three minerals of nickel-hydrogen waste batteries (Ni content 35.27%, Fe content 30.19%), zinc oxide concentrate (Zn content 50.62%) and iron filings (Fe content 96.78%) according to a certain proportion, adding the three minerals and a certain amount of sulfuric acid solution into a leaching tank, and controlling acid leaching conditions as follows: the leaching control conditions are as follows: liquid to solid ratio 6:1, firstThe concentration of the initial sulfuric acid is 500g/L, the time is 3.0h, the temperature is controlled at 90 ℃, and the stirring speed is 500 r/min. The leaching rates of nickel, zinc, iron and rare earth are 96.17%, 95.63%, 93.42% and 99.56%.
Filtering after acid leaching is finished, adding ammonium sulfate into filtrate to precipitate rare earth, and controlling the conditions as follows: the temperature is 60 ℃, the time is 1h, and the molar ratio of the rare earth to the ammonium sulfate is 1: 4. The rare earth precipitation rate is 92.31%. Adding lime milk as a neutralizer into the precipitated rare earth solution, neutralizing until the pH value of the solution is 4.5, controlling the temperature to be 80 ℃, reacting for 1h, adding a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide for primary impurity removal and purification, and adding ammonium sulfate into the solution after primary purification for deep purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.
Example 2
According to the formula Ni of nickel-zinc ferrite0.6Zn0.4Fe2O4Weighing three minerals of nickel-hydrogen waste batteries (Ni content 35.27%, Fe content 30.19%), zinc oxide concentrate (Zn content 50.62%) and iron filings (Fe content 96.78%) according to a certain proportion, adding the three minerals and a certain amount of sulfuric acid solution into a leaching tank, and controlling acid leaching conditions as follows: the leaching control conditions are as follows: the liquid-solid ratio is 10:1, the initial sulfuric acid concentration is 300g/L, the time is 2.0h, the temperature is controlled at 70 ℃, and the stirring speed is 800 r/min. The leaching rates of nickel, zinc, iron and rare earth are 94.63%, 96.83%, 91.79% and 99.54%.
Filtering after acid leaching is finished, adding ammonium sulfate into filtrate to precipitate rare earth, and controlling the conditions as follows: the temperature is 60 ℃, the time is 1.5h, and the molar ratio of the rare earth to the ammonium sulfate is 1: 6. The rare earth precipitation rate is 94.17%. Adding lime milk as a neutralizer into the precipitated rare earth solution, neutralizing until the pH value of the solution is 4.0, controlling the temperature to be 90 ℃, reacting for 1.5h, adding a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide for primary impurity removal and purification, and adding ammonium sulfate into the solution for deep purification after primary purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.
Example 3
According to the formula Ni of nickel-zinc ferrite0.6Zn0.4Fe2O4Weighing a certain ratioThe three minerals of the nickel-metal hydride waste battery (Ni content 39.74%, Fe content 27.31%), zinc oxide concentrate (Zn content 48.77%) and iron filings (Fe content 96.78%) are added into a leaching tank together with a certain amount of sulfuric acid solution, and the acid leaching conditions are controlled as follows: the leaching control conditions are as follows: the liquid-solid ratio is 8:1, the initial sulfuric acid concentration is 300g/L, the time is 2.5h, the temperature is controlled at 95 ℃, and the stirring speed is 700 r/min. The leaching rates of nickel, zinc, iron and rare earth are 95.73%, 97.18%, 92.48% and 99.37%.
Filtering after acid leaching is finished, adding ammonium sulfate into filtrate to precipitate rare earth, and controlling the conditions as follows: the temperature is 80 ℃, the time is 1.5h, and the molar ratio of the rare earth to the ammonium sulfate is 1: 6. The rare earth precipitation rate is 94.89%. Adding lime milk as a neutralizer into the precipitated rare earth solution, neutralizing until the pH value of the solution is 4.5, controlling the temperature at 70 ℃, reacting for 2 hours, adding a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide for primary impurity removal and purification, and adding ammonium sulfate into the solution after primary purification for deep purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.
Example 4
According to the formula Ni of nickel-zinc ferrite0.35Zn0.65Fe2O4Weighing three minerals of nickel-hydrogen waste batteries (Ni content 39.74%, Fe content 27.31%), zinc oxide concentrate (Zn content 48.77%) and iron filings (Fe content 96.78%) according to a certain proportion, adding the three minerals and a certain amount of sulfuric acid solution into a leaching tank, and controlling acid leaching conditions as follows: the leaching control conditions are as follows: the liquid-solid ratio is 6:1, the initial sulfuric acid concentration is 400g/L, the time is 4h, the temperature is controlled at 80 ℃, and the stirring speed is 600 r/min. The leaching rates of nickel, zinc, iron and rare earth are 96.34%, 97.75%, 93.53% and 99.68%.
Filtering after acid leaching is finished, adding ammonium sulfate into filtrate to precipitate rare earth, and controlling the conditions as follows: the temperature is 70 ℃, the time is 1h, and the molar ratio of the rare earth to the ammonium sulfate is 1: 5. The rare earth precipitation rate is 93.17%. Adding lime milk as a neutralizer into the precipitated rare earth solution, neutralizing until the pH value of the solution is 4.0, controlling the temperature at 60 ℃, reacting for 1.5h, adding a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide for primary impurity removal and purification, and adding ammonium sulfate into the solution for deep purification after primary purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.
Example 5
According to the formula Ni of nickel-zinc ferrite0.35Zn0.65Fe2O4Weighing three minerals of nickel-hydrogen waste batteries (Ni content 39.74%, Fe content 27.31%), zinc oxide concentrate (Zn content 48.77%) and iron filings (Fe content 96.78%) according to a certain proportion, adding the three minerals and a certain amount of sulfuric acid solution into a leaching tank, and controlling acid leaching conditions as follows: the leaching control conditions are as follows: the liquid-solid ratio is 10:1, the initial sulfuric acid concentration is 400g/L, the time is 3h, the temperature is controlled at 95 ℃, and the stirring speed is 600 r/min. The leaching rates of nickel, zinc, iron and rare earth are 97.51%, 98.26%, 94.77% and 99.72%.
Filtering after acid leaching is finished, adding ammonium sulfate into filtrate to precipitate rare earth, and controlling the conditions as follows: the temperature is 90 ℃, the time is 1.5h, and the molar ratio of the rare earth to the ammonium sulfate is 1: 6. The rare earth precipitation rate is 95.03%. Adding lime milk as a neutralizer into the precipitated rare earth solution, neutralizing until the pH value of the solution is 4.5, controlling the temperature at 70 ℃, reacting for 1h, adding a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide for primary impurity removal and purification, and adding ammonium sulfate into the solution after primary purification for deep purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.
The specific working principle of the invention is as follows:
taking dealkalized and roasted waste nickel-hydrogen batteries, zinc oxide ores and scrap iron as raw materials, weighing three raw materials according to a certain proportion according to a formula of nickel-zinc ferrite, and leaching by taking a sulfuric acid solution as a leaching agent. Mainly takes the following reaction (1) ZnO + H2SO4＝ZnSO4+H2O；
(2)Fe+H2SO4＝FeSO4+H2；
(3)2NiO(OH)+Fe+3H2SO4＝2NiSO4+FeSO4+4H2O；
(4)Ni(OH)2+H2SO4＝NiSO4+2H2O。
The leaching solution contains valuable metal ions of nickel, zinc and iron, and also contains impurities of rare earth, silicon, aluminum, copper, cadmium, cobalt, calcium, magnesium and the like, the leaching solution firstly needs to recover the rare earth, and then the impurities of copper, cadmium, silicon, aluminum, calcium, magnesium and the like are removed, and finally pure nickel, zinc and iron sulfate solution is obtained.
The leaching solution is firstly used for recovering rare earth, rare earth ions are easy to generate double sulfate precipitates, and ammonium sulfate can be added to preferentially and selectively precipitate and separate the rare earth. Purifying and removing impurities, firstly adding lime milk for neutralization and precipitation to remove silicon and aluminum, then adding ammonium sulfide for precipitation to remove copper and cadmium, then adding ammonium fluoride for precipitation to remove calcium and magnesium for primary purification, then obtaining pure nickel, zinc and iron sulfate solution through the deep purification process of sulfate double salt precipitation, and adding pure sulfate solution. The method for directly preparing the nickel-zinc ferrite from the waste nickel-hydrogen battery has the advantages of advanced process, high leaching rates of the valuable metals of nickel, zinc and iron, low cost, high efficiency utilization of iron and shortened process flow.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention may be readily implemented by those of ordinary skill in the art as illustrated in the accompanying drawings and described above; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries is characterized by comprising the following steps:
firstly, weighing three minerals of nickel-hydrogen waste batteries, zinc oxide mineral powder and scrap iron after dealkalization roasting according to the mass ratio of nickel, zinc and iron in the product nickel-zinc ferrite, adding the three raw materials and a sulfuric acid solution with a certain concentration into a leaching tank, and stirring and leaching;
step two, filtering the leached ore pulp in the step one to respectively obtain filter residues and leachate, washing the filter residues and then piling the filter residues, and returning washing water to the leaching process; leaching rare earth metals in the nickel-metal hydride battery into a solution, firstly recovering the rare earth metals in the solution, and adding ammonium sulfate into filtrate to precipitate rare earth metals;
thirdly, purifying and decontaminating the solution after recovering the rare earth, and obtaining a sulfate double salt precipitate through two steps of primary purification and deep purification in the purification process;
and fourthly, adding a sulfuric acid solution into the double-salt sulfate precipitate for dissolving, simultaneously adding a certain amount of pure nickel sulfate, zinc sulfate and ferrous sulfate solution according to the proportion of nickel, zinc and iron of the nickel-zinc ferrite product, then adding slightly excessive ammonium oxalate for coprecipitation to obtain oxalate precipitates of nickel, zinc and iron, and finally washing and drying the oxalate precipitates of nickel, zinc and iron to obtain the product.
2. The method for preparing the nickel-zinc ferrite from the waste nickel-hydrogen batteries according to claim 1, wherein in the first step, the leaching conditions are controlled as follows: the liquid-solid ratio is 3-10: 1.
3. The method for preparing the nickel-zinc ferrite from the waste nickel-hydrogen batteries according to claim 1, wherein in the first step, the leaching conditions are controlled as follows: the initial sulfuric acid concentration is 100g/L to 600 g/L.
4. The method for preparing the nickel-zinc ferrite from the waste nickel-hydrogen batteries according to claim 1, wherein in the first step, the leaching conditions are controlled as follows: the time is 0.5h-5.0 h.
5. The method for preparing the nickel-zinc ferrite from the waste nickel-hydrogen batteries according to claim 1, wherein in the first step, the leaching conditions are controlled as follows: the temperature is controlled between 40 ℃ and 100 ℃.
6. The method for preparing the nickel-zinc ferrite from the waste nickel-hydrogen batteries according to claim 1, wherein in the first step, the leaching conditions are controlled as follows: the stirring speed is 300r/min-700 r/min.
7. The method for preparing the nickel-zinc ferrite from the waste nickel-hydrogen batteries according to claim 1, wherein in the second step, the filtrate is added with ammonium sulfate to precipitate the rare earth under the control conditions that: the temperature is 20-100 ℃, and the time is 0.5-4 h.
8. The method for preparing the nickel-zinc ferrite from the waste nickel-hydrogen batteries according to claim 1, wherein in the second step, the filtrate is added with ammonium sulfate to precipitate the rare earth under the control conditions that: the molar ratio of the rare earth to the ammonium sulfate is 1: 2-10.
9. The method for preparing nickel-zinc ferrite from waste nickel-hydrogen waste batteries according to claim 1, wherein in the third step, the preliminary purification comprises the steps of firstly adding lime milk as a neutralizer, neutralizing until the pH of the solution is 2.0-6.0, controlling the temperature to be 30-95 ℃, controlling the time to be 0.5-2 h, adding a certain amount of flocculant PMA to remove silicon and aluminum, simultaneously adding a certain amount of ammonium sulfide to remove copper and cadmium, adding a certain amount of ammonium fluoride to remove calcium, magnesium and rare earth, further respectively obtaining a purified liquid and slag, and using the slag for recovering rare earth.
10. The method for preparing nickel-zinc ferrite from waste nickel-hydrogen batteries according to claim 1, wherein in the third step, the deep purification process comprises adding a certain amount of ammonium sulfate into the purified solution, most of nickel, zinc and iron generate double sulfate salt to precipitate, and impurity elements remain in the solution, so that most of impurities in the solution can be removed.
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| WO2024072435A1 (en) * | 2022-09-30 | 2024-04-04 | Ascend Elements, Inc. | Nickel-metal hydride (nimh) battery recycling |
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