CN111807414B - Method for producing fluorine-free ultrapure manganese sulfate monohydrate by using basic salt method - Google Patents
Method for producing fluorine-free ultrapure manganese sulfate monohydrate by using basic salt method Download PDFInfo
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Abstract
The invention discloses a method for producing fluorine-free ultrapure manganese sulfate monohydrate by using an alkali salt method, belongs to the field of hydrometallurgy, and utilizes Mg with a pH value of 8-9.52+Ion failure to form Mg (OH)2Precipitate, Ca2+Ion formation Ca (OH)2The solubility of the compound is higher, and the addition of EDTA chelates calcium ions and inhibits the homoionic effect of calcium sulfate when the basic manganese sulfate is precipitated. The product has no fluorine pollution, the content of calcium, magnesium, potassium and sodium elements is extremely low, and the content of the calcium, magnesium, potassium and sodium elements in the product is respectively 0.00005-0.0005 percent of Ca, 0.00002-0.0005 percent of Mg, 0.00005-0.0002 percent of K and 0.00005-0.0002 percent of Na, which is far lower than the quality of the ultrapure manganese sulfate monohydrate.
Description
Technical Field
The invention belongs to a new method for removing calcium, magnesium, potassium and sodium in the field of wet metallurgy, and particularly relates to a method for producing fluorine-free ultrapure manganese sulfate monohydrate by using an alkali salt method.
Background
The manganese salt industry in China started earlier, and has a large scale from the 20 th century to the 50 th. The core technology of the high-purity manganese sulfate monohydrate is the separation of calcium, magnesium, potassium, sodium and manganese ions, which has always been a technical problem troubling the hydrometallurgy industry. The production method of the ultra-pure manganese sulfate is monopolized abroad and is strictly kept secret from the outside. At present, the method for removing calcium and magnesium from high-purity manganese sulfate monohydrate mainly comprises the processes of recrystallization, high-temperature crystallization, fluoride precipitation and the like. The method for removing potassium and sodium is mainly an iron vitriol method, and the cost is higher.
The recrystallization method removes calcium and magnesium, the product does not contain fluorine, but can meet the requirements of high-purity manganese sulfate on the content of calcium and magnesium by three times of recrystallization, the equipment investment is large, the energy consumption is high, and no cost advantage can be said. The high-temperature crystallization method is characterized in that the phenomenon that the solubility of manganese sulfate is gradually reduced when the temperature is higher than 27 ℃, particularly the solubility of manganese sulfate is rapidly reduced when the temperature exceeds 100 ℃, manganese sulfate is separated out at high temperature, and calcium, magnesium, potassium and sodium are reserved in a solution so as to be separated from manganese ions. However, the production mode has high energy consumption, and the contents of calcium, magnesium, potassium and sodium ions in the product are difficult to reach the standard due to the influence of water content of manganese sulfate precipitate.
At present, the main mode for removing calcium and magnesium in the metal ion solution is to add fluoride, the adding amount of fluoride ions is 3-4.5 g/L, and F is utilized-Ion and Ca2+、Mg2+Ion generation of CaF2、MgF2The insoluble matter is precipitated and removed by filtration. However, in the process of removing calcium and magnesium by adding fluoride, the addition amount of fluoride is far greater than the theoretical amount due to the interference of background manganese metal ions, and the content of calcium and magnesium ions in the solution can be reduced to the requirement of the solution required by producing qualified products. So that the fluorine ion content in the solution is very high, and the subsequent fluorine removal treatment cost of the solution is increased.
In addition, in the process of adding fluoride to remove calcium and magnesium, colloidal precipitates of calcium fluoride and magnesium fluoride with extremely high viscosity are formed, so that the solution is extremely difficult to filter, and nanoscale colloidal particles of calcium fluoride and magnesium fluoride are easily formed to be suspended in the solution and are extremely difficult to separate from the solution. The engineering problem puzzles the hydrometallurgy industry for a long time, and can not be solved all the time, so that the production efficiency is low, and the cost is high.
The fluorine content of the high-purity manganese sulfate monohydrate product also has a strict standard, so that the solution purification and fluorine removal become a new problem. In addition to the production cost of removing potassium and sodium from the product, the cost for producing the high-purity manganese sulfate monohydrate is saved and increased, so that a plurality of manufacturers have no profit space, the competition of the high-purity manganese sulfate monohydrate industry is quitted in a dispute, and the production of the ultra-pure manganese sulfate monohydrate is the market blank.
Disclosure of Invention
The invention aims to: aiming at the defects of the production technology of high-purity manganese sulfate monohydrate, the invention provides a method for producing fluorine-free ultrapure manganese sulfate monohydrate by using an alkali salt method, and realizes a fluorine-free, environment-friendly and high-efficiency production scheme of ultrapure manganese sulfate monohydrate.
The technical scheme adopted by the invention is as follows:
a method for producing fluorine-free ultrapure manganese sulfate monohydrate by using a basic salt method comprises the following steps:
s1, preparing a mixed solution of complexing agent EDTA and alkali;
s2, slowly adding the mixed solution prepared in the step S1 into a manganese sulfate solution containing calcium, magnesium, potassium and sodium, wherein the addition amount of the mixed solution is NH according to a molar ratio3:Mn2+0.8-1.4 of Ca in a molar ratio2+EDTA 0.1-2, keeping the temperature of the reaction solution at 40-80 ℃, and the pH value at 8-9.5, according to the reaction equation: 2NH3·H2O+2MnSO4＝Mn2(OH)2SO4↓ (basic manganese sulfate) + (NH)4)2SO4Generating basic manganese sulfate precipitate, and after the reaction is finished, keeping the temperature of the solution for 40-50 min; mn in manganese sulfate solution2+：80～150g/L、Ca2+:40～670mg/L、Mg2+:40～ 500mg/L、K+:0.01～10g/L、Na+:0.01～10g/L；
S3, filtering, and washing the filtered precipitate;
and S4, adding sulfuric acid to dissolve in the step S3, filtering to obtain filtrate, namely, a high-concentration manganese sulfate solution with low calcium, magnesium and potassium and sodium, and evaporating and crystallizing to obtain the ultra-pure manganese sulfate monohydrate product. According to Mn2(OH)2SO4：H2SO4Adding concentrated sulfuric acid with the mass concentration of 98 percent into the mixture 1:1 (molar ratio);
mg is contained in a manganese sulfate solution containing ammonium sulfate within the pH value range of 8-9.52+Ions not forming Mg (OH)2Precipitate, Ca2+Ion formation Ca (OH)2The solubility is high, calcium ions are chelated by adding EDTA, and the same ion effect of calcium sulfate in the process of precipitating the basic manganese sulfate is inhibited, so the calcium sulfate can be separated from manganese in a washing mode, and the precipitate is filtered, washed by adding pure water, dissolved by adding acid and filtered, and the filtrate is high-concentration manganese sulfate solution with low calcium, magnesium and potassium and sodium, and then is evaporated, crystallized and dried to obtain the ultrapure manganese sulfate monohydrate.
Preferably, the alkali is any one or more of ammonia water, hydrazine hydrate and sodium hydroxide.
Preferably, the method further comprises step S5: the washing liquid in step S3 is combined with the filtrate, still containing Mn in concentration2+Adding a mixed precipitator to precipitate unreacted manganese ions and Ca (calcium chloride) 6-10 g/L2+And Mg2+According to Mn2+And NH4HCO3Adding a mixed precipitant into the mixture with the molar ratio of 0.8-1.2, washing the precipitate to obtain wet material, returning the wet material to a leaching working section process to be used as a pH regulator, carrying out acid dissolution, filtering out solid, adding a reducing agent for reduction, returning the solid to an acid dissolution process for recycling, deaminating all generated waste water containing ammonium sulfate to prepare ammonia water, and returning the ammonia water to the step S1 for recycling.
Preferably, the mixed precipitant of step S5 is NH3And NH4HCO3The molar ratio of 1 (0.5-1.5).
Preferably, the reducing agent in step S5 is one or more of oxalic acid, metal manganese powder, sulfur dioxide and sulfite.
Compared with the prior art, the invention has the beneficial effects that:
the method for producing the ultrapure manganese sulfate monohydrate utilizes Mg with the pH value within the range of 8-9.52+Ions not forming Mg (OH)2Precipitate, Ca2+Ion formation Ca (OH)2The solubility of the manganese sulfate is high, calcium ions are chelated by adding EDTA, and the same ion effect of calcium sulfate when the basic manganese sulfate is precipitated is inhibited; compared with the prior production technology, the product has no fluorine pollution, the content of calcium, magnesium, potassium and sodium elements is extremely low, and the content of the calcium, the magnesium, the potassium and the sodium elements in the product is respectively 0.00005-0.0005 percent of Ca, 0.00002-0.0005 percent of Mg, 0.00005-0.0002 percent of K, 0.00005-0.0002 percent of Na and far lower than the quality of the ultrapure manganese sulfate monohydrate; the production process is simple, and the requirement on equipment is low; the process flow is short, and the production efficiency is high; the method has low requirement on the quality of raw material ores, is particularly suitable for the raw material ores containing high magnesium, and has strong adaptability. The production method has the advantages of economy, environmental protection, high efficiency, wide raw material application range, high product quality and the like, and has very high production application value and wide market space.
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FIG. 1 is a process flow diagram of a process for the production of fluorine-free ultrapure manganese sulfate monohydrate.
Detailed Description
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A method for producing fluorine-free ultrapure manganese sulfate monohydrate by using an alkali salt method comprises the following steps:
(1) 309g of 10% ammonia water solution is prepared, and 2.8g of EDTA is dissolved and added to prepare mixed solution of ammonia water and EDTA;
(2) slowly dripping into 1L manganese sulfate solution to be removed of calcium, magnesium, potassium and sodium(1) And (3) precipitating manganese from the prepared mixed solution, wherein the manganese precipitation time is 3 hours and the temperature is 70 ℃. After the reaction is finished, the temperature is kept for 45 min. The manganese sulfate solution to be subjected to calcium, magnesium, potassium and sodium removal is subjected to element detection and analysis as follows, Mn2+100g/L, 300Mg/L of Ca, 250Mg/L of Mg and 150Mg/L of K; 300mg/L of Na. Wherein Ca is ICP detection result, Mg is atomic absorption detection result, the same is as below.
(3) After the heat preservation is finished, the mixture is filtered while the mixture is hot and is added with 1000mL of water for rinsing.
(4) And (4) adding the precipitate filtered and washed in the step (3) into 133.64g/L sulfuric acid-containing solution 600mL to dissolve, and filtering to obtain 700mL filtrate, wherein the filtrate is the high-concentration manganese sulfate solution with low calcium, magnesium, potassium and sodium. The detection result of the high-concentration manganese sulfate solution is as follows: mn2+:128g/L，Ca:3mg/L，Mg:2mg/L，K:1.5mg/L；Na:1.0mg/L。
(5) Evaporating and crystallizing the high-concentration manganese sulfate solution, and drying to obtain the ultra-pure manganese sulfate monohydrate product. The results of the measurements showed 32.23% of Mn, 0.0003% of Ca, 0.00019% of Mg, 0.00015% of K, 0.0001% of Na and no detectable F.
Example 2
A method for producing fluorine-free ultrapure manganese sulfate monohydrate by using an alkali salt method comprises the following steps:
(1) 370g of ammonia water solution with the mass ratio of 10 percent is prepared, 4.7g of EDTA is dissolved and added in the ammonia water solution to prepare mixed solution of ammonia water and EDTA;
(2) slowly dripping the mixed solution prepared in the step (1) into 1L of manganese sulfate solution to be subjected to calcium, magnesium, potassium and sodium removal to precipitate manganese, wherein the manganese precipitation time is 3 hours and the temperature is 70 ℃. After the reaction is finished, the temperature is kept for 45 min. The manganese sulfate solution to be subjected to calcium, magnesium, potassium and sodium removal is subjected to element detection and analysis as follows, Mn2+:120g/L，Ca:580mg/L，Mg:300mg/L，K:300mg/L；Na:500mg/L
(3) After the heat preservation is finished, the mixture is filtered while the mixture is hot, and 1000mL of water is added for rinsing.
(4) And (4) adding the precipitate filtered and washed in the step (3) into 600mL of 160g/L sulfuric acid-containing solution for dissolving, and filtering to obtain 700mL of filtrate, wherein the filtrate is the high-concentration manganese sulfate solution with low calcium, magnesium, potassium and sodium. The solution detection result is as follows:Mn2+:150g/L，Ca:4mg/L，Mg:2mg/L，K:2mg/L；Na:1.5mg/L。
(5) evaporating and crystallizing the high-concentration manganese sulfate solution, and drying to obtain the ultra-pure manganese sulfate monohydrate product. The results of the tests showed that Mn was 32.21%, Ca was 0.00008%, Mg was 0.00007%, K was 0.00001%, Na was 0.00001%, and F was not detected.
Example 3
A method for producing fluorine-free ultrapure manganese sulfate monohydrate by using a basic salt method comprises the following steps:
(1) 463g of 10% ammonia water solution by mass ratio is prepared, 4.7g of EDTA is dissolved and added in the solution, and mixed solution of ammonia water and EDTA is prepared;
(2) and (2) slowly dripping the mixed solution prepared in the step (1) into a manganese sulfate solution to be subjected to calcium, magnesium, potassium and sodium removal for manganese precipitation for 3 hours at the temperature of 70 ℃. After the reaction is finished, the temperature is kept for 45 min. The detection and analysis of elements in the manganese sulfate solution to be removed of calcium, magnesium, potassium and sodium are as follows, Mn2+:150g/L，Ca:550mg/L，Mg:10g/L，K:300mg/L；Na:500mg/L
(3) After the heat preservation is finished, the mixture is filtered while the mixture is hot and is added with 1000mL of water for rinsing.
(4) The precipitate obtained after the filtration and washing in the step (3) is taken and dissolved in 700mL of 171.81g/L sulfuric acid-containing solution. And after the dissolution is complete, filtering. Obtaining 900mL of filtrate, namely the filtrate is high-concentration manganese sulfate solution with low calcium, magnesium, potassium and sodium. The result of the solution test was Mn2+:150g/L，Ca:4mg/L，Mg:2mg/L，K:2mg/L；Na:1.5mg/L。
(5) Evaporating and crystallizing the high-concentration manganese sulfate solution, and drying to obtain the ultra-pure manganese sulfate monohydrate product. The results of the tests showed that Mn was 32.20%, Ca was 0.00005%, Mg was 0.00004%, K was 0.00001%, Na was 0.00005%, and F was not detected.
In conclusion, the invention produces the ultrapure manganese sulfate monohydrate by utilizing Mg within the pH value range of 8-9.52+Ion failure to form Mg (OH)2Precipitate, Ca2+Ion formation Ca (OH)2The solubility of the manganese sulfate is high, calcium ions are chelated by adding EDTA, and the same ion effect of calcium sulfate when the basic manganese sulfate is precipitated is inhibited; the calcium, magnesium, potassium and sodium elements in the productThe contents of Ca are 0.00005-0.0005%, Mg is 0.00002-0.0005%, K is 0.00005-0.0002%, Na is 0.00005-0.0002%, and the quality of the product is far lower than that of the ultrapure manganese sulfate monohydrate.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (5)
1. A method for producing fluorine-free ultrapure manganese sulfate monohydrate by using an alkali salt method is characterized by comprising the following steps:
s1, preparing a mixed solution of complexing agent EDTA and alkali;
s2, slowly adding the mixed solution prepared in the step S1 into a manganese sulfate solution containing calcium, magnesium, potassium and sodium, wherein the addition amount of the mixed solution is NH according to a molar ratio3:Mn2+Adding the mixture in an amount which satisfies the molar ratio of Ca to 0.8-1.42+EDTA = 0.1-2, keeping the temperature of the reaction solution between 40 ℃ and 80 ℃, keeping the pH value between 8-9.5 to generate basic manganese sulfate precipitate, and keeping the temperature of the solution for 40-50 min after the reaction is finished;
s3, filtering, washing the filtered precipitate;
and S4, adding sulfuric acid to dissolve in the step S3, filtering to obtain filtrate, namely, a high-concentration manganese sulfate solution with low calcium, magnesium and potassium and sodium, and evaporating and crystallizing to obtain the ultra-pure manganese sulfate monohydrate product.
2. The method for producing fluorine-free ultrapure manganese sulfate monohydrate by using the basic salt method according to claim 1, wherein the alkali is any one or more of ammonia water and hydrazine hydrate.
3. The method for producing fluorine-free ultrapure manganese sulfate monohydrate according to claim 1 further comprising the step of S5: filtering the washing liquid in the step S3Mixing the solutions, and keeping the Mn concentration2+= 6-10 g/L, adding mixed precipitant, precipitating to remove unreacted manganese ion and Ca2+And Mg2+According to Mn2+And NH4HCO3Adding a mixed precipitant with a molar ratio of 0.8-1.2, washing the precipitate to obtain a wet material, returning the wet material to a leaching working section process to be used as a pH regulator, carrying out acid dissolution, filtering out a solid, adding a reducing agent for reduction, returning to an acid dissolution process for recycling, deaminating all generated wastewater containing ammonium sulfate to prepare ammonia water, and returning to the step S1 for recycling.
4. The method for producing fluorine-free ultrapure manganese sulfate monohydrate by utilizing the basic salt method as claimed in claim 3, wherein said mixed precipitant of step S5 is in accordance with NH3And NH4HCO3The molar ratio of 1 (0.5-1.5).
5. The method for producing fluorine-free ultrapure manganese sulfate monohydrate by using the basic salt method as claimed in claim 3, wherein said reducing agent in step S5 is one or more selected from oxalic acid, manganese metal powder, sulfur dioxide and sulfite.
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| CN114988478B (en) * | 2022-06-09 | 2024-03-22 | 四川大学 | Method for preparing battery-grade manganese sulfate by synergistic dissolution crystallization of chelating agent |
| CN115806350A (en) * | 2022-12-07 | 2023-03-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Deep calcium removal method for high-magnesium sodium chloride brine |
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