CN112499687A - Preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate - Google Patents

Preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate Download PDF

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CN112499687A
CN112499687A CN202011531713.2A CN202011531713A CN112499687A CN 112499687 A CN112499687 A CN 112499687A CN 202011531713 A CN202011531713 A CN 202011531713A CN 112499687 A CN112499687 A CN 112499687A
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manganese dioxide
low
potassium
electrolytic manganese
sodium
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CN112499687B (en
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罗冰
陈其胜
覃丽丽
涂忠益
黄朝辉
梁彩玲
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Guangxi Xiatian Manganese Mine Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate. The method comprises the steps of carrying out chemical combination reaction on waste water and waste liquid generated in the electrolytic manganese dioxide preparation process, manganese carbonate powder and sulfuric acid to prepare liquid, removing potassium, sodium and iron elements accompanying raw material acidolysis by utilizing the principles of potassium-iron-vanadium and sodium-iron-vanadium in a high-temperature acidic environment in the liquid preparation process, neutralizing, carrying out solid-liquid separation to obtain a rough manganese sulfate solution, purifying in three steps to remove various harmful heavy metals, electrolyzing to obtain an electrolytic manganese dioxide semi-finished product, rinsing, grinding and magnetizing by adopting manganese hydroxide as a neutralizer to remove simple substance iron, mixing uniformly and packaging to obtain a finished product. The electrolytic manganese dioxide has single crystal form, the crystal form structure is pure gamma-type, the activity is high, and better physical and chemical properties are achieved; and because the impurity content is low, the potassium and sodium content is less than 100ppm, the requirements of low potassium and low sodium of electrolytic manganese dioxide for lithium manganate are met, and the battery capacity and the cycle performance of the lithium ion battery can be effectively improved.

Description

Preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate
Technical Field
The invention belongs to the technical field of metallurgy and battery material preparation, and particularly relates to a preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate.
Background
The electrolytic manganese dioxide is an excellent depolarizer of the battery, it has large discharge capacity, activity is strong, the volume is small, characteristic such as being long of life compared with the dry cell produced by natural discharge manganese dioxide, mix with 20% -30% electrolytic manganese dioxide make dry cell its discharge capacity can improve 50% -100% than make dry cell totally with natural MnO2, mix with 50% -70% electrolytic manganese dioxide in the zinc chloride battery of high performance, its discharge capacity can improve 2-3 times, all make alkaline manganese cell of electrolytic manganese dioxide, its discharge capacity can improve 5-7 times, therefore electrolytic manganese dioxide becomes a very important raw materials of the battery industry.
In the production process of electrolytic manganese dioxide, sodium bicarbonate, sodium carbonate and sodium hydroxide are usually adopted as neutralizing agents in the rinsing process of the traditional process, so that the potassium content and the sodium content of the product exceed the standards, and particularly the sodium content generally reaches 3000 ppm. Potassium impurities in the electrolytic manganese dioxide are easy to form cryptomelane type MnO2The potassium ion positioned in the center of the crystal lattice blocks the migration of protons in the discharge process of the battery, reduces the density of EMD (electron-brain diffusion), makes the discharge process difficult to carry out, and has more obvious influence particularly in heavy current discharge; when the Na + content is excessively high, residual sodium ions are released by battery discharge, which causes sodium-lithium exchange in the electrolyte of the battery, and the Li + movement is hindered by Na +, which seriously affects the battery capacity and cycle performance.
In view of the above problems, the production method of low-sodium electrolytic manganese dioxide of prior art application No. CN201010183376.2 discloses a technical scheme for preparing lithium manganate type electrolytic manganese dioxide by using lithium hydroxide or lithium carbonate as a neutralizing agent instead of baking soda or sodium hydroxide, which solves the problem of high sodium content in the product, but forms a strong corrosive solution in water due to the strong corrosivity of lithium hydroxide; lithium hydroxide can burn eyes and skin, inhalation can cause throat, bronchitis, spasm, chemical pneumonia, pulmonary edema and the like, water sources, air and soil can be polluted by carelessness in the using and storing process, the lithium hydroxide and the lithium carbonate are required to be operated in a closed space, operators are required to be trained strictly to carry out strict protection, the operation is carried out according to strict operation rules, hidden dangers can be brought to safety production, and the application is difficult in practical production.
Disclosure of Invention
The invention provides a preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate, and the electrolytic manganese dioxide prepared by the method not only has the advantages of low potassium and low sodium, but also has good safety and can be used for actual production.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method comprises the following steps:
A. leaching: mixing waste water and waste liquid generated in the electrolytic manganese dioxide preparation process, putting the mixture into a chemical combination reactor, and putting manganese carbonate powder and sulfuric acid into the chemical combination reactor for chemical combination reaction, wherein the reaction temperature is controlled to be 95-98 ℃, and the pH value is controlled to be 1.5-2.5; wherein the weight ratio of the manganese carbonate powder to the sulfuric acid is 1: 0.65-0.72, liquid-solid ratio of 9.6-17: 1;
B. removing potassium, sodium and iron: when the combination reaction reaches 3 hours, firstly detecting whether the reaction product solution in the combination reactor contains Fe or not2+If detected, contains Fe2+Adding manganese dioxide powder to the mixture to make the Fe contained in the mixture2+Oxidation conversion of Fe3+Then converting the Fe into Fe under high-temperature acidic environment3+And K+、Na+Reacting to form jarosite and jarosite precipitate; next, the potassium and sodium contents of the reaction product solution at this time were measured, and if either or both of them were more than 50ppm, ferric sulfate was added so that the potassium and sodium contents were: k is less than or equal to 50ppm, Na is less than or equal to 50 ppm;
C. hydrolysis, purification and iron removal: after the combination reaction reaches 5 hours, adding calcium carbonate powder into the combination reactor to adjust the pH value of the reaction product solution to 4.0-4.5 so that Fe3+The content of (A) is less than or equal to 2 x 10-6(ii) a Followed byContinuously adding calcium carbonate powder to adjust the pH value of the reaction product solution to 5.0-6.0, and then carrying out solid-liquid separation on the ore pulp to obtain a rough manganese sulfate solution;
D. removing heavy metal impurities by a vulcanization precipitation method: pouring the crude manganese sulfate solution obtained in the step C into a purifier, adding barium sulfide, and purifying at 68-72 ℃ to ensure that Cu is in a state of being dissolved in water2+、Co2+、Ni2+、Pb2+Respectively until: cu is less than or equal to 2ppm, Co is less than or equal to 2ppm, Ni is less than or equal to 2ppm, Pb is less than or equal to 4ppm, and then filtering is carried out to obtain a primarily purified manganese sulfate solution;
E. removing molybdenum, arsenic and lead: and D, injecting the primarily purified manganese sulfate solution obtained in the step D into a molybdenum remover, adjusting the pH value of the manganese sulfate solution to be 3.0-5.0, adding electrolytic manganese dioxide powder as an adsorbent to remove molybdenum, and enabling the contents of molybdenum, arsenic and lead to be respectively: mo is less than or equal to 0.5ppm, As is less than or equal to 0.5ppm and Pb is less than or equal to 2ppm, and then filtering is carried out to obtain a secondary purified manganese sulfate solution;
F. precipitation of calcium and magnesium ions: e, storing and standing the secondary purified manganese sulfate solution obtained in the step E through neutral liquid to respectively crystallize and separate out calcium sulfate and magnesium sulfate;
G. electrolysis: f, conveying the third purified manganese sulfate solution obtained in the step F to an electrolytic cell for electrolysis to obtain a semi-finished electrolytic manganese dioxide product; wherein the electrolysis conditions are as follows: the anode current density is 50A/m2～90A/m2The concentration of electrolyte sulfuric acid is 0.40-0.45 mol/L, the concentration of manganese sulfate is 0.38-0.42 mol/L, and the electrolysis period is 10-12 days;
H. rinsing: d, conveying the electrolytic manganese dioxide semi-finished product obtained in the step G into a rinsing barrel, rinsing by adopting a three-stage rinsing process of water washing, alkali washing and water washing, and then grinding and magnetizing for removing iron; wherein, the alkaline washing in the rinsing process adopts manganese hydroxide as a neutralizer.
In the above technical solution, a more specific technical solution may also be: in the step A, H in the mixture of the wastewater and the waste liquid is respectively detected before the manganese carbonate powder and the sulfuric acid are added2SO4And the content of Mn +; wherein the wastewater is generated in the preparation process of electrolytic manganese dioxide and detected electrolytic incompatibilityAnd waste condensed water and waste rinsing water are obtained, and the waste liquid is waste anolyte generated in the electrolytic manganese dioxide preparation process.
Further, in the step A, the manganese carbonate powder is processed to have the granularity of-200 meshes and 90 percent.
Further, in the step B, the manganese dioxide ore powder is manganese dioxide ore powder with a manganese content of 18%.
Furthermore, in the step E, the particle size of the electrolytic manganese dioxide is less than or equal to 8 mu, and the concentration of the electrolytic manganese dioxide powder added with the primarily purified manganese sulfate solution is 1.33 g/L-2.0 g/L.
Further, in the step H, the temperature of the first washing process in the rinsing process is controlled to be above 90 ℃, the temperature of the alkaline washing process is controlled to be above 75 ℃, the temperature of the second washing process is above 90 ℃, the rinsing cycle is 30-35 hours, and the temperature of the rinsing liquid is directly heated by steam; the water used for washing is waste condensed water which is generated in the electrolytic manganese dioxide preparation process and qualified through detection and electrolysis.
Further, after the step H, conveying the product obtained in the step into a gravity mixing bin in a dense phase conveying manner for mixing.
Further, the preparation of the manganese hydroxide comprises the following steps: reacting ammonia water with manganese sulfate solution to generate white precipitate, and collecting the white precipitate and washing with water.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the electrolytic manganese dioxide prepared by the invention has single crystal form, pure gamma-shaped structure, high activity and better physical and chemical properties.
2. The method can well remove impurities such as potassium, sodium, iron, copper, cobalt, nickel, lead, calcium, magnesium, molybdenum and the like, has low impurity content, and the potassium and sodium content is less than 100ppm, so that the requirement of low potassium and low sodium of electrolytic manganese dioxide for lithium manganate is met, and the battery capacity and the cycle performance of the lithium ion battery can be effectively improved.
3. The invention can well remove impurities such as potassium, sodium, iron, copper, cobalt, nickel, lead, calcium, magnesium, molybdenum and the like, so the grade of the used manganese carbonate ore powder can be as low as 18 percent, the rich low-grade manganese ore resources in Guangxi can be fully utilized, and the invention has good economic benefit and social benefit for reasonably utilizing the manganese ore resources and reducing the production cost.
4. On the basis of utilizing manganese oxide mineral powder to remove iron, ferric sulfate is additionally added to deeply remove potassium and sodium.
5. The invention detects H in the mixture of the wastewater and the waste liquid respectively before adding the manganese carbonate powder and the sulfuric acid2SO4And Mn2+The content of the manganese carbonate powder and the sulfuric acid is determined more accurately, the reaction raw materials are ensured not to be wasted, and the combination reaction can also be carried out according to the preset reaction.
6. The invention directly uses the condensate water qualified by the detection of electrolysis in the rinsing process, and returns the condensate water unqualified by the detection of electrolysis and the rinsing water to the chemical combination reaction process for preparing liquid, thereby realizing the cyclic utilization of the wastewater.
7. The invention uses manganese hydroxide as a post-treatment neutralizer in the rinsing process to remove residual SO in the product4 2-Without introducing new impurities into the system.
8. According to the invention, after the electrolytic manganese dioxide semi-finished product is rinsed, ground and magnetized to remove iron, the electrolytic manganese dioxide semi-finished product is sent into a gravity type blending bunker to be blended in a dense phase conveying mode, so that the quality difference of products is eliminated, the uniformity of the products is ensured, the granularity of the products is controlled, the mesh number of the products is-325 meshes and reaches more than 98.0 percent, and the requirements of the electrolytic manganese dioxide special for lithium manganate batteries are met.
Detailed Description
The technical solution of the present invention is further described below with reference to examples.
EXAMPLE 1 preparation of electrolytic manganese dioxide for Low Potassium and sodium type lithium manganate
It comprises the following steps:
A. leaching: waste condensate water and waste rinsing water generated in the electrolytic manganese dioxide preparation process and detected as unqualified in electrolysis are mixed with waste anolyte and put into chemical reactionIn the combined reactor, H in the mixture of the waste water and the waste liquid is detected2SO4Is 0.3mol/L and is Mn2+The content of the manganese carbonate is 0.30mol/L, and simultaneously, the manganese carbonate powder and the sulfuric acid are put into the combination reactor for combination reaction, the reaction temperature is controlled to be 95-98 ℃, and the PH value is controlled to be 1.5-2.5; wherein the weight ratio of the manganese carbonate powder to the sulfuric acid is 1: 0.65, liquid-solid ratio 9.6: 1, the manganese content of the manganese carbonate powder is 18 percent, and the processing granularity is 90 percent of-200 meshes;
B. removing potassium, sodium and iron: when the combination reaction reaches 3 hours, detecting that the reaction product solution in the combination reactor contains Fe2+Adding manganese dioxide ore powder with 18% of manganese content to the mixture to ensure that the manganese dioxide ore powder contains Fe2+Oxidation conversion of Fe3+Then converting the Fe into Fe under high-temperature acidic environment3+And K+、Na+Reacting to form jarosite and jarosite precipitate; next, the potassium and sodium contents of the reaction product solution at this time were measured to find that the potassium (or sodium) content was more than 50ppm, and ferric sulfate was added so that the potassium and sodium contents became: k is less than or equal to 50ppm, Na is less than or equal to 50 ppm;
C. hydrolysis, purification and iron removal: when the combination reaction reaches 5 hours, adding calcium carbonate powder into the combination reactor to adjust the pH value of the reaction product solution to 4.0-4.5 so that Fe3+The content of (A) is less than or equal to 2 x 10-6(ii) a Then, continuously adding calcium carbonate powder to adjust the pH value of the reaction product solution to 5.0-6.0, and then carrying out solid-liquid separation on the ore pulp to obtain a crude manganese sulfate solution;
D. removing heavy metal impurities by a vulcanization precipitation method: pouring the crude manganese sulfate solution obtained in the step C into a purifier, adding barium sulfide, and purifying at 68-72 ℃ to ensure that Cu is in a state of being dissolved in water2+、Co2+、Ni2+、Pb2+Respectively until: cu is less than or equal to 2ppm, Co is less than or equal to 2ppm, Ni is less than or equal to 2ppm, Pb is less than or equal to 4ppm, and then filtering is carried out to obtain a primarily purified manganese sulfate solution;
E. removing molybdenum, arsenic and lead: and D, injecting the primarily purified manganese sulfate solution obtained in the step D into a molybdenum remover, adjusting the pH value of the manganese sulfate solution to be 3.0-5.0, adding electrolytic manganese dioxide powder as an adsorbent to remove molybdenum, and enabling the contents of molybdenum, arsenic and lead to be respectively: mo is less than or equal to 0.5ppm, As is less than or equal to 0.5ppm, Pb is less than or equal to 2ppm, filtering is carried out, so As to obtain a secondary purified manganese sulfate solution, the granularity of electrolytic manganese dioxide is less than or equal to 8 mu, and the adding concentration of the electrolytic manganese dioxide powder is 2.0 g/L;
F. precipitation of calcium and magnesium ions: e, storing and standing the secondary purified manganese sulfate solution obtained in the step E through a neutral solution to respectively crystallize and separate out calcium sulfate and magnesium sulfate, and then filtering to obtain a tertiary purified manganese sulfate solution;
G. electrolysis: f, carrying out superfine filtration on the manganese sulfate solution purified for three times obtained in the step F, and then conveying the manganese sulfate solution to an electrolytic cell for electrolysis to obtain a semi-finished electrolytic manganese dioxide product; wherein the electrolysis conditions are as follows: the anode current density is 50A/m2The concentration of sulfuric acid in the electrolyte is 0.40mol/L, the concentration of manganese sulfate is 0.380mol/L, and the electrolysis period is 10 days;
H. rinsing: d, conveying the electrolytic manganese dioxide semi-finished product obtained in the step G into a rinsing device, rinsing by adopting a three-level rinsing process of water washing, alkali washing and water washing, then grinding, magnetizing and deironing, and conveying the electrolytic manganese dioxide semi-finished product into a gravity type blending bunker for blending in a dense phase conveying mode; the rinsing process comprises the following steps: feeding the electrolytic manganese dioxide semi-finished product into a rinsing device, firstly washing impurities such as residual sulfuric acid, manganese sulfate and the like in the semi-finished product with water, and controlling the sulfuric acid content in the water to be below 1.0g/L as a washing end point; then, neutralizing the residual sulfuric acid with alkali, adopting manganese hydroxide as a neutralizer, and preparing the manganese hydroxide as follows: reacting ammonia water with a manganese sulfate solution to generate a white precipitate, and collecting the white precipitate and washing with water; controlling the alkali washing temperature to be 75 ℃, washing residual neutralizing agent on the surface of the semi-finished product with water again after the alkali washing is finished, wherein the water washing temperature is over 90 ℃, the rinsing cycle is 30 hours, and the temperature of the rinsing liquid is directly heated by steam; the water used for washing is waste condensed water which is generated in the electrolytic manganese dioxide preparation process and is qualified through detection.
The main indicators of the product obtained in this example are shown in table 1:
TABLE 1 product quality situation table
Figure 179028DEST_PATH_IMAGE001
。
Example 2 preparation of electrolytic manganese dioxide for Low Potassium and sodium lithium manganate
It comprises the following steps:
A. leaching: mixing waste condensate water and waste rinsing water generated in the electrolytic manganese dioxide preparation process and detected as unqualified in electrolysis with waste anolyte, putting the mixture into a chemical combination reactor, and detecting H in the mixture of the waste water and the waste liquid2SO4Is 0.32mol/L and is Mn2+The content of the manganese carbonate is 0.35mol/L, and simultaneously, the manganese carbonate powder and the sulfuric acid are put into the combination reactor for combination reaction, the reaction temperature is controlled to be 95-98 ℃, and the PH value is controlled to be 1.5-2.5; wherein the weight ratio of the manganese carbonate powder to the sulfuric acid is 1: 0.68, liquid-solid ratio 12: 1, the manganese content of the manganese carbonate powder is 20%, and the processing granularity is 90% of-200 meshes;
B. removing potassium, sodium and iron: when the combination reaction reaches 3 hours, detecting that the reaction product solution in the combination reactor contains Fe2+Adding manganese dioxide powder with 18 percent of manganese content to lead Fe2+Oxidation conversion of Fe3+Then converting the Fe into Fe under high-temperature acidic environment3+And K+、Na+Reacting to form jarosite and jarosite precipitate; next, the potassium and sodium contents of the reaction product solution at this time were measured to find that the sodium content was more than 50ppm, and ferric sulfate was added so that the potassium and sodium contents became: k is less than or equal to 50ppm, Na is less than or equal to 50 ppm;
C. hydrolysis, purification and iron removal: when the combination reaction reaches 5 hours, adding calcium carbonate powder into the combination reactor to adjust the pH value of the reaction product solution to 4.0-4.5 so that Fe3+The content of (A) is less than or equal to 2 x 10-6(ii) a Then, continuously adding calcium carbonate powder to adjust the pH value of the reaction product solution to 5.0-6.0, and then carrying out solid-liquid separation on the ore pulp to obtain a crude manganese sulfate solution;
D. removing heavy metal impurities by a vulcanization precipitation method: pouring the crude manganese sulfate solution obtained in the step C into a purifier, adding barium sulfide, and purifying at 68-72 ℃ to ensure that Cu is in a state of being dissolved in water2+、Co2+、Ni2+、Pb2+Respectively until: cu is less than or equal to 2ppm, Co is less than or equal to 2ppm, Ni is less than or equal to 2ppm, Pb is less than or equal to 4ppm, and then filtering is carried out to obtain a primarily purified manganese sulfate solution;
E. removing molybdenum, arsenic and lead: and D, injecting the primarily purified manganese sulfate solution obtained in the step D into a molybdenum remover, adjusting the pH value of the manganese sulfate solution to be 3.0-5.0, adding electrolytic manganese dioxide powder as an adsorbent to remove molybdenum, and enabling the contents of molybdenum, arsenic and lead to be respectively: mo is less than or equal to 0.5ppm, As is less than or equal to 0.5ppm and Pb is less than or equal to 2ppm, filtering is carried out to obtain a secondary purified manganese sulfate solution, the granularity of electrolytic manganese dioxide is less than or equal to 8 mu, and the adding concentration of the electrolytic manganese dioxide powder is 1.66 g/L;
F. precipitation of calcium and magnesium ions: e, storing and standing the secondary purified manganese sulfate solution obtained in the step E through a neutral solution to respectively crystallize and separate out calcium sulfate and magnesium sulfate, and then filtering to obtain a tertiary purified manganese sulfate solution;
G. electrolysis: f, carrying out superfine filtration on the manganese sulfate solution purified for three times obtained in the step F, and then conveying the manganese sulfate solution to an electrolytic cell for electrolysis to obtain a semi-finished electrolytic manganese dioxide product; wherein the electrolysis conditions are as follows: the anode current density is 75A/m2The concentration of electrolyte sulfuric acid is 0.42mol/L, the concentration of manganese sulfate is 0.40mol/L, and the electrolysis period is 11 days;
H. rinsing: d, conveying the electrolytic manganese dioxide semi-finished product obtained in the step G into a rinsing device, rinsing by adopting a three-level rinsing process of water washing, alkali washing and water washing, then grinding, magnetizing and deironing, and conveying the electrolytic manganese dioxide semi-finished product into a gravity type blending bunker for blending in a dense phase conveying mode; the rinsing process comprises the following steps: feeding the electrolytic manganese dioxide semi-finished product into a rinsing device, firstly washing impurities such as residual sulfuric acid, manganese sulfate and the like in the semi-finished product with water, and controlling the sulfuric acid content in the water to be below 1.0g/L as a washing end point; then neutralizing the residual sulfuric acid with alkali, adopting manganese hydroxide as a neutralizing agent, and preparing the manganese hydroxide as follows: reacting ammonia water with a manganese sulfate solution to generate a white precipitate, and collecting the white precipitate and washing with water; controlling the alkali washing temperature to be 75 ℃, washing residual neutralizing agent on the surface of the semi-finished product with water again after the alkali washing is finished, wherein the water washing temperature is over 90 ℃, the rinsing cycle is 35 hours, and the rinsing liquid temperature is directly heated by adopting steam; the water used for washing is waste condensed water which is generated in the electrolytic manganese dioxide preparation process and is qualified through detection.
The main indicators of the product obtained in this example are shown in table 2:
TABLE 2 product quality situation table
Figure 993400DEST_PATH_IMAGE002
。
EXAMPLE 3 preparation of electrolytic manganese dioxide for Low Potassium and sodium lithium manganate
It comprises the following steps:
A. leaching: mixing waste condensate water and waste rinsing water generated in the electrolytic manganese dioxide preparation process and detected as unqualified in electrolysis with waste anolyte, putting the mixture into a chemical combination reactor, and detecting H in the mixture of the waste water and the waste liquid2SO4Is 0.40mol/L and is Mn2+The content of the manganese carbonate is 0.42mol/L, and simultaneously, the manganese carbonate powder and the sulfuric acid are put into the combination reactor for combination reaction, the reaction temperature is controlled to be 95-98 ℃, and the PH value is controlled to be 1.5-2.5; wherein the weight ratio of the manganese carbonate powder to the sulfuric acid is 1: 0.72, liquid-solid ratio 17: 1, the content of the manganese carbonate powder is 22 percent, and the processing granularity is 90 percent of 200 meshes;
B. removing potassium, sodium and iron: when the combination reaction reaches 3 hours, detecting that the reaction product solution in the combination reactor contains Fe2+Adding manganese dioxide ore powder with 18 percent of manganese content to the mixture to ensure that the mixture contains Fe2+Oxidation conversion of Fe3+Then converting the Fe into Fe under high-temperature acidic environment3+And K+、Na+Reacting to form jarosite and jarosite precipitate; then, the contents of potassium and sodium in the reaction product solution at this time were measured, and it was found that the contents of potassium and sodium were each more than 50ppm, and iron sulfate was added so that the contents of potassium and sodium were: k is less than or equal to 50ppm, Na is less than or equal to 50 ppm;
C. hydrolysis, purification and iron removal: when the combination reaction reaches 5 hours, adding calcium carbonate powder into the combination reactor to adjust the pH value of the reaction product solution to 4.0-4.5 so that Fe3+The content of (A) is less than or equal to 2 x 10-6(ii) a Then, continuously adding calcium carbonate powder to adjust the pH value of the reaction product solution to 5.0-6.0, and then carrying out solid-liquid separation on the ore pulp to obtain a crude manganese sulfate solution;
D. removing heavy metal impurities by a vulcanization precipitation method: pouring the crude manganese sulfate solution obtained in the step C into a purifier, adding barium sulfide, and purifying at 68-72 ℃ to ensure that Cu is in a state of being dissolved in water2+、Co2+、Ni2+、Pb2+Respectively until: cu is less than or equal to 2ppm, Co is less than or equal to 2ppm, Ni is less than or equal to 2ppm, Pb is less than or equal to 4ppm, and then filtering is carried out to obtain a primarily purified manganese sulfate solution;
E. removing molybdenum, arsenic and lead: and D, injecting the primarily purified manganese sulfate solution obtained in the step D into a molybdenum remover, adjusting the pH value of the manganese sulfate solution to be 3.0-5.0, adding electrolytic manganese dioxide powder as an adsorbent to remove molybdenum, and enabling the contents of molybdenum, arsenic and lead to be respectively: mo is less than or equal to 0.5ppm, As is less than or equal to 0.5ppm and Pb is less than or equal to 2ppm, and then filtering is carried out to obtain a secondary purified manganese sulfate solution; the granularity of the electrolytic manganese dioxide powder is less than or equal to 8 mu, and the adding concentration of the electrolytic manganese dioxide powder is 1.33 g/L;
F. precipitation of calcium and magnesium ions: e, storing and standing the secondary purified manganese sulfate solution obtained in the step E through a neutral solution to respectively crystallize and separate out calcium sulfate and magnesium sulfate, and then filtering to obtain a tertiary purified manganese sulfate solution;
G. electrolysis: f, carrying out superfine filtration on the manganese sulfate solution purified for three times obtained in the step F, and then conveying the manganese sulfate solution to an electrolytic cell for electrolysis to obtain a semi-finished electrolytic manganese dioxide product; wherein the electrolysis conditions are as follows: the anode current density is 90A/m2The concentration of sulfuric acid in the electrolyte is 0.45mol/L, the concentration of manganese sulfate is 0.42mol/L, and the electrolysis period is 12 days;
H. rinsing: d, conveying the electrolytic manganese dioxide semi-finished product obtained in the step G into a rinsing device, rinsing by adopting a three-level rinsing process of water washing, alkali washing and water washing, then grinding, magnetizing and deironing, and conveying the electrolytic manganese dioxide semi-finished product into a gravity type blending bunker for blending in a dense phase conveying mode; the rinsing process comprises the following steps: feeding the electrolytic manganese dioxide semi-finished product into a rinsing device, and firstly washing impurities such as residual sulfuric acid, manganese sulfate and the like in the semi-finished product by using water; controlling the sulfuric acid content in the water to be below 1.0g/L as a washing end point; then neutralizing the residual sulfuric acid with alkali, adopting manganese hydroxide as a neutralizing agent, and preparing the manganese hydroxide as follows: reacting ammonia water with a manganese sulfate solution to generate a white precipitate, and collecting the white precipitate and washing with water; controlling the alkali washing temperature to be 75 ℃; after the alkaline washing is finished, washing the residual neutralizing agent on the surface of the semi-finished product by water again, wherein the washing temperature is more than 90 ℃; the rinsing cycle is 33 hours, and the temperature of the rinsing liquid is directly heated by adopting steam; the water used for washing is waste condensed water which is generated in the electrolytic manganese dioxide preparation process and is qualified through detection.
The main indicators of the product obtained in this example are shown in table 3:
TABLE 3 product quality condition table
Figure 379644DEST_PATH_IMAGE003
。

Claims (8)

1. A preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate is characterized by comprising the following steps:
A. leaching: mixing waste water and waste liquid generated in the electrolytic manganese dioxide preparation process, putting the mixture into a chemical combination reactor, and putting manganese carbonate powder and sulfuric acid into the chemical combination reactor for chemical combination reaction, wherein the reaction temperature is controlled to be 95-98 ℃, and the pH value is controlled to be 1.5-2.5; wherein the weight ratio of the manganese carbonate powder to the sulfuric acid is 1: 0.65-0.72, liquid-solid ratio of 9.6-17: 1;
B. removing potassium, sodium and iron: when the combination reaction reaches 3 hours, firstly detecting whether the reaction product solution in the combination reactor contains Fe or not2+If detected, contains Fe2+Adding manganese dioxide powder to the mixture to make the Fe contained in the mixture2+Oxidation conversion of Fe3+Then converting the Fe into Fe under high-temperature acidic environment3+And K+、Na+Reacting to form jarosite and jarosite precipitate; next, the potassium and sodium contents of the reaction product solution at this time were measured, and if either or both of them were more than 50ppm, ferric sulfate was added so that the potassium and sodium contents were:K≤50ppm、Na≤50ppm；
C. hydrolysis, purification and iron removal: after the combination reaction reaches 5 hours, adding calcium carbonate powder into the combination reactor to adjust the pH value of the reaction product solution to 4.0-4.5 so that Fe3+The content of (A) is less than or equal to 2 x 10-6(ii) a Then, continuously adding calcium carbonate powder to adjust the pH value of the reaction product solution to 5.0-6.0, and then carrying out solid-liquid separation on the ore pulp to obtain a crude manganese sulfate solution;
D. removing heavy metal impurities by a vulcanization precipitation method: pouring the crude manganese sulfate solution obtained in the step C into a purifier, adding barium sulfide, and purifying at 68-72 ℃ to ensure that Cu is in a state of being dissolved in water2+、Co2+、Ni2+、Pb2+Respectively until: cu is less than or equal to 2ppm, Co is less than or equal to 2ppm, Ni is less than or equal to 2ppm, Pb is less than or equal to 4ppm, and then filtering is carried out to obtain a primarily purified manganese sulfate solution;
E. removing molybdenum, arsenic and lead: and D, injecting the primarily purified manganese sulfate solution obtained in the step D into a molybdenum remover, adjusting the pH value of the manganese sulfate solution to be 3.0-5.0, adding electrolytic manganese dioxide powder as an adsorbent to remove molybdenum, and enabling the contents of molybdenum, arsenic and lead to be respectively: mo is less than or equal to 0.5ppm, As is less than or equal to 0.5ppm and Pb is less than or equal to 2ppm, and then filtering is carried out to obtain a secondary purified manganese sulfate solution;
F. precipitation of calcium and magnesium ions: e, storing and standing the secondary purified manganese sulfate solution obtained in the step E through neutral liquid to respectively crystallize and separate out calcium sulfate and magnesium sulfate;
G. electrolysis: f, conveying the third purified manganese sulfate solution obtained in the step F to an electrolytic cell for electrolysis to obtain a semi-finished electrolytic manganese dioxide product; wherein the electrolysis conditions are as follows: the anode current density is 50A/m2～90A/m2The concentration of electrolyte sulfuric acid is 0.40-0.45 mol/L, the concentration of manganese sulfate is 0.38-0.42 mol/L, and the electrolysis period is 10-12 days;
H. rinsing: d, conveying the electrolytic manganese dioxide semi-finished product obtained in the step G into a rinsing barrel, rinsing by adopting a three-stage rinsing process of water washing, alkali washing and water washing, and then grinding and magnetizing for removing iron; wherein, the alkaline washing in the rinsing process adopts manganese hydroxide as a neutralizer.
2. The method for preparing electrolytic manganese dioxide for low-potassium low-sodium lithium manganate according to claim 1, characterized in that: in the step A, H in the mixture of the wastewater and the waste liquid is respectively detected before the manganese carbonate powder and the sulfuric acid are added2SO4And Mn2+The content of (A); the waste water is waste condensed water and waste rinsing water which are generated in the electrolytic manganese dioxide preparation process and are detected to be unqualified in electrolysis, and the waste liquid is waste anolyte generated in the electrolytic manganese dioxide preparation process.
3. The method for preparing electrolytic manganese dioxide for low-potassium low-sodium lithium manganate according to claim 2, characterized in that: in the step A, the manganese carbonate powder is processed to have the granularity of-200 meshes and 90 percent.
4. The method for preparing electrolytic manganese dioxide for low-potassium low-sodium lithium manganate according to claim 3, characterized in that: in the step B, the manganese dioxide ore powder is manganese dioxide ore powder with the manganese content of 18%.
5. The method for preparing electrolytic manganese dioxide for low-potassium low-sodium lithium manganate according to claim 4, characterized in that: in the step E, the granularity of the electrolytic manganese dioxide is less than or equal to 8 mu, and the concentration of the electrolytic manganese dioxide powder added into the primarily purified manganese sulfate solution is 1.33 g/L-2.0 g/L.
6. The method for preparing electrolytic manganese dioxide for low-potassium low-sodium lithium manganate according to claim 5, characterized in that: in the step H, the temperature of the first washing process in the rinsing process is controlled to be above 90 ℃, the temperature of the alkaline washing process is controlled to be 75 ℃, the temperature of the second washing process is controlled to be above 90 ℃, the rinsing period is 30-35 hours, and the temperature of the rinsing liquid is directly heated by steam; the water used for washing is waste condensed water which is generated in the electrolytic manganese dioxide preparation process and qualified through detection and electrolysis.
7. The method for preparing electrolytic manganese dioxide for low-potassium low-sodium lithium manganate according to claim 6, characterized in that: and (D) after the step H, conveying the product obtained in the step into a gravity mixing bunker for mixing in a dense phase conveying mode.
8. The method for preparing electrolytic manganese dioxide for low-potassium low-sodium lithium manganate according to claims 1, 2, 3, 4, 5, 6 and 7, characterized by comprising:
the preparation of the manganese hydroxide comprises the following steps: reacting ammonia water with manganese sulfate solution to generate white precipitate, and collecting the white precipitate and washing with water.
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