CN114212828B - Impurity removing method for manganese sulfate solution - Google Patents
Impurity removing method for manganese sulfate solution Download PDFInfo
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Abstract
The invention belongs to the field of metallurgy, and in particular relates to a process for removing impurities from a manganese sulfate solution, for example, the manganese sulfate solution is subjected to BaS heavy metal removal, then precipitation treatment is carried out to obtain manganese hydroxide precipitate, and then the manganese hydroxide precipitate is added into manganese hydroxide slurry
And introducing carbon dioxide to remove calcium and/or magnesium in the manganese alloy to obtain a high-quality manganese product. The invention not only can obtain high-purity manganese sulfate solution, but also avoids the problems that a large amount of fluorine ions are needed to be added for removing calcium and magnesium and then the fluorine ions in the solution are needed to be removed to generate a large amount of fluorine-containing slag in the traditional method due to innovatively adopting a cheap and feasible separation mode of calcium carbonate and magnesium, and is also environment-friendly, and has remarkable economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for removing impurities from a manganese sulfate solution.
Background
The battery-grade manganese sulfate is one of main raw materials for preparing the ternary cathode material of the lithium ion battery, wherein K, na, ca, mg content is generally required to be not higher than 50ppm, fe, cu, zn and Pb content is not higher than 10ppm, cd content is not higher than 5ppm, as content is less than 1ppm and F content is less than 700ppm; in addition, along with the slope returning of the electric vehicle patch, the manufacturing enterprises of the battery materials are forced to continuously reduce the cost. The preparation of battery grade raw materials by using industrial grade manganese sulfate is a low-cost scheme, but because K, na, ca, mg, fe, cu, zn, pb and other elements inevitably exist in manganese ores, particularly Ca and Mg are main accompanying elements in manganese ores, the lithiation property of the manganese ore is similar to that of manganese, and therefore, the impurity content in the industrial grade manganese sulfate is high.
In order to remove impurities in the manganese sulfate solution, many methods have been developed. Patent 200910161306.4 provides a method for circularly purifying manganese sulfate and manganese carbonate, but according to the patent examples, manganese sulfate with the concentration of less than 50ppm is required to be circularly obtained for a plurality of times, and the amount of generated wastewater is large; the patent 201010243859.7 adopts four steps to remove impurities, and the manganese fluoride is used, so that a low-calcium magnesium product can be obtained; however, from literature (Su Sha, chu An, wu Zhouhua, chen Haiqing. Study of the removal of calcium and magnesium impurities from manganese sulfate solutions [ J ]]Research on Hunan nonferrous metals, 2016,32 (2): 57-61) shows that manganese fluoride must be a certain multiple to achieve high calcium and magnesium removalThey found that the addition of manganese fluoride was 5 times the theoretical value to achieve a calcium magnesium removal efficiency of 90% or more, but this would tend to leave a large amount of fluoride ions in the solution, and if the removal of fluorine would tend to produce a large amount of fluorine removal slag. The patent 200910161306.4 and 2011010137708.3 obtain manganese sulfate products with the impurity content reaching the battery grade standard by adopting processes including the procedures of conversion, precipitation, washing, dissolution, fine filtration and the like, but the process products are difficult to meet the requirements of the battery industry for producing high-quality anode materials due to no special procedures for removing calcium and magnesium. The 201710552066.5 patent provides a scheme for preparing battery-grade manganese sulfate by two-stage extraction-sulfuric acid back extraction, and has the problems of large extraction wastewater and the like although the process is simpler. Paper "He Yinhui, zhang Haijing, xiong Shan. MnSO 4 Purification of solution and preparation of cell grade high purity manganese sulfate [ J ]]Hydrometallurgy, 2019,38 (5): 380-384) "provides a purification process of manganese sulfate solution, mainly comprising the procedures of removing K and Na by jarosite method, removing iron by oxidation method, removing Ca and Mg by manganese fluoride, removing heavy metal by sulfide and the like, wherein although K, na, ca, mg, fe, cu, zn, pb and other impurities reach very low, fluoride ions in the solution are not removed, and in addition, the process is long and complex. Patent 201810016993.X provides a method for removing calcium in manganese sulfate by a recrystallization method, but the recrystallization method has higher difficulty in making calcium and magnesium in the product reach the standard of high-end battery materials; he Yulin et al (rain forest, li Fujie, luo Zhihong, luo. Research on preparation of battery grade manganese sulfate by high temperature crystallization purification of industrial manganese sulfate [ J)]The mining and metallurgy engineering, 2019,39 (3): 85-88), the impurity content in the manganese sulfate reaches the battery level standard through 3 times of crystallization and purification, but the repeated crystallization has larger energy consumption and seriously affects the recovery efficiency of the manganese sulfate. As can be seen from the manganese sulfate impurity removal technology developed by the prior art, the problems of the prior art are mainly characterized by complex process, or large discharge amount of extraction wastewater and circulating wastewater, or the problems of easy corrosion of evaporation crystallization equipment and large amount of fluorine removal slag caused by high content of harmful element fluorine in solution after impurity removal, or difficult application of the product to manufacturing of high-end battery materials due to no special calcium and magnesium removal procedure, etc.
Disclosure of Invention
The invention aims to provide a deep impurity removal method for a manganese sulfate solution, which aims to effectively remove heavy metals, calcium, magnesium, iron and other impurities in manganese sulfate and obtain a high-purity manganese sulfate solution.
According to the impurity removal method (embodiment A) of the manganese sulfate solution, baS is adopted to carry out a first-stage impurity removal reaction on the manganese sulfate solution, and the impurity a in the solution is removed to obtain the treated manganese sulfate solution; the impurity a is a heavy metal impurity.
In the invention, baS is used as a heavy metal impurity remover, which can realize the co-precipitation of heavy metal and the impurity remover, improve the impurity removing effect, improve the selective separation effect of manganese and heavy metal, and in addition, the impurity ions are not introduced.
The impurity a is an ionic impurity of a heavy metal element, and the heavy metal impurity element is at least one of Pb, co, ni, cd, as, cu and Zn;
preferably, the pH of the starting solution of the first stage impurity removal reaction is from 5.5 to 6;
preferably, the barium sulfide is added in an amount of 15-20 times the total mass of heavy metal ions in the solution.
In the scheme A, after the first section impurity removal reaction, solid-liquid separation is carried out, so that the impurity a enters slag, and the treated manganese sulfate solution with the impurity a removed is obtained. The impurity removal of the present invention means that the impurity content of the treated system is reduced compared with the system before the treatment.
As the same impurity removal concept, when the manganese sulfate solution after the first stage treatment also contains other impurities, the subsequent impurity removal process can be optionally further performed, for example, another embodiment (embodiment B) of the present invention further comprises a step of performing a second stage impurity removal treatment on the manganese sulfate solution after the first stage impurity removal treatment to remove the impurity B or the mixed impurity of the impurity B and the impurity c; the impurity b is at least one of calcium ions and magnesium ions, and the impurity c is at least one of Na, K and ammonium ions. The impurity b and the impurity c can be introduced from an initial manganese sulfate solution or introduced in the first stage of impurity removal process.
The second section impurity removal treatment comprises the following steps: carrying out precipitation treatment on the manganese sulfate solution subjected to the first impurity removal treatment to obtain manganese hydroxide precipitation; mixing manganese hydroxide precipitate and a compound of formula 1 in a liquid phase to obtain slurry, introducing carbon dioxide into the slurry, performing second-stage impurity removal treatment, and then performing solid-liquid separation to obtain impurity-removed manganese hydroxide;
r is H, alkyl, carboxyl or substituted alkyl; or R and the amino ring are synthesized into five-membered or six-membered ring groups;
m is H + 、Na + 、K + Or NH 4 + 。
In the invention, impurities of calcium and/or magnesium and manganese are accompanied by precipitation, and the impurities and manganese hydroxide have similar phase properties, so that the treatment difficulty is high. Aiming at the problem of selective separation of manganese hydroxide and calcium and/or magnesium impurities, the invention researches that the high-selectivity separation of Mn and impurities such as calcium and magnesium can be realized with the aid of a formula 1 and carbon dioxide, and the method is beneficial to improving the purity of the treated manganese hydroxide and improving the recovery rate.
In the embodiment B of the present invention, the manganese sulfate solution may further contain at least one impurity (soluble impurity) selected from sodium ion, potassium ion and ammonium ion. According to the invention, for the manganese sulfate solution containing soluble ion-insoluble impurity ions (calcium ions and/or magnesium ions), synchronous precipitation of manganese ions, magnesium ions and calcium ions can be realized by an alkali precipitation mode, so that impurity removal of the soluble ions is realized. In the manganese hydroxide precipitation, impurities are hydroxide phases of impurity elements, but the situation that other salt phases exist is not excluded. In the invention, the manganese hydroxide precipitate containing calcium and magnesium impurities is innovatively subjected to carbon dioxide treatment with the assistance of the formula 1, so that the calcium and magnesium impurities in the precipitate can be selectively dissolved out, and high-quality manganese hydroxide can be obtained.
In the present invention, the conditions of the precipitation reaction stage are not particularly required. For example, the base used may be at least one of ammonia, sodium hydroxide, and potassium hydroxide. The end point pH of the precipitation reaction may be 10-11.5.
After the precipitation reaction, the compound of the formula 1 and carbon dioxide assist in removing calcium and/or magnesium to obtain high-quality manganese hydroxide.
In the invention, manganese hydroxide to be treated and the compound of formula 1 can be dispersed with water to obtain slurry, and then carbon dioxide gas is blown into the slurry system.
The solvent in the slurry is water or a mixed solvent of water and an organic solvent, and the organic solvent can be, for example, C1-C4 alcohol.
In the invention, the proportion of the manganese hydroxide to be treated and the solvent in the slurry is not particularly required, so long as the prepared slurry has good fluidity, and the stirring and the conveying are convenient. Considering the treatment efficiency, the solvent: the ratio of manganese hydroxide can be between 1:1 and 10:1.
In the present invention, the combination of the alpha-amino-carboxylic acid structure of formula 1 and carbon dioxide gas is a key to improve the selective separation of manganese hydroxide and impurities.
In the invention, in the formula 1, the alkyl is a linear alkyl of C1-C10, more preferably a C1-C4 alkyl;
preferably, the substituted alkyl is a C1-C10 linear alkyl containing 1-3 substituents; the substituent is hydroxyl, C1-C4 alkoxy, aminoacyl, amido, carboxyl, sulfhydryl, C1-C4 alkylthio, phenyl, substituted phenyl, five-membered heterocyclic aryl, benzo five-membered heterocyclic aryl or benzo six-membered heterocyclic aryl.
Preferably, the substituted alkyl is R 1 R 2 -CH-, wherein R1 is an alkyl group of H, C1 to C4; r2 is hydroxyl, C1-C4 alkoxy, aminoacyl, amido, carboxyl, sulfhydryl, C1-C4 alkylthio, phenyl, substituted phenyl, five-membered heterocyclic aryl, benzo five-membered heterocyclic aryl and benzo six-membered heterocyclic aryl.
Preferably, R is H, C-C4 alkyl, hydroxyl-substituted C1-C4 alkyl or phenyl-substituted C1-C4 alkyl;
in the invention, the dosage of the compound of the formula 1 can be adjusted according to the impurity content requirement, for example, the compound of the formula 1 is not lower than the theoretical reaction amount; for cost of treatment, the compound of formula 1 is preferably 1 to 2 times the theoretical molar amount of reaction. The theoretical reaction amount refers to a theoretical molar amount for completely converting the total amount of calcium and/or magnesium impurities in manganese hydroxide to be treated (refer to manganese hydroxide precipitation). Preferably, the compound of formula 1 is added in an amount of 10-15 times the total mass of calcium and magnesium in manganese hydroxide.
In the invention, based on the formula 1, the chemical action of carbon dioxide is further matched, which is helpful for synergistically improving the selective separation of manganese hydroxide and impurity phases.
Preferably, the air pressure of the carbon dioxide is maintained at 0.2-0.5MPa;
preferably, the time of the impurity removal treatment is 1-3 hours.
As the same impurity removing concept, when the treated manganese hydroxide also contains other impurities, the subsequent impurity removing process can be optionally further performed, for example, the embodiment (embodiment C) of the field of the present invention further comprises a third stage of impurity removing step for the manganese hydroxide after impurity removal to remove the impurity d therein; the impurity d is at least one impurity of iron, aluminum and fluorine;
the method comprises the following steps:
dissolving the obtained purified manganese hydroxide with sulfuric acid, and adding MnO in advance 2 Subsequent addition of BaF 2 And finally adding a defluorinating agent, and carrying out solid-liquid separation after the reaction to obtain a purified manganese sulfate solution.
In scheme C, the impurity may be introduced in the starting manganese sulfate solution or in the treated manganese hydroxide during the treatment.
In scheme C, the concentration of sulfuric acid is 50-70%;
preferably, in scheme C, mnO 2 The addition amount of the catalyst is 1.2 to 2.0 times of the molar amount of residual iron of the purified manganese hydroxide;
preferably, in scheme C, mnO 2 The final pH of the treatment stage is 5.5-6;
preferably, in scheme C, baF 2 The temperature of the treatment stage is 70-95 ℃;
preferably, in scheme C, baF 2 Treatment stage, baF 2 The addition concentration of (2) is 0.1-0.5g/L;
preferably, in scheme C, the fluorine removal agent treatment stage, the fluorine removal agent application amount is 1-5 g/L.
The invention relates to a more specific method for deeply removing impurities from a manganese sulfate solution, wherein the manganese sulfate solution contains impurities a, b, c, d, and the treatment process comprises the following steps:
step (1):
adjusting the pH value of the manganese sulfate solution to be treated to 5.5-6, then adding barium sulfide, stirring and reacting, standing to precipitate heavy metal elements in the form of sulfides, and filtering to obtain a manganese sulfate solution A, wherein the adding amount of the barium sulfide is 15-20 times of the total amount of heavy metal ions in the manganese sulfate solution;
step (2):
under the condition of stirring, adding alkali liquor into the manganese sulfate solution A, stopping adding the alkali liquor when the pH value of the solution reaches 10-11.5, and filtering to obtain manganese hydroxide precipitate;
step (3):
mixing manganese hydroxide precipitate, a compound shown in formula 1 and water to obtain slurry, then introducing carbon dioxide into the system for 1-3h, and maintaining the pressure of the system at 0.2-0.5MPa, so that calcium and magnesium in the manganese hydroxide precipitate stably enter the solution in an ion form, and the removal of calcium and magnesium in the manganese hydroxide is realized;
step (4):
step 1:
mixing the manganese hydroxide obtained in the step (3) with MnO 2 Adding the mixture into a sulfuric acid solution with the concentration of 50-70%, controlling the pH value of the end point to be 5.5-6, and then heating to 70-95 ℃;
step 2:
adding 0.1-0.5g/L BaF into the above solution 2 Stirring for 1-2h to enable the residual calcium and magnesium in the solution to enter into precipitation in the form of fluoride;
step 3:
adding 3-5g/L aluminum sulfate or 1-2g/L commercial fluorine removing agent into the solution, stirring for 1-2h, and standing for 1-2 h;
finally filtering to obtain the high-purity manganese sulfate solution.
The more preferable deep impurity removal method of the manganese sulfate solution comprises the following specific steps:
step (1): the heavy metal removal:
firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by alkali, then adding barium sulfide, stirring and reacting for 1-2 hours, standing for 1-2 hours, precipitating Pb, co, ni, cd, as, cu and Zn and other heavy metal elements (expressed as Me) in the form of sulfide, filtering the obtained filtrate, and then performing an alkali-adding manganese precipitation process, wherein the adding amount of the barium sulfide is 15-20 times of the total amount of heavy metal ions in the solution. The reaction that occurs in this step is: bas+me 2+ +SO 4 2- →MeS↓+BaSO 4 ↓。
Step (2): adding alkali to precipitate manganese:
under the condition of stirring, adding alkali liquor with the concentration of 6-10mol/L into the manganese sulfate solution treated in the step (1), stopping adding the alkali liquor when the pH value of the solution reaches 10-11.5, and filtering to obtain manganese hydroxide precipitate. The main reactions of this step are for example:
Mn 2+ +2NH 4 OH→Mn(OH) 2 ↓+2(NH 4 ) +
Ca 2+ +Mg 2+ +4NH 4 OH→Ca(OH) 2 ↓+Mg(OH) 2 ↓+4(NH 4 ) +
step (3): pulping and carbonating the manganese hydroxide precipitate:
adding the manganese hydroxide precipitate and the formula 1 into deionized water, then introducing carbon dioxide into the system for 1-3h, and maintaining the pressure of the system at 0.2-0.5MPa, so that calcium and magnesium in the manganese hydroxide precipitate stably enter the solution in an ion form, and the removal of calcium and magnesium in the manganese hydroxide is realized. The compound of formula 1 is a compound of formula 1-A
1-B->
1-C
The addition amount of the calcium and magnesium is 10-15 times of the total mass of the calcium and magnesium in the solution. The reaction is as follows:
carbonation reaction: ca (OH) 2 +2CO 2 →Ca(HCO 3 ) 2 ，Mg(OH) 2 +2CO 2 →Mg(HCO 3 ) 2
The reaction of formula 1-A: ca (Ca) 2+ +Mg 2+ +4(C 4 H 9 NO 3 )→[Ca(C 4 H 9 NO 3 ) 2 ] 2+ +[Mg(C 4 H 9 NO 3 ) 2 ] 2+
The reaction of formula 1-B: ca (Ca) 2+ +Mg 2+ +4(C 9 H 11 NO 2 )→[Ca(C 9 H 11 NO 2 ) 2 ] 2+ +[Mg(C 9 H 11 NO 2 ) 2 ] 2+
The reaction of formula 1-C: ca (Ca) 2+ +Mg 2+ +4(C 2 H 5 NO 2 )→[Ca(C 2 H 5 NO 2 ) 2 ] 2+ +[Mg(C 2 H 5 NO 2 ) 2 ] 2+
Step (4): the deep purification of the acid solution and the acid solution comprises the following steps:
(1) removing MnO with the molar quantity of 1.2-2.0 times of the iron ions in the solution to be removed after calcium and magnesium are removed 2 Adding the solution into 50-70% sulfuric acid solution, controlling the pH value of the end point to be 5.5-6, and then heating to 70-95 ℃ to enable iron ions and aluminum ions in the solution to become precipitates, wherein the main reaction is as follows: 2Fe 2+ +MnO 2 +4H + →2Fe 3+ +Mn 2+ +2H 2 O，Fe 3+ +H 2 O→Fe(OH) 3 ↓+3H +
Al 3+ +H 2 O→Al(OH) 3 ↓+3H +
(2) Adding 0.1-0.5g/L BaF into the above solution 2 Stirring for 1-2h to enable the residual calcium and magnesium in the solution to enter into precipitation in the form of fluoride, wherein the main reaction comprises the following steps: 2BaF 2 +Ca 2+ +Mg 2+ +2SO 4 2- →2BaSO 4 ↓+BaF 2 ↓+MgF 2 ↓
(3) Adding 3-5g/L aluminum sulfate or 1-2g/L commercial fluorine removing agent into the solution, stirring for 1-2h, and standing for 1-2h to remove residual fluorine ions in the solution, wherein the main reaction comprises the following steps: 3F- +Al 3+ →AlF 3 ↓,Al 3+ +H 2 O→Al(OH) 3 ↓+3H +
And finally, performing precise filtration to obtain the high-purity manganese sulfate solution.
Advantageous effects
(1) The BaS is used for removing heavy metal ions in the manganese sulfate solution, so that impurity cations cannot enter the solution, and the reason is that barium sulfide can be hydrolyzed into H in the manganese sulfate solution 2 S and Ba (OH) 2 PK in which sulfide precipitate is formed by sulfur ions and Pb, co, ni, cd, as, cu and Zn and other heavy metal elements SP Are all very large, and in addition, baSO 4 PK of (2) SP 9.96 is also reached;
(2): adding alkali to precipitate manganese can realize the separation of manganese hydroxide precipitation and K, na and ammonium in the solution; further, with the aid of formula 1 and carbon dioxide, mn and impurities such as calcium and magnesium in Mn can be separated in a high selectivity manner, so that the purity of treated manganese hydroxide is improved, and the recovery rate is improved. Therefore, the method not only can reduce the trouble brought by the process of removing a large amount of fluoride from calcium and magnesium and then removing fluorine, but also has no environmental pollution and low cost of removing calcium and magnesium.
(3) Slightly soluble BaF combined with barium fluoride 2 (BaF 2 1.84×10 of (2) -7 ) With BaSO 4 The solubility product of (2) is 1.08X10) -10 The (25 ℃) is larger than that of barium fluoride, and other cation impurities (only introduced cation Ba) can not be introduced while the deep removal of heavy metals such as Cu, pb, zn, ni, co, ca and Mg is realized 2+ Will be barium sulfateForm precipitation) is a great advantage of the present invention over other known techniques.
(4) The insoluble aluminum fluoride can be formed by utilizing Al and fluoride ions, and the aluminum ions can be hydrolyzed and precipitated at about pH5 to deeply remove a small amount of free fluorine from the acid solution, so that the invention overcomes the defect that a large amount of fluorine removal slag is generated in the traditional process.
Drawings
FIG. 1 is a flow chart of an embodiment of the invention
The invention will now be further described with reference to the accompanying drawings, without however being limited thereto.
Detailed Description
See fig. 1.
The invention provides a deep impurity removal method of a manganese sulfate solution, which mainly comprises the steps of heavy metal removal in the manganese sulfate solution, alkaline precipitation of manganese, carbonation of manganese hydroxide precipitation slurry, acid dissolution, deep purification of an acid solution and the like.
The heavy metal is removed, namely firstly, the pH value of a manganese sulfate solution is adjusted to 5.5-6 by alkali, then barium sulfide is added, stirring reaction is carried out for 1-2 hours, standing is carried out for 1-2 hours, pb, co, ni, cd, as, cu and Zn and other heavy metal elements (expressed as Me) are precipitated in the form of sulfide, the filtrate obtained by filtering is subjected to an alkali-adding manganese precipitation process, and the adding amount of the barium sulfide is 15-20 times of the total amount of heavy metal ions in the solution.
The alkaline precipitation of manganese is to add alkaline solution with the concentration of 6-10mol/L into manganese sulfate solution under the condition of stirring, stop adding alkaline solution after the pH value of the solution reaches 10-11.5, and filter to obtain manganese hydroxide precipitate.
The pulping carbonation of the manganese hydroxide sediment refers to adding the manganese hydroxide sediment and the liquid-solid ratio (mL/g) of the formula 1 (3-5): 1 into deionized water, then introducing carbon dioxide into the system for 1-3h, and maintaining the pressure of the system for 0.2-0.5MPa, so that calcium and magnesium in the manganese hydroxide sediment stably enter the solution in an ion form, and the removal of calcium and magnesium in the manganese hydroxide is realized. The addition amount of the formula 1 is 10-15 times of the total amount of calcium and magnesium in the solution.
The deep purification of the acid-soluble and acid-soluble solution comprises the following stepsThe steps are as follows: (1) removing MnO with the molar quantity of 1.2-2.0 times of the iron ions in the solution to be removed after calcium and magnesium are removed 2 Adding the solution into 50-70% sulfuric acid solution, controlling the pH value of the end point to be 5.5-6, and then heating to 70-95 ℃ to enable iron ions and aluminum ions in the solution to be precipitated; (2) adding 0.1-0.5g/L BaF into the above solution 2 Stirring for 1-2h to enable the residual calcium and magnesium in the solution to enter into precipitation in the form of fluoride; (3) adding 3-5g/L aluminum sulfate or 1-2g/L commercial fluorine removing agent into the solution, stirring for 1-2h, and standing for 1-2h to remove residual fluorine ions in the solution.
And finally, performing precise filtration to obtain the high-purity manganese sulfate solution.
The alkali refers to any one of ammonia water, sodium hydroxide or potassium hydroxide.
Example 1 deep removal of impurities from manganese sulfate solution in pyrolusite leaching Process in certain enterprises
The manganese sulfate solution used in this example was from a pyrolusite leaching process in an enterprise, and the impurity content is shown in the following table.
TABLE 1 Main impurity content (mg/L) in the treated solution of example 1
The experimental solution of this example was 5000mL, and the deep purification steps were as follows:
step (1): firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by ammonia water, then adding 20g of barium sulfide (which is equivalent to 20 times of the sum of the weight of Pb, co, ni, cd, as, cu and Zn and other heavy metals in the solution), stirring and reacting for 2 hours, standing for 2 hours, and filtering, wherein Table 2 shows the situation of impurities in the solution obtained in the step 1, and obviously, the addition of the barium sulfide can basically remove the heavy metals in the manganese sulfate solution; and the solution has no residual barium element; the iron ions are reduced by more than half, indicating that +3 valent iron (+3 iron ions) are present in the solution and almost completely hydrolyzed into precipitate at pH 3.5-5
TABLE 2 Main impurity content (mg/L) in the solution after the treatment of step (1)
Step (2): adding ammonia water with the concentration of 6mol/L into the manganese sulfate solution under the stirring condition, stopping adding the ammonia water when the pH value of the solution reaches 11-11.5, and filtering to obtain manganese hydroxide precipitate; the precipitate was washed with hot deionized water, the wash water was combined with the filtrate and evaporated to 5000mL in volume, table 3 shows the impurity profile in the filtrate obtained after the second treatment. It is apparent that almost all K, na goes to the filtrate, while almost all Ca, mg and other impurities go to the precipitation in the night after the treatment of step (1).
TABLE 3 Main impurity content (mg/L) in the solution after the second treatment step
Adding the manganese hydroxide precipitate obtained in the step two into deionized water, wherein the liquid-solid ratio (mL/g) of the manganese hydroxide to the deionized water is 3:1, then adding a formula 1-A (which is 11.6 times of the total mass of calcium and magnesium in the solution), then introducing carbon dioxide into the system, maintaining the pressure of the system at 0.4MPa, immediately filtering after introducing the carbon dioxide for 2 hours, and washing a filter cake; the wash water was combined with the filtrate and concentrated by evaporation to 5000mL. As can be seen from analysis of the filtrate, ca and Mg concentrations in the filtrate are 562Mg/L and 375Mg/L, respectively, and the calculated separation rates of Ca and Mg are 98.42% and 98.68% respectively. That is, trace Ca and Mg remain in the filter cake, but most Ca and Mg enter the solution. This step does not lose Mn, and the Mn recovery rate is 100%.
Step (4), acid dissolution and deep purification of acid solution, which comprises the following steps: (1) adding manganese hydroxide with calcium and magnesium removed and 25g of MnO2 (1.5 times of the molar quantity of iron element) into a sulfuric acid solution with 60% concentration, controlling the pH value of an end point to be 5.5-6, then heating to 70-95 ℃ and controlling the volume of the solution to be 5000mL; (2) to the above solution was added 2.5g (equivalent to 0.5 g/L) of BaF 2 Stirring for 1.5h; (3) namely, adding to the above solutionAdding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8), stirring for 1h, and standing for 2 h; and finally, performing precise filtration. Table 4 shows the impurity content of the treated manganese sulfate solution according to the present invention, and it is apparent that the purity of the manganese sulfate solution obtained according to the present invention is quite high.
TABLE 4 Main impurity content (mg/L) in the solution obtained by the treatment of EXAMPLE 1
| Element(s) | Pb | Co | Ni | Cd | As | Cu | Zn |
| Content (mg/L) | - | 0.11 | 0.14 | - | - | - | 0.1 |
| Element(s) | K | Na | Ca | Mg | Al | Fe | F |
| Content (mg/L) | 0.35 | 0.42 | 0.19 | 0.21 | - | 0.71 | 3.5 |
Example 2 deep removal of impurities from manganese sulfate solution in pyrolusite leaching Process in certain enterprises
The manganese sulfate solution used in this example was obtained from a pyrolusite leaching process in an enterprise, and was obtained from the same manufacturer as in example 1, with only the sampling time being different, and the impurity content was shown in table 5.
TABLE 5 content of major impurities (mg/L) in the treated solution of example 2
The experimental solution of this example was 5000mL, and the deep purification steps were as follows:
step (1), firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by ammonia water, then adding 20g of barium sulfide (which is equivalent to 20 times of the sum of the weight of Pb, co, ni, cd, as, cu and Zn and other heavy metals in the solution), stirring and reacting for 2 hours, standing for 2 hours, and filtering, wherein Table 6 shows the situation of impurities in the solution obtained in the step (1), and obviously, the addition of the barium sulfide can basically remove heavy metals in the manganese sulfate solution; and the solution has no residual barium element; the iron ions are reduced by more than half, indicating that +3 valent iron (+3 iron ions) are present in the solution and almost completely hydrolyzed into precipitate at pH 3.5-5
TABLE 6 Main impurity content (mg/L) in the solution after the treatment of step (1)
Adding ammonia water with the concentration of 6mol/L into the manganese sulfate solution under the stirring condition, stopping adding the ammonia water when the pH value of the solution reaches 11-11.5, and filtering to obtain manganese hydroxide precipitate; the precipitate was washed with hot deionized water, the wash water was combined with the filtrate and evaporated to 5000mL in volume, table 3 shows the impurity profile in the filtrate obtained after the second treatment. It is apparent that almost all K, na goes to the filtrate, while almost all Ca, mg and other impurities go to the precipitation in the night after the treatment of step (1).
TABLE 7 Main impurity content (mg/L) in the solution after the second treatment
Adding the manganese hydroxide precipitate obtained in the step two into deionized water, wherein the liquid-solid ratio (mL/g) of the manganese hydroxide to the deionized water is 3:1, then adding a formula 1-B (which is 14 times of the total mass of calcium and magnesium in the solution), then introducing carbon dioxide into the system, maintaining the pressure of the system at 0.4MPa, immediately filtering after introducing the carbon dioxide for 2 hours, and washing a filter cake; the wash water was combined with the filtrate and concentrated by evaporation to 5000mL. As a result of analysis of the filtrate, ca and Mg concentrations in the filtrate were 625Mg/L and 227Mg/L, respectively, and separation rates of Ca and Mg were 99.36% and 98.27%, respectively, as calculated. That is, trace Ca and Mg remain in the filter cake, but most Ca and Mg enter the solution. This step does not lose Mn, and the Mn recovery rate is 100%.
Step (4), acid dissolution and deep purification of acid solution, which comprises the following steps: (1) adding the manganese hydroxide with removed calcium and magnesium and 40g of MnO2 (1.6 times of the molar quantity of the iron element) into a sulfuric acid solution with 60 percent concentration,controlling the pH value of the end point to be 5.5-6, then heating to 70-95 ℃ and controlling the volume of the solution to be 5000mL; (2) to the above solution was added 2.5g (equivalent to 0.5 g/L) of BaF 2 Stirring for 1.5h; (3) namely adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1h, and standing for 2 h; and finally, performing precise filtration. Table 4 shows the impurity content of the treated manganese sulfate solution according to the present invention, and it is apparent that the purity of the manganese sulfate solution obtained according to the present invention is quite high.
TABLE 8 Main impurity content (mg/L) in the solution obtained by the treatment of EXAMPLE 2
| Element(s) | Pb | Co | Ni | Cd | As | Cu | Zn |
| Content (mg/L) | - | 0.09 | 0.07 | - | - | - | 0.08 |
| Element(s) | K | Na | Ca | Mg | Al | Fe | F |
| Content (mg/L) | 0.22 | 0.39 | 0.22 | 0.15 | - | 0.63 | 4.1 |
Example 3 deep removal of impurities from manganese sulfate solution in pyrolusite leaching Process in certain enterprises
The manganese sulfate solution used in this example was obtained from a pyrolusite leaching process in a business, and was obtained from a different manufacturer from examples 1 and 2, wherein the K, na, ca, mg content was higher than those in examples 1 and 2, and the impurity content was shown in Table 9.
TABLE 9 content of major impurities (mg/L) in the treated solution of example 3
The experimental solution of this example was 5000mL, and the deep purification steps were as follows:
step (1), firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by ammonia water, then adding 9g of barium sulfide (which is 19.7 times of the sum of the weight of Pb, co, ni, cd, as, cu and Zn and other heavy metals in the solution), stirring and reacting for 2 hours, standing for 2 hours, and filtering, wherein table 10 is the condition of impurities in the solution obtained in step 1, and obviously, the addition of the barium sulfide can basically remove the heavy metals in the manganese sulfate solution; and the solution has no residual barium element; the iron ions are reduced by more than half, indicating that +3 valent iron (+3 iron ions) are present in the solution and almost completely hydrolyzed into precipitate at pH 3.5-5
TABLE 10 content of Main impurity (mg/L) in solution after the treatment of step (1)
Adding ammonia water with the concentration of 6mol/L into the manganese sulfate solution under the stirring condition, stopping adding the ammonia water when the pH value of the solution reaches 11-11.5, and filtering to obtain manganese hydroxide precipitate; the precipitate was washed with hot deionized water, the wash water was combined with the filtrate and evaporated to 5000mL in volume, table 3 shows the impurity profile in the filtrate obtained after the second treatment. It is apparent that almost all K, na goes to the filtrate, while almost all Ca, mg and other impurities go to the precipitation in the night after the treatment of step (1).
TABLE 11 Main impurity content (mg/L) in the solution after the step (2) treatment
Adding the manganese hydroxide precipitate obtained in the step two into deionized water, wherein the liquid-solid ratio (mL/g) of the manganese hydroxide to the deionized water is 3:1, then adding a formula 1-A (which is 11 times of the total mass of calcium and magnesium in the solution), then introducing carbon dioxide into the system, maintaining the pressure of the system at 0.4MPa, immediately filtering after introducing the carbon dioxide for 2 hours, and washing a filter cake; the wash water was combined with the filtrate and concentrated by evaporation to 5000mL. As can be seen from analysis of the filtrate, the Ca and Mg concentrations in the filtrate were 3230Mg/L and 2127Mg/L, respectively, and the calculated separation rates of Ca and Mg were 99.78% and 99.85%, respectively. That is, trace Ca and Mg remain in the filter cake, but most Ca and Mg enter the solution. This step does not lose Mn, and the Mn recovery rate is 100%.
Step (4), acid dissolution and deep purification of acid solution, which comprises the following steps: (1) adding manganese hydroxide with calcium and magnesium removed and 15g of MnO2 (which is 2 times of the molar quantity of iron element) into a sulfuric acid solution with 60 percent concentration, controlling the pH value of an end point to be 5.5-6, then heating to 70-95 ℃ and controlling the volume of the solution to be 5000mL; (2) to the above solution was added 2.5g (equivalent to 0.5 g/L) of BaF 2 Stirring for 1.5h; (3) namely adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1h, and standing for 2 h; and finally, performing precise filtration. Table 12 shows the impurity content of the treated manganese sulfate solution of the present invention, and it is apparent that the purity of the manganese sulfate solution obtained by the present invention is quite high.
TABLE 12 Main impurity content (mg/L) in the solution obtained by the treatment of EXAMPLE 3
| Element(s) | Pb | Co | Ni | Cd | As | Cu | Zn |
| Content (mg/L) | - | 0.03 | 0.04 | - | - | - | 0.03 |
| Element(s) | K | Na | Ca | Mg | Al | Fe | F |
| Content (mg/L) | 0.12 | 0.12 | 0.19 | 0.14 | - | 0.53 | 2.1 |
Comparative example 1 removal of impurities from manganese sulfate solution in pyrolusite leaching Process of certain enterprises
The manganese sulfate solution used in this example was the same as in example 1, and the specific composition is shown in Table 1.
Step (1): firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by ammonia water, then adding sodium sulfide nonahydrate (the molar quantity of which is the same as that of BaS in the embodiment 1), stirring and reacting for 2 hours, standing for 2 hours, and filtering, wherein Table 13 shows the situation of impurities in the solution obtained in the step (1), and obviously, the impurity removing effect of the sodium sulfide in the step is equivalent to that of barium sulfide; however, this step causes a further increase in the Na content of the solution (about 1080 mg/L), which is difficult to remove by conventional treatment methods, and this presents great difficulties in deep impurity removal of the manganese sulfate solution.
TABLE 13 Main impurity content (mg/L) in the solution after the treatment of step (1)
Step (2): slowly adding 70g of MnF into the manganese sulfate solution obtained in the step (1) under stirring 2 (equivalent to 5 times of the total molar amount of Ca and Mg) and stirring and reacting for 1h. This step is very prone to gel formation, making the filtration process very difficult. After standing for 48 hours, the filtering performance is improved, but the total process period is also greatly prolonged. Meanwhile, a large amount of F is introduced in the step, and great challenges are brought to further impurity removal. The impurity content of the solution obtained by this step is shown in Table 14.
TABLE 14 Main impurity content (mg/L) in the solution after the step (2) treatment
As can be seen from the comparison example, the manganese sulfate solution with the impurity content meeting the production requirement (K, na, ca, mg content is not higher than 50ppm, fe, cu, zn and Pb content is not higher than 10ppm, cd content is not higher than 5ppm, as content is less than 1ppm and F content is less than 700 ppm) is difficult to obtain by the traditional treatment method; and new impurities are often introduced in the impurity removal process of the traditional process, and meanwhile, the problem of difficult solid-liquid separation is generated, so that great challenges are brought to practical production and application.
Comparative example 2
The difference compared with example 1 is only that in step (3), the compound of formula 1-A is not added, the steps are:
the manganese sulfate solution used in this comparative example was the same as in example 1, and the specific composition is shown in Table 1.
Step (1) and step (2): step (1) and step (2) of comparative example 2 were operated in the same manner as in example (1), and the impurity content of the obtained solution was also the same as in example 1, and the specific content is shown in Table 3.
Step (3): adding the manganese hydroxide precipitate obtained in the step (2) into deionized water, wherein the liquid-solid ratio (mL/g) of the deionized water to the manganese hydroxide is 3:1, then introducing carbon dioxide into the system, maintaining the pressure of the system at 0.4MPa, introducing the carbon dioxide for 2 hours, immediately filtering, and washing a filter cake; the wash water was combined with the filtrate and concentrated by evaporation to 5000mL. As can be seen from analysis of the filtrate, the Ca and Mg concentrations in the filtrate are 157Mg/L and 106Mg/L, and the calculated separation rates of Ca and Mg are only 27.50% and 27.89%, respectively, so that good separation of calcium and magnesium from manganese sulfate cannot be realized.
Step (4), acid dissolution and deep purification of acid solution, which comprises the following steps: (1) the manganese hydroxide after removing the calcium and the magnesium is mixed with 25g of MnO 2 Adding (1.5 times of the molar quantity of the iron element) into a sulfuric acid solution with the concentration of 60%, controlling the pH value of an end point to be 5.5-6, then heating to 70-95 ℃ and controlling the volume of the solution to be 5000mL; (2) to the above solution was added 2.5g (equivalent to 0.5 g/L) of BaF 2 Stirring for 1.5h; (3) namely adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1h, and standing for 2 h; and finally, performing precise filtration. Table 15 shows the impurity content of the treated manganese sulfate solution of the present invention, and it is apparent that the purity of the manganese sulfate solution obtained by the present invention cannot meet the production requirements.
TABLE 15 Main impurity content (mg/L) in the treated solution of comparative example 2
| Element(s) | Pb | Co | Ni | Cd | As | Cu | Zn |
| Content (mg/L) | - | 0.13 | 0.15 | - | - | - | 0.12 |
| Element(s) | K | Na | Ca | Mg | Al | Fe | F |
| Content (mg/L) | 0.33 | 0.37 | 319 | 271 | - | 0.75 | 7.23 |
Comparative example 3
The difference compared with example 1 is only that in step (3), which is not carried out with the aid of carbon dioxide, the steps are:
the manganese sulfate solution used in this comparative example was the same as in example 1, and the specific composition is shown in Table 1.
Step (1) and step (2): step (1) and step (2) of comparative example 2 were operated in the same manner as in example (1), and the impurity content of the obtained solution was also the same as in example 1, and the specific content is shown in Table 3.
Step (3): adding the manganese hydroxide precipitate obtained in the step (2) into deionized water, wherein the liquid-solid ratio (mL/g) of the deionized water to the manganese hydroxide is 3:1, then adding the solution shown in the formula 1-A (which is 11.6 times of the total mass of calcium and magnesium in the solution), stirring and reacting for 2 hours, immediately filtering, and washing a filter cake; the wash water was combined with the filtrate and concentrated by evaporation to 5000mL. As can be seen from analysis of the filtrate, the Ca and Mg concentrations in the filtrate are respectively 7Mg/L and 6Mg/L, and the calculated separation rates of Ca and Mg are respectively only 1.23% and 1.57%, so that good separation of calcium and magnesium from manganese sulfate cannot be realized.
Step (4), acid dissolution and deep purification of acid solution, which comprises the following steps: (1) adding manganese hydroxide with calcium and magnesium removed and 25g of MnO2 (1.5 times of the molar quantity of iron element) into a sulfuric acid solution with 60% concentration, controlling the pH value of an end point to be 5.5-6, then heating to 70-95 ℃ and controlling the volume of the solution to be 5000mL; (2) to the above solution was added 2.5g (equivalent to 0.5 g/L) of BaF 2 Stirring for 1.5h; (3) namely adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1h, and standing for 2 h; and finally, performing precise filtration. Table 16 shows the impurity content of the treated manganese sulfate solution of the present invention, and it is apparent that the purity of the manganese sulfate solution obtained by the present invention cannot meet the production requirements.
TABLE 16 Primary impurity content (mg/L) in the solution obtained by the treatment of comparative example 2
| Element(s) | Pb | Co | Ni | Cd | As | Cu | Zn |
| Content (mg/L) | - | 0.08 | 0.12 | - | - | - | 0.14 |
| Element(s) | K | Na | Ca | Mg | Al | Fe | F |
| Content (mg/L) | 0.40 | 0.31 | 560 | 371 | - | 0.66 | 6.10 |
Comparative example 4
The difference compared with example 1 is only that in step (3), the following structural compound is used instead of formula 1-A.
The method comprises the following specific steps:
the manganese sulfate solution used in this comparative example was the same as in example 1, and the specific composition is shown in Table 1.
Step (1) and step (2): step (1) and step (2) of comparative example 2 were operated in the same manner as in example (1), and the impurity content of the obtained solution was also the same as in example 1, and the specific content is shown in Table 3.
Step (3): adding the manganese hydroxide precipitate obtained in the step (2) into deionized water, wherein the liquid-solid ratio (mL/g) of the deionized water to the manganese hydroxide is 3:1, then adding a substance shown in a formula 2 (which is 11.6 times of the total mass of calcium and magnesium in the solution), then introducing carbon dioxide into the system, maintaining the pressure of the system at 0.4MPa, introducing the carbon dioxide for 2 hours, immediately filtering, and washing a filter cake; the wash water was combined with the filtrate and concentrated by evaporation to 5000mL. As can be seen from analysis of the filtrate, the Ca and Mg concentrations in the filtrate are 162Mg/L and 119Mg/L respectively, and the calculated separation rates of Ca and Mg are only 28.37% and 31.32% respectively, so that good separation of calcium and magnesium from manganese sulfate cannot be realized.
Step (4), acid dissolution and deep purification of acid solution, which comprises the following steps: (1) the manganese hydroxide after removing the calcium and the magnesium is mixed with 25g of MnO 2 Adding (1.5 times of the molar quantity of the iron element) into a sulfuric acid solution with the concentration of 60%, controlling the pH value of an end point to be 5.5-6, then heating to 70-95 ℃ and controlling the volume of the solution to be 5000mL; (2) to the above solution was added 2.5g (equivalent to 0.5 g/L) of BaF 2 Stirring for 1.5h; (3) namely adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1h, and standing for 2 h; and finally, performing precise filtration. Table 17 shows the sulfur after the treatment of the present inventionThe impurity content in the manganese acid solution, it is evident that the purity of the manganese sulphate solution obtained by the invention cannot meet the production requirements.
TABLE 17 Primary impurity content (mg/L) in the treated solution of comparative example 3
| Element(s) | Pb | Co | Ni | Cd | As | Cu | Zn |
| Content (mg/L) | - | 0.09 | 0.17 | - | - | - | 0.09 |
| Element(s) | K | Na | Ca | Mg | Al | Fe | F |
| Content (mg/L) | 0.41 | 0.51 | 409 | 261 | - | 0.74 | 5.43 |
In summary, the compound of formula 1 and carbon dioxide can unexpectedly realize synergy, can bring better effect of removing calcium and/or magnesium, and can further cooperate with other steps and condition control to help realize deep impurity removal of manganese sulfate.
Claims (20)
1. A method for removing impurities from a manganese sulfate solution is characterized in that BaS is adopted to carry out a first section of impurity removal reaction on the manganese sulfate solution, and impurity a in the solution is removed to obtain a treated manganese sulfate solution;
the impurity a is a heavy metal impurity of at least one of Pb, co, ni, cd, as, cu and Zn;
carrying out second-stage impurity removal treatment on the treated manganese sulfate solution to remove impurity b or mixed impurities of the impurity b and the impurity c; the impurity b is at least one of calcium ions and magnesium ions, and the impurity c is at least one of Na, K and ammonium ions;
the second section impurity removal step is as follows: carrying out precipitation reaction on the treated manganese sulfate solution to obtain manganese hydroxide precipitate;
mixing a liquid phase containing manganese hydroxide precipitate and a compound shown in a formula 1 to obtain slurry, introducing carbon dioxide into the slurry, performing second-stage impurity removal treatment, and then performing solid-liquid separation to obtain impurity-removed manganese hydroxide;
R is H, alkyl, carboxyl or substituted alkyl; or R and the amino ring are synthesized into five-membered or six-membered ring groups;
m is H + 、Na + 、K + Or NH 4 + ；
The alkali of the precipitation reaction is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
2. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein the initial solution of the first stage of the impurity removal reaction has a pH of 5.5 to 6.
3. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein the addition amount of barium sulfide is 15 to 20 times of the total mass of heavy metal ions in the solution.
4. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein the end point pH of the precipitation reaction is 10 to 11.5.
5. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein said alkyl group is C 1 ~C 10 A linear alkyl group of (a);
the substituted alkyl is C containing 1-3 substituents 1 ~C 10 A linear alkyl group of (a); the substituent is hydroxy, C 1 ~C 4 Alkoxy, aminoacyl, amide, carboxyl, mercapto, C 1 ~C 4 Alkylmercapto, phenyl, substituted phenyl, five membered heterocyclic aryl, benzo five membered heterocyclic aryl or benzo six membered heterocyclic aryl.
6. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein R is H,C 1 ~C 4 C substituted by alkyl or hydroxy 1 ~C 4 C substituted by alkyl or phenyl 1 ~C 4 Is a hydrocarbon group.
7. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein the compound of formula 1 is not less than a theoretical reaction amount.
8. The method for removing impurities from a manganese sulfate solution according to claim 7, wherein the compound of formula 1 is 1 to 2 times the theoretical reaction molar amount.
9. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein the solvent in the slurry is water or a mixed solvent of water and an organic solvent, and the organic solvent is a C1-C4 alcohol.
10. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein the weight ratio of the solvent to the manganese hydroxide to be treated in the slurry is 1-10:1.
11. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein the air pressure of carbon dioxide is maintained at 0.2 to 0.5MPa during the second-stage impurity removal process.
12. The method for removing impurities from a manganese sulfate solution according to claim 1, wherein the second stage of the impurity removal treatment is performed for 1 to 3 hours.
13. The method for removing impurities from a manganese sulfate solution according to any one of claims 1 to 12, further comprising a third step of removing impurities d from the removed manganese hydroxide; the impurity d is at least one impurity of iron, aluminum and fluorine;
the third section of impurity removal step is as follows:
dissolving the obtained purified manganese hydroxide with sulfuric acid, and adding MnO in advance 2 Subsequent addition of BaF 2 FinallyAdding a defluorinating agent, and carrying out solid-liquid separation after the reaction to obtain a purified manganese sulfate solution.
14. The method for removing impurities from a manganese sulfate solution according to claim 13, wherein the concentration of sulfuric acid is 50 to 70%.
15. The method for removing impurities from a manganese sulfate solution according to claim 13, wherein MnO 2 The addition amount of the catalyst is 1.2-2.0 times of the molar amount of residual iron of the purified manganese hydroxide.
16. The method for removing impurities from a manganese sulfate solution according to claim 13, wherein MnO 2 The end pH of the treatment stage is 5.5-6.
17. The method for removing impurities from a manganese sulfate solution according to claim 13, wherein BaF 2 The temperature of the treatment stage is 70-95 ℃.
18. The method for removing impurities from a manganese sulfate solution according to claim 17, wherein BaF 2 Treatment stage, baF 2 The addition concentration of (C) is 0.1-0.5g/L.
19. The method for removing impurities from a manganese sulfate solution according to claim 13, wherein the fluorine removing agent is applied in an amount of 1 to 5g/L in the fluorine removing agent treatment stage.
20. The treatment method of the manganese sulfate solution is characterized in that the manganese sulfate solution contains heavy metal impurities and at least one impurity ion of calcium and magnesium; at least one impurity ion and fluoride ion impurity in iron and aluminum, the treatment process comprises the following steps:
step one:
adjusting the pH value of the manganese sulfate solution to be treated to 5.5-6, then adding barium sulfide, stirring and reacting, standing to precipitate heavy metal elements in the form of sulfides, and filtering to obtain a manganese sulfate solution A, wherein the adding amount of the barium sulfide is 15-20 times of the total amount of heavy metal ions in the manganese sulfate solution;
step two:
under the condition of stirring, adding alkali liquor into the manganese sulfate solution A, stopping adding the alkali liquor when the pH value of the solution reaches 10-11.5, and filtering to obtain manganese hydroxide precipitate; the alkali of the precipitation reaction is at least one of sodium hydroxide, potassium hydroxide and ammonia water;
step three:
mixing manganese hydroxide precipitate, a compound shown in formula 1 and water to obtain slurry, then introducing carbon dioxide into the system for 1-3h, and maintaining the pressure of the system at 0.2-0.5MPa, so that calcium and magnesium in the manganese hydroxide precipitate stably enter the solution in an ion form, and the removal of calcium and magnesium in the manganese hydroxide is realized;
step four:
step 1:
mixing the manganese hydroxide obtained in the step three with MnO 2 Adding the mixture into a sulfuric acid solution with the concentration of 50-70%, controlling the pH value of the end point to be 5.5-6, and then heating to 70-95 ℃;
step 2:
adding 0.1-0.5g/L BaF into the above solution 2 Stirring for 1-2h to enable the residual calcium and magnesium in the solution to enter into precipitation in the form of fluoride;
step 3:
adding 3-5g/L aluminum sulfate or 1-2g/L commercial fluorine removing agent into the solution, stirring for 1-2h, and standing for 1-2 h;
finally filtering to obtain the high-purity manganese sulfate solution.
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