CN113444880A - Method for preparing ternary precursor by pressure acid leaching - Google Patents

Method for preparing ternary precursor by pressure acid leaching Download PDF

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CN113444880A
CN113444880A CN202110647930.6A CN202110647930A CN113444880A CN 113444880 A CN113444880 A CN 113444880A CN 202110647930 A CN202110647930 A CN 202110647930A CN 113444880 A CN113444880 A CN 113444880A
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acid leaching
pressure
ternary precursor
nickel
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罗文波
罗勋
季登会
郑凯
张琼
周东波
洪开发
谢瑶
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Guizhou Institute of Technology
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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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/02—Apparatus therefor
    • 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
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B47/00—Obtaining manganese
    • 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 discloses a method for preparing a ternary precursor by pressure acid leaching, which comprises the following steps: firstly, weighing three raw materials of nickel sulfide concentrate, pyrolusite and roasted lithium cobaltate waste battery according to the mass ratio of nickel, cobalt and manganese in a ternary precursor, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and carrying out pressure heating and stirring; and step two, filtering the ore pulp obtained by the acid leaching under oxygen pressure in the step one to respectively obtain filter residues and leachate, washing the filter residues and piling up the filter residues, returning washing water to the acid leaching under oxygen pressure, and oxidizing bivalent iron in the leachate into trivalent iron. The method for preparing the manganese-zinc ferrite from the raw ore and the waste battery has the advantages of advanced process, high leaching rate of valuable metals of manganese, nickel and cobalt, low cost, simple and convenient operation, continuous production, small environmental pollution and high heat utilization rate. The invention is suitable for nickel sulfide concentrate, pyrolusite and waste lithium cobalt oxide batteries with various contents.

Description

Method for preparing ternary precursor by pressure acid leaching
Technical Field
The invention relates to the technical field of preparation methods of ternary precursors, in particular to a method for preparing a ternary precursor by pressure acid leaching.
Background
The ternary precursor material is nickel-cobalt-manganese hydroxide, and is a key material for producing the ternary lithium ion battery anode. The ternary cathode material has the advantages of low price, stable performance and the like, is widely applied, and along with the increase of the demand of the ternary lithium ion battery, the demand of the ternary precursor material is increased year by year, and the yield of China in 2020 is expected to reach 31 ten thousand tons. The mainstream production process of the ternary precursor is a chemical coprecipitation method, and the raw materials of the chemical coprecipitation method mainly comprise pure nickel, cobalt and manganese sulfates and the anode material of a waste ternary lithium ion battery.
1. Pure nickel, cobalt and manganese sulfates as raw materials. The method uses water to dissolve three sulfates according to a certain proportion, adjusts parameters such as solution concentration, pH value, reaction time, reaction temperature, stirring speed and the like, and can prepare ternary precursor materials with different granularities, morphologies, densities and crystallization degrees. The method is mature, has the advantages of low impurity content, high product quality, accurate control of the content of each component and the like, is the most mature method for preparing the soft magnetic ferrite with earliest application, and has high production cost by using pure substances as raw materials.
2. The waste ternary lithium ion anode material is used as a raw material. The method comprises the steps of leaching waste ternary lithium ion cathode materials by acid, leaching nickel, cobalt, manganese and other impurities into a solution, removing impurities such as iron, aluminum, silicon, copper, cadmium, calcium, magnesium and the like by an impurity removal process, and finally adding sodium hydroxide and ammonia water to precipitate a ternary precursor material. The method takes the ternary lithium ion anode material as a raw material, and can efficiently recycle waste to directly produce the ternary precursor material. But the method has the defects of high impurity content, low valuable metal leaching rate, large environmental pollution, long process flow and the like.
In summary, the preparation method of the ternary precursor by taking the pure sulfate as the raw material has the defect of high production cost, and the preparation method of the ternary precursor by taking the waste ternary lithium ion positive electrode material as the raw material has the defects of high impurity content, long process flow, low metal leaching rate, great environmental pollution and the like. Therefore, the research and development of a new method for preparing the ternary precursor by taking raw ore and waste battery as raw materials has very important significance for overcoming the problems in the conventional ternary precursor preparation process.
Disclosure of Invention
The invention provides a method for preparing a ternary precursor by pressure acid leaching, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a ternary precursor by pressure acid leaching comprises the following steps:
firstly, weighing three raw materials of nickel sulfide concentrate, pyrolusite and roasted lithium cobaltate waste battery according to the mass ratio of nickel, cobalt and manganese in a ternary precursor, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and carrying out pressure heating and stirring;
step two, filtering the ore pulp obtained by the acid leaching under oxygen pressure in the step one to respectively obtain filter residues and a leaching solution, washing the filter residues and piling up the filter residues, returning washing water to the acid leaching under oxygen pressure, oxidizing bivalent iron in the leaching solution into trivalent iron, and adding hydrogen peroxide into the filtrate for oxidation;
thirdly, purifying and decontaminating the solution in the second step, wherein the decontamination process is divided into a primary purification section and a deep purification section, the primary purification section is characterized in that lime milk is added into the solution as a neutralizer, the solution is neutralized until the pH value of the solution is 2.0-6.0, the temperature is controlled to be 25-100 ℃, the time is 0.5-2 h, a certain amount of flocculant PMA is added for removing iron, aluminum and silicon, a certain amount of ammonium sulfide is added for removing copper and cadmium, a certain amount of ammonium fluoride is added for removing calcium and magnesium, the obtained primary purified solution is subjected to deep purification, a certain amount of ammonium sulfate is added into the solution, most of nickel, cobalt and manganese generate double-salt sulfate precipitates, impurity elements are left in the solution, most of impurities in the solution can be removed in the process, the double-salt sulfate precipitates are added into a sulfuric acid solution for dissolving, and a certain amount of nickel sulfate, cobalt sulfate and manganese sulfate solution are added according to the proportion of nickel, cobalt and manganese of a ternary precursor of the product, and finally, adding sodium hydroxide and ammonia water for coprecipitation to obtain a ternary precursor of nickel, cobalt and manganese.
As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the liquid-solid ratio is 3-10: 1.
As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the initial sulfuric acid concentration is 100g/L to 500 g/L.
As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the time is 0.5h-4.0 h.
As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the temperature is controlled between 100 ℃ and 250 ℃.
As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the time is 0.5h-4 h.
As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are 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 oxidation reaction conditions are as follows: the dosage of the hydrogen peroxide is 1.2 to 4 times of the theoretical amount.
As a further improvement scheme of the technical scheme: in the second step, the oxidation reaction conditions are as follows: the temperature is 25-100 ℃, and the time is 0.5-4 h.
As a further improvement scheme of the technical scheme: in the second step, the oxidation reaction conditions are as follows: the stirring speed is 300r/min-700 r/min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the leaching rate of the valuable metals of nickel, cobalt and manganese is high, and the cost is low. Compared with the traditional ternary precursor preparation process, the method takes the nickel sulfide ore, pyrolusite and lithium cobaltate waste batteries as raw materials, and utilizes the advantages of high temperature, high pressure, strong oxidizing atmosphere and the like of the pressure acidification process, so that the leaching rate of nickel, cobalt and manganese is as high as more than 95%, and the leaching rate of valuable metals such as nickel, cobalt and manganese is high. Compared with the traditional oxide method and coprecipitation method, the process takes the raw ore as the source of nickel and manganese, the raw material is cheap and has wide source, and the production cost is greatly reduced.
(2) Simple operation, reduced labor intensity and continuous production. Compared with the traditional ternary precursor preparation process, the pressurized kettle of the oxygen pressure acid leaching process adopted by the invention basically realizes automation, so that the operation is simpler and more convenient, the labor intensity can be reduced, and the production continuity is realized.
(3) Little environmental pollution and high heat utilization rate. The reaction of the invention is carried out in a pressurized reaction kettle, no toxic and harmful gas is generated, and no environmental pollution is caused basically. The autoclave has good tightness, and is provided with a heat insulation sleeve, so that the heat dissipation is small. The traditional ternary precursor preparation process is open, a large amount of polluted gas is discharged, and heat is also dissipated greatly.
In conclusion, the method for preparing the manganese-zinc ferrite from the raw ore and the waste battery has the advantages of advanced process, high leaching rate of valuable metals of manganese, nickel and cobalt, low cost, simple and convenient operation, continuous production, small environmental pollution and high heat utilization rate. The invention is suitable for nickel sulfide concentrate, pyrolusite and waste lithium cobalt oxide batteries with various contents.
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 a ternary precursor by pressure acid leaching 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 a ternary precursor by pressure acid leaching includes the following steps:
firstly, weighing three raw materials of nickel sulfide concentrate, pyrolusite and roasted lithium cobaltate waste battery according to the mass ratio of nickel, cobalt and manganese in a ternary precursor, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and carrying out pressure heating and stirring;
step two, filtering the ore pulp obtained by the acid leaching under oxygen pressure in the step one to respectively obtain filter residues and a leaching solution, washing the filter residues and piling up the filter residues, returning washing water to the acid leaching under oxygen pressure, oxidizing bivalent iron in the leaching solution into trivalent iron, and adding hydrogen peroxide into the filtrate for oxidation;
thirdly, purifying and decontaminating the solution in the second step, wherein the decontamination process is divided into a primary purification section and a deep purification section, the primary purification section is characterized in that lime milk is added into the solution as a neutralizer, the solution is neutralized until the pH value of the solution is 2.0-6.0, the temperature is controlled to be 25-100 ℃, the time is 0.5-2 h, a certain amount of flocculant PMA is added for removing iron, aluminum and silicon, a certain amount of ammonium sulfide is added for removing copper and cadmium, a certain amount of ammonium fluoride is added for removing calcium and magnesium, the obtained primary purified solution is subjected to deep purification, a certain amount of ammonium sulfate is added into the solution, most of nickel, cobalt and manganese generate double-salt sulfate precipitates, impurity elements are left in the solution, most of impurities in the solution can be removed in the process, the double-salt sulfate precipitates are added into a sulfuric acid solution for dissolving, and a certain amount of nickel sulfate, cobalt sulfate and manganese sulfate solution are added according to the proportion of nickel, cobalt and manganese of a ternary precursor of the product, and finally, adding sodium hydroxide and ammonia water for coprecipitation to obtain a ternary precursor of nickel, cobalt and manganese.
Preferably, in the first step, the pressure acid leaching conditions are as follows: the liquid-solid ratio is 3-10: 1.
Preferably, in the first step, the pressure acid leaching conditions are as follows: the initial sulfuric acid concentration is 100g/L to 500 g/L.
Preferably, in the first step, the pressure acid leaching conditions are as follows: the time is 0.5h-4.0 h.
Preferably, in the first step, the pressure acid leaching conditions are as follows: the temperature is controlled between 100 ℃ and 250 ℃.
Preferably, in the first step, the pressure acid leaching conditions are as follows: the time is 0.5h-4 h.
Preferably, in the first step, the pressure acid leaching conditions are as follows: the stirring speed is 300r/min-700 r/min.
Preferably, in the second step, the oxidation reaction conditions are: the dosage of the hydrogen peroxide is 1.2 to 4 times of the theoretical amount.
Preferably, in the second step, the oxidation reaction conditions are: the temperature is 25-100 ℃, and the time is 0.5-4 h.
Preferably, in the second step, the oxidation reaction conditions are: the stirring speed is 300r/min-700 r/min.
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 ternary precursor formula Ni1/3Co1/3Mn1/3(OH)2Weighing three raw materials of nickel sulfide concentrate (5.37% of Ni and 30.63% of Fe), pyrolusite (32.41% of Zn and 8.35% of Fe) and roasted lithium cobaltate waste battery (45.48% of Co) according to a certain proportion, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and controlling the pressure acid leaching conditions as follows: the liquid-solid ratio is 6:1, the initial sulfuric acid concentration is 240g/L, the time is 2h, the temperature is controlled at 220 ℃, the pressure is 1.5MPa, and the stirring speed is 600 r/min. The leaching rates of nickel, cobalt, manganese and iron are respectively 98.56%, 95.17%, 96.43% and 70.27%.
Filtering the leached ore pulp, washing filter residues and piling up, returning washing water to the oxygen pressure acid leaching process, and oxidizing bivalent iron in the solution by using hydrogen peroxide as an oxidant. The oxidation conditions are controlled as follows: the dosage of the hydrogen peroxide is 1.5 times of the theoretical amount, the temperature is 90 ℃, the time is 2 hours, and the stirring speed is 600 r/min. The oxidation rate of ferrous iron in the solution is 98.42%, lime milk is firstly added into the oxidation solution as a neutralizer, the solution is neutralized until the pH value of the solution is 5.0, the temperature is controlled to be 70 ℃, the reaction time is 1.5h, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. And adding sodium hydroxide and ammonia water for coprecipitation after the solution preparation to obtain a ternary precursor of nickel, cobalt and manganese.
Example 2
Preparing Ni according to a ternary precursor1/3Co1/3Mn1/3(OH)2Weighing three raw materials of nickel sulfide concentrate (5.37% of Ni and 30.63% of Fe), pyrolusite (32.41% of Zn and 8.35% of Fe) and roasted lithium cobaltate waste battery (45.48% of Co) according to a certain proportion, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and controlling the pressure acid leaching conditions as follows: the liquid-solid ratio is 5:1, the initial sulfuric acid concentration is 180g/L, the time is 1.5h, the temperature is controlled at 180 ℃, the pressure is 0.8MPa, and the stirring speed is 600 r/min. The leaching rates of nickel, cobalt, manganese and iron are 93.19%, 94.56%, 96.24% and 12.37%, respectively.
Filtering the leached ore pulp, washing filter residues and piling up, returning washing water to the oxygen pressure acid leaching process, and oxidizing bivalent iron in the solution by using hydrogen peroxide as an oxidant. The oxidation conditions are controlled as follows: the dosage of the hydrogen peroxide is 2.0 times of the theoretical amount, the temperature is 95 ℃, the time is 1.5h, and the stirring speed is 600 r/min. The oxidation rate of ferrous iron in the solution is 97.38%, lime milk is firstly added into the oxidation solution as a neutralizer, the solution is neutralized until the pH value of the solution is 4.5, the temperature is controlled to be 60 ℃, the reaction time is 2 hours, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. And adding sodium hydroxide and ammonia water for coprecipitation after the solution preparation to obtain a ternary precursor of nickel, cobalt and manganese.
Example 3
According to the ternary precursor formula Ni1/3Co1/3Mn1/3(OH)2Weighing three raw materials of nickel sulfide concentrate (5.37% of Ni and 30.63% of Fe), pyrolusite (32.41% of Zn and 8.35% of Fe) and roasted lithium cobaltate waste battery (45.48% of Co) according to a certain proportion, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and controlling the pressure acid leaching conditions as follows: the liquid-solid ratio is 8:1, the initial sulfuric acid concentration is 200g/L, the time is 2.5h, and the temperature is controlled to be 180 DEGThe temperature is lower, the pressure is 1.2MPa, and the stirring speed is 600 r/min. The leaching rates of nickel, cobalt, manganese and iron are 96.55%, 95.82%, 98.36% and 85.06%, respectively.
Filtering the leached ore pulp, washing filter residues and piling up, returning washing water to the oxygen pressure acid leaching process, and oxidizing bivalent iron in the solution by using hydrogen peroxide as an oxidant. The oxidation conditions are controlled as follows: the dosage of the hydrogen peroxide is 1.5 times of the theoretical amount, the temperature is 80 ℃, the time is 2 hours, and the stirring speed is 600 r/min. The oxidation rate of ferrous iron in the solution is 95.84%, lime milk is firstly added into the oxidation solution as a neutralizer, the solution is neutralized until the pH value of the solution is 4.5, the temperature is controlled to be 80 ℃, the reaction time is 1.5h, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. And adding sodium hydroxide and ammonia water for coprecipitation after the solution preparation to obtain a ternary precursor of nickel, cobalt and manganese.
Example 4
According to the ternary precursor formula Ni1/2Co1/5Mn3/10(OH)2Weighing three raw materials of nickel sulfide concentrate (5.37% of Ni and 30.63% of Fe), pyrolusite (32.41% of Zn and 8.35% of Fe) and roasted lithium cobaltate waste battery (45.48% of Co) according to a certain proportion, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and controlling the pressure acid leaching conditions as follows: the liquid-solid ratio is 5:1, the initial sulfuric acid concentration is 250g/L, the time is 1.5h, the temperature is controlled at 200 ℃, the pressure is 1.5MPa, and the stirring speed is 600 r/min. The leaching rates of nickel, cobalt, manganese and iron are 97.27%, 96.35%, 97.42% and 64.68%, respectively.
Filtering the leached ore pulp, washing filter residues and piling up, returning washing water to the oxygen pressure acid leaching process, and oxidizing bivalent iron in the solution by using hydrogen peroxide as an oxidant. The oxidation conditions are controlled as follows: the dosage of the hydrogen peroxide is 2.5 times of the theoretical amount, the temperature is 70 ℃, the time is 2 hours, and the stirring speed is 600 r/min. The oxidation rate of ferrous iron in the solution is 98.15%, lime milk is firstly added into the oxidation solution as a neutralizer, the solution is neutralized until the pH value of the solution is 5.0, the temperature is controlled to be 90 ℃, the reaction time is 2 hours, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. And adding sodium hydroxide and ammonia water for coprecipitation after the solution preparation to obtain a ternary precursor of nickel, cobalt and manganese.
Example 5
According to the ternary precursor formula Ni1/2Co1/5Mn3/10(OH)2Weighing three raw materials of nickel sulfide concentrate (5.37% of Ni and 30.63% of Fe), pyrolusite (32.41% of Zn and 8.35% of Fe) and roasted lithium cobaltate waste battery (45.48% of Co) according to a certain proportion, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and controlling the pressure acid leaching conditions as follows: the liquid-solid ratio is 6:1, the initial sulfuric acid concentration is 160g/L, the time is 2.0h, the temperature is controlled at 200 ℃, the pressure is 1.5MPa, and the stirring speed is 600 r/min. The leaching rates of nickel, cobalt, manganese and iron are 94.36%, 95.24%, 96.62% and 16.17%, respectively.
Filtering the leached ore pulp, washing filter residues and piling up, returning washing water to the oxygen pressure acid leaching process, and oxidizing bivalent iron in the solution by using hydrogen peroxide as an oxidant. The oxidation conditions are controlled as follows: the dosage of the hydrogen peroxide is 2.0 times of the theoretical amount, the temperature is 90 ℃, the time is 1.5h, and the stirring speed is 600 r/min. The oxidation rate of ferrous iron in the solution is 97.44%, lime milk is firstly added into the oxidation solution as a neutralizer, the solution is neutralized until the pH value of the solution is 4.5, the temperature is controlled to be 60 ℃, the reaction time is 2 hours, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. And adding sodium hydroxide and ammonia water for coprecipitation after the solution preparation to obtain a ternary precursor of nickel, cobalt and manganese.
The working principle of the invention is as follows:
controlling the temperature to be 100-250 ℃ and the pressure to be 0.4-2.0 MPa, and carrying out proper pressure acid leaching to ensure that valuable metals such as nickel, cobalt and manganese in the raw material nickel sulfide concentrate, pyrolusite and lithium cobaltate waste battery are leached into the solution, and simultaneously controlling the leaching of iron in the raw material to ensure that the leached iron is precipitated into slag. Mainly takes place by the reaction of (1) NiS +1/2O2+H2SO4＝NiSO4+S+H2O；
(2)FeS+1/2O2+H2SO4＝FeSO4+S+H2O；
(3)NiS+MnO2+2H2SO4＝ZnSO4+MnSO4+S+H2O；
(4)FeS+MnO2+2H2SO4＝FeSO4+MnSO4+S+H2O；
(5)4FeSO4+O2+2H2SO4＝2Fe2(SO4)3+2H2O；
(6)2LiCoO2+NiS+4H2SO4＝2CoSO4+Li2SO4+NiSO4+S+2H2O；
(7)2LiCoO2+FeS+4H2SO4＝2CoSO4+Li2SO4+FeSO4+S+2H2And O. And then using hydrogen peroxide as an oxidant, and oxidizing ferrous ions in the leaching solution into ferric ions, so that the iron can be removed in the subsequent neutralization and precipitation process. The oxidized solution contains valuable metal ions of nickel, cobalt and manganese, and also contains impurities of iron, silicon, aluminum, copper, cadmium, calcium, magnesium and the like, lime milk is firstly added into the oxidized solution to neutralize and precipitate the solution to remove iron, aluminum and silicon, ammonium sulfide is then added to precipitate the solution to remove copper and cadmium, ammonium fluoride is then added to precipitate the solution to remove calcium and magnesium for primary purification, finally, the deep purification process of sulfate precipitation is carried out to obtain pure nickel, cobalt and manganese sulfate solution, and pure sulfate solution is added. Adding a precipitator ammonium oxalate into the prepared solution to obtain coprecipitated powder of nickel, cobalt and manganese, and washing and roasting the precipitate to obtain the ternary precursor of the product.
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. The method for preparing the ternary precursor by using the pressurized acid leaching is characterized by comprising the following steps of:
firstly, weighing three raw materials of nickel sulfide concentrate, pyrolusite and roasted lithium cobaltate waste battery according to the mass ratio of nickel, cobalt and manganese in a ternary precursor, adding the three raw materials and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and carrying out pressure heating and stirring;
step two, filtering the ore pulp obtained by the acid leaching under oxygen pressure in the step one to respectively obtain filter residues and a leaching solution, washing the filter residues and piling up the filter residues, returning washing water to the acid leaching under oxygen pressure, oxidizing bivalent iron in the leaching solution into trivalent iron, and adding hydrogen peroxide into the filtrate for oxidation;
thirdly, purifying and decontaminating the solution in the second step, wherein the decontamination process is divided into a primary purification section and a deep purification section, the primary purification section is characterized in that lime milk is added into the solution as a neutralizer, the solution is neutralized until the pH value of the solution is 2.0-6.0, the temperature is controlled to be 25-100 ℃, the time is 0.5-2 h, a certain amount of flocculant PMA is added for removing iron, aluminum and silicon, a certain amount of ammonium sulfide is added for removing copper and cadmium, a certain amount of ammonium fluoride is added for removing calcium and magnesium, the obtained primary purified solution is subjected to deep purification, a certain amount of ammonium sulfate is added into the solution, most of nickel, cobalt and manganese generate double-salt sulfate precipitates, impurity elements are left in the solution, most of impurities in the solution can be removed in the process, the double-salt sulfate precipitates are added into a sulfuric acid solution for dissolving, and a certain amount of nickel sulfate, cobalt sulfate and manganese sulfate solution are added according to the proportion of nickel, cobalt and manganese of a ternary precursor of the product, and finally, adding sodium hydroxide and ammonia water for coprecipitation to obtain a ternary precursor of nickel, cobalt and manganese.
2. The method for preparing the ternary precursor by pressure acid leaching according to claim 1, wherein the conditions of the pressure acid leaching in the first step are as follows: the liquid-solid ratio is 3-10: 1.
3. The method for preparing the ternary precursor by pressure acid leaching according to claim 1, wherein the conditions of the pressure acid leaching in the first step are as follows: the initial sulfuric acid concentration is 100g/L to 500 g/L.
4. The method for preparing the ternary precursor by pressure acid leaching according to claim 1, wherein the conditions of the pressure acid leaching in the first step are as follows: the time is 0.5h-4.0 h.
5. The method for preparing the ternary precursor by pressure acid leaching according to claim 1, wherein the conditions of the pressure acid leaching in the first step are as follows: the temperature is controlled between 100 ℃ and 250 ℃.
6. The method for preparing the ternary precursor by pressure acid leaching according to claim 1, wherein the conditions of the pressure acid leaching in the first step are as follows: the time is 0.5h-4 h.
7. The method for preparing the ternary precursor by pressure acid leaching according to claim 1, wherein the conditions of the pressure acid leaching in the first step are as follows: the stirring speed is 300r/min-700 r/min.
8. The method for preparing ternary precursor by pressure acid leaching according to claim 1, wherein in the second step, the oxidation reaction conditions are as follows: the dosage of the hydrogen peroxide is 1.2 to 4 times of the theoretical amount.
9. The method for preparing ternary precursor by pressure acid leaching according to claim 1, wherein in the second step, the oxidation reaction conditions are as follows: the temperature is 25-100 ℃, and the time is 0.5-4 h.
10. The method for preparing ternary precursor by pressure acid leaching according to claim 1, wherein in the second step, the oxidation reaction conditions are as follows: the stirring speed is 300r/min-700 r/min.
CN202110647930.6A 2021-06-10 2021-06-10 Method for preparing ternary precursor by pressure acid leaching Pending CN113444880A (en)

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Application publication date: 20210928