CN114212828A - Method for removing impurities from manganese sulfate solution - Google Patents
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Abstract
The invention belongs to the field of metallurgy, and particularly relates to an impurity removal process for a manganese sulfate solution, for example, heavy metal in the manganese sulfate solution is removed by BaS, then manganese hydroxide precipitate is obtained by precipitation treatment, and then manganese hydroxide slurry is added
And introducing carbon dioxide to remove calcium and/or magnesium in the manganese dioxide synergistically and deeply to obtain a high-quality manganese product. The method not only can obtain the high-purity manganese sulfate solution, but also avoids the problem that a large amount of fluoride ions are required to be added to remove calcium and magnesium and then to be removed from the solution to generate a large amount of fluorine-containing slag due to the innovative adoption of a cheap and feasible carbonation calcium and magnesium separation mode, and has remarkable environmental protection, economic benefit and social benefit.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to an impurity removal method for a manganese sulfate solution.
Background
The battery-grade manganese sulfate is one of main raw materials for preparing a ternary cathode material of a lithium ion battery, and generally requires that the contents of K, Na, Ca and Mg in the battery-grade manganese sulfate are not higher than 50ppm, the contents of Fe, Cu, Zn and Pb are not higher than 10ppm, the content of Cd is not higher than 5ppm, the content of As is less than 1ppm, and the content of F is less than 700 ppm; in addition, along with the subsiding of the electric vehicle, the cost of battery material manufacturing enterprises is forced to be reduced continuously. The technical manganese sulfate is a low-cost scheme for preparing the battery-grade raw material, but elements such as K, Na, Ca, Mg, Fe, Cu, Zn, Pb and the like cannot be avoided in manganese ore, particularly Ca and Mg are main associated elements in the manganese ore, and the lithiation property of the manganese ore is similar to that of manganese, so that the technical manganese sulfate has high impurity content.
In order to remove impurities from manganese sulfate solutions, 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, the manganese sulfate below 50ppm needs to be circularly purified for many times, and the amount of waste water generated is large; patent 201010243859.7 adopts four steps to remove impurities, and because manganese fluoride is used, a low calcium magnesium product can be obtained; however, in the literature (Susha, Chuguang, Wuzhou Hua, Chenhaiqing, manganese sulfate solution for the removal of calcium and magnesium impurities [ J]As shown in 2016,32(2):57-61) researches of Hunan nonferrous metal, manganese fluoride can achieve high calcium and magnesium removal effect only by reaching a certain multiple, and the researches find that the calcium and magnesium removal efficiency of more than 90% can be achieved only by adding the multiple of manganese fluoride to 5 times of a theoretical value, but a large amount of fluoride ions are likely to remain in the solution, and a large amount of fluorine removal slag is likely to be generated if fluorine removal is carried out. In the patents 200910161306.4 and 2011010137708.3, manganese sulfate products with impurity content reaching the battery grade standard are obtained by adopting processes including the working procedures of conversion, precipitation, washing, dissolution, fine filtration and the like, but the products of the processes are difficult to meet the requirement of producing high-quality cathode materials in the battery industry because no special working procedure is used for removing calcium and magnesium. Patent 201710552066.5 provides a scheme for preparing battery-grade manganese sulfate by two-stage extraction-sulfuric acid back extraction, and although the process is simpler, the problems of large extraction waste water and the like exist. Paper "Helichrysum, Zhang Hai Jing, Xiong shan. MnSO4Purification of solution and preparation of battery grade high-purity manganese sulfate [ J ]]2019,38(5):380-384) "provides a process for purifying a manganese sulfate solution, which mainly comprises the steps of removing K and Na by jarosite method, removing iron by oxidation method, removing Ca and Mg by manganese fluoride, removing heavy metals by sulfides and the like, although K, Na, Ca, Mg, Fe, Cu, Zn, Mn, Fe, Cu, Mn, Mg, Cu, Mg, Cu, Mn, Mg, Mn, Mg, Cu, Mn, Mg, Mn, Cu, Mn, Mg, and Mg, Mn, Cu, Mn, and Mg, Mn, Cu, Mn, and Mg, Mn, Ca, Mg, Mn, Mg, and Mg, Cu, Mn, Cu, Mn, Cu, and Mg, Mn, Cu, Mn, Mg, Cu, and Mg, Cu, and Mg, Cu, Mn, Cu, and Mg, Cu, Mn, Cu, and Mg, Cu, Mn, Cu, Mg, Cu, Mg, and Mg, Cu, Mn, and Mg, and Mg, and Mg, Cu, and Mg, and,Impurities such as Pb and the like are very low, but fluorine ions in the solution are not removed, and in addition, the flow is long and the process is complex. Patent 201810016993.X provides a method for removing calcium in manganese sulfate by a recrystallization method, but the recrystallization method has great difficulty in making calcium and magnesium in products reach the standard of high-end battery materials; research on preparation of battery-grade manganese sulfate by high-temperature crystallization and purification of industrial manganese sulfate [ J]The impurity content in manganese sulfate reaches the battery level standard through 3 times of crystallization and purification, but the repeated crystallization not only has higher energy consumption, but also seriously affects the recovery efficiency of the manganese sulfate. As can be seen from the manganese sulfate impurity removal technology developed by people before analysis, the problems existing in the prior art are mainly shown in the problems that the process is complex, the discharge amount of extraction wastewater and circulating wastewater is large, evaporation crystallization equipment is easy to corrode and generate a large amount of fluorine removal slag due to the high content of harmful element fluorine in the solution after impurity removal, products are difficult to apply to the manufacture of high-end battery materials due to the fact that no special calcium and magnesium removal process is provided, and the like.
Disclosure of Invention
The invention aims to provide a method for deeply removing impurities from a manganese sulfate solution, and aims to effectively remove impurities such as heavy metal, calcium, magnesium, iron and the like in manganese sulfate to obtain a high-purity manganese sulfate solution.
According to the impurity removal method for the manganese sulfate solution (embodiment A), BaS is adopted to carry out first-stage impurity removal reaction on the manganese sulfate solution, so that impurity a in the manganese sulfate solution is removed, and the treated manganese sulfate solution is obtained; the impurity a is a heavy metal impurity.
According to the invention, BaS is used as a heavy metal impurity removing agent, so that the heavy metal and the impurity removing agent can be synergistically precipitated, the impurity removing effect is improved, the selective separation effect of manganese and the heavy metal is improved, and in addition, impurity ions cannot be 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 initial solution of the first stage impurity removal reaction is 5.5-6;
preferably, the amount of barium sulfide added is 15-20 times of the total mass of heavy metal ions in the solution.
In the scheme A, after the first-stage impurity removal reaction, solid-liquid separation is carried out, so that the impurity a enters slag, and the treated manganese sulfate solution without the impurity a is obtained. It should be noted that the impurity removal in the present invention means that the impurity content of the system after treatment is reduced compared with the system before treatment.
As the same impurity removal concept, when the manganese sulfate solution after the first-stage treatment also contains other impurities, a subsequent impurity removal process can be optionally further performed, for example, another embodiment (embodiment B) of the present invention further includes a step of performing a second-stage impurity removal treatment on the manganese sulfate solution after the first-stage impurity removal treatment to remove impurity B or mixed impurities of impurity B and 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 impurities b and c can be introduced by the original manganese sulfate solution or introduced in the first stage impurity removal process.
The second stage 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 precipitate; mixing the manganese hydroxide precipitate and the compound of the formula 1 in a liquid phase to obtain slurry, introducing carbon dioxide into the slurry, carrying out second-stage impurity removal treatment, and then carrying out 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 a five-membered or six-membered ring group;
m is H+、Na+、K+Or NH4 +。
In the invention, impurities of calcium and/or magnesium and manganese are accompanied with precipitation, and the impurities and the 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 research of the invention finds that the high-selectivity separation of Mn and impurities such as calcium and magnesium can be realized under the assistance of the formula 1 and carbon dioxide, which 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 ions, potassium ions, and ammonium ions. In the invention, aiming at the manganese sulfate solution containing soluble ion-insoluble impurity ion (calcium ion and/or magnesium ion) type, synchronous precipitation of manganese ion, magnesium ion and calcium ion can be realized by an alkali precipitation mode, thereby realizing impurity removal of soluble ion. In the manganese hydroxide precipitate, the impurities are hydroxide phases of impurity elements, but the presence of other salt phases is not excluded. In the invention, the manganese hydroxide sediment 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 manganese hydroxide sediment can be selectively dissolved out, and high-quality manganese hydroxide can be obtained.
In the present invention, the conditions in 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 high-quality manganese hydroxide is obtained by the calcium and/or magnesium removal process with the assistance of the compound shown in the formula 1 and carbon dioxide.
In the present invention, the manganese hydroxide to be treated and the compound of formula 1 may be dispersed with water to obtain a slurry, and then carbon dioxide gas may be bubbled 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 C1-C4 alcohol, for example.
In the invention, the proportion of the manganese hydroxide to be treated and the solvent in the slurry has no special requirement, as long as the prepared slurry has good fluidity and is convenient for stirring and conveying. In view of the treatment efficiency, solvent: the ratio of the manganese hydroxide can be 1: 1-10: 1.
In the present invention, the combination of the α -amino-carboxylic acid structure of formula 1 and carbon dioxide gas is key to improving the selective separation of manganese hydroxide and impurities.
In the present invention, in the formula 1, the alkyl group is a linear or linear alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms;
preferably, the substituted alkyl is a C1-C10 straight-chain or straight-chain alkyl containing 1-3 substituents; the substituent group is hydroxyl, alkoxy of C1-C4, aminoacyl, acylamino, carboxyl, sulfydryl, alkylsulfydryl of C1-C4, phenyl, substituted phenyl, five-membered heterocyclic aryl, benzo six-membered heterocyclic aryl or amidino.
Preferably, the substituted alkyl is R1R2-CH-, wherein R1 is alkyl of H, C1 to C4; r2 is hydroxyl, alkoxy of C1-C4, aminoacyl, acylamino, carboxyl, sulfydryl, alkylsulfydryl of C1-C4, phenyl, substituted phenyl, five-membered heterocyclic aryl, benzo six-membered heterocyclic aryl or amidino.
Preferably, R is H, C1-C4 alkyl, hydroxyl substituted C1-C4 alkyl or phenyl substituted C1-C4 alkyl;
in the present invention, the amount of the compound of formula 1 can be adjusted according to the requirement of impurity content, for example, the compound of formula 1 is not less than the theoretical reaction amount; for the treatment cost, the compound of formula 1 is preferably 1 to 2 times the theoretical reaction molar amount. The theoretical reaction amount refers to the theoretical molar amount of completely converting the total amount of calcium and/or magnesium impurities in the manganese hydroxide (referring to manganese hydroxide precipitation) to be treated. Preferably, the compound of formula 1 is added in an amount of 10-15 times the total mass of calcium and magnesium in the manganese hydroxide.
In the invention, on the basis of the formula 1, the chemical action of carbon dioxide is further matched, which is beneficial to synergistically improving the selective separation of phases of manganese hydroxide and impurities.
Preferably, the pressure of the carbon dioxide is maintained at 0.2 to 0.5 MPa;
preferably, the time for impurity removal treatment is 1-3 h.
As the same impurity removal concept, when the processed manganese hydroxide also contains other impurities, a subsequent impurity removal process can be optionally further performed, for example, in an embodiment (embodiment C) in the field of the present invention, a third stage impurity removal step is further performed on the manganese hydroxide after impurity removal to remove the impurity d; the impurity d is at least one of iron, aluminum and fluorine;
the method comprises the following steps:
dissolving the obtained manganese hydroxide after impurity removal with sulfuric acid, and adding MnO in advance2Followed by the addition of BaF2And finally adding a fluorine removing agent, and carrying out solid-liquid separation after reaction to obtain a purified manganese sulfate solution.
In case C, the impurities may be introduced into the initial manganese sulfate solution or into the treated manganese hydroxide during the treatment.
In the scheme C, the concentration of the sulfuric acid is 50-70%;
preferably, in scheme C, MnO2The addition amount of (b) is 1.2-2.0 times of the molar amount of the residual iron of the purified manganese hydroxide;
preferably, in scheme C, MnO2The end point pH of the treatment stage is 5.5-6;
preferably, in scheme C, BaF2The temperature of the treatment stage is 70-95 ℃;
preferably, in scheme C, BaF2Treatment stage, BaF2The addition concentration of (A) is 0.1-0.5 g/L;
preferably, in the scheme C, in the treatment stage of the fluorine removal agent, the application amount of the fluorine removal agent 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 and 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, adding barium sulfide, stirring for reaction, standing to precipitate heavy metal elements in a sulfide form, and filtering to obtain a manganese sulfate solution A, wherein the addition amount of 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;
and (3):
mixing the manganese hydroxide precipitate, the compound shown in the formula 1 and water to obtain slurry, and then introducing carbon dioxide into the system for 1-3 hours, and maintaining the pressure of the system at 0.2-0.5MPa to ensure that calcium and magnesium in the manganese hydroxide precipitate stably enter the solution in an ion form, thereby realizing the removal of calcium and magnesium in the manganese hydroxide;
and (4):
step 1:
mixing the manganese hydroxide obtained in the step (3) with MnO2Adding into 50-70% sulfuric acid solution, controlling the end point pH value to 5.5-6, and heating to 70-95 deg.C;
step 2:
adding 0.1-0.5g/L BaF into the solution2Stirring for 1-2h to make the residual calcium and magnesium in the solution enter the precipitation in the form of fluoride;
and 3, step 3:
adding 3-5g/L aluminum sulfate or 1-2g/L commercial defluorinating agent into the solution, stirring for 1-2h, and standing for 1-2 h;
and finally, filtering to obtain the high-purity manganese sulfate solution.
The more preferable method for deeply removing the impurities from the manganese sulfate solution comprises the following steps:
step (1): and (3) removing the heavy metal:
firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by using alkali, then adding barium sulfide, stirring for reaction for 1-2h, standing for 1-2h to enable heavy metal elements (expressed by Me) such As Pb, Co, Ni, Cd, As, Cu, Zn and the like to be precipitated in a sulfide form, filtering to obtain filtrate, and entering an alkali-adding manganese precipitation process, wherein the addition amount of the barium sulfide is 15-20 times of the total amount of heavy metal ions in the solution. The reaction that takes place in this step is: BaS + Me2++SO4 2-→MeS↓+BaSO4↓。
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:
Mn2++2NH4OH→Mn(OH)2↓+2(NH4)+
Ca2++Mg2++4NH4OH→Ca(OH)2↓+Mg(OH)2↓+4(NH4)+
and (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, thereby realizing the removal of calcium and magnesium in the manganese hydroxide. The compound of formula 1 is formula 1-A
Formula 1-B
Formula 1-C
The addition amount of the one of the calcium and the magnesium is 10-15 times of the total mass of the calcium and the magnesium in the solution. The reaction is as follows:
and (3) carbonation reaction: ca (OH)2+2CO2→Ca(HCO3)2，Mg(OH)2+2CO2→Mg(HCO3)2
Reaction of formula 1-A: ca2++Mg2++4(C4H9NO3)→[Ca(C4H9NO3)2]2++[Mg(C4H9NO3)2]2+
Reaction of formula 1-B: ca2++Mg2++4(C9H11NO2)→[Ca(C9H11NO2)2]2++[Mg(C9H11NO2)2]2+
Reaction of formula 1-C: ca2++Mg2++4(C2H5NO2)→[Ca(C2H5NO2)2]2++[Mg(C2H5NO2)2]2+
And (4): the acid dissolution and the deep purification of the acid solution comprise the following steps:
firstly, MnO with the molar weight of manganese hydroxide and iron ions in the solution to be removed being 1.2-2.0 times is added to the manganese hydroxide after calcium and magnesium removal2Adding into 50-70% sulphuric acid solution, controlling the end point pH value to 5.5-6, heating to 70-95 deg.C to make the iron ion and aluminum ion in the solution become precipitate, which has the following main reactions: 2Fe2++MnO2+4H+→2Fe3++Mn2++2H2O，Fe3++H2O→Fe(OH)3↓+3H+
Al3++H2O→Al(OH)3↓+3H+
② adding 0.1-0.5g/L of BaF into the above solution2And stirring for 1-2h to ensure that the calcium and magnesium remained in the solution enter precipitation in the form of fluoride, and the main reactions are as follows: 2BaF2+Ca2++Mg2++2SO4 2-→2BaSO4↓+BaF2↓+MgF2↓
Adding 3-5g/L aluminum sulfate or 1-2g/L commercial defluorinating agent into the solution, stirring for 1-2h, standing for 1-2h to remove residual fluorine ions in the solution, and carrying out main reaction: 3F-+Al3+→AlF3↓,Al3++H2O→Al(OH)3↓+3H+
And finally, carrying out precision filtration to obtain the high-purity manganese sulfate solution.
Advantageous effects
(1) The BaS is utilized to remove 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 barium sulfide in the manganese sulfate solutionH2S and Ba (OH)2The sulfide precipitate PK formed by sulfide ions and heavy metal elements such As Pb, Co, Ni, Cd, As, Cu and ZnSPAre all very large, in addition to BaSO4PK ofSP9.96 is also achieved;
(2): the separation of K, Na and ammonium in the manganese hydroxide precipitate and the solution can be realized by adding alkali to precipitate manganese; further, with the aid of the formula 1 and carbon dioxide, high-selectivity separation of Mn and impurities therein such as calcium and magnesium can be realized, which is helpful for improving the purity of the treated manganese hydroxide and improving the recovery rate. Therefore, the trouble caused by the process that a large amount of fluoride is needed to be added for removing calcium and magnesium and then removing fluorine can be reduced, the method has no environmental pollution, and the calcium and magnesium removal cost is low.
(3) Sparingly soluble BaF in combination with barium fluoride2(BaF21.84X 10-7) With BaSO4Solubility product of 1.08X 10-10The temperature of (25 ℃) is larger than that of barium fluoride, and other cation impurities (the only introduced cation Ba) can not be introduced while realizing the deep removal of heavy metals such as Cu, Pb, Zn, Ni, Co and the like, Ca and Mg2+Will precipitate in the form of barium sulfate) is a great advantage of the present invention over other known techniques.
(4) The method overcomes the defect that a large amount of fluorine removal slag is generated in the traditional process by utilizing the fact that insoluble aluminum fluoride can be formed by Al and fluorine ions and the aluminum ions can be hydrolyzed and precipitated at the pH value of 5 to deeply remove a small amount of free fluorine from an acid solution.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention
The following further describes the practice of the present invention with reference to the drawings, but the present invention is not limited thereto.
Detailed Description
See fig. 1.
The invention provides a method for deeply removing impurities from a manganese sulfate solution, which mainly comprises the steps of removing heavy metals in the manganese sulfate solution, adding alkali to precipitate manganese, carbonating manganese hydroxide precipitate slurry, carrying out acid dissolution, deeply purifying an acid solution and the like.
And the heavy metal removal means that firstly, the pH value of the manganese sulfate solution is adjusted to 5.5-6 by alkali, then barium sulfide is added, the mixture is stirred to react for 1-2 hours and is kept stand for 1-2 hours, so that heavy metal elements (expressed by Me) such As Pb, Co, Ni, Cd, As, Cu, Zn and the like are precipitated in a sulfide form, the filtrate obtained by filtration enters an alkali adding manganese precipitation process, and the addition amount of the barium sulfide is 15-20 times of the total amount of heavy metal ions in the solution.
And the step of adding alkali to precipitate manganese refers to adding alkali liquor with the concentration of 6-10mol/L into the manganese sulfate solution under the condition of stirring, stopping adding the alkali liquor when the pH value of the solution reaches 10-11.5, and filtering to obtain manganese hydroxide precipitate.
The manganese hydroxide precipitation pulping and carbonating refers to adding the manganese hydroxide precipitation and the formula 1 into deionized water according to a liquid-solid ratio (mL/g) of (3-5):1, 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 precipitation stably enter the solution in an ion form, and the removal of calcium and magnesium in the manganese hydroxide is realized. The adding amount of the formula 1 is 10-15 times of the total amount of calcium and magnesium in the solution.
The acid dissolution and the deep purification of the acid solution comprise the following steps: firstly, MnO with the molar weight of manganese hydroxide and iron ions in the solution to be removed being 1.2-2.0 times is added to the manganese hydroxide after calcium and magnesium removal2Adding into 50-70% sulphuric acid solution, controlling the end point pH value to 5.5-6, heating to 70-95 deg.C to make the iron ion and aluminum ion in the solution become precipitate; ② adding 0.1-0.5g/L of BaF into the above solution2Stirring for 1-2h to make the residual calcium and magnesium in the solution enter the precipitation in the form of fluoride; thirdly, adding 3-5g/L of aluminum sulfate or 1-2g/L of commercial defluorinating agent into the solution, stirring for 1-2h, and standing for 1-2h to remove residual fluorine ions in the solution.
And finally, carrying out precision filtration to obtain the high-purity manganese sulfate solution.
The alkali in the invention refers to any one of ammonia water, sodium hydroxide or potassium hydroxide.
Example 1 deep removal of manganese sulfate solution from pyrolusite leach step in an Enterprise
The manganese sulfate solution adopted in the embodiment is from a pyrolusite leaching process of an enterprise, and the impurity content of the manganese sulfate solution is shown in the following table.
TABLE 1 content of major impurities (mg/L) in the solution treated in example 1
The experimental solution of this example was 5000mL, and the deep purification procedure was as follows:
step (1): firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by using ammonia water, then adding 20g of barium sulfide (which is equal to 20 times of the sum of the weight of heavy metals such As Pb, Co, Ni, Cd, As, Cu and Zn in the solution), stirring for reaction for 2h, standing for 2h, and filtering, wherein the table 2 shows the condition of impurities in the solution obtained in the step 1, obviously, the addition of the barium sulfide can basically remove the heavy metals in the manganese sulfate solution; moreover, no barium element remains in the solution; the iron ions are reduced by more than half, which indicates that the solution contains + 3-valent iron (+3 iron ions which are almost completely hydrolyzed to enter precipitation when the pH value is 3.5-5)
TABLE 2 content of major impurities (mg/L) in the solution after treatment in step (1)
Step (2): under the condition of stirring, adding ammonia water with the concentration of 6mol/L into the manganese sulfate solution, 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 the volume evaporated to 5000mL, Table 3 is the impurity profile in the filtrate obtained after the treatment in step two. It is evident that almost all K, Na had entered the filtrate, while almost all Ca, Mg and other impurities had entered the precipitate overnight after the treatment in step (1).
TABLE 3 content of major impurities (mg/L) in the solution after the second treatment in step two
Step (3), adding the manganese hydroxide precipitate obtained in the step two into deionized water, wherein the liquid-solid ratio (mL/g) of the deionized water to the manganese hydroxide is 3:1, then adding the compound 1-A (which is 11.6 times of the total mass of calcium and magnesium in the solution), 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 with water; the wash water was combined with the filtrate and evaporated to 5000 mL. Analysis of the filtrate revealed that the concentrations of Ca and Mg in the filtrate were 562Mg/L and 375Mg/L, respectively, and that the Ca and Mg separation rates were calculated to be 98.42% and 98.68%, respectively. That is, a small amount of Ca and Mg remains in the filter cake, but most of Ca and Mg enter the solution. This step did not lose Mn, and the recovery of Mn was 100%.
And (4) acid dissolution and deep purification of the acid solution, which specifically comprises the following steps: adding manganese hydroxide after calcium and magnesium removal and 25g of MnO2 (equivalent to 1.5 times of the molar weight of iron element) into a 60% sulfuric acid solution, controlling the end-point pH value to be 5.5-6, then heating to 70-95 ℃, and controlling the volume of the solution to be 5000 mL; ② adding 2.5g (equivalent to 0.5g/L) of BaF2 into the solution, and stirring for 1.5 h; ③ adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1 hour, and standing for 2 hours; and finally, performing precision filtration. Table 4 shows the impurity content of the treated manganese sulfate solution, and it is clear that the purity of the manganese sulfate solution obtained by the present invention is quite high.
TABLE 4 content of major impurities (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 manganese sulfate solution from pyrolusite leach step in certain enterprises
The manganese sulfate solution adopted in the embodiment is from a pyrolusite leaching process of a certain enterprise, is from the same manufacturer as that of the embodiment 1, is different only in sampling time, and the impurity content is shown in table 5.
TABLE 5 content of major impurities (mg/L) in the solution treated in example 2
The experimental solution of this example was 5000mL, and the deep purification procedure was as follows:
step (1), firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by using ammonia water, then adding 20g of barium sulfide (which is equal to 20 times of the sum of the weight of heavy metals such As Pb, Co, Ni, Cd, As, Cu and Zn in the solution), stirring for reaction for 2h, standing for 2h, and filtering, wherein the table 6 shows the condition of impurities in the solution obtained in the step (1), obviously, the addition of the barium sulfide can basically remove the heavy metals in the manganese sulfate solution; moreover, no barium element remains in the solution; the iron ions are reduced by more than half, which indicates that the solution contains + 3-valent iron (+3 iron ions which are almost completely hydrolyzed to enter precipitation when the pH value is 3.5-5)
TABLE 6 content of major impurities (mg/L) in the solution after the treatment in step (1)
Step (2), under the condition of stirring, adding ammonia water with the concentration of 6mol/L into the manganese sulfate solution, 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 the volume evaporated to 5000mL, Table 3 is the impurity profile in the filtrate obtained after the treatment in step two. It is evident that almost all K, Na had entered the filtrate, while almost all Ca, Mg and other impurities had entered the precipitate overnight after the treatment in step (1).
TABLE 7 Main impurity content (mg/L) in the solution after step two treatment
Step (3), adding the manganese hydroxide precipitate obtained in the step two into deionized water, wherein the liquid-solid ratio (mL/g) of the deionized water to the manganese hydroxide is 3:1, then adding the formula 1-B (equivalent to 14 times of the total mass of calcium and magnesium in the solution), 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 with water; the wash water was combined with the filtrate and evaporated to 5000 mL. Analysis of the filtrate revealed that the concentrations of Ca and Mg in the filtrate were 625Mg/L and 227Mg/L, respectively, and that the Ca and Mg separation rates were calculated to be 99.36% and 98.27%, respectively. That is, a small amount of Ca and Mg remains in the filter cake, but most of Ca and Mg enter the solution. This step did not lose Mn, and the recovery of Mn was 100%.
And (4) acid dissolution and deep purification of the acid solution, which specifically comprises the following steps: adding manganese hydroxide after calcium and magnesium removal and 40g of MnO2 (equivalent to 1.6 times of the molar weight of iron element) into a 60% sulfuric acid solution, controlling the end-point pH value to be 5.5-6, then heating to 70-95 ℃, and controlling the volume of the solution to be 5000 mL; ② adding 2.5g (equivalent to 0.5g/L) of BaF2 into the solution, and stirring for 1.5 h; ③ adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1 hour, and standing for 2 hours; and finally, performing precision filtration. Table 4 shows the impurity content of the treated manganese sulfate solution, and it is clear that the purity of the manganese sulfate solution obtained by the present invention is quite high.
TABLE 8 main impurities 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 manganese sulfate solution from pyrolusite leach step in certain enterprises
The manganese sulfate solution adopted in the embodiment is from a pyrolusite leaching process of an enterprise, is from a manufacturer different from the manufacturers in the embodiments 1 and 2, has higher contents of K, Na, Ca and Mg than the contents in the embodiments 1 and 2, and has impurity contents shown in Table 9.
TABLE 9 content of major impurities (mg/L) in the solution treated in example 3
The experimental solution of this example was 5000mL, and the deep purification procedure was as follows:
step (1), firstly, adjusting the pH value of a manganese sulfate solution to 5.5-6 by using ammonia water, then adding 9g of barium sulfide (equivalent to 19.7 times of the sum of the weights of heavy metals such As Pb, Co, Ni, Cd, As, Cu and Zn in the solution), stirring for reaction for 2 hours, standing for 2 hours, and filtering, wherein the table 10 shows the condition of impurities in the solution obtained in the step (1), obviously, the addition of the barium sulfide can basically remove the heavy metals in the manganese sulfate solution; moreover, no barium element remains in the solution; the iron ions are reduced by more than half, which indicates that the solution contains + 3-valent iron (+3 iron ions which are almost completely hydrolyzed to enter precipitation when the pH value is 3.5-5)
TABLE 10 content of major impurities (mg/L) in the solution after treatment in step (1)
Step (2), under the condition of stirring, adding ammonia water with the concentration of 6mol/L into the manganese sulfate solution, 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 the volume evaporated to 5000mL, Table 3 is the impurity profile in the filtrate obtained after the treatment in step two. It is evident that almost all K, Na had entered the filtrate, while almost all Ca, Mg and other impurities had entered the precipitate overnight after the treatment in step (1).
TABLE 11 content of major impurities (mg/L) in the solution after the treatment of step (2)
Step (3), adding the manganese hydroxide precipitate obtained in the step two into deionized water, wherein the liquid-solid ratio (mL/g) of the deionized water to the manganese hydroxide is 3:1, then adding the compound 1-A (which is 11 times of the total mass of calcium and magnesium in the solution), 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 with water; the wash water was combined with the filtrate and evaporated to 5000 mL. Analysis of the filtrate revealed that the concentrations of Ca and Mg 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, a small amount of Ca and Mg remains in the filter cake, but most of Ca and Mg enter the solution. This step did not lose Mn, and the recovery of Mn was 100%.
And (4) acid dissolution and deep purification of the acid solution, which specifically comprises the following steps: adding manganese hydroxide after calcium and magnesium removal and 15g of MnO2 (equivalent to 2 times of the molar weight of iron element) into a 60% sulfuric acid solution, controlling the end-point pH value to be 5.5-6, then heating to 70-95 ℃, and controlling the volume of the solution to be 5000 mL; ② adding 2.5g (equivalent to 0.5g/L) of BaF2 into the solution, and stirring for 1.5 h; ③ adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1 hour, and standing for 2 hours; and finally, performing precision filtration. Table 12 shows the impurity content of the treated manganese sulfate solution, and it is clear that the purity of the manganese sulfate solution obtained by the present invention is quite high.
TABLE 12 main impurities 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 manganese sulfate solution from pyrolusite leaching procedure in 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 using ammonia water, then adding sodium sulfide nonahydrate (the molar weight of BaS is the same as that in example 1), stirring for reaction for 2 hours, standing for 2 hours, and then filtering, wherein Table 13 shows the impurity removal effect of the sodium sulfide in the step (1) is equivalent to that of barium sulfide; however, the Na content in the solution is further increased (about 1080mg/L) by the step, and the Na is difficult to remove by using a conventional treatment method, which brings great difficulty to deep impurity removal of the manganese sulfate solution.
TABLE 13 content of major impurities (mg/L) in the solution after treatment in step (1)
Step (2): slowly adding 70g of MnF into the manganese sulfate solution obtained in the step (1) under the stirring state2(corresponding to 5 times of the total molar amount of Ca and Mg), and the reaction was continued for 1 hour with stirring. This step is very prone to gel formation, making the filtration process very difficult. After standing for 48h, the filtration performance was improved, but the overall process cycle was also greatly extended. Meanwhile, a large amount of F is introduced in the step, so that great challenge is brought to further impurity removal. The impurity content of the solution obtained by this step is shown in Table 14.
TABLE 14 content of major impurities (mg/L) in the solution after treatment in step (2)
As can be seen from the comparative example, the manganese sulfate solution with impurity content meeting the production requirements (the contents of K, Na, Ca and Mg are not higher than 50ppm, the contents of Fe, Cu, Zn and Pb are not higher than 10ppm, the content of Cd is not higher than 5ppm, the content of As is less than 1ppm and the content of F is less than 700ppm) is difficult to obtain by the traditional treatment mode; and in the impurity removal process of the traditional process, new impurities are often introduced, and meanwhile, the problem of difficulty in solid-liquid separation is caused, so that great challenges are brought to practical production and application.
Comparative example 2
The only difference compared to example 1 is that in step (3), no compound of formula 1-a is added, the step consisting in:
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): the operation of step (1) and step (2) of comparative example 2 is the same as that of example (1), and the impurity content of the obtained solution is also the same as that of example 1, and the specific contents are shown in Table 3.
And (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, 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 with water; the wash water was combined with the filtrate and evaporated to 5000 mL. Analysis of the filtrate shows that the concentrations of Ca and Mg in the filtrate are 157Mg/L and 106Mg/L respectively, and the calculated separation rates of Ca and Mg are only 27.50 percent and 27.89 percent respectively, so that good separation of calcium and magnesium from manganese sulfate cannot be realized.
And (4) acid dissolution and deep purification of the acid solution, which specifically comprises the following steps: adding manganese hydroxide and 25g of MnO after removing calcium and magnesium2Adding (equivalent to 1.5 times of molar weight of iron element) into 60% sulfuric acid solution, controlling end point pH value to 5.5-6, heating to 70-95 deg.C, and controlling solution volume to 5000 mL; ② adding 2.5g (equivalent to 0.5g/L) of BaF to the above solution2Stirring for 1.5 h; ③ adding 1g/L self-made defluorinating agent into the solution (see patent 201810659493.8 for preparation method), stirringStanding for 1 hour for 2 hours; and finally, performing precision filtration. Table 15 shows the impurity content of the treated manganese sulfate solution, and it is clear that the purity of the manganese sulfate solution obtained by the present invention can not meet the production requirements.
TABLE 15 content of major impurities (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) | - | 0.13 | 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 only difference compared to example 1 is 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): the operation of step (1) and step (2) of comparative example 2 is the same as that of example (1), and the impurity content of the obtained solution is also the same as that of example 1, and the specific contents are shown in Table 3.
And (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 compound 1-A (which is 11.6 times of the total mass of calcium and magnesium in the solution), stirring for reacting for 2 hours, immediately filtering, and washing a filter cake with water; the wash water was combined with the filtrate and evaporated to 5000 mL. Analysis of the filtrate shows that the concentrations of Ca and Mg in the filtrate are respectively 7Mg/L and 6Mg/L, the separation rates of Ca and Mg obtained by calculation are respectively only 1.23 percent and 1.57 percent, and good separation of calcium and magnesium from manganese sulfate cannot be realized.
And (4) acid dissolution and deep purification of the acid solution, which specifically comprises the following steps: firstly, the manganese hydroxide after the removal of calcium and magnesium is mixed with 25g of MnO2 (equivalent to the mole of iron element)1.5 times of the molar quantity) is added into a 60 percent sulfuric acid solution, the pH value of the end point is controlled to be 5.5 to 6, then the temperature is raised to 70 to 95 ℃, and the volume of the solution is controlled to be 5000 mL; ② adding 2.5g (equivalent to 0.5g/L) of BaF to the above solution2Stirring for 1.5 h; ③ adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1 hour, and standing for 2 hours; and finally, performing precision filtration. Table 16 shows the impurity content of the manganese sulfate solution treated by the method, and obviously, the purity of the manganese sulfate solution obtained by the method cannot meet the production requirement.
TABLE 16 content of major impurities (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 only difference compared to example 1 is that in step (3), the compound of the following structure 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): the operation of step (1) and step (2) of comparative example 2 is the same as that of example (1), and the impurity content of the obtained solution is also the same as that of example 1, and the specific contents are shown in Table 3.
And (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 the formula 2 (which is 11.6 times of the total mass of calcium and magnesium in the solution), 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 with water; the wash water was combined with the filtrate and evaporated to 5000 mL. Analysis of the filtrate shows that the concentrations of Ca and Mg 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.
And (4) acid dissolution and deep purification of the acid solution, which specifically comprises the following steps: adding manganese hydroxide and 25g of MnO after removing calcium and magnesium2Adding (equivalent to 1.5 times of molar weight of iron element) into 60% sulfuric acid solution, controlling end point pH value to 5.5-6, heating to 70-95 deg.C, and controlling solution volume to 5000 mL; ② adding 2.5g (equivalent to 0.5g/L) of BaF to the above solution2Stirring for 1.5 h; ③ adding 1g/L self-made defluorinating agent (the preparation method is shown in patent 201810659493.8) into the solution, stirring for 1 hour, and standing for 2 hours; and finally, performing precision filtration. Table 17 shows the impurity content of the manganese sulfate solution treated by the method, and obviously, the purity of the manganese sulfate solution obtained by the method cannot meet the production requirement.
TABLE 17 content of major impurities (mg/L) in the solution obtained by the treatment 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 conclusion, the compound of the formula 1 and the carbon dioxide are used for assisting, the synergy can be realized unexpectedly, a better calcium and/or magnesium removing effect can be brought, and in addition, other steps and condition control are further matched, so that the deep impurity removal of the manganese sulfate is facilitated.
Claims (10)
1. The impurity removal method of the manganese sulfate solution is characterized in that BaS is adopted to carry out a first-stage impurity removal reaction on the manganese sulfate solution, so that impurity a in the manganese sulfate solution is removed, and the treated manganese sulfate solution is obtained;
the impurity a is a heavy metal impurity.
2. The method for removing impurities from manganese sulfate solution As claimed in claim 1, wherein the impurities a are at least one of Pb, Co, Ni, Cd, As, Cu and Zn;
preferably, the pH of the initial solution of the first stage impurity removal reaction is 5.5-6;
preferably, the amount of barium sulfide added is 15-20 times of the total mass of heavy metal ions in the solution.
3. The method for removing impurities from a manganese sulfate solution as claimed in claim 1 or 2, further comprising the step of performing a second stage of impurity removal treatment on the treated manganese sulfate solution to remove impurities b or mixed impurities of the impurities b and the impurities 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 stage impurity removal step is as follows: carrying out precipitation treatment on the treated manganese sulfate solution to obtain manganese hydroxide precipitate;
mixing the manganese hydroxide precipitate and the compound shown in the formula 1 to obtain slurry, introducing carbon dioxide into the slurry, performing second-stage impurity removal treatment, and 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 a five-membered or six-membered ring group;
m is H+、Na+、K+Or NH4 +。
4. The method for removing impurities from manganese sulfate solution as claimed in claim 3, wherein the alkali used in the precipitation reaction is at least one of sodium hydroxide, potassium hydroxide and ammonia water;
preferably, the end point of the precipitation reaction is 10-11.5.
5. The method for removing impurities from manganese sulfate solution as claimed in claim 3, wherein the alkyl is C1-C10 straight chain or straight chain alkyl;
preferably, the substituted alkyl is a C1-C10 straight-chain or straight-chain alkyl containing 1-3 substituents; the substituent is hydroxyl, alkoxy of C1-C4, aminoacyl, acylamino, carboxyl, sulfydryl, alkylsulfydryl of C1-C4, phenyl, substituted phenyl, five-membered heterocyclic aryl, benzo six-membered heterocyclic aryl or amidino;
preferably, the R is H, C1-C4 alkyl, hydroxyl substituted C1-C4 alkyl or phenyl substituted C1-C4 alkyl.
6. The method for removing impurities from manganese sulfate solution as claimed in claim 3, wherein the compound represented by formula 1 is not less than the theoretical reaction amount, preferably 1-2 times of the theoretical reaction molar amount;
preferably, 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;
preferably, in the slurry, the weight ratio of the solvent to the manganese hydroxide to be treated is 1-10: 1;
preferably, in the second stage impurity removal process, the pressure of the carbon dioxide is maintained to be 0.2-0.5 MPa;
preferably, the time of the second impurity removal treatment is 1-3 h.
7. The impurity removal method for manganese sulfate solution according to any one of claims 3 to 6, further comprising a third impurity removal step of removing impurities from the manganese hydroxide after impurity removal to remove impurities d; the impurity d is at least one of iron, aluminum and fluorine;
the third stage impurity removal step is as follows:
dissolving the obtained manganese hydroxide after impurity removal with sulfuric acid, and adding MnO in advance2Followed by the addition of BaF2And finally adding a fluorine removing agent, and carrying out solid-liquid separation after reaction to obtain a purified manganese sulfate solution.
8. An impurity removal method for manganese sulfate solution as claimed in claim 7, wherein the concentration of sulfuric acid is 50-70%;
preferably, MnO2The addition amount of (b) is 1.2-2.0 times of the molar amount of the residual iron of the purified manganese hydroxide;
preferably, MnO2The end pH of the treatment stage is between 5.5 and 6.
9. The process for decontaminating a manganese sulfate solution according to claim 8, wherein BaF2The temperature of the treatment stage is 70-95 ℃;
preferably, BaF2Treatment stage, BaF2The addition concentration of (A) is 0.1-0.5 g/L;
preferably, in the treatment stage of the fluorine removal agent, the application amount of the fluorine removal agent is 1-5 g/L.
10. 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 of iron and aluminum and fluorine ion impurity, and the treatment process comprises the following steps:
the method comprises the following steps:
adjusting the pH value of the manganese sulfate solution to be treated to 5.5-6, adding barium sulfide, stirring for reaction, standing to precipitate heavy metal elements in a sulfide form, and filtering to obtain a manganese sulfate solution A, wherein the addition amount of 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;
step three:
mixing the manganese hydroxide precipitate, the compound shown in the formula 1 and water to obtain slurry, and then introducing carbon dioxide into the system for 1-3 hours, and maintaining the pressure of the system at 0.2-0.5MPa to ensure that calcium and magnesium in the manganese hydroxide precipitate stably enter the solution in an ion form, thereby realizing the removal of calcium and magnesium in the manganese hydroxide;
step four:
step 1:
mixing the manganese hydroxide obtained in the step (3) with MnO2Adding into 50-70% sulfuric acid solution, controlling the end point pH value to 5.5-6, and heating to 70-95 deg.C;
step 2:
adding 0.1-0.5g/L BaF into the solution2Stirring for 1-2h to make the residual calcium and magnesium in the solution enter the precipitation in the form of fluoride;
and 3, step 3:
adding 3-5g/L aluminum sulfate or 1-2g/L commercial defluorinating agent into the solution, stirring for 1-2h, and standing for 1-2 h;
and finally, filtering to obtain the high-purity manganese sulfate solution.
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| CN114162872A (en) * | 2021-12-31 | 2022-03-11 | 湖南烯富环保科技有限公司 | Method for preparing battery-grade manganese sulfate from manganese oxide ore |
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