CN114671466A - High-purity manganese sulfate and method for preparing high-purity manganese sulfate by using solubility property - Google Patents
High-purity manganese sulfate and method for preparing high-purity manganese sulfate by using solubility property Download PDFInfo
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Abstract
The invention relates to high-purity manganese sulfate, which is characterized in that the content of manganese in the high-purity manganese sulfate is more than 32%, the content of K, Na, Ca and Mg impurities is less than 0.1%, and the content of heavy metal impurities and Fe impurities is less than 0.001%. The method can provide the high-purity manganese sulfate meeting the requirement of the lithium ion battery anode material, has the advantages of simple process, easy operation and low cost, and provides wide prospects for the industrial application of the high-purity manganese sulfate.
Description
Technical Field
The invention relates to the field of manganese sulfate, in particular to high-purity manganese sulfate and a method for preparing the same by utilizing solubility property.
Background
Manganese sulfate is an important basic manganese salt and has wide application. At present, the production method of high-purity manganese sulfate mainly comprises a chemical precipitation method, an electrolysis method and high-temperature high-pressure crystallizationMethods, and the like. During the enrichment of manganese, a large amount of impurities enter the leaching solution at the same time, so the leached manganese sulfate solution must be purified to ensure MnSO4The purity requirement of the product.
Currently, high-purity manganese sulfate is generally obtained by purifying industrial-grade manganese sulfate, the industrial-grade manganese sulfate contains numerous impurities, such as potassium salt, sodium salt, calcium salt and other metal salt impurities, the impurities are relatively easy to remove in the process of removing the impurities, and the calcium salt and the magnesium salt which are impurities are difficult to remove from a finished product in the purification process due to the chemical properties of the calcium sulfate, the magnesium sulfate and the manganese sulfate are very similar, so that the impurity content in the product exceeds the standard.
At present, the existing process can not obtain a high-purity manganese sulfate solution or has higher refining cost, for example, Chinese patent CN102923783A discloses a battery grade high-purity manganese sulfate monohydrate and a preparation method thereof. The preparation method comprises the steps of taking pyrolusite, manganosite or pyrite and industrial sulfuric acid as raw materials, adding hydrogen peroxide, controlling the temperature to be 50-70 ℃, adding BaS, controlling the temperature to be 30-50 ℃, adding hydrofluoric acid, and adding a neutralizer MnCO3Adjusting to 5-6, adding polyaluminium sulfate and polyacrylamide solution for flocculation and precipitation, filtering, adding activated carbon, standing for adsorption, finally introducing into a circulating device filled with activated alumina balls, then concentrating and crystallizing at normal pressure, washing and drying to obtain the high-purity manganese sulfate monohydrate. For example, chinese patent CN103626235A relates to a method for preparing high-purity manganese sulfate by recrystallization. The method for preparing the high-purity manganese sulfate by recrystallization uses the common manganese sulfate as a raw material, and obtains the high-purity manganese sulfate by secondary filter pressing and four-time recrystallization, so that the index requirement of the high-purity manganese sulfate is met, and the method for preparing the high-purity manganese sulfate by recrystallization is technically feasible.
Disclosure of Invention
Aiming at the problems, the invention provides the high-purity manganese sulfate which has low content of K, Na, Ca and Mg impurities, low content of heavy metal impurities and Fe impurities and high manganese content and can meet the requirement of a lithium ion battery anode material, and simultaneously provides the method for preparing the high-purity manganese sulfate by utilizing the solubility property, which has low cost, small investment and good product effect.
The technical scheme adopted by the invention for solving the technical problems is as follows: the high-purity manganese sulfate contains more than 32% of manganese, less than 0.1% of K, Na, Ca and Mg impurities and less than 0.001% of heavy metal impurities and Fe impurities.
Preferably, the heavy metal impurities include one or more of Co, Ni, Zn, Cu, Pb, Cr, Cd.
A method for preparing high-purity manganese sulfate by utilizing solubility property comprises the following steps:
step one, adding water to a crude manganese sulfate product for dissolving, and stirring for 2 hours at normal temperature to obtain a 50% sample solution 1;
step two, standing the 50% sample solution 1 obtained in the step one for 15 hours, centrifuging, and filtering to obtain a filtrate 1 and a filter residue 1, wherein the filtrate 1 is used for recycling, and the filter residue 1 is manganese sulfate precipitate;
thirdly, washing the manganese sulfate precipitate until the manganese sulfate precipitate meets the washing requirement to obtain a manganese sulfate solid;
adding water into the manganese sulfate solid, and stirring for 2 hours at normal temperature to obtain a sample solution 2;
step five, filtering the sample solution 2 obtained in the step four to obtain a filtrate 2 and a filter residue 2, wherein the filtrate 2 is a manganese sulfate solution, and the filter residue 2 is used for recycling;
step six, crystallizing the manganese sulfate solution obtained in the step five by using a rotary evaporator, stopping crystallization until precipitated solids are about to submerge the mother liquor, and then filtering to obtain manganese sulfate solids;
and seventhly, washing the manganese sulfate solid obtained in the sixth step for three times, drying and weighing to obtain a high-purity manganese sulfate product.
Preferably, the manganese sulfate crude product in the first step contains a large amount of metal elements, wherein K is+、Na+、Ca2+、Mg2 +The impurity content is high, the water added in the step one and the step four is deionized water, and the added water quantity is controlled to ensure the solid-to-liquid ratioAll are 1: 1.
Preferably, in the sixth step, the oil bath temperature at the time of the rotary evaporator crystallization is set to 120 ℃.
Preferably, the drying temperature in the seventh step is set to 80 ℃.
Preferably, the manganese sulfate crude product in the first step is subjected to constant-temperature water dissolution in a water bath.
Preferably, a reduced pressure suction filtration apparatus is used for filtration in all steps.
Preferably, the washing in the third step requires that BaCl is added into the washed solution2The solution did not become cloudy.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method can obviously reduce the contents of K, Na, Ca, Mg impurities, heavy metal impurities and Fe impurities in industrial manganese sulfate or manganese ore solution which is leached by sulfuric acid, particularly can ensure that the contents of the K, Na, Ca and Mg impurities are lower than 0.1 percent, simultaneously ensure that the contents of the heavy metal impurities and the Fe impurities are lower than 0.0005 percent, and ensure that the manganese content in the obtained high-purity manganese sulfate is more than 32 percent, thereby meeting the requirement of high-purity manganese sulfate for ternary materials of power lithium ion battery anode materials;
2. the process only utilizes the solubility difference of the manganese sulfate and other sulfates to separate the manganese sulfate, avoids adding other chemical reagents and complicated chemical reaction, does not need complicated and expensive operation equipment, has relatively simple and easily controlled process and relatively low process cost, and provides wide prospect for the industrialized application of the high-purity manganese sulfate.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a schematic representation of the solubility curves of manganese sulfate at different temperatures;
FIG. 3 is a table of the solubilities of different sulfates in a crude manganese sulfate product;
remarking: all data in FIG. 3 are for aqueous solubility at 1atm in g/100 mL.
Detailed Description
The invention will now be described in detail with reference to fig. 1-3, wherein the exemplary embodiments and descriptions of the invention are provided to illustrate the invention, but not to limit the invention.
The high-purity manganese sulfate comprises more than 32% of manganese, less than 0.1% of K, Na, Ca and Mg impurities, less than 0.001% of heavy metal impurities and less than 0.001% of Fe impurities, wherein the heavy metal impurities comprise one or more of Co, Ni, Zn, Cu, Pb, Cr and Cd.
A method for preparing high-purity manganese sulfate by utilizing solubility property comprises the following steps:
step one, adding water into a crude manganese sulfate product, placing the crude manganese sulfate product into a water bath kettle for dissolving, wherein the reaction temperature can be kept constant when the dissolving process is carried out in the water bath kettle due to a little heat release phenomenon, the crude manganese sulfate product in the step one contains a large amount of metal elements, wherein K is+、Na+、Ca2+、Mg2+The impurity content is high, water is added while stirring in the adding process, the added water amount is controlled to keep the solid-to-liquid ratio at 1:1, stirring is continued after the water is added, and stirring is carried out for 2 hours at normal temperature to fully dissolve a manganese sulfate crude product, so that a 50% sample solution 1 is obtained;
step two, standing the 50% sample solution 1 obtained in the step one for 15 hours, centrifuging and filtering to obtain a filtrate 1 and a filter residue 1, and better performing solid-liquid separation through standing and centrifuging, wherein the filtrate 1 contains impurities but has high manganese content, and can be subjected to centralized treatment after a certain amount of impurities are accumulated so as to be recycled, the filter residue 1 is manganese sulfate precipitate, and only the filter residue 1 is reserved in the filtering process so as to separate other sulfates with higher solubility than manganese sulfate, such as Fe2+、Na+、K+Etc.;
step three, washing the manganese sulfate precipitate until the manganese sulfate precipitate meets the washing requirement, specifically adding BaCl into the washed solution2If the solution is not turbid, the washing requirement is met, otherwise, the precipitate needs to be continuously cleaned until the washing requirement is met, and finally, manganese sulfate solid is obtained;
adding water into the manganese sulfate solid, controlling the amount of the added water to ensure that the solid-to-liquid ratio is 1:1, and stirring for 2 hours at normal temperature to obtain a sample solution 2;
step five, filtering the sample solution 2 obtained in the step four to obtain a filtrate 2 and a filter residue 2, wherein the filtrate 2 is a manganese sulfate solution, the filter residue 2 is used for recycling, and only the filtrate 2 is reserved for separating sulfate with low solubility, such as CaSO4；
Step six, crystallizing the manganese sulfate solution obtained in the step five by using a rotary evaporator, setting the oil bath temperature during crystallization of the rotary evaporator to be 120 ℃, and separating the manganese sulfate from other impurity ions by utilizing the particularity that the solubility of the manganese sulfate changes along with the temperature according to the fact that the solubility of the manganese sulfate reverses, namely the solubility of the manganese sulfate increases and then decreases along with the temperature rise, wherein the crystallization temperature can be further controlled, the amount of the remaining mother liquor needs to be controlled during crystallization, if the mother liquor is completely evaporated to dryness, other residual impurity ions can be separated out, if the mother liquor is too much, the product is excessively lost, so that the crystallization process is finished when the separated solid is about to fall through the mother liquor, namely a small amount of the mother liquor, and then filtering to obtain a manganese sulfate solid;
and seventhly, washing the manganese sulfate solid obtained in the sixth step three times, drying and weighing at the temperature of 80 ℃ to obtain a high-purity manganese sulfate product.
The water added in all the steps is deionized water, a reduced-pressure suction filtration device is used for filtering in all the steps, and the solution is slowly poured into a funnel during filtering so as to prevent sediment at the bottom from being poured into the funnel.
Example 1
Taking 50g of a manganese sulfate crude product, adding 50mL of deionized water for dissolving, ensuring that the solid-to-liquid ratio is 1:1 by the amount of the added deionized water, stirring at normal temperature for 2h, fixing the volume to 50% of the sample solution 1, adding water for dissolving the manganese sulfate crude product, stirring at normal temperature for 2h to obtain 50% of the sample solution 1, standing 50% of the sample solution 1 for 15h to separate solid from liquid, centrifuging and filtering to obtain a filtrate 1 and a filter residue 1, only retaining the filter residue 1 in the step, retaining other metal sulfates with high solubility in the filtrate 1, separating the metal sulfates from the filtrate 1, precipitating the filter residue 1 with manganese sulfate, and fully precipitating the manganese sulfateWashing to obtain manganese sulfate solid, adding deionized water into the manganese sulfate solid, controlling the solid-to-liquid ratio to be 1:1, stirring for 2h at normal temperature to obtain sample solution 2, wherein the sample solution 2 is darker in color, the manganese sulfate content in the solution can be preliminarily determined to be higher, fully dissolving the sample solution 2, filtering to obtain filtrate 2 and filter residue 2, only leaving the filtrate 2 in the step, and adding slightly soluble CaSO4And (3) remaining in the filter residue 2, wherein the filtrate 2 is a manganese sulfate solution, finally, carrying out concentration crystallization on the manganese sulfate solution by using a rotary evaporator to control the temperature, filtering to obtain a manganese sulfate solid, and washing, drying and weighing the manganese sulfate solid to obtain a pink high-purity manganese sulfate product.
The following tabular data represent the quality of the product of example 1:
| element(s) | Unit of | Crude manganese sulfate product | Example 1 product |
| Mn (manganese) | ％ | 36.17 | 34.82 |
| Ca (calcium) | ％ | 0.180 | 0.020 |
| Fe (iron) | ％ | 0.007 | <0.0005 |
| K (Potassium) | ％ | 0.002 | 0.001 |
| Mg (magnesium) | ％ | 0.480 | 0.100 |
| Na (sodium) | ％ | 0.150 | 0.025 |
Example 2
Taking 100g of a manganese sulfate crude product, adding 100mL of deionized water for dissolving, ensuring that the solid-liquid ratio is 1:1 by adding the deionized water, stirring for 2h at normal temperature, fixing the volume to 50% of the sample solution 1, adding water for dissolving the manganese sulfate crude product, stirring for 2h at normal temperature to obtain 50% of the sample solution 1, standing for 15h by using the 50% of the sample solution 1, layering solid and liquid, centrifuging and filtering to obtain a filtrate 1 and a filter residue 1, only keeping the filter residue 1 in the step, keeping other metal sulfates with high solubility in the filtrate 1, separating the metal sulfates from the filter residue 1 to obtain a manganese sulfate precipitate, fully washing the manganese sulfate precipitate to obtain a manganese sulfate solid, adding the deionized water into the manganese sulfate solid, similarly controlling the solid-liquid ratio to be 1:1, stirring for 2h at normal temperature to obtain a sample solution 2, wherein the sample solution 2 has a darker color and can be determined that the manganese sulfate content in the solution is higher initially, fully dissolving the sample solution 2, filtering to obtain filtrate 2 and filter residue 2, only retaining the filtrate 2 in the step, and adding slightly soluble CaSO4Remaining in the filter residue 2, collecting the filtrate 2 as manganese sulfate solution, concentrating and crystallizing the manganese sulfate solution with rotary evaporator at controlled temperature, and filtering to obtain sulfurAnd (3) washing, drying and weighing the manganese sulfate solid to obtain a pink high-purity manganese sulfate product.
The following tabular data are for the quality of the product of example 2:
example 3
Taking 25g of a manganese sulfate crude product, adding 25mL of deionized water for dissolving, ensuring that the solid-liquid ratio is 1:1 by adding the deionized water, stirring at normal temperature for 2h, fixing the volume to 50% of the sample solution 1, adding water for dissolving the manganese sulfate crude product, stirring at normal temperature for 2h to obtain 50% of the sample solution 1, standing 50% of the sample solution 1 for 15h to separate solid from liquid, centrifuging and filtering to obtain a filtrate 1 and a filter residue 1, only keeping the filter residue 1 in the step, keeping other metal sulfates with high solubility in the filtrate 1, separating the metal sulfates from the filter residue 1 to obtain a manganese sulfate precipitate, fully washing the manganese sulfate precipitate to obtain a manganese sulfate solid, adding the deionized water into the manganese sulfate solid, similarly controlling the solid-liquid ratio to be 1:1, stirring at normal temperature for 2h to obtain a sample solution 2, wherein the sample solution 2 is darker in color, and can be primarily determined as higher in manganese sulfate content in the solution, fully dissolving the sample solution 2, filtering to obtain a filtrate 2 and a filter residue 2, only retaining the filtrate 2 in the step, and adding slightly soluble CaSO4And (3) remaining in the filter residue 2, wherein the filtrate 2 is a manganese sulfate solution, finally, carrying out concentration crystallization on the manganese sulfate solution by using a rotary evaporator to control the temperature, filtering to obtain a manganese sulfate solid, and washing, drying and weighing the manganese sulfate solid to obtain a pink high-purity manganese sulfate product.
The following tabular data represent the quality of the product of example 3:
| element(s) | Unit of | Crude manganese sulfate product | EXAMPLE 3 product |
| Mn (manganese) | ％ | 36.17 | 36.24 |
| Ca (calcium) | ％ | 0.180 | 0.022 |
| Fe (iron) | ％ | 0.007 | <0.0005 |
| K (Potassium) | ％ | 0.002 | 0.001 |
| Mg (magnesium) | ％ | 0.480 | 0.075 |
| Na (sodium) | ％ | 0.150 | 0.021 |
As can be seen from the product qualities of example 1, example 2 and example 3, the preparation method of the invention can significantly reduce the contents of K, Na, Ca and Mg impurities, heavy metal impurities and Fe impurities in industrial manganese sulfate or manganese sulfate obtained by leaching manganese ore with sulfuric acid, particularly, the contents of K, Na, Ca and Mg impurities can be reduced to be less than 0.1%, the contents of heavy metal impurities and Fe impurities can be reduced to be less than 0.0005%, and the manganese content in the obtained high-purity manganese sulfate is more than 32%2+、Na+、K+Filtering to remove metal ions with solubility lower than manganese sulfate, and removing metal ions such as CaSO in residue 24And in the third step, the characteristics of different sulfate solubilities changing with the temperature are utilized to separate in the recrystallization process, the method further utilizes the physical properties of the sulfate to separate the sulfate, other chemical reagents and complex chemical reactions are avoided, and the method has higher practical value when applied to an actual process.
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the embodiments are only used to help understanding the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, there may be variations in the specific implementation manners and application ranges, and in summary, the content of the present description should not be construed as a limitation to the present invention.
Claims (9)
1. High-purity manganese sulfate is characterized in that: the content of manganese in the high-purity manganese sulfate is more than 32%, the content of K, Na, Ca and Mg impurities is lower than 0.1%, and the content of heavy metal impurities and Fe impurities is lower than 0.001%.
2. The high-purity manganese sulfate according to claim 1, wherein: the heavy metal impurities comprise one or more of Co, Ni, Zn, Cu, Pb, Cr and Cd.
3. A method for preparing high-purity manganese sulfate according to any one of claims 1-2 by using solubility properties, which comprises the following steps:
step one, adding water to a crude manganese sulfate product for dissolving, and stirring for 2 hours at normal temperature to obtain a 50% sample solution 1;
step two, standing the 50% sample solution 1 obtained in the step one for 15 hours, centrifuging, and filtering to obtain a filtrate 1 and a filter residue 1, wherein the filtrate 1 is used for recycling, and the filter residue 1 is manganese sulfate precipitate;
washing the manganese sulfate precipitate until the manganese sulfate precipitate meets the washing requirement to obtain a manganese sulfate solid;
adding water into the manganese sulfate solid, and stirring for 2 hours at normal temperature to obtain a sample solution 2;
step five, filtering the sample solution 2 obtained in the step four to obtain a filtrate 2 and a filter residue 2, wherein the filtrate 2 is a manganese sulfate solution, and the filter residue 2 is used for recycling;
step six, crystallizing the manganese sulfate solution obtained in the step five by using a rotary evaporator, and then filtering to obtain a manganese sulfate solid;
and seventhly, washing the manganese sulfate solid obtained in the sixth step for three times, drying and weighing to obtain a high-purity manganese sulfate product.
4. The method for preparing high-purity manganese sulfate according to claim 3, wherein the solubility property of the manganese sulfate is as follows: the manganese sulfate crude product in the step I contains a large amount of metal elements, wherein K is+、Na+、Ca2+、Mg2+And (3) the impurity content is higher, the water added in the first step and the fourth step is deionized water, and the added water amount is controlled to ensure that the solid-to-liquid ratio is 1: 1.
5. The method for preparing high-purity manganese sulfate according to claim 4, wherein the solubility property of the manganese sulfate is as follows: the oil bath temperature during the rotary evaporator crystallization in the sixth step was set to 120 ℃.
6. The method for preparing high-purity manganese sulfate according to claim 5, wherein the solubility property of the manganese sulfate is as follows: and in the seventh step, the drying temperature is set to be 80 ℃.
7. The method for preparing high-purity manganese sulfate according to claim 3, wherein the solubility property of the manganese sulfate is as follows: and (3) dissolving the manganese sulfate crude product in a water bath kettle in constant-temperature water.
8. The high-purity manganese sulfate and the method for preparing the high-purity manganese sulfate by using the solubility property according to claim 3, wherein the method comprises the following steps: a reduced-pressure suction filtration device was used for filtration in all steps.
9. The method for preparing high-purity manganese sulfate according to claim 3, wherein the solubility property of the manganese sulfate is as follows: the washing requirement in the third step is that BaCl is added into the washed solution2The solution did not become cloudy.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114212828A (en) * | 2021-12-31 | 2022-03-22 | 湖南烯富环保科技有限公司 | Method for removing impurities from manganese sulfate solution |
| CN115259231A (en) * | 2022-07-13 | 2022-11-01 | 绵阳师范学院 | Method for removing calcium and magnesium impurities in manganese sulfate |
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| FR1076015A (en) * | 1952-06-03 | 1954-10-21 | Electric Furnace Prod Co | Process for the treatment of materials containing manganese |
| CN101875507A (en) * | 2010-08-04 | 2010-11-03 | 湖南汇通科技有限责任公司 | High purity manganese sulfate monohydrate and preparation method thereof |
| CN103030180A (en) * | 2012-12-07 | 2013-04-10 | 中信大锰矿业有限责任公司 | Production method of high-purity manganese sulfate |
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2022
- 2022-04-11 CN CN202210375903.2A patent/CN114671466A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1076015A (en) * | 1952-06-03 | 1954-10-21 | Electric Furnace Prod Co | Process for the treatment of materials containing manganese |
| CN101875507A (en) * | 2010-08-04 | 2010-11-03 | 湖南汇通科技有限责任公司 | High purity manganese sulfate monohydrate and preparation method thereof |
| CN103030180A (en) * | 2012-12-07 | 2013-04-10 | 中信大锰矿业有限责任公司 | Production method of high-purity manganese sulfate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114212828A (en) * | 2021-12-31 | 2022-03-22 | 湖南烯富环保科技有限公司 | Method for removing impurities from manganese sulfate solution |
| CN115259231A (en) * | 2022-07-13 | 2022-11-01 | 绵阳师范学院 | Method for removing calcium and magnesium impurities in manganese sulfate |
| CN115259231B (en) * | 2022-07-13 | 2023-04-18 | 绵阳师范学院 | Method for removing calcium and magnesium impurities in manganese sulfate |
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