CN113716613A - Preparation method of high-purity manganese sulfate - Google Patents
Preparation method of high-purity manganese sulfate Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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- C01G45/00—Compounds of manganese
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Abstract
The invention relates to the technical field of new energy ternary lithium battery anode materials, and provides a preparation method of high-purity manganese sulfate. In addition, the method can also remove heavy metal impurity ions firstly, and then remove calcium and magnesium ions through ammonium bicarbonate precipitation. The method provided by the invention can conveniently remove calcium and magnesium ions by controlling the precipitation conditions, the obtained high-purity manganese sulfate meets the requirements of electronic-grade manganese sulfate, and the method is low in operation cost, simple in steps and easy to industrialize.
Description
Technical Field
The invention relates to the technical field of new energy ternary lithium battery cathode materials, in particular to a preparation method of high-purity manganese sulfate.
Background
High-purity manganese sulfate (electronic grade manganese sulfate) is one of production raw materials of anode materials of ternary lithium batteries and lithium manganate batteries. The high-purity manganese sulfate has high requirements on impurities, for example, the requirements on various impurities in the high-purity manganese sulfate by the product quality standard of the Ministry of industry and communications (HG/T4823-:
TABLE 1. department of industry and trust regarding purity requirements for electronic grade manganese sulfate (HG/T4823-
The difficulty of the existing high-purity manganese sulfate production process is the impurity removal process because the requirement on the content of impurities is high. And of all impurities, the removal of calcium and magnesium, especially calcium, is most difficult. Other metal impurities such as iron, zinc, copper, lead, cadmium, nickel and cobalt can be well removed by adjusting the pH value (removing iron), adding sodium ferulate or other vulcanizing agents (removing heavy metals), and sodium and potassium can be removed in the form of insoluble precipitates such as jarosite and the like. Therefore, the removal process of other impurities except calcium and magnesium is simple and mature, and can basically meet the requirement of a demander.
In the processes of removing calcium and magnesium, the process commonly adopted in coastal zones at present is to select pyrolusite with very low calcium and magnesium contents, reduce tetravalent manganese in the pyrolusite into divalent manganese by carbon or sulfur dioxide, leach the divalent manganese by sulfuric acid to obtain a manganese sulfate solution with very low calcium and magnesium contents, and repeatedly recrystallize the manganese sulfate solution to obtain electronic-grade manganese sulfate. However, the process has the following disadvantages: (1) pyrolusite with low contents of calcium and magnesium is only produced in individual countries in Africa at present, and the source is very limited. In addition, the current shipping cost is increased, so that the production cost of the high-purity manganese sulfate is greatly increased. (2) In the recrystallization process, the concentration of calcium and magnesium in the solution is gradually increased along with the evaporation of water to a certain degree, and the calcium sulfate, the magnesium sulfate and the product manganese sulfate form eutectic precipitation, so that the purity of the product is reduced. In order to make the product meet the requirement of the needed prescription, the crystallization amount must be controlled so that calcium and magnesium in the solution are not separated out. Therefore, the yield of the high-purity manganese sulfate is low, and the comprehensive cost of the product is higher. Other processes for removing calcium and magnesium, such as converting manganese sulfate into manganese carbonate with ammonium bicarbonate, and then dissolving with sulfuric acid (publication No. CN 101704555A). Theoretically, when ammonium bicarbonate is used for precipitating manganese, calcium and magnesium ions in the original manganese sulfate solution are remained in the solution and cannot be precipitated together with manganese carbonate due to the generation of calcium bicarbonate or magnesium bicarbonate, but the solubility of calcium bicarbonate is very limited (1.6g/L), and the partial pH value is too high after the ammonium bicarbonate is added, so that the calcium magnesium and the manganese carbonate can form coprecipitation, and the method cannot achieve the aim in practice.
In the patent with publication number CN 102674467a, electrolytic manganese is used as a raw material, and electronic-grade manganese sulfate is obtained by removing heavy metals from manganese sulfide, oxidizing iron from hydrogen peroxide and other processes. Because the purity of the adopted raw material electrolytic manganese is very high, the electronic-grade manganese sulfate can be successfully obtained, but because the price of the electrolytic manganese is high, the cost of the process is high.
In patent publication CN101508467, manganese fluoride is used to remove calcium and magnesium. Theoretically, it is calculated that the removal of calcium and magnesium by manganese fluoride or other fluorides (such as ammonium fluoride) can achieve very ideal effects, but in practice, the solution has high ionic strength due to the high concentration of the manganese sulfate solution, and the dissolution of calcium fluoride and magnesium fluoride is promoted, so that the calcium and magnesium impurities cannot meet the requirements in terms of the impurity concentration except the difficulty in filtration in the process. In addition, fluorine ions as impurities are carried in. On one hand, the removal cost of the fluoride ions is higher, and on the other hand, the limitation on the concentration of the impurity fluoride ions is higher and higher, so that the process cannot produce a high-purity manganese sulfate product meeting the requirements.
In summary, the existing high-purity manganese sulfate production technology adopts electrolytic manganese or pyrolusite with low calcium and magnesium content as raw materials, and other processes have the problems that calcium and magnesium are difficult to remove, and the purity of manganese sulfate is difficult to meet the requirement.
Disclosure of Invention
In view of the above, the invention provides a preparation method of high-purity manganese sulfate. The method provided by the invention has the advantages of simple steps and low cost, can effectively remove calcium and magnesium ions, and can obtain the electronic-grade manganese sulfate meeting the requirements.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the high-purity manganese sulfate comprises the following steps:
(1) mixing the crude manganese salt solution with a pH value control agent, adding an ammonium bicarbonate solution into the obtained mixed solution for reaction, and after the ammonium bicarbonate solution is added, sequentially aging and carrying out solid-liquid separation on the obtained reaction mixture to obtain manganese carbonate;
(2) dissolving the manganese carbonate in electronic-grade sulfuric acid, adding ammonium sulfide into the obtained dissolved solution, sequentially stirring, standing and carrying out solid-liquid separation, and evaporating the obtained filtrate to obtain high-purity manganese sulfate;
or comprises the following steps:
(a) mixing the crude manganese salt solution with ammonium sulfide, and sequentially stirring, standing and carrying out solid-liquid separation to obtain a refined manganese salt solution;
(b) mixing the refined manganese salt solution with a pH value control agent, adding an ammonium bicarbonate solution into the obtained mixed solution for reaction, and after the ammonium bicarbonate solution is added, sequentially aging and carrying out solid-liquid separation on the obtained reaction mixture to obtain high-purity manganese carbonate;
(c) dissolving the high-purity manganese carbonate in electronic-grade sulfuric acid, and evaporating the obtained dissolved solution to obtain high-purity manganese sulfate;
wherein the pH value is controlled to be at least one of ammonium chloride and ammonium nitrate; the pH value control agent controls the pH value of the system to be 5-6; and (c) controlling the temperature to be higher than 100 ℃ when the mixed solution reacts with the ammonium bicarbonate solution in the step (1) and the step (b).
Preferably, the crude manganese salt in the crude manganese salt solution is feed-grade manganese sulfate, agricultural-grade manganese sulfate, crude manganese chloride or crude manganese nitrate; the purity of the crude manganese chloride and the crude manganese nitrate is industrial grade purity or lower than the industrial grade purity.
Preferably, the concentration of the pH control agent in the mixed solution obtained by mixing the crude manganese salt solution and the pH control agent in the step (1) is 150-300 g/L;
and (c) mixing the refined manganese salt solution and the pH control agent in the step (b) to obtain a mixed solution, wherein the concentration of the pH control agent in the mixed solution is 150-300 g/L.
Preferably, the temperature of the mixed solution and the ammonium bicarbonate solution in the step (1) and the step (b) during the reaction is independently 102-110 ℃.
Preferably, in the step (1) and the step (b), the adding amount of the ammonium bicarbonate is 2.2-2.6 times of the molar amount of the manganese ions.
Preferably, the concentration of the ammonium bicarbonate solution in the step (1) and the step (b) is 0.5-2 mol/L independently;
and (b) slowly adding the ammonium bicarbonate solution in the step (1) and the step (b) into the mixed solution under the condition of stirring, wherein the adding amount of the ammonium bicarbonate solution per minute is not more than 1/50 of the total volume of the solution in the reaction tank.
Preferably, the aging time in the step (1) and the step (b) is independently 1-2 h.
Preferably, the addition amount of the ammonium sulfide in the step (2) and the step (a) is independently 2-4 g/L.
Preferably, the stirring time in the step (2) and the stirring time in the step (a) are independently 1-6 hours, and the standing time is independently 2-10 hours.
Preferably, the concentration of manganese ions in the solution obtained in the step (2) and the step (c) is 130-180 g/L.
The invention provides a preparation method of high-purity manganese sulfate, which utilizes the pH value of an ammonium chloride and/or ammonium nitrate control system to mix a crude manganese salt solution and an ammonium bicarbonate solution at the temperature higher than 100 ℃, manganese ions in the solution generate manganese carbonate, meanwhile, the ammonium chloride or ammonium nitrate can quickly dissolve the generated calcium carbonate precipitate at high temperature so that calcium enters the solution again, and the residual ammonium carbonate (hydrogen) in the solution can be quickly decomposed into ammonia gas and carbon dioxide at high temperature, thereby reducing the chance of calcium ion precipitation, wherein the solubility of magnesium is higher, and the residual ammonium carbonate (hydrogen) in the solution can be kept in the solution without being precipitated by the ammonium bicarbonate under the pH value control condition of the invention; after the manganese carbonate precipitate is obtained, dissolving the manganese carbonate precipitate in electronic-grade sulfuric acid, adding ammonium sulfide to remove heavy metal impurity ions in the manganese carbonate precipitate, filtering, and evaporating the obtained filtrate to obtain the high-purity manganese sulfate.
In addition, the method can also remove heavy metal impurity ions in the crude manganese salt solution by adding ammonium sulfide, then remove calcium and magnesium ions by ammonium bicarbonate precipitation to obtain high-purity manganese carbonate, and then obtain the high-purity manganese sulfate by dissolving and evaporating sulfuric acid.
The preparation method provided by the invention can conveniently remove calcium and magnesium ions by controlling the precipitation conditions, the obtained high-purity manganese sulfate meets the requirements of electronic-grade manganese sulfate, and the preparation method is low in operation cost, simple in steps and easy to industrialize. The example result shows that the indexes of various impurity ions in the high-purity manganese sulfate prepared by the method are superior to the quality standard of an electronic-grade manganese sulfate product released by the Ministry of industry and communications.
Detailed Description
The invention provides a preparation method of high-purity manganese sulfate, which can remove calcium and magnesium ions firstly and then remove heavy metal ions, or can remove heavy metal ions firstly and then remove calcium and magnesium ions, wherein the method of removing calcium and magnesium ions firstly and then removing heavy metal ions is recorded as method I, and the method of removing heavy metal ions firstly and then removing calcium and magnesium ions is recorded as method II, which are introduced respectively.
In the present invention, the first method comprises the following steps:
(1) mixing the crude manganese salt solution with a pH value control agent, adding an ammonium bicarbonate solution into the obtained mixed solution for reaction, and after the ammonium bicarbonate solution is added, sequentially aging and carrying out solid-liquid separation on the reaction mixture to obtain manganese carbonate;
(2) dissolving the manganese carbonate in electronic-grade sulfuric acid, adding ammonium sulfide into the obtained dissolved solution, sequentially stirring, standing and carrying out solid-liquid separation, and evaporating the obtained filtrate to obtain high-purity manganese sulfate;
the invention firstly mixes the coarse manganese salt solution and the pH value control agent. In the invention, the crude manganese salt in the crude manganese salt solution is preferably feed-grade manganese sulfate, agricultural-grade manganese sulfate, crude manganese chloride or crude manganese nitrate; the purity of the crude manganese chloride or the crude manganese nitrate is industrial grade purity or lower than the industrial grade purity; the concentration of magnesium ions in the crude manganese salt solution is preferably not more than 3g/L, and the concentration of calcium ions is preferably not more than 2g/L, the concentration of magnesium ions in the crude manganese salt solution is controlled below 3g/L, and the concentration of calcium ions in the crude manganese salt solution is controlled below 2g/L, so that calcium and magnesium precipitates can be prevented from being generated in the subsequent manganese carbonate precipitation process; in the field, the content of calcium and magnesium in the crude manganese salt is generally hundreds to two thousand ppm, and the concentration of calcium and magnesium ions in the crude manganese salt solution can not reach more than 2g/L basically, so that most of the crude manganese salt can be used as the raw material of the invention. The invention has no special requirement on the concentration of other impurity ions in the crude manganese salt solution.
In the invention, the concentration of manganese ions in the mixed solution obtained by mixing the crude manganese salt solution and the pH value control agent is preferably 100-180 g/L; in the embodiment of the present invention, it is preferable that the crude manganese salt is dissolved, then the pH control agent is added to the solution, and after the pH control agent is completely dissolved, the concentration of the manganese ions in the solution is adjusted to the desired concentration.
In the present invention, the pH adjuster is preferably at least one of ammonium nitrate and ammonium chloride; the concentration of the pH value control agent in the mixed solution is preferably 150-300 g/L, and more preferably 200-250 g/L; according to the method, sufficient ammonium nitrate and ammonium chloride are added into the crude manganese salt solution, so that the pH value of the system can be controlled to be 5-6; because the content of calcium and magnesium ions in the raw material manganese salt is small (generally less than 2000ppm), the calcium and magnesium ions can not be precipitated theoretically under the pH value condition.
After the crude manganese salt solution and the pH value control agent are mixed, the invention adds ammonium bicarbonate solution into the obtained mixed solution for reaction, and after the ammonium bicarbonate solution is added, the obtained reaction mixture is sequentially aged and subjected to solid-liquid separation to obtain the manganese carbonate. In the invention, the molar weight of ammonium bicarbonate in the ammonium bicarbonate solution is preferably 2.2 to 2.6 times, and more preferably 2.3 to 2.5 times that of manganese ions; the concentration of the ammonium bicarbonate solution is preferably 0.5-2 mol/L, and more preferably 1-1.5 mol/L; the ammonium bicarbonate solution is preferably added slowly to the mixture under stirring, and the amount of ammonium bicarbonate solution added per minute is preferably not more than 1/50 of the total volume of the solution in the reaction tank.
In the invention, the temperature of the reaction of the mixed solution and the ammonium bicarbonate solution is more than 100 ℃, preferably 102-110 ℃, in the specific embodiment of the invention, a reaction kettle with a heat conduction oil interlayer is preferably used, the mixed solution of the crude manganese salt and the pH value control agent is placed in the reaction kettle, the mixed solution is heated to more than 100 ℃ by utilizing the heat conduction oil interlayer, and then the ammonium bicarbonate solution is added into the reaction kettle by utilizing a peristaltic pump. In the specific embodiment of the invention, the invention preferably adds a proper amount of boiling water in the process of adding the ammonium bicarbonate solution to supplement the water lost due to evaporation, and avoids the residual coarse manganese salt in the system from being separated out due to the evaporation of the solution.
The ammonium bicarbonate solution is added under the condition of more than 100 ℃, and one of the two solutions is that the ammonium chloride or the ammonium nitrate can quickly dissolve the generated calcium carbonate precipitate so as to enable the calcium to enter the solution again; and secondly, residual ammonium carbonate (hydrogen) in the solution is decomposed into ammonia gas and carbon dioxide as soon as possible, so that the chance of calcium ion precipitation is reduced. Due to the solubility product of manganese carbonate (Ksp ═ 3 × 10)-9) Bisbalcium carbonate (Ksp ═ 3X 10)-8) Small, so manganese ions precipitate first and manganese carbonate is more difficult to dissolve in hot ammonium chloride or ammonium nitrate than calcium carbonate. By utilizing the difference of the dissolution speed of the manganese carbonate and the calcium carbonate, the calcium carbonate which is possibly precipitated can be conveniently removed from the manganese carbonate, thereby ensuring the high purity of the manganese carbonate. In addition, during the process of producing manganese carbonate, the solubility of magnesium is relatively high (Ksp ═ 6 × 10)-5) And thus may remain in solution without precipitation by ammonium bicarbonate.
After the ammonium bicarbonate solution is added, the obtained reaction mixture is aged; the time for aging is preferably 1-2 h, the temperature for aging is the same as the temperature for adding the ammonium bicarbonate solution, namely, the heat preservation and aging are carried out after the ammonium bicarbonate solution is added.
After aging, the invention carries out solid-liquid separation on the aged system. The present invention has no special requirement on the solid-liquid separation mode, and the mode known to those skilled in the art can be used, such as filtration. The invention preferably naturally cools the system to room temperature, and then carries out solid-liquid separation; the solid product obtained by solid-liquid separation is manganese carbonate, and the liquid is a filtrate containing calcium and magnesium ions; the invention preferably regenerates the filtrate, and the regeneration method is preferably as follows: adding ammonium carbonate into the filtrate to precipitate calcium and magnesium ions in the filtrate, filtering, and heating the filtrate to decompose the residual ammonium carbonate to obtain regenerated filtrate; the regenerated filtrate is preferably used for dissolving crude manganese salt, so that the filtrate is recycled, and the discharge of a large amount of waste liquid is avoided.
After filtration, the manganese carbonate obtained is preferably washed by the invention, and the washing water is preferably high-purity water or ultrapure water; the number of washing is preferably 5.
After the manganese carbonate is obtained, the manganese carbonate is dissolved in electronic-grade sulfuric acid, ammonium sulfide is added into the obtained dissolved solution, stirring, standing and solid-liquid separation are sequentially carried out, and the obtained filtrate is evaporated to obtain high-purity manganese sulfate. In the invention, the concentration of the electronic grade sulfuric acid is preferably 5 mol/L; in the specific embodiment of the invention, the electronic-grade sulfuric acid can be directly added into the manganese carbonate filter cake, or the manganese carbonate is prepared into a manganese carbonate-ultrapure water suspension, and then the electronic-grade sulfuric acid is slowly added into the manganese carbonate-ultrapure water suspension until the manganese carbonate is completely dissolved; the concentration of manganese ions in the dissolving solution is preferably 130-180 g/L, and more preferably 140-160 g/L; if the pH value of the solution is lower than 5, manganese powder (the manganese powder is generally used in a small amount when the pH value is adjusted, the final manganese concentration is not greatly influenced, and the manganese ion concentration in the solution can be kept within the range) is preferably used for adjusting the pH value of the solution to 5-6.5, and then ammonium sulfide is added. In the invention, the excessive acidity of the dissolving solution can cause the addition of ammonium sulfide to generate hydrogen sulfide gas, which pollutes the working environment, and the ammonium sulfide generates hydrogen sulfide radicals or hydrogen sulfide, which reduces the capability of precipitating heavy metals; meanwhile, the manganese is oxidized by air due to too high pH value to generate black manganese oxide, and the pH value of the solution is adjusted to 5-6.5, so that the problems can be avoided.
In the invention, the addition amount of the ammonium sulfide is preferably 2-4 g/L, and more preferably 3-3.5 g/L; namely, 2-4 g of ammonium sulfide is added into each liter of the dissolving solution, and in the specific embodiment of the invention, the volume of the dissolving solution can be adjusted to be an integer by using ultrapure water so as to facilitate the calculation of the adding amount of the ammonium sulfide.
In the invention, the stirring time is preferably 1-6 h, more preferably 2-5 h, and the standing time is preferably 2-10 h, more preferably 3-8 h. According to the invention, ammonium sulfide is added, and then the mixture is stirred and stood to enable heavy metal ions in the system to form precipitates, and further the heavy metal ions are removed through solid-liquid separation.
The present invention has no special requirement on the solid-liquid separation mode, and the mode known to those skilled in the art can be used, such as filtration. After filtration, the filtrate obtained by the method is evaporated to obtain the high-purity manganese sulfate. The evaporation method has no special requirements, and the evaporation method which is common in the field can be adopted. After evaporation to obtain high-purity manganese sulfate crystals, the high-purity manganese sulfate crystals are preferably dried in vacuum; the temperature of the vacuum drying is preferably 100 ℃, and the drying time is not particularly required in the invention, so that the vacuum drying is preferably sufficient.
In the present invention, the second method comprises the following steps:
(a) mixing the crude manganese salt solution with ammonium sulfide, and sequentially stirring, standing and carrying out solid-liquid separation to obtain a refined manganese salt solution;
(b) mixing the refined manganese salt solution with a pH value control agent, adding an ammonium bicarbonate solution into the obtained mixed solution for reaction, and after the ammonium bicarbonate solution is added, sequentially aging and carrying out solid-liquid separation on the obtained reaction mixture to obtain high-purity manganese carbonate;
(c) and dissolving the high-purity manganese carbonate in electronic-grade sulfuric acid, and evaporating the obtained dissolved solution to obtain the high-purity manganese sulfate.
The method mixes the crude manganese salt solution and ammonium sulfide, and sequentially carries out stirring, standing and solid-liquid separation to obtain the refined manganese salt solution. In the invention, the types of the crude manganese salt, the concentration of manganese ions in the crude manganese salt solution and the concentrations of calcium ions and magnesium ions are consistent with the scheme, and are not described again; the addition amount of the ammonium sulfide is consistent with that of the scheme, and is not described again; manganese powder is preferably used for adjusting the pH value of the crude manganese salt solution before the ammonium sulfide is added, and the specific adjusting method is consistent with the scheme and is not described again; the specific conditions of stirring, standing and solid-liquid separation are consistent with the scheme, and are not described again.
After obtaining the refined manganese salt solution, mixing the refined manganese salt solution with the pH value control agent, adding an ammonium bicarbonate solution into the obtained mixed solution for reaction, and after the ammonium bicarbonate solution is added, sequentially aging and carrying out solid-liquid separation on the reaction mixture to obtain the high-purity manganese carbonate. In the present invention, the operating conditions of step (b) and step (1) in the first method are completely the same, and only the crude manganese salt solution is replaced by the refined manganese salt solution, which is not described herein again.
After the high-purity manganese sulfate is obtained, the high-purity manganese carbonate is dissolved in electronic-grade sulfuric acid, and the obtained dissolved solution is evaporated to obtain the high-purity manganese sulfate. In the present invention, the operating conditions of step (c) and step (2) in the first method are completely the same, and only the step of adding ammonium sulfide is omitted, which is not described herein again.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
1 kg of feed-grade manganese sulfate (the concentrations of Ca and Mg are 135ppm and 406ppm respectively) is taken and dissolved in 2L of water, 400g of ammonium chloride is added, and after the solution is stirred and dissolved, the manganese concentration of the solution is adjusted to 100 g/L. 1.5L of the solution is put into a 10L glass reaction kettle and heated to 102 ℃ by a heat conduction oil interlayer. Under the condition of keeping the solution temperature at equal to or higher than 102 ℃ and continuously stirring, 6L of ammonium bicarbonate solution with the concentration of 1mol/L (the molar ratio of ammonium bicarbonate to manganese sulfate is 2.2:1) is added by a peristaltic pump at the flow rate of 30 mL/min. An appropriate amount of boiling water is added as necessary to replenish water lost to evaporation in the reaction kettle. After the ammonium bicarbonate solution is added, the temperature is kept at 102 ℃ for aging for 1h, and then the temperature is naturally reduced to the room temperature. Filtration and washing of the filter cake five times with high purity water. Transferring the filter cake into a beaker in batches, slowly adding 5mol/L electronic-grade sulfuric acid solution until the manganese carbonate is completely dissolved, adjusting the acidity of the solution to pH value of 5 by using manganese powder, adjusting the volume of the solution to 3L, then adding 6g of ammonium sulfide (2 g of ammonium sulfide per liter of solution), stirring for 1h, and aging for 10 h. Filtering, collecting filtrate, evaporating to obtain manganese sulfate crystals, drying at 100 ℃ in vacuum, and then sending the manganese sulfate crystals to a sample for analysis.
Example 2
The operation steps are completely consistent with those of the embodiment 1, only ammonium chloride is replaced by ammonium nitrate, and the obtained manganese sulfate product is dried at 100 ℃ in vacuum and then is sent for sample analysis.
Example 3
Dissolving coarse manganese chloride in water, and then adding ammonium chloride to obtain a manganese chloride feed liquid, wherein the manganese chloride feed liquid comprises the following components in percentage by weight: manganese: 180 g/L; calcium: 220 ppm; magnesium: 330 ppm; ammonium chloride: 300 g/L.
3L of manganese chloride feed liquid is taken and led into a 30L interlayer reaction kettle, and the temperature is raised to slight boiling (actually measured 110 ℃) by heat conducting oil. Then 13L of 2mol/L ammonium bicarbonate solution is pumped in, the flow rate is pumped in, 60mL/min, and the molar ratio of ammonium bicarbonate to manganese chloride is 2.6: 1. During the process of adding the ammonium bicarbonate solution, the heat-conducting oil is continuously used for heating the maintenance system to be in a slight boiling state (110 ℃). After the ammonium bicarbonate solution is added, the mixture is kept warm and aged for 1 hour, and then the mixture is naturally cooled to the room temperature. Filtration was carried out, and the cake was washed five times with ultrapure water. The filter cake was then transferred to a beaker and a 5mol/L electronic grade sulfuric acid solution was slowly added. After the manganese carbonate is dissolved, the pH value of the solution is adjusted to 5 by manganese powder, the volume of the solution is adjusted to 4L, 16g of ammonium sulfide (4 g of ammonium sulfide per liter of solution) is added, the solution is stirred for 1 hour, the solution is aged for 2 hours, and then the solution is filtered. Evaporating the filtrate to obtain a manganese sulfate crystal product, drying the product at 100 ℃ in vacuum, and feeding the product for analysis.
Example 4
Dissolving crude manganese nitrate in water, and then adding ammonium nitrate to obtain a manganese nitrate feed liquid, wherein in the manganese nitrate feed liquid: manganese: 160 g/L; calcium: 200 ppm; magnesium: 410 ppm; ammonium nitrate: 300 g/L.
4L of manganese nitrate feed liquid is introduced into a 30L interlayer reaction kettle, and the temperature is raised to slight boiling (108 ℃ measured by the actual measurement) by using heat conduction oil. Then 13 liters of 2mol/L ammonium bicarbonate solution is pumped in, the flow rate is 70 mL/min, and the molar ratio of ammonium bicarbonate to manganese chloride is 2.2: 1. During the process of adding the ammonium bicarbonate solution, the heat-conducting oil is continuously used for heating the maintenance system to be in a slight boiling state (108 ℃). After the ammonium bicarbonate solution is added, preserving the heat and aging for 2 hours, and then naturally cooling to room temperature. Filtration was carried out, and the cake was washed five times with ultrapure water. The filter cake was then transferred to a beaker and a 5mol/L electronic grade sulfuric acid solution was slowly added. After the manganese carbonate is dissolved, the pH value of the solution is adjusted to 5 by manganese powder, the volume of the solution is adjusted to 4.5L, 9g of ammonium sulfide (2 g of ammonium sulfide per liter of solution) is added, the solution is stirred for 1 hour, and the solution is aged for 2 hours and then filtered. Evaporating the filtrate to obtain a manganese sulfate crystal product, drying the product at 100 ℃ in vacuum, and feeding the product for analysis.
Example 5
One kilogram of feed-grade manganese sulfate monohydrate is prepared into 2L solution, and the concentrations of manganese, calcium and magnesium in the solution are respectively Mn: 162.7g/L, calcium: 784mg/L, magnesium: 1147 mg/L. 6g of ammonium sulfide (3 g of ammonium sulfide per liter of solution) was added to the manganese sulfate solution, and after stirring for 1.5 hours, it was aged for 2 hours and then filtered. After filtration, 900 g of ammonium chloride was added to the manganese sulfate solution, and the solution volume was adjusted to 3L with distilled water, and then the solution was transferred to a 10L laminated glass reaction vessel. After the temperature of the solution in the reaction kettle is heated to 103 ℃ by using heat conduction oil, 7.1L of 2mol/L ammonium bicarbonate solution (the mol ratio of ammonium bicarbonate to manganese sulfate is 2.4:1) is pumped in at the flow rate of 60 mL/min. And in the reaction process, maintaining the temperature at 103-105 ℃. After the addition of ammonium bicarbonate was complete, it was aged for 2.5 hours and then filtered. The filter cake was washed with ultrapure water until no sulfate was detected with barium ions. The filter cake was transferred to a 5L glass beaker, and manganese carbonate was dissolved in 4mol/L electronic-grade sulfuric acid solution to prepare a manganese sulfate solution. Evaporating to obtain a manganese sulfate crystal product. The product was dried under vacuum at 100 ℃ and sampled for analysis.
The analysis results of the products obtained in examples 1 to 5 are shown in Table 2:
TABLE 2 analysis results of the products obtained in examples 1 to 5
| Element(s) | Silicon | Zinc | Lead (II) | Cadmium (Cd) | Nickel (II) | Calcium carbonate | Chromium (III) | Sodium salt | Iron | Potassium salt | Magnesium alloy | Copper (Cu) | Cobalt | Manganese oxide |
| Unit of | μg/g | μg/g | μg/g | μg/g | μg/g | μg/g | μg/g | μg/g | μg/g | μg/g | μg/g | μg/g | μg/g | ％ |
| Example 1 | 44.2 | 0.96 | 7.10 | <0.021 | 12.8 | 33.3 | <0.2 | 14.2 | <9 | 2.40 | 19.2 | <0.5 | <0.2 | 32.2 |
| Example 2 | 32.3 | 0.05 | 9.05 | — | — | 28.5 | <0.2 | 10.1 | — | 3.10 | 20.6 | — | — | 32.4 |
| Example 3 | 18.1 | — | 6.01 | — | 2.02 | 23.0 | — | 1.01 | — | 1.05 | 10.3 | — | — | 32.5 |
| Example 4 | 36.3 | — | 10.5 | — | 3.32 | 18.6 | <0.2 | 5.31 | — | 2.14 | 9.82 | — | — | 32.5 |
| Example 5 | 24.5 | — | 4.53 | — | 8.21 | 20.3 | <0.2 | 13.7 | — | 3.22 | 15.6 | — | — | 32.5 |
("-" indicates no detection)
As can be seen from the results in Table 2, the high-purity manganese sulfate prepared by the method is superior to the quality standard of electronic-grade manganese sulfate products released by the Ministry of industry and communications.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of high-purity manganese sulfate is characterized by comprising the following steps of:
(1) mixing the crude manganese salt solution with a pH value control agent, adding an ammonium bicarbonate solution into the obtained mixed solution for reaction, and after the ammonium bicarbonate solution is added, sequentially aging and carrying out solid-liquid separation on the obtained reaction mixture to obtain manganese carbonate;
(2) dissolving the manganese carbonate in electronic-grade sulfuric acid, adding ammonium sulfide into the obtained dissolved solution, sequentially stirring, standing and carrying out solid-liquid separation, and evaporating the obtained filtrate to obtain high-purity manganese sulfate;
or comprises the following steps:
(a) mixing the crude manganese salt solution with ammonium sulfide, and sequentially stirring, standing and carrying out solid-liquid separation to obtain a refined manganese salt solution;
(b) mixing the refined manganese salt solution with a pH value control agent, adding an ammonium bicarbonate solution into the obtained mixed solution for reaction, and after the ammonium bicarbonate solution is added, sequentially aging and carrying out solid-liquid separation on the obtained reaction mixture to obtain high-purity manganese carbonate;
(c) dissolving the high-purity manganese carbonate in electronic-grade sulfuric acid, and evaporating the obtained dissolved solution to obtain high-purity manganese sulfate;
wherein the pH value is controlled to be at least one of ammonium chloride and ammonium nitrate; the pH value control agent controls the pH value of the system to be 5-6; and (c) controlling the temperature to be higher than 100 ℃ when the mixed solution reacts with the ammonium bicarbonate solution in the step (1) and the step (b).
2. The method according to claim 1, wherein the crude manganese salt in the crude manganese salt solution is feed-grade manganese sulfate, agricultural-grade manganese sulfate, crude manganese chloride, or crude manganese nitrate; the purity of the crude manganese chloride and the crude manganese nitrate is industrial grade purity or lower than the industrial grade purity.
3. The preparation method according to claim 1, wherein the concentration of the pH control agent in the mixed solution obtained by mixing the crude manganese salt solution and the pH control agent in the step (1) is 150 to 300 g/L;
and (c) mixing the refined manganese salt solution and the pH control agent in the step (b) to obtain a mixed solution, wherein the concentration of the pH control agent in the mixed solution is 150-300 g/L.
4. The method according to claim 1, wherein the temperature of the mixed solution and the ammonium bicarbonate solution in the step (1) and the step (b) is 102-110 ℃ independently.
5. The method according to claim 1, wherein in the steps (1) and (b), the amount of ammonium bicarbonate added is 2.2 to 2.6 times the molar amount of manganese ions.
6. The method according to claim 1 or 5, wherein the concentration of the ammonium bicarbonate solution in the step (1) and the step (b) is 0.5 to 2mol/L independently;
and (b) slowly adding the ammonium bicarbonate solution in the step (1) and the step (b) into the mixed solution under the condition of stirring, wherein the adding amount of the ammonium bicarbonate solution per minute is not more than 1/50 of the total volume of the solution in the reaction tank.
7. The method according to claim 1, wherein the aging time in step (1) and step (b) is independently 1-2 h.
8. The method according to claim 1, wherein the ammonium sulfide is added in the steps (2) and (a) in an amount of 2 to 4g/L independently.
9. The method according to claim 1, wherein the stirring time in the step (2) and the stirring time in the step (a) are independently 1 to 6 hours, and the standing time is independently 2 to 10 hours.
10. The preparation method of claim 1, wherein the concentration of manganese ions in the solution obtained in the step (2) and the step (c) is 130-180 g/L.
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| 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 |
| CN114408978A (en) * | 2022-03-07 | 2022-04-29 | 珠海市科立鑫金属材料有限公司 | Process for preparing battery-grade manganese sulfate by using manganese in cobalt raw material |
| CN114702075A (en) * | 2022-04-11 | 2022-07-05 | 中南大学 | Purification preparation method of manganese sulfate |
| CN114772648A (en) * | 2022-04-17 | 2022-07-22 | 张响 | Method for producing battery-grade manganese sulfate by purifying industrial-grade manganese sulfate |
| CN115108570A (en) * | 2022-06-17 | 2022-09-27 | 中南大学 | Process for preparing basic magnesium carbonate and ammonium sulfate by innocent treatment in manganese-containing wastewater |
| CN115259231A (en) * | 2022-07-13 | 2022-11-01 | 绵阳师范学院 | Method for removing calcium and magnesium impurities in manganese sulfate |
| CN116081693A (en) * | 2023-01-10 | 2023-05-09 | 何长荣 | Method for refining manganese sulfate product by removing impurities from calcium and magnesium |
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| 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 |
| CN114408978A (en) * | 2022-03-07 | 2022-04-29 | 珠海市科立鑫金属材料有限公司 | Process for preparing battery-grade manganese sulfate by using manganese in cobalt raw material |
| CN114702075A (en) * | 2022-04-11 | 2022-07-05 | 中南大学 | Purification preparation method of manganese sulfate |
| CN114772648A (en) * | 2022-04-17 | 2022-07-22 | 张响 | Method for producing battery-grade manganese sulfate by purifying industrial-grade manganese sulfate |
| CN114772648B (en) * | 2022-04-17 | 2023-12-01 | 张响 | Method for producing battery-grade manganese sulfate by purifying industrial-grade manganese sulfate |
| CN115108570A (en) * | 2022-06-17 | 2022-09-27 | 中南大学 | Process for preparing basic magnesium carbonate and ammonium sulfate by innocent treatment in manganese-containing wastewater |
| 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 |
| CN116081693A (en) * | 2023-01-10 | 2023-05-09 | 何长荣 | Method for refining manganese sulfate product by removing impurities from calcium and magnesium |
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