CN109650458B - Preparation method and application of battery-grade manganese sulfate - Google Patents
Preparation method and application of battery-grade manganese sulfate Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention belongs to the technical field of hydrometallurgy, and relates to a preparation method and application of battery-grade manganese sulfate. The preparation method of the battery-grade manganese sulfate comprises the following steps: (A) precipitating copper ions, calcium ions and zinc ions in the copper-manganese chloride solution to obtain a first filtrate; (B) mixing the first filtrate, a manganese precipitation agent and a base solution under a protective atmosphere, performing manganese precipitation reaction, and performing solid-liquid separation to obtain manganese hydroxide; (C) mixing the manganese hydroxide with concentrated sulfuric acid, carrying out neutralization reaction to obtain crude manganese sulfate, and refining to obtain battery-grade manganese sulfate; wherein, in the step (B), the manganese precipitation agent comprises ammonia water; the base solution comprises ammonia water and soluble hydroxide. The method can realize the preparation of the battery-grade manganese sulfate, is beneficial to the respective recovery of zinc, copper, calcium and the like, realizes the maximum utilization of the copper-manganese chloride waste liquid, reduces the cost and conforms to the concept of sustainable development.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a preparation method and application of battery-grade manganese sulfate.
Background
Due to the wide use of the nickel cobalt lithium manganate cathode material in the lithium ion battery, the demand of battery-grade manganese sulfate is increasing. The existing preparation method of the battery-grade manganese sulfate is complex in process, so that the cost of the battery-grade manganese sulfate product is higher.
The wet extraction process of cobalt produces a waste liquid mainly containing copper and manganese, which is called copper-manganese chloride liquid, is a waste acid liquid with high recovery value, and can be used as a raw material for recovering battery-grade manganese sulfate.
In the prior art, a method for preparing battery-grade manganese sulfate by using copper-manganese chloride solution as a raw material is available. However, in the prior art, some preparation methods have weak reaction participation due to the homoionic effect, so that more manganese sulfide is needed to achieve the same precipitation effect, and the cost is high. In some preparation methods, when copper, cobalt and zinc ions in a sodium sulfide precipitation solution are used, the precipitation slag can be mixed with a plurality of ions, so that the precipitation slag is difficult to recover the ions in the subsequent ion recovery process.
In view of this, the present invention is particularly proposed to solve at least one of the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a preparation method of battery-grade manganese sulfate, which realizes one-by-one separation of other metal ions in copper chloride manganese solution while preparing the battery-grade manganese sulfate.
The second purpose of the invention is to provide an application of the preparation method of the battery-grade manganese sulfate in preparation of the lithium ion battery cathode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to one aspect of the invention, a preparation method of battery-grade manganese sulfate is provided, which comprises the following steps:
(A) precipitating copper ions, calcium ions and zinc ions in the copper-manganese chloride solution to obtain a first filtrate;
(B) mixing the first filtrate, a manganese precipitation agent and a base solution under a protective atmosphere, performing manganese precipitation reaction, and performing solid-liquid separation to obtain manganese hydroxide;
(C) mixing the manganese hydroxide with concentrated sulfuric acid, carrying out neutralization reaction to obtain crude manganese sulfate, and refining to obtain battery-grade manganese sulfate;
wherein, in the step (B), the manganese precipitation agent comprises ammonia water;
the base solution comprises ammonia water and soluble hydroxide.
As a further preferable technical scheme, in the step (B), the ammonia content of the base solution is 5-8g/L, preferably 6-7 g/L;
preferably, in step (B), the pH of the manganese precipitation reaction is 10.5-10.8, preferably 10.6-10.7.
As a further preferable technical scheme, in the step (B), the manganese precipitation agent is ammonia water and hydroxide solution;
preferably, in the step (B), the concentration of ammonia water in the manganese precipitation agent is 6-10mol/L, and more preferably 7-8 mol/L;
preferably, in the step (B), the concentration of the hydroxide solution in the manganese precipitation agent is 8-12mol/L, and more preferably 8-10 mol/L.
As a further preferred embodiment, the soluble hydroxide comprises sodium hydroxide.
As a further preferable technical solution, in the step (C), the refining includes recrystallization, and the temperature of the recrystallization is 70 to 100 ℃, preferably 80 to 90 ℃;
preferably, the recrystallization time is 1 to 4 hours, preferably 2 to 3 hours.
As a further preferable technical solution, the method for preparing the first filtrate comprises the steps of:
(A1) mixing the copper-manganese chloride solution with soluble sulfate, performing primary calcium precipitation reaction, adding a copper-calcium precipitation agent, performing copper precipitation reaction and secondary calcium precipitation reaction, and performing solid-liquid separation to obtain copper-calcium slag and a copper-calcium precipitation solution;
(A2) mixing the solution after copper and calcium precipitation with soluble fluoride salt, performing three calcium precipitation reactions, and performing solid-liquid separation to obtain calcium slag and a solution after three calcium precipitation;
(A3) and mixing the liquid after the three times of calcium precipitation with soluble sulfide, performing zinc precipitation reaction, and performing solid-liquid separation to obtain a first filtrate.
As a further preferred technical solution, in the step (a1), the soluble sulfate includes any one or a combination of at least two of sodium sulfate, potassium sulfate, or ammonium sulfate, preferably sodium sulfate;
preferably, in the step (A1), the soluble sulfate is used in an amount of 80-130g/L, preferably 90-110 g/L;
preferably, in the step (a1), the pH value of the primary calcium precipitation reaction is 2.5 to 3.5, and more preferably 2.8 to 3.2;
preferably, in the step (a1), the pH value of the copper precipitation reaction and the secondary calcium precipitation reaction is 5.0-5.5;
preferably, in the step (a1), the copper-calcium precipitating agent comprises soluble hydroxide and/or soluble carbonate;
preferably, in step (a1), the soluble hydroxide comprises sodium hydroxide and/or potassium hydroxide;
preferably, in step (a1), the soluble carbonate salt comprises sodium carbonate and/or ammonium bicarbonate;
preferably, in the step (A1), the time of the primary calcium precipitation reaction is 1-5h, preferably 2-4 h.
As a further preferred technical solution, in the step (a2), the soluble fluoride includes any one or a combination of at least two of sodium fluoride, potassium fluoride or ammonium fluoride, preferably sodium fluoride and/or ammonium fluoride;
preferably, in the step (A2), the dosage of the soluble fluoride is 8-10 times of the mass of calcium ions in the solution after copper and calcium deposition;
preferably, in the step (A2), the pH value of the third calcium precipitation reaction is 5.0-6.0;
preferably, the pH in step (a2) is adjusted using a basic substance comprising any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium bicarbonate or ammonium bicarbonate, preferably sodium carbonate and/or ammonium bicarbonate;
preferably, in the step (A2), the time of the third calcium precipitation reaction is 2-6h, preferably 3-5 h;
preferably, in step (A2), the temperature of the third calcium precipitation is 70-90 ℃, preferably 80-85 ℃.
As a further preferable mode, in the step (a3), the soluble sulfide includes any one or a combination of at least two of sodium sulfide, potassium sulfide, and ammonium sulfide;
preferably, in step (A3), the concentration of the soluble sulfide is 100-150g/L, preferably 120-130 g/L;
preferably, in the step (A3), the dosage of the soluble sulfide is 3-5 times of the mass of zinc ions in the copper manganese chloride solution;
preferably, in the step (A3), the time of the zinc precipitation reaction is 8-24h, preferably 10-20 h;
preferably, in the step (A3), the temperature of the zinc precipitation reaction is 20-50 ℃, preferably 30-40 ℃.
According to another aspect of the invention, the application of the preparation method of the battery-grade manganese sulfate in the preparation of the lithium ion battery cathode material is provided.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the battery-grade manganese sulfate, provided by the invention, the characteristic that ammonium ions ionized by ammonia water can be complexed with various metals is fully utilized, trace Co, Cu and Zn which are not precipitated before are subjected to complexing reaction with the ammonium ions in a manganese precipitation reaction and are retained in a solution, so that the double effects of generating manganese hydroxide and removing impurities are realized, the purity of the final product manganese sulfate is ensured, and the process of extracting and removing impurities is reduced.
2. The preparation method of the battery-grade manganese sulfate provided by the invention not only can realize the preparation of the battery-grade manganese sulfate, but also can realize the one-by-one separation of other metal ions in the copper chloride manganese solution, is beneficial to the respective recovery of zinc, copper, calcium and the like, realizes the maximum utilization of the copper chloride manganese waste solution, reduces the cost and conforms to the concept of sustainable development.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In a first aspect, there is provided in at least one embodiment a method of preparing battery grade manganese sulfate, comprising the steps of:
(A) precipitating copper ions, calcium ions and zinc ions in the copper-manganese chloride solution to obtain a first filtrate;
(B) mixing the first filtrate, a manganese precipitation agent and a base solution under a protective atmosphere, performing manganese precipitation reaction, and performing solid-liquid separation to obtain manganese hydroxide;
(C) mixing manganese hydroxide and concentrated sulfuric acid, performing neutralization reaction to obtain crude manganese sulfate, and refining to obtain battery-grade manganese sulfate;
wherein, in the step (B), the manganese precipitation agent comprises ammonia water;
the base solution comprises ammonia and soluble hydroxide.
According to the preparation method of the battery-grade manganese sulfate, provided by the invention, the characteristic that ammonium ions ionized by ammonia water can be complexed with various metals is fully utilized, and trace Co, Cu and Zn which are not precipitated before are subjected to complexing reaction with the ammonium ions in a manganese precipitation reaction and are retained in a solution, so that the double effects of generating manganese hydroxide and removing impurities are realized.
The invention mainly aims at the problem that non-manganese ions in the copper-manganese chloride liquid are difficult to recover independently in the prior art, and provides a preparation method which can realize one-by-one separation of other metal ions in the copper-manganese chloride liquid while obtaining battery-grade manganese sulfate, so that the utilization of the copper-manganese chloride waste liquid is maximized, the cost is reduced, and the concept of sustainable development is met.
The copper-manganese chloride solution is a backwashing waste acid solution after extraction and impurity removal in the extraction process of the cobalt raw material, and usually contains metal ions such as calcium, copper, zinc, manganese and the like.
The preparation process of the base solution comprises the following steps: mixing ammonia water and soluble hydroxide solution in a certain proportion, and regulating the ammonia content and pH value of the base solution within a certain range.
The 'bottom solution' is used for complexing impurity ions in the solution to prevent the impurities from precipitating, and simultaneously, a stable environment can be provided for the manganese precipitation reaction to ensure that the manganese ions are uniformly precipitated. If the base solution is not added, the local manganese hydroxide can be rapidly precipitated, and other trace impurity ions are clamped in the local manganese hydroxide to be precipitated, so that the purity of the subsequent manganese sulfate is influenced.
Since manganese hydroxide is easily oxidized in air, the manganese precipitation reaction needs to be performed under a protective atmosphere. For example: nitrogen or argon can be introduced into the vessel in which the manganese precipitation reaction is carried out to provide a protective environment.
The ammonia water in the manganese precipitation agent can be partially ionized in the solution to generate ammonium ions and hydroxide ions. The ammonium ions and a small amount of residual Co, Zn and Cu ions in the first filtrate are subjected to a complex reaction and are retained in the solution; the hydroxyl ions react with Mn ions in the first filtrate to generate manganese hydroxide which is precipitated. And (3) carrying out neutralization reaction on the manganese hydroxide to generate crude manganese sulfate, and refining the crude manganese sulfate to finally obtain the battery-grade manganese sulfate.
In addition, the intermediate product manganese hydroxide in the preparation process is directly mixed with concentrated sulfuric acid without being dried after being washed, heat generated in the dissolving process can be utilized in the subsequent evaporation and crystallization process, additional heating is not needed, and the production cost is reduced.
In a preferred embodiment, the ammonia content of the base solution is from 5 to 8g/L, preferably from 6 to 7 g/L;
preferably, in step (B), the pH of the manganese precipitation reaction is 10.5-10.8, preferably 10.6-10.7.
It is to be understood that the base solution is ensured to function by controlling the ammonia content of the base solution. Typically, but not by way of limitation, the ammonia content of the base solution may be 5g/L, 6g/L, 7g/L, or 8 g/L;
likewise, in order to ensure the manganese precipitation reaction to proceed smoothly, the pH of the manganese precipitation reaction needs to be controlled within a suitable range, and typically, but not limited to, the pH of the manganese precipitation reaction may be 10.5, 10.6, 10.7 or 10.8.
In a preferred embodiment, in the step (B), the manganese precipitation agent is ammonia water and hydroxide solution;
preferably, in the step (B), the concentration of ammonia water in the manganese precipitation agent is 6-10mol/L, and more preferably 7-8 mol/L;
preferably, in the step (B), the concentration of the hydroxide solution in the manganese precipitation agent is 8-12mol/L, and more preferably 8-10 mol/L.
The manganese precipitating agent can be prepared by combining ammonia water and hydroxide solution, and typically but not by limitation, the concentration of the ammonia water in the manganese precipitating agent can be 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10 mol/L; the concentration of the hydroxide solution in the manganese precipitation agent can be 8mol/L, 9mol/L, 10mol/L, 11mol/L or 12 mol/L.
In a preferred embodiment, the soluble hydroxide comprises sodium hydroxide.
The soluble hydroxide in the base solution can adjust the ammonia content of the base solution and keep the pH value of the manganese precipitation reaction within a certain range. The soluble hydroxide may be sodium hydroxide.
In a preferred embodiment, in step (C), the refining comprises recrystallization, the temperature of recrystallization being from 70 to 100 ℃, preferably from 80 to 90 ℃;
preferably, the recrystallization time is from 1 to 4h, preferably from 2 to 3 h.
The refining aims at purifying the obtained crude manganese sulfate so as to meet the requirement of being used as a raw material of a positive electrode material of a lithium ion battery. The invention has no special requirements for the refining method, as long as the refining purpose is achieved. For example: the method of recrystallization may be selected.
The invention has no special requirements on the temperature and time of recrystallization. Typically, but not by way of limitation, the temperature of recrystallization may be 70 ℃, 80 ℃, 90 ℃, 95 ℃ or 100 ℃; the recrystallization time can be 1h, 2h, 3h or 4 h.
In a preferred embodiment, the method for preparing the first filtrate comprises the following steps:
(A1) mixing the copper-manganese chloride solution with soluble sulfate, performing primary calcium precipitation reaction, adding a copper-calcium precipitation agent, performing copper precipitation reaction and secondary calcium precipitation reaction, and performing solid-liquid separation to obtain copper-calcium slag and a copper-calcium precipitation solution;
(A2) mixing the solution after copper and calcium precipitation with soluble fluoride salt, performing three calcium precipitation reactions, and performing solid-liquid separation to obtain calcium slag and a solution after three calcium precipitation;
(A3) and mixing the liquid obtained after the three calcium precipitations with soluble sulfide, carrying out zinc precipitation reaction, and carrying out solid-liquid separation to obtain a first filtrate.
In the first calcium precipitation reaction, calcium is precipitated in the form of calcium sulfate; in the secondary calcium precipitation reaction, calcium is precipitated in the form of calcium hydroxide or calcium carbonate; in the third calcium precipitation reaction, calcium is precipitated in the form of calcium fluoride. Wherein, the secondary calcium precipitation reaction has a small amount of calcium precipitation along with the copper precipitation reaction, and the calcium can be abandoned when the calcium is recovered. In addition, if only sulfate is used for precipitating calcium, the calcium is difficult to completely precipitate, and if fluoride is directly used for precipitating calcium, excessive fluoride ions are introduced into the filtrate, so that the quality of the product manganese sulfate is influenced.
After the primary calcium precipitation reaction, a copper-calcium precipitation agent is directly added without filtration, so that a large amount of copper and a small amount of calcium are precipitated. And dissolving the obtained copper-calcium slag by using a sulfuric acid solution, filtering to obtain a copper sulfate solution containing a small amount of calcium and cobalt impurities (the calcium sulfate slag is to be recovered), and extracting and removing impurities from the obtained copper sulfate solution containing a small amount of calcium and cobalt impurities to obtain a pure copper solution.
And mixing the calcium fluoride slag obtained by the third calcium precipitation reaction with the calcium sulfate slag, dissolving by concentrated hydrochloric acid, and removing impurities to obtain a pure calcium solution.
Dissolving zinc sulfide slag obtained by zinc precipitation reaction with dilute hydrochloric acid, and removing impurities to obtain a pure zinc solution.
It is understood that very small amounts of copper ions (less than 0.002g/L), calcium ions (less than 0.003g/L) and zinc ions (less than 0.002g/L) remain in the first filtrate, but the remaining amount is small, and the quality of the subsequently prepared battery-grade manganese sulfate is not affected.
In a preferred embodiment, in step (a1), the soluble sulfate salt comprises any one or a combination of at least two of sodium sulfate, potassium sulfate, or ammonium sulfate, preferably sodium sulfate;
preferably, in step (A1), the amount of soluble sulfate is 80-130g/L, preferably 90-110 g/L;
preferably, in the step (a1), the pH value of the first calcium precipitation reaction is 2.5 to 3.5, and more preferably 2.8 to 3.2;
preferably, in the step (A1), the pH value of the copper precipitation reaction and the secondary calcium precipitation reaction is 5.0-5.5;
preferably, in the step (a1), the copper-calcium precipitating agent comprises soluble hydroxide and/or soluble carbonate;
preferably, in step (a1), the soluble hydroxide comprises sodium hydroxide and/or potassium hydroxide;
preferably, in step (a1), the soluble carbonate salt comprises sodium carbonate and/or ammonium bicarbonate;
preferably, in the step (A1), the time of the first calcium precipitation reaction is 1-5h, preferably 2-4 h.
It should be noted that, the kind and amount of the soluble sulfate and the time of the first calcium precipitation reaction are not particularly limited, as long as the calcium can be precipitated in the form of calcium sulfate. Typically, but not limited to, the soluble sulfate can be selected from sodium sulfate, potassium sulfate, and a mixed salt of ammonium sulfate and calcium sulfate; the dosage of the soluble sulfate can be 80g/L, 90g/L, 100g/L, 110g/L, 125g/L or 130 g/L; the time of the first calcium precipitation reaction can be 1h, 2h, 3h, 4h or 5 h.
The pH values of the primary calcium precipitation reaction, the copper precipitation reaction and the secondary calcium precipitation reaction are in a proper range, so that the precipitation reaction can be smoothly carried out. Typically, but not by way of limitation, the pH of the primary calcium precipitation reaction may be 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, or 3.5; the pH value of the copper precipitation reaction and the secondary calcium precipitation reaction can be 5.0, 5.1, 5.2, 5.3, 5.4 or 5.5.
The selection of different copper and calcium precipitating agents can cause copper ions and calcium ions to precipitate in different forms. For example: when the soluble hydroxide is selected as the copper deposition calcium agent, copper is deposited in the form of copper hydroxide, calcium is deposited in the form of calcium hydroxide, when the soluble carbonate is selected as the copper deposition calcium agent, calcium is deposited in the form of calcium carbonate, and copper is deposited in the form of basic copper carbonate. Wherein, the soluble hydroxide can be sodium hydroxide or potassium hydroxide; the soluble carbonate can be sodium carbonate or ammonium bicarbonate.
In a preferred embodiment, in step (a2), the soluble fluoride comprises any one or a combination of at least two of sodium fluoride, potassium fluoride or ammonium fluoride, preferably sodium fluoride and/or ammonium fluoride;
preferably, in the step (A2), the dosage of the soluble fluoride is 8-10 times of the mass of calcium ions in the solution after the copper and calcium precipitation;
preferably, in the step (A2), the pH value of the third calcium precipitation reaction is 5.0-6.0;
preferably, the pH value in step (a2) is adjusted using a basic substance, the basic substance comprising any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium bicarbonate or ammonium bicarbonate, preferably sodium carbonate and/or ammonium bicarbonate;
preferably, in the step (A2), the time of the third calcium precipitation reaction is 2-6h, preferably 3-5 h;
preferably, in step (A2), the temperature of the third calcium precipitation is 70-90 deg.C, preferably 80-85 deg.C.
The invention selects soluble fluoride to carry out three calcium precipitation reactions on the residual calcium ions in the solution, and the type and the dosage of the soluble fluoride are not specially limited. Typically, but not by way of limitation, the soluble fluoride may be selected from sodium fluoride, potassium fluoride, ammonium fluoride, and mixed salts of sodium fluoride and potassium fluoride; the dosage of the soluble fluoride can be 8 times of the mass of calcium ions in the solution after copper and calcium deposition, can be 9 times of the mass of calcium ions in the solution after copper and calcium deposition, and can also be 10 times of the mass of calcium ions in the solution after copper and calcium deposition.
Likewise, the pH value, temperature and time of the third calcium precipitation reaction are not particularly limited in the present invention. Typically, but not by way of limitation, the pH of the third calcium precipitation reaction may be 5.0, 5.2, 5.3, 5.7, 5.8 or 6.0; the temperature of the third calcium precipitation reaction can be 70 ℃, 75 ℃, 80 ℃, 82 ℃, 85 ℃ or 90 ℃; the time of the third calcium precipitation reaction can be 2h, 3h, 4h, 5h or 6 h.
In a preferred embodiment, in step (a3), the soluble sulfide includes any one or a combination of at least two of sodium sulfide, potassium sulfide, or ammonium sulfide;
preferably, in step (A3), the concentration of soluble sulfide is 100-150g/L, preferably 120-130 g/L;
preferably, in the step (A3), the dosage of the soluble sulfide is 3-5 times of the mass of zinc ions in the copper manganese chloride solution;
preferably, in the step (A3), the time of the zinc precipitation reaction is 8-24h, preferably 10-20 h;
preferably, in the step (A3), the temperature of the zinc precipitation reaction is 20-50 ℃, preferably 30-40 ℃.
The invention selects soluble sulfide to carry out zinc precipitation reaction on zinc ions in the solution, and the type and the dosage of the soluble sulfide are not specially limited. Typically, but not by way of limitation, the soluble sulfide may be selected from sodium sulfide, potassium sulfide, ammonium sulfide, or a mixed salt of sodium sulfide and potassium sulfide; the dosage of the soluble sulfide can be 3 times of the mass of zinc ions in the copper and manganese chloride solution, can be 4 times of the mass of the zinc ions in the copper and manganese chloride solution, and can also be 5 times of the mass of the zinc ions in the copper and manganese chloride solution.
Likewise, the temperature and time of the zinc deposition reaction are not particularly limited in the present invention. Typically, but not by way of limitation, the temperature of the zinc precipitation reaction may be 20 ℃, 30 ℃, 32 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃; the time of the zinc precipitation reaction can be 8h, 10h, 12h, 15h, 20h, 22h or 24 h.
It should be noted that the soluble sulfide is prepared in advance into a solution with a certain concentration and then used. When the method is used, the soluble sulfide solution is added to the bottom of the solution after the three-time calcium precipitation, so that the whole reaction system is more uniform. If the soluble sulfide solid is directly added into the liquid after the three-time calcium precipitation, the phenomenon of entrainment and precipitation can occur due to overhigh local concentration, and the loss of manganese is caused. Typically, but not by way of limitation, the concentration of soluble sulfide may be 100g/L, 110g/L, 120g/L, 125g/L, 130g/L, 140g/L, or 150 g/L.
In a second aspect, there is provided in at least one embodiment a use of a method of producing battery grade manganese sulfate in the production of a positive electrode material for a lithium ion battery.
The battery-grade manganese sulfate prepared by the preparation method of the battery-grade manganese sulfate can provide a raw material for preparing a lithium ion battery anode material. The preparation method is simple to operate, low in cost and environment-friendly, the prepared battery-grade manganese sulfate not only meets the requirements of industrial production, but also can further reduce the preparation cost of the lithium ion battery anode material due to the low cost of the preparation method, and the application prospect is good.
The present invention will be further described with reference to the following examples.
Note: the contents of main metal elements in the copper manganese chloride solutions (pH 0.74) used in the following examples are shown in table 1.
Table 1: table of contents of main metal elements in copper manganese chloride solution
| Metallic element | Co | Cu | Ca | Mn | Zn |
| Content (g/L) | 3.87 | 12.87 | 6.89 | 92.99 | 5.14 |
Example 1
The embodiment provides a preparation method of battery-grade manganese sulfate, which comprises the following steps:
(1) adding sodium sulfate solid into the copper-manganese chloride solution according to the proportion of 110g/L, adjusting the pH value of the solution to 2.5, and carrying out primary calcium precipitation reaction. After 2h, continuing adding sodium carbonate solid, adjusting the pH value of the solution to 5.0, carrying out copper precipitation reaction and secondary calcium precipitation reaction, and filtering after the reaction is finished to obtain copper-calcium slag and a copper-calcium precipitation solution;
(2) heating the solution after copper and calcium precipitation to 85 ℃, adding sodium fluoride solid according to 8 times of the mass of calcium ions in the solution after copper and calcium precipitation, adjusting the pH value of the solution to 5.16 by using ammonium bicarbonate solid, preserving heat, reacting for 3 hours, and filtering to obtain calcium slag and solution after calcium precipitation;
(3) adding a sodium sulfide solution (the concentration is 120g/L) with the mass 5 times of that of zinc into the solution after calcium precipitation, reacting for 20 hours at 40 ℃, and then filtering to obtain zinc slag and first filtrate;
(4) and simultaneously adding the first filtrate, 7mol/L ammonia water serving as a manganese precipitation agent and 10mol/L sodium hydroxide solution into a base solution (prepared from ammonia water and sodium hydroxide solution) with the ammonia content of 6g/L and the pH value of 10.7, and introducing nitrogen protection gas and keeping the pH value of the solution between 10.7 +/-0.05 in the reaction process. Filtering after the reaction is finished to obtain manganese hydroxide;
(5) dissolving manganese hydroxide by using concentrated sulfuric acid to obtain crude manganese sulfate, and evaporating and concentrating the obtained crude manganese sulfate at 80 ℃ for 2h (the concentration of manganese sulfate is 55 degrees Be) to obtain battery-grade manganese sulfate.
Example 2
The embodiment provides a preparation method of battery-grade manganese sulfate, which comprises the following steps:
(1) adding ammonium sulfate solid into the copper-manganese chloride solution according to the proportion of 80g/L, adjusting the pH value of the solution to 3.5, and carrying out primary calcium precipitation reaction. After 1h, continuing to add sodium hydroxide solid, adjusting the pH value of the solution to 5.2, carrying out copper precipitation reaction and secondary calcium precipitation reaction, and filtering after the reaction is finished to obtain copper-calcium slag and a copper-calcium precipitation solution;
(2) heating the solution after copper and calcium precipitation to 70 ℃, adding potassium fluoride solid according to 10 times of the mass of calcium ions in the solution after copper and calcium precipitation, adjusting the pH value of the solution to 6 by using ammonium bicarbonate solid, carrying out heat preservation reaction for 2 hours, and filtering to obtain calcium slag and solution after calcium precipitation;
(3) adding a sodium sulfide solution (the concentration is 100g/L) with the mass 3 times of that of zinc into the solution after calcium precipitation, reacting for 24 hours at 20 ℃, and then filtering to obtain zinc slag and first filtrate;
(4) simultaneously adding the first filtrate, 6mol/L ammonia water serving as a manganese precipitation agent and 8mol/L sodium hydroxide solution into a base solution (prepared from ammonia water and sodium hydroxide solution) with the ammonia content of 5g/L and the pH value of 10.8, and introducing nitrogen protection gas and keeping the pH value of the solution between 10.8 +/-0.05 in the reaction process. Filtering after the reaction is finished to obtain manganese hydroxide;
(5) dissolving manganese hydroxide by using concentrated sulfuric acid to obtain crude manganese sulfate, and evaporating and concentrating the obtained crude manganese sulfate at 70 ℃ for 4h (the concentration of manganese sulfate is 53 DEG Be) to obtain battery-grade manganese sulfate.
Example 3
The embodiment provides a preparation method of battery-grade manganese sulfate, which comprises the following steps:
(1) adding sodium sulfate solid into the copper-manganese chloride solution according to the proportion of 130g/L, adjusting the pH value of the solution to 2.8, and carrying out primary calcium precipitation reaction. After 4h, continuously adding sodium carbonate solid, adjusting the pH value of the solution to 5.5, carrying out copper precipitation reaction and secondary calcium precipitation reaction, and filtering after the reaction is finished to obtain copper-calcium slag and a copper-calcium precipitation solution;
(2) heating the solution after copper and calcium precipitation to 90 ℃, adding sodium fluoride solid according to 9 times of the mass of calcium ions in the solution after copper and calcium precipitation, adjusting the pH value of the solution to 5.0 by using sodium bicarbonate solid, preserving heat, reacting for 5 hours, and filtering to obtain calcium slag and solution after calcium precipitation;
(3) adding a potassium sulfide solution (the concentration is 130g/L) with the mass of 4 times that of zinc into the solution after calcium precipitation, reacting for 8 hours at 30 ℃, and then filtering to obtain zinc slag and first filtrate;
(4) and simultaneously adding the first filtrate, 8mol/L ammonia water serving as a manganese precipitation agent and 12mol/L sodium hydroxide solution into a base solution (prepared from ammonia water and sodium hydroxide solution) with the ammonia content of 7g/L and the pH value of 10.6, and introducing nitrogen protection gas and keeping the pH value of the solution between 10.6 +/-0.05 in the reaction process. Filtering after the reaction is finished to obtain manganese hydroxide;
(5) dissolving manganese hydroxide by using concentrated sulfuric acid to obtain crude manganese sulfate, and evaporating and concentrating the obtained crude manganese sulfate at 90 ℃ for 3h (the concentration of manganese sulfate is 54 DEG Be) to obtain battery-grade manganese sulfate.
Example 4
The embodiment provides a preparation method of battery-grade manganese sulfate, which comprises the following steps:
(1) adding sodium sulfate solid into the copper-manganese chloride solution according to the proportion of 90g/L, adjusting the pH value of the solution to 3.2, and carrying out primary calcium precipitation reaction. After 5h, continuously adding sodium carbonate solid, adjusting the pH value of the solution to 5.5, carrying out copper precipitation reaction and secondary calcium precipitation reaction, and filtering after the reaction is finished to obtain copper-calcium slag and a copper-calcium precipitation solution;
(2) heating the solution after copper and calcium precipitation to 85 ℃, adding sodium fluoride solid according to 8 times of the mass of calcium ions in the solution after copper and calcium precipitation, adjusting the pH value of the solution to 5.16 by using ammonium bicarbonate solid, preserving heat, reacting for 4 hours, and filtering to obtain calcium slag and solution after calcium precipitation;
(3) adding an ammonium sulfide solution (the concentration is 150g/L) with the mass of 5 times that of zinc into the solution after calcium precipitation, reacting for 10 hours at 50 ℃, and then filtering to obtain zinc slag and first filtrate;
(4) simultaneously adding the first filtrate, 6mol/L ammonia water serving as a manganese precipitation agent and 8mol/L sodium hydroxide solution into a base solution (prepared from ammonia water and sodium hydroxide solution) with the ammonia content of 8g/L and the pH value of 10.5, and introducing nitrogen protection gas and keeping the pH value of the solution between 10.5 +/-0.05 in the reaction process. Filtering after the reaction is finished to obtain manganese hydroxide;
(5) dissolving manganese hydroxide by using concentrated sulfuric acid to obtain crude manganese sulfate, and evaporating and concentrating the obtained crude manganese sulfate at 100 ℃ for 1h (the concentration of manganese sulfate is 55 degrees Be) to obtain battery-grade manganese sulfate.
Example 5
This example provides a method for preparing battery-grade manganese sulfate, which is the same as example 1 except that in step (4), the concentration of ammonia water in the manganese precipitation agent is changed to 10 mol/L.
Example 6
This example provides a method for preparing battery-grade manganese sulfate, which is the same as that of example 1 except that in step (4), the concentration of sodium hydroxide in the manganese precipitation agent is changed to 8 mol/L.
Example 7
This example provides a method for preparing battery-grade manganese sulfate, which is the same as that of example 1 except that 7mol/L ammonia water is used as the only component of the manganese precipitation agent in step (4).
Example 8
This example provides a method for preparing battery-grade manganese sulfate, which is the same as that of example 1 except that in step (4), the ammonia content of the base solution (prepared from a sodium hydroxide solution and ammonia water) is changed to 8g/L and the pH value is changed to 10.8.
Comparative example
The comparative example provides a preparation method of battery-grade manganese sulfate, except that in the step (4), 7mol/L ammonia water and 10mol/L sodium hydroxide solution which are used as manganese precipitating agents are directly added into the solution after zinc precipitation at the same time without adding base solution, and the other preparation steps are the same as those in the example 1. Note: the contents of each element in battery-grade manganese sulfate and the recovery of the main metals in the copper-manganese chloride solution prepared according to the preparation methods of examples 1 to 8 and comparative example are shown in tables 2 and 3, respectively.
TABLE 2 contents of elements in manganese sulfate for battery grade prepared in examples 1-8 and comparative example
TABLE 3 recovery of the main metals in the copper manganese chloride liquor
As can be seen from tables 2 and 3, the quality of manganese sulfate obtained by the comparative example without adding the base solution is obviously inferior to that of manganese sulfate obtained by each example with adding the base solution, it is necessary to control the environment of manganese precipitation reaction by the base solution, and it can be seen that the main metals of the copper-manganese chloride solution in each example and the comparative example are separated one by one.
In conclusion, the battery-grade manganese sulfate prepared by the preparation method provided by the invention meets the production requirements. In addition, in the preparation process, the metals in the copper chloride manganese liquid are effectively separated one by one, the metals are conveniently and independently recovered, the utilization of the copper chloride manganese waste liquid is maximized, the cost is reduced, and the concept of sustainable development is met.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (46)
1. The preparation method of battery-grade manganese sulfate is characterized by comprising the following steps:
(A) precipitating copper ions, calcium ions and zinc ions in the copper-manganese chloride solution to obtain a first filtrate;
(B) mixing the first filtrate, a manganese precipitation agent and a base solution under a protective atmosphere, performing manganese precipitation reaction, and performing solid-liquid separation to obtain manganese hydroxide;
(C) mixing the manganese hydroxide with concentrated sulfuric acid, carrying out neutralization reaction to obtain crude manganese sulfate, and refining to obtain battery-grade manganese sulfate;
wherein, in the step (B), the manganese precipitation agent comprises ammonia water;
the base solution comprises ammonia water and soluble hydroxide, and the soluble hydroxide comprises sodium hydroxide.
2. The method for preparing battery-grade manganese sulfate according to claim 1, wherein in step (B), the ammonia content of the base solution is 5-8 g/L.
3. The method for preparing battery-grade manganese sulfate according to claim 2, wherein in step (B), the ammonia content of the base solution is 6-7 g/L.
4. The method for preparing battery-grade manganese sulfate according to claim 2, wherein in step (B), the pH of the manganese precipitation reaction is 10.5-10.8.
5. The method for preparing battery-grade manganese sulfate according to claim 2, wherein in step (B), the pH of the manganese precipitation reaction is 10.6-10.7.
6. The method for preparing battery-grade manganese sulfate according to claim 1, wherein in step (B), the manganese precipitation agent is ammonia water and hydroxide solution.
7. The method for preparing battery-grade manganese sulfate according to claim 6, wherein in step (B), the concentration of ammonia water in the manganese precipitation agent is 6-10 mol/L.
8. The method for preparing battery-grade manganese sulfate according to claim 6, wherein in step (B), the concentration of ammonia water in the manganese precipitation agent is 7-8 mol/L.
9. The method for preparing battery-grade manganese sulfate according to claim 6, wherein in step (B), the concentration of the hydroxide solution in the manganese precipitation agent is 8-12 mol/L.
10. The method for preparing battery-grade manganese sulfate according to claim 6, wherein in step (B), the concentration of the hydroxide solution in the manganese precipitation agent is 8-10 mol/L.
11. The method for preparing battery-grade manganese sulfate according to claim 1, wherein in step (C), the refining includes recrystallization, and the temperature of recrystallization is 70-100 ℃.
12. The method for preparing battery-grade manganese sulfate according to claim 11, wherein in step (C), the temperature of recrystallization is 80-90 ℃.
13. The method for preparing battery-grade manganese sulfate according to claim 11, wherein in step (C), the recrystallization time is 1-4 hours.
14. The method for preparing battery-grade manganese sulfate according to claim 11, wherein in step (C), the recrystallization time is 2-3 hours.
15. The method for preparing battery-grade manganese sulfate according to any one of claims 1 to 14, wherein the method for preparing the first filtrate comprises the following steps:
(A1) mixing the copper-manganese chloride solution with soluble sulfate, performing primary calcium precipitation reaction, adding a copper-calcium precipitation agent, performing copper precipitation reaction and secondary calcium precipitation reaction, and performing solid-liquid separation to obtain copper-calcium slag and a copper-calcium precipitation solution;
(A2) mixing the solution after copper and calcium precipitation with soluble fluoride salt, performing three calcium precipitation reactions, and performing solid-liquid separation to obtain calcium slag and a solution after three calcium precipitation;
(A3) and mixing the liquid after the three times of calcium precipitation with soluble sulfide, performing zinc precipitation reaction, and performing solid-liquid separation to obtain a first filtrate.
16. The method for preparing battery-grade manganese sulfate according to claim 15, wherein in step (A1), the soluble sulfate salt comprises any one of sodium sulfate, potassium sulfate, or ammonium sulfate, or a combination of at least two thereof.
17. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (a1), the soluble sulfate is sodium sulfate.
18. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (A1), the amount of the soluble sulfate is 80-130 g/L.
19. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (A1), the amount of the soluble sulfate is 90-110 g/L.
20. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (A1), the pH value of the primary calcium precipitation reaction is 2.5-3.5.
21. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (A1), the pH value of the primary calcium precipitation reaction is 2.8-3.2.
22. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (a1), the pH of the copper precipitation reaction and the secondary calcium precipitation reaction is 5.0-5.5.
23. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (a1), the copper-calcium precipitating agent includes a soluble hydroxide and/or a soluble carbonate.
24. The method for preparing battery-grade manganese sulfate according to claim 23, wherein in step (a1), the soluble hydroxide comprises sodium hydroxide and/or potassium hydroxide.
25. The method for preparing battery-grade manganese sulfate according to claim 23, wherein in step (a1), the soluble carbonate salt comprises sodium carbonate and/or ammonium bicarbonate.
26. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (A1), the time of the primary calcium precipitation reaction is 1-5 h.
27. The method for preparing battery-grade manganese sulfate according to claim 16, wherein in step (A1), the time of the primary calcium precipitation reaction is 2-4 h.
28. The method for preparing battery-grade manganese sulfate according to claim 15, wherein in step (A2), the soluble fluoride comprises any one of sodium fluoride, potassium fluoride or ammonium fluoride or a combination of at least two of them.
29. The method for preparing battery-grade manganese sulfate according to claim 28, wherein in step (a2), the soluble fluoride is sodium fluoride and/or ammonium fluoride.
30. The method for preparing battery-grade manganese sulfate according to claim 28, wherein in step (a2), the amount of soluble fluoride is 8-10 times the mass of calcium ions in the solution after copper and calcium precipitation.
31. The method for preparing battery-grade manganese sulfate according to claim 28, wherein in step (a2), the pH of the third calcium precipitation reaction is 5.0-6.0.
32. The method for preparing battery-grade manganese sulfate according to claim 28, wherein the pH value in step (A2) is adjusted by using alkaline substances including any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium bicarbonate or ammonium bicarbonate.
33. The method of claim 32, wherein the alkaline material is sodium carbonate and/or ammonium bicarbonate.
34. The method for preparing battery-grade manganese sulfate according to claim 28, wherein in step (A2), the time of the third calcium precipitation reaction is 2-6 h.
35. The method for preparing battery-grade manganese sulfate according to claim 28, wherein in step (A2), the time of the third calcium precipitation reaction is 3-5 h.
36. The method for preparing battery-grade manganese sulfate according to claim 28, wherein in step (A2), the temperature of the third calcium precipitation is 70-90 ℃.
37. The method for preparing battery-grade manganese sulfate according to claim 28, wherein in step (A2), the temperature of the third calcium precipitation is 80-85 ℃.
38. The method for preparing battery-grade manganese sulfate according to claim 15, wherein in step (A3), the soluble sulfide includes any one of sodium sulfide, potassium sulfide or ammonium sulfide or a combination of at least two thereof.
39. The method for preparing battery-grade manganese sulfate according to claim 38, wherein in step (A3), the concentration of the soluble sulfide is 100-150 g/L.
40. The method for preparing battery-grade manganese sulfate according to claim 38, wherein in step (A3), the concentration of the soluble sulfide is 120-130 g/L.
41. The method for preparing battery-grade manganese sulfate according to claim 38, wherein in step (A3), the amount of soluble sulfide is 3-5 times the mass of zinc ions in the copper manganese chloride solution.
42. The method for preparing battery-grade manganese sulfate according to claim 38, wherein in step (A3), the time for the zinc precipitation reaction is 8-24 h.
43. The method for preparing battery-grade manganese sulfate according to claim 38, wherein in step (A3), the time for the zinc precipitation reaction is 10-20 h.
44. The method for preparing battery-grade manganese sulfate according to claim 38, wherein in step (A3), the temperature of the zinc precipitation reaction is 20-50 ℃.
45. The method for preparing battery-grade manganese sulfate according to claim 38, wherein in step (A3), the temperature of the zinc precipitation reaction is 30-40 ℃.
46. Use of the method of any one of claims 1-45 for the preparation of battery grade manganese sulfate for the preparation of a positive electrode material for a lithium ion battery.
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