CN116081693A - Method for refining manganese sulfate product by removing impurities from calcium and magnesium - Google Patents
Method for refining manganese sulfate product by removing impurities from calcium and magnesium Download PDFInfo
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- CN116081693A CN116081693A CN202310030293.7A CN202310030293A CN116081693A CN 116081693 A CN116081693 A CN 116081693A CN 202310030293 A CN202310030293 A CN 202310030293A CN 116081693 A CN116081693 A CN 116081693A
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- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 74
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 74
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 74
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 74
- 239000011575 calcium Substances 0.000 title claims abstract description 65
- 239000011777 magnesium Substances 0.000 title claims abstract description 58
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 52
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 50
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 50
- 239000012535 impurity Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007670 refining Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 55
- 239000000047 product Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 8
- 229940005657 pyrophosphoric acid Drugs 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- KNKYYBLUVDJKDL-UHFFFAOYSA-J calcium;magnesium;phosphonato phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O KNKYYBLUVDJKDL-UHFFFAOYSA-J 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- -1 pyrophosphoric acid manganese salt Chemical class 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 238000011027 product recovery Methods 0.000 abstract description 2
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 238000005070 sampling Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001655 manganese mineral Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for refining manganese sulfate by removing impurities from calcium and magnesium, which comprises the steps of firstly dissolving a common or crude manganese sulfate product to prepare a manganese sulfate solution, adding pyrophosphoric acid or a manganese pyrophosphate salt solution into the solution after filtering, stirring the solution for reaction, forming insoluble calcium and magnesium pyrophosphate precipitate after the reaction is finished, standing and aging the precipitate, and separating impurities by a precise filtering device to prepare a high-purity manganese sulfate solution; and naturally crystallizing the high-purity manganese sulfate solution under an acidic condition to prepare the manganese sulfate product with the concentration index of the calcium/magnesium impurity completely conforming to the allowable value range of the first-order product specified in the HG/T4823-2015 standard. The process has the characteristics of safe and simple operation, low processing cost, high product recovery rate and small influence on environment.
Description
Technical Field
The invention relates to a method for refining manganese sulfate by removing impurity calcium and magnesium, which aims at a refining process for producing refined high-quality manganese sulfate by using byproduct and recovered crude impurity manganese sulfate waste liquid or using manganese mineral aggregate, manganese-containing waste material, crude manganese sulfate and the like as raw materials.
Background
In the process of producing and manufacturing battery-grade high-purity manganese sulfate, the requirement of product quality standard is high (for example, the quality standard of impurity calcium/magnesium specified in first-class product in manganese sulfate for HG/T4823-2015 battery is less than or equal to 0.01% Ca/Mg), so that large-scale and stable product supply is difficult for a plurality of manufacturers in China. After running for years, the method is difficult to effectively maintain continuous mass production because of the problems of over-standard fluorine ions in the product, lengthy calcium and magnesium purification process, high auxiliary material consumption, high cost, too low manganese recovery rate, unstable product quality and the like. It can be said that the process and cost control of removing calcium and magnesium in the refining process of manganese sulfate are the bottleneck for many enterprises to develop greatly.
Disclosure of Invention
The invention provides a process method for removing impurities of calcium and magnesium in the process of refining manganese sulfate, which has the characteristics of safe and simple operation, low processing cost, high product recovery rate and small influence on environment.
The technical scheme adopted by the invention is as follows: a method for refining manganese sulfate by removing impurities from calcium and magnesium is characterized by comprising the following steps: the manganese sulfate product with low impurity concentration of calcium and magnesium is prepared by adopting pyrophosphoric acid or pyrophosphoric acid manganese salt to form coprecipitation with calcium and magnesium ions in manganese sulfate solution, filtering and separating to remove calcium and magnesium slag, and then crystallizing the solution through acid.
Firstly, dissolving a common or crude manganese sulfate product to prepare a manganese sulfate solution, filtering, adding pyrophosphoric acid or a manganese pyrophosphate salt solution, stirring for reaction, forming insoluble calcium magnesium pyrophosphate precipitate after the reaction is finished, standing for aging, and separating impurities by a precise filtering device to prepare the high-purity manganese sulfate solution.
And naturally crystallizing the high-purity manganese sulfate solution under an acidic condition to prepare the manganese sulfate product with the concentration index of the calcium/magnesium impurity completely conforming to the allowable value range of the first-order product specified in the HG/T4823-2015 standard.
The process method comprises the following steps:
(1) Preparing a manganese sulfate solution: preparing a concentrated solution with the manganese concentration of 9.5-11.0% from crude manganese sulfate or solution with the magnesium concentration of less than 0.25% and deionized water according to a proportion, standing for several hours, and filtering;
(2) Purifying and removing impurities: slowly and dropwise adding a proper amount of 12-20% concentration manganese pyrophosphate solution into the filtrate obtained in the step (1) under the condition of uniformly stirring at the temperature of 45-60 ℃, simultaneously adjusting the pH value of a stable solution by manganese carbonate to be 3.0-3.5, carrying out constant-temperature reaction for 1 hour after the addition, standing and ageing for 30 minutes, filtering, separating and removing calcium and magnesium slag separated out of the solution, and collecting filtrate for later use;
(3) Acidifying and crystallizing: and (3) regulating the pH value of the filtrate collected in the step (2) to be 2.5-3.0 by sulfuric acid, dropwise adding a plurality of drops of ethylene glycol into the solution, concentrating and crystallizing at a low temperature, rapidly centrifuging the formed crystals and mother liquor, collecting and drying manganese sulfate crystals, wherein the recovery rate of manganese sulfate is more than 99.4%.
The manganese sulfate solution is prepared by dropwise adding sulfurous acid to adjust the pH value to be 3.5-4.0, and the dissolution temperature is controlled to be 55-60 ℃ until the solid in the feed liquid is basically dissolved and the solution is clear.
And (3) drying the manganese sulfate crystal, wherein the water content of the crystal grains is controlled to be less than or equal to 6.5%.
The beneficial effects achieved by the invention are as follows:
1. the investment cost is low: the facilities required by the process are a reaction kettle, a filter press (or a precision filter) and the like which are commonly used in metallurgy and chemical industry, other special equipment is not needed, and the used auxiliary materials are simple in variety and easy to purchase.
2. The process flow is short, and the energy consumption is low: only three steps are needed from the feeding to the reaction finishing, the operation is simple, the labor investment is less, the labor intensity is low, the production and processing efficiency is high, and the water/electricity/gas energy consumption is low.
3. The recovery rate of the product is high: in view of the short operation procedure, good selectivity of the used impurity removal purification material and secondary recycling of the filter residue after precipitation, the recovery rate of the final product can reach more than 99.4 percent.
4. The purification process is safe to operate and has little influence on environment: in view of the characteristics of simple varieties of used auxiliary materials, no toxic or side effect, short process flow, high yield, no wastewater and waste gas emission and the like, the influence of the purification process on the human and the environment is objectively avoided.
5. Creating good economic benefit: for the byproduct crude manganese sulfate (or common grade manganese sulfate), the economic value of the product is generally lower, and even the product is regarded as waste to influence the environment.
Detailed Description
The invention is further illustrated by the following examples.
A method for refining manganese sulfate by removing impurities from calcium and magnesium comprises the following steps:
(1) Screening and selecting materials: screening the byproduct crude calcium-magnesium impurity manganese sulfate or common grade manganese sulfate by a vibrating screen with the mesh of-80 to sort out entrained mechanical impurities;
(2) Dissolving and filtering: stirring and slurrying the screened material and deionized water in a reaction kettle, dropwise adding sulfurous acid to adjust the pH value of the feed liquid to 3.5-4.0, and controlling the dissolution temperature to 55-60 ℃ until the solid in the feed liquid is basically dissolved and the solution is clear. If insoluble solid still can be filtered by a filter press, the filtrate enters a purification process, and filter residues are washed and scrapped after being qualified.
(3) Purifying and removing impurities: sampling and analyzing the filtered solution, adding 15% concentration manganese pyrophosphate solution into a reaction kettle according to the calcium/magnesium impurity components and the concentration in the solution, and separating calcium and magnesium ions from manganese sulfate solution in the form of calcium magnesium pyrophosphate precipitate at the temperature of 52-60 ℃ and the pH value of 3.0-3.5; and then standing/aging, precisely filtering and separating to remove calcium-magnesium precipitate slag, and obtaining purer manganese sulfate solution for the next step.
(4) Concentrating and crystallizing after acidification: and (3) regulating the pH value of the purified and impurity-removed manganese sulfate solution to 2.0-2.5 by sulfuric acid, concentrating and crystallizing, removing mother liquor by a centrifuge after crystals are formed, controlling the water content of crystal grains to be less than or equal to 6.5%, and drying in time.
Example 1:
passing manganese sulfate solid waste material containing 29.43% of manganese, 0.19% of calcium and 0.63% of magnesium through a vibrating screen of-80 meshes, weighing 100kg of screened material, adding 0.3 cube of deionized water, stirring and slurrying, dropwise adding 165ml of sulfurous acid solution to adjust the pH value of the feed liquid to 3.5, controlling the dissolution temperature to 55 ℃, sampling and detecting the impurity concentration (Ca-0.46 g/l and Mg-1.34 g/l) of calcium/magnesium contained in the feed liquid when the solid matters in the feed liquid are dissolved completely and the solution is basically clear, and slowly adding 1 according to the total amount of calcium/magnesium: 1.05 9.5 liters of 12% concentration manganese pyrophosphate solution (molar ratio), stirring and reacting for 50 minutes at constant temperature, standing and aging for 30 minutes, sampling and detecting to obtain Ca-0.0087g/l and Mg-0.011g/l, filtering the feed liquid, adjusting the pH value of the filtrate to 2.0 by sulfuric acid, concentrating and crystallizing, centrifuging and dehydrating the crystallized substances, drying and detecting to obtain 86.92kg of finished product of crystallized manganese sulfate, wherein the calcium/magnesium in the finished product of crystallized manganese sulfate is Ca:0.0073%, mg:0.0081 percent, which accords with the allowable value of first-grade calcium/magnesium (Ca/Mg is less than or equal to 0.01 percent) in the manganese sulfate standard for HG/T4823-2015 batteries.
Example 2:
passing manganese sulfate solid waste material containing 29.43% of manganese, 0.19% of calcium and 0.63% of magnesium through a vibrating screen of-80 meshes, weighing 50kg of screened material, adding 0.15 cube of deionized water, stirring and slurrying, dropwise adding 185ml of sulfurous acid solution to adjust the pH value of the feed liquid to 4.05, controlling the dissolution temperature to 60 ℃, sampling and detecting the impurity concentration (Ca-0.51 g/l and Mg-1.46 g/l) of calcium/magnesium contained in the feed liquid when the solid matters in the feed liquid are dissolved completely and the solution is basically clear, and slowly adding 1 according to the total amount of calcium/magnesium: 1.06 (molar ratio) 8.3 liters of 15% concentration manganese pyrophosphate solution, stirring at constant temperature for reaction for 60 minutes, standing for aging for 30 minutes, sampling and detecting to obtain Ca-0.0069g/l and Mg-0.0077g/l, precisely filtering the feed liquid, adjusting the pH value of the filtrate to 2.5 by sulfuric acid, concentrating and crystallizing, centrifuging and dehydrating the crystallized substances, drying and detecting to obtain 41.86kg of calcium/magnesium in crystalline manganese sulfate, wherein the calcium/magnesium in the crystalline manganese sulfate is Ca:0.0071%, mg:0.0079%, meets the allowable value of first-grade calcium/magnesium (Ca/Mg is less than or equal to 0.01%) in the standard of manganese sulfate for HG/T4823-2015 batteries.
Example 3:
passing manganese sulfate recovery waste material containing 28.65% of manganese, 0.26% of calcium and 0.91% of magnesium through a vibrating screen of-80 meshes, weighing 60kg of screened material, adding 0.18 cube of deionized water, stirring and slurrying, dropwise adding 230ml of sulfurous acid solution to adjust the pH value of the feed liquid to 3.75, controlling the dissolution temperature to 58 ℃, sampling and detecting the impurity concentration (Ca-0.57 g/l and Mg-1.83 g/l) of calcium/magnesium contained in the feed liquid when the solid matters in the feed liquid are dissolved completely and the solution is basically clear, and slowly adding 1 according to the total amount of calcium/magnesium: 1.04 9.2 liters of 13.6 percent manganese pyrophosphate solution with the molar ratio, stirring and reacting for 60 minutes at constant temperature, standing and aging for 30 minutes, sampling and sending to obtain Ca-0.0092g/l and Mg-0.011g/l, precisely filtering the feed liquid, adjusting the pH value of the filtrate to 2.0 by sulfuric acid, concentrating and crystallizing, centrifugally dehydrating the crystallized substances, drying and sending to detect, and obtaining 49.69kg of calcium/magnesium in the crystallized manganese sulfate as Ca:0.0089%, mg:0.0094%, and meets the allowable value of first-grade calcium/magnesium (Ca/Mg is less than or equal to 0.01%) in the manganese sulfate standard for HG/T4823-2015 batteries.
Example 4:
filtering byproduct manganese sulfate solution containing 0.93g/L of calcium, 2.06g/L of magnesium and 85.37g/L of manganese by a filter press, measuring 0.5 cube of filtrate, slowly adding 1.25 liter of sulfurous acid solution under stirring to adjust the pH value of the feed liquid to 4.34, slowly heating and keeping the temperature at about 56 ℃, and slowly adding 1 according to the total amount of calcium/magnesium: 1.08 12.85L of 12.8 percent manganese pyrophosphate solution with the molar ratio, stirring and reacting for 60 minutes at constant temperature, standing and aging for 45 minutes, sampling and sending to obtain Ca-0.0081g/l and Mg-0.0067g/l, carrying out precise filtration on the feed liquid, adjusting the pH value of the filtrate to 2.3 by sulfuric acid, concentrating and crystallizing, centrifuging and dehydrating the crystallized substances, drying and sending to detect, and measuring the Ca/Mg in 117.34kg of crystallized manganese sulfate to be Ca:0.0062%, mg:0.0059%, and meets the allowable value of first-grade calcium/magnesium (Ca/Mg is less than or equal to 0.01%) in the manganese sulfate standard for HG/T4823-2015 batteries.
Example 5:
filtering byproduct manganese sulfate solution containing 0.93g/L of calcium, 2.06g/L of magnesium and 85.37g/L of manganese in the same example 4 by a filter press, measuring 0.35 cube of filtrate, slowly adding 800ml of sulfurous acid solution under stirring to adjust the pH value of the feed liquid to 4.26, slowly heating and keeping the temperature at about 58 ℃, and slowly adding 1 according to the total amount of calcium/magnesium: 1.04 7.5 liters of 15.23 percent manganese pyrophosphate solution (molar ratio), stirring and reacting for 65 minutes at constant temperature, standing and aging for 50 minutes, sampling and sending to obtain Ca-0.0088g/l and Mg-0.0094g/l, precisely filtering the feed liquid, adjusting the pH value of the filtrate to 2.05 by sulfuric acid, concentrating and crystallizing, centrifugally dehydrating the crystal, drying and sending to detect, and measuring the Ca/Mg in 75.13kg of crystallized manganese sulfate to be Ca:0.0067%, mg:0.0072 percent, which accords with the allowable value of first-class calcium/magnesium (Ca/Mg is less than or equal to 0.01 percent) in the manganese sulfate standard for HG/T4823-2015 batteries.
Claims (6)
1. A method for refining manganese sulfate by removing impurities from calcium and magnesium is characterized by comprising the following steps: the manganese sulfate product with low impurity concentration of calcium and magnesium is prepared by adopting pyrophosphoric acid or pyrophosphoric acid manganese salt to form coprecipitation with calcium and magnesium ions in manganese sulfate solution, filtering and separating to remove calcium and magnesium slag, and then crystallizing the solution through acid.
2. The method for refining manganese sulfate by removing impurities from calcium and magnesium according to claim 1, which is characterized in that: firstly, dissolving a common or crude manganese sulfate product to prepare a manganese sulfate solution, filtering, adding pyrophosphoric acid or a manganese pyrophosphate salt solution, stirring for reaction, forming insoluble calcium magnesium pyrophosphate precipitate after the reaction is finished, standing for aging, and separating impurities by a precise filtering device to prepare the high-purity manganese sulfate solution.
3. The method for refining manganese sulfate by removing impurities from calcium and magnesium according to claim 2, which is characterized in that: and naturally crystallizing the high-purity manganese sulfate solution under an acidic condition to prepare the manganese sulfate product with the concentration index of the calcium/magnesium impurity completely conforming to the allowable value range of the first-order product specified in the HG/T4823-2015 standard.
4. A method for refining manganese sulfate by removing impurities from calcium and magnesium according to claim 3, wherein the method comprises the following steps: the process method comprises the following steps:
(1) Preparing a manganese sulfate solution: preparing a concentrated solution with the manganese concentration of 5-12% from crude manganese sulfate or solution with the magnesium concentration of less than 0.25% and deionized water according to a proportion, standing for several hours, and filtering;
(2) Purifying and removing impurities: slowly and dropwise adding a proper amount of 12-20% concentration manganese pyrophosphate solution into the filtrate obtained in the step (1) under the condition of uniformly stirring at the temperature of 45-60 ℃, simultaneously adjusting the pH value of a stable solution by manganese carbonate to be 3.0-3.5, carrying out constant-temperature reaction for 1 hour after the addition, standing and ageing for 30 minutes, filtering, separating and removing calcium and magnesium slag separated out of the solution, and collecting filtrate for later use;
acidifying and crystallizing: and (3) regulating the pH value of the filtrate collected in the step (2) to be 2.5-3.0 by sulfuric acid, dropwise adding a plurality of drops of ethylene glycol into the solution, concentrating and crystallizing at a low temperature, rapidly centrifuging the formed crystals and mother liquor, collecting and drying manganese sulfate crystals, wherein the recovery rate of manganese sulfate is more than 99.4%.
5. The method for refining manganese sulfate by removing impurities from calcium and magnesium according to claim 4, which is characterized in that: the manganese sulfate solution is prepared by dropwise adding sulfurous acid to adjust the pH value to be 3.5-4.0, and the dissolution temperature is controlled to be 55-60 ℃ until the solid in the feed liquid is basically dissolved and the solution is clear.
6. The method for refining manganese sulfate by removing impurities from calcium and magnesium according to claim 4, which is characterized in that: and (3) drying the manganese sulfate crystal, wherein the water content of the crystal grains is controlled to be less than or equal to 6.5%.
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CN115520900A (en) * | 2022-09-30 | 2022-12-27 | 广东邦普循环科技有限公司 | Phosphorus-doped nanoscale trimanganese tetroxide, preparation method thereof and battery |
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