CN114162872B - Method for preparing battery-grade manganese sulfate from manganese oxide ore - Google Patents
Method for preparing battery-grade manganese sulfate from manganese oxide ore Download PDFInfo
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Abstract
The invention belongs to the field of smelting, and particularly relates to a method for preparing battery-grade manganese sulfate from manganese oxide ores, which comprises the following steps: (1) leaching: carrying out first-stage leaching on manganese oxide ores, biomass and sulfuric acid, roasting leaching residues, mixing roasting materials with the first-stage leaching solution, carrying out second-stage leaching, and separating to obtain leaching solution; (2) first section edulcoration: adding ferric sulfate, a manganese oxidant and sulfides into the leaching solution to obtain a first-stage impurity-removing solution; (3) and (3) impurity removal in the second section: carrying out manganese precipitation treatment on the first-stage impurity removal liquid to obtain manganese hydroxide precipitate, dispersing the precipitate and the compound shown in the formula 1 in a solvent to obtain slurry, introducing carbon dioxide into the slurry, carrying out second-stage impurity removal, and carrying out solid-liquid separation to obtain purified manganese hydroxide; (3) and (3) impurity removal in the third section: dissolving the purified manganese hydroxide with sulfuric acid, and then adding BaS and BaF2 to obtain a battery-grade manganese sulfate solution. The method has high recovery rate and can prepare high-quality battery-grade manganese sulfate.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for preparing battery-grade manganese sulfate from manganese oxide ores.
Background
The battery-grade manganese sulfate is one of main raw materials for preparing the ternary cathode material of the lithium ion battery, wherein the K, na, ca, mg content is generally required to be not higher than 50ppm, the Fe, cu, zn and Pb content is not higher than 10 nom, the Cd content is not higher than 5ppm, the As content is less than 1ppm and the 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. Therefore, the low-grade raw materials are adopted, and the low-cost impurity removal technology is developed, so that the method has important significance for battery-grade manganese sulfate manufacturing enterprises. At present, a considerable amount of processes have been developed in the aspect of preparing battery-grade manganese sulfate in China, and the processes can be summarized into two routes which take manganese products as raw materials and manganese ores as raw materials. Preparing battery-grade manganese sulfate by taking a manganese product as a raw material refers to preparing the battery-grade manganese sulfate by directly acid-dissolving metal manganese or electrolytic manganese dioxide or taking industrial manganese sulfate as the raw material through impurity removal; the technological process of using manganese ore as raw material mainly includes the procedures of acid dissolution and impurity removal, etc..
Because K, na, ca, mg, fe, cu, zn, pb and other elements inevitably exist in manganese ores, ca and Mg are main accompanying elements in manganese ores, and the lithiation property of the elements is similar to that of manganese, more processes are developedTechnical route. Patent 201610001688.4 discloses a process for preparing battery-grade manganese sulfate by using pyrolusite as a raw material, which comprises the steps of reduction leaching by taking pyrite as a reducing agent, flocculation by adding activated carbon and a flocculating agent, manganese precipitation by ammonia water to obtain manganese hydroxide, washing by manganese hydroxide, evaporation crystallization of acid-soluble manganese hydroxide and manganese sulfate and the like, and although the manganese sulfate with good performance can be obtained, the patent does not have a special calcium removal process, and only the pH value of the precipitated manganese is controlled and the manganese hydroxide is washed by water to reduce the K, na, ca, mg content of the product, so that the content of the impurities of the product is difficult to ensure to reach the standard, in addition, the process flow is long, residual manganese is difficult to avoid in leaching residues, and the leaching efficiency of manganese element in the ore cannot be very high. 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)]Mining engineering, 2019,39 (3): 85-88) is purified by 3 times of crystallization to lead the impurity content in the manganese sulfate to reach the battery level standard, but the repeated crystallization has larger energy consumption and seriously affects the recovery efficiency of the manganese sulfateThe rate.
Disclosure of Invention
The invention aims to prepare a battery-grade manganese sulfate solution by using manganese oxide ore with complex components.
A method for preparing battery-grade manganese sulfate from manganese oxide ore, which comprises the following steps:
step (1): two stage leaching
Carrying out first stage leaching on manganese oxide ores, biomass and sulfuric acid, and then carrying out solid-liquid separation to obtain first stage leaching liquid and leaching slag;
roasting leaching residues in an oxygen-free atmosphere, mixing the obtained roasting material with the first-stage leaching solution, carrying out second-stage leaching, and separating to obtain leaching solution;
step (2): first stage impurity removal
Adding ferric sulfate and manganese oxidant into the leaching solution, heating to perform primary precipitation reaction of sodium and/or potassium, then adding sulfide into the system, performing secondary precipitation reaction of heavy metal, and then separating to obtain first-stage impurity-removing solution;
step (3): second stage impurity removal
Carrying out manganese precipitation treatment on the first-stage impurity removal liquid to obtain manganese hydroxide precipitate, dispersing the precipitate and the compound shown in the formula 1 in a solvent to obtain slurry, introducing carbon dioxide into the slurry, carrying out second-stage impurity removal, and carrying out solid-liquid separation to obtain purified 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 + ；
Step (4): third stage of impurity removal
Dissolving the purified manganese hydroxide with sulfuric acid, then adding BaS and BaF2, finally adding aluminum sulfate or defluorinating agent, and carrying out solid-liquid separation after treatment to obtain the battery-grade manganese sulfate solution.
According to the invention, the research discovers that the combination of the two-stage leaching process and the first-stage impurity removal and third-stage impurity removal processes can be innovatively adopted, so that the extraction and recovery rate of manganese can be improved, the separation selectivity of manganese and other impurity elements can be improved, and the battery-grade manganese sulfate solution can be prepared cooperatively.
In the present invention, the manganese oxide ore may be a mineral containing an oxide such as manganese dioxide, which is known in the industry. For example, the manganese oxide ore is at least one of pyrolusite, pyrolusite and pyrolusite.
In the technical scheme of the invention, the method is applicable to any grade of manganese oxide ore in theory, and is especially applicable to minerals which are difficult to process in industry and have high Ca and Mg contents (5-15%). According to the technical scheme, no special requirement is imposed on the grade of the manganese oxide ore, and the high-grade and low-grade minerals can be utilized to effectively prepare the battery-grade manganese sulfate solution.
In the present invention, the manganese oxide ore may be subjected to a treatment such as crushing in advance based on the conventional means. For example, the granularity of the manganese oxide ore is controlled below 150 um.
In the invention, the two-stage combined leaching is carried out with the aid of the reducing agent, so that the leaching of manganese is improved, and the subsequent selective separation of manganese and impurities is facilitated.
In the present invention, the biomass is biomass waste material containing at least one of cellulose, hemicellulose or crude fiber. For example, the biomass is at least one of straw, corn stalk or corn cob;
the biomass can be dehydrated and crushed before use, for example, the granularity of the biomass is controlled between 38um and 74um;
preferably, the mass ratio of the manganese oxide ore to the biomass waste is (1:1) - (3:1);
preferably, the concentration of sulfuric acid is 1-3mol/L;
preferably, the first stage of leaching has a liquid to solid ratio of (3-10): 1 (mL/g);
preferably, the temperature of the first stage of leaching is 85-95 ℃;
preferably, the time of the first leaching stage is 4-10 hours.
In the invention, the first-stage leaching slag is roasted, and then the second-stage leaching treatment is carried out by adopting the first-stage leaching liquid, so that the leaching of manganese is improved, and the separation of manganese and impurity elements is facilitated.
In the present invention, the oxygen-free atmosphere is at least one of nitrogen and inert gas;
preferably, the temperature of calcination is 850-1000 ℃;
preferably, the roasting time is 2-4 hours;
the slag is treated by the first leaching solution after roasting, which is beneficial to improving the recovery of manganese, and is also beneficial to removing impurities from the leaching solution and separating manganese and impurities subsequently.
Preferably, the temperature of the second stage of leaching is 50-70 ℃;
preferably, the time of the second leaching stage is 0.5 to 2 hours.
In the invention, the leaching solution is subjected to a potassium (sodium) iron vitriol process in advance, so that the selective separation of sodium and/or potassium and manganese in the system is realized, and then sulfide can be directly added without solid-liquid separation, so that the secondary precipitation of heavy metals is realized.
In the step (2), the pH value of the initial solution of the first-stage precipitation reaction is 1.5-2;
preferably, manganese hydroxide is used to regulate the pH;
preferably, the dosage of the ferric sulfate is 40-50 times of the total amount of sodium ions and potassium ions in the leaching solution;
preferably, the manganese-based oxidizing agent is a positive tetravalent and higher valent manganese oxide, preferably manganese dioxide;
preferably, the dosage of the manganese-based oxidant is 8-10 times of the total mass of sodium ions and potassium ions in the leaching solution;
preferably, the temperature of the primary precipitation reaction is greater than or equal to 90 ℃; the reaction time is preferably 1 to 2 hours, and the reaction time is preferably 1 to 2 hours after the reaction.
In the step (2), the pH value of the initial solution of the second-stage precipitation reaction is 5.5-6; preferably, manganese hydroxide is used to regulate the pH;
preferably, the sulfide is sodium thiram. According to the invention, sodium thiram is adopted as a precipitator, so that manganese and heavy metal elements can be selectively separated.
In the present invention, the heavy metals include Pb, co, ni, cd, as, cu and Zn, for example.
Preferably, the dosage of sulfide is 15-20 times of the total mass of heavy metals in the solution system;
preferably, the time of the second-stage precipitation reaction is 1-2 hours;
preferably, after the second-stage precipitation reaction, standing for 1-2 hours, and then carrying out solid-liquid separation to obtain the first impurity removing liquid.
In the invention, the solution after the first section of impurity removal is subjected to precipitation treatment, and the calcium hydroxide and magnesium hydroxide impurities in the solution are selectively and synergistically dissolved out by adopting a process in the assistance of the formula 1 and carbon dioxide, so that the selective separation of manganese and calcium-magnesium is realized.
In the present invention, in the step (3), the alkali used in the manganese precipitation treatment stage may be ammonia, sodium hydroxide, potassium hydroxide or the like, and the alkali is preferably ammonia in view of easiness of treatment.
Preferably, the concentration of the ammonia water is 6-10mol/L;
preferably, the end point of the manganese precipitation reaction is 10-11.5.
In the present invention, the combination of formula 1 and carbon dioxide gas is a key to improving the selective separation of manganese and calcium-magnesium.
Preferably, the alkyl is a C1-C10 linear or linear alkyl;
preferably, the substituted alkyl is a C1-C10 linear or 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 six-membered heterocyclic aryl or amidino;
preferably, R is H, C-C4 alkyl, hydroxyl-substituted C1-C4 alkyl or phenyl-substituted C1-C4 alkyl;
preferably, the compound of formula 1 is not less than the theoretical reaction amount, preferably 1 to 2 times 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 of impurity removal, the end point pH of the introduced carbon dioxide is 6.5-7.5; further preferably 6.8 to 7.2.
In the invention, after carbon dioxide is introduced to reach the pH value, solid-liquid separation is carried out to obtain the treated manganese hydroxide.
In the invention, the purified manganese hydroxide is re-dissolved by sulfuric acid, and then the combined impurity removal component of BaS and BaF2 is adopted, thereby being beneficial to further improving the selective separation of manganese and other impurities (such as iron, calcium, magnesium and the like).
In the step (4), the concentration of sulfuric acid is 50-70%;
preferably, the temperature of the acid dissolution stage is 70-95 ℃;
preferably, the pH of the acid-dissolved manganese sulfate solution is 5.5-6;
preferably, the BaS is added at a concentration of 0.5-1g/L;
the addition concentration of BaF2 is 0.5-1g/L.
And (3) treating the battery-grade manganese sulfate solution by adopting aluminum sulfate or a defluorinating agent after the combined treatment of the BaS and the BaF 2. In the invention, the application concentration of the aluminum sulfate is 3-5g/L; the application concentration of the defluorinating agent is 1-2g/L.
The prepared manganese sulfate solution can be further used for preparing corresponding products based on the existing means.
The invention relates to a method for preparing battery-grade manganese sulfate from pyrolusite, which comprises the following steps:
step one, high-efficiency reduction leaching of manganese element in pyrolusite;
step two, removing other impurity ions except calcium and magnesium in the pickle liquor;
precipitating manganese with ammonia water and removing calcium and magnesium in manganese hydroxide;
fourthly, acid dissolution of manganese hydroxide, deep impurity removal of manganese sulfate solution and concentration crystallization thereof.
The high-efficiency reduction leaching of manganese element in pyrolusite in the step one refers to wet leaching by taking biomass waste as a reducing agent and sulfuric acid as a leaching agent, and the leaching solution and leaching slag are obtained after filtration, wherein the leaching process comprises the following steps:
adding pyrolusite and biomass waste into sulfuric acid solution with concentration of 1-3mol/L according to mass ratio of (1:1) - (3:1), and reacting for 4-10h at 85-95 ℃, wherein the liquid-solid ratio (mL/g) in the reaction system is (3-10): 1. The low-grade pyrolusite refers to manganese dioxide ore with Mn grade of about 20%, and granularity is less than 150um; the biomass waste used as the reducing agent refers to biomass waste rich in cellulose, hemicellulose or crude fiber and the like, wherein the cellulose, the hemicellulose or the crude fiber can be hydrolyzed into reducing sugar under an acidic condition, and preferably any one of straw, corn stalk or corncob with the granularity of 38-74 um. The main reactions occurring in step one include the hydrolysis of cellulose and hemicellulose in the biomass waste material to glucose, oligosaccharides or monosaccharides by concentrated sulfuric acid, these reducing sugars reacting with MnO having oxidizing properties 2 A redox reaction occurs to reduce the +4 valent manganese in pyrolusite into +2 valent manganese, and the reaction formula of the whole leaching process is as follows:
(C 6 H 10 O 5 )n+nH 2 SO 4 →n(C 5 H 11 O 5 )HSO 4
n(C 5 H 11 O 5 )HSO 4 +nH 2 O→(C 6 H 12 O 6 )n+nH 2 SO 4
12MnO 2 +C 6 H 12 O 6 +12H 2 SO 4 →12MnSO 4 +6CO 2 +18H 2 O
the general reaction formula is: 12MnO 2 +(C 6 H 12 O 6 )n+12nH 2 SO 4 →12MnSO 4 +6nCO 2 +17nH 2 O
The first step further comprises deep recovery of manganese element in the leaching slag, firstly, the leaching slag is subjected to heat treatment, namely, the slag is placed in a high-temperature furnace isolated from air, the temperature is raised to 850-1000 ℃ at a heating rate of 5-20 ℃/min, then the temperature is kept for 2-4h, the positive pressure range in the high-temperature furnace is maintained to be 0.1-0.2MPa, then the heat treatment slag is added into the pickle liquor with the temperature maintained at 50-70 ℃ for continuous stirring reaction, so that the manganese element in the slag is fully dissolved out after the heat treatment, meanwhile, the removal of organic matters in the pickle liquor is realized, and the filtrate obtained after the stirring reaction is filtered to be the pickle liquor after the removal of the organic matters. The leaching slag is subjected to heat treatment to realize efficient leaching of manganese element in the slag, because: the biomass waste used as the reducing agent cannot be saccharified completely in the aforementioned reducing leaching step, and a large amount of organic matter component C remains n H m O, these organic components generate reducing substances including CO and C when subjected to high temperature heat treatment in the air insulation, and they react with pyrolusite MnO 2 Reducing to MnO, and mixing with residual H in pickling solution 2 SO 4 Generating MnSO 4 The main reaction formula is as follows:
2MnO 2 +C→2MnO+CO 2
MnO 2 +CO→MnO+CO 2
MnO+H 2 SO 4 →MnSO 4 +H 2 O
the step two of removing impurity ions except calcium and magnesium in the pickle liquor refers to removing K, na, fe, al, pb, co, ni, cd, as, cu, zn and other elements in the pickle liquor, and the specific steps comprise:
step 1, useMn(OH) 2 Adjusting the pH value of the pickle liquor after removing the organic matters to 1.5-2, and adding K into the solution system + 、Na + Fe 40-50 times of the sum of ion masses 2 (SO 4 ) 3 With 8-10 times MnO 2 ，MnO 2 Is added for oxidizing the +2 valent iron ions in the solution to +3 valent iron ions; then heating the solution to above 90 ℃, standing for 1-2h after reacting for 1-2h, at this time, K in the solution + 、Na + Ions enter the precipitate in the form of jarosite and sodium jarosite. The main reaction of the step is as follows:
2Fe 2+ +MnO 2 +4H + →2Fe 3+ +Mn 2+ +2H 2 O
K + +3Fe 3+ +2SO 4 2- +6H 2 O→KFe 3 [SO 4 (OH) 3 ] 2 ↓+6H +
Na + +3Fe 3+ +2SO 4 2- +6H 2 O→NaFe 3 [SO 4 (OH) 3 ] 2 ↓+6H +
Fe 3+ +3H 2 O→Fe(OH) 3 ↓+3H + ，2[(C 2 H 5 ) 2 NCSS] - +Me 2+ →[(C 2 H 5 ) 2 NCSS] 2 Me↓
the step three means that the ammonia water is used for precipitating manganese and the removal of calcium and magnesium in manganese hydroxide,
and 1, adding ammonia water to precipitate manganese. Adding ammonia water into the manganese sulfate solution obtained in the second step after removing impurities outside calcium and magnesium, so that manganese in the solution is precipitated in the form of manganese hydroxide, wherein the concentration of the added ammonia water is 6-10mol/L, and the final pH value of the solution after the ammonia water is added is 10-11.5. Because calcium and magnesium ions are difficult to remove in the previous step, the reaction in the step comprises a precipitation reaction of manganese ions, and also comprises a precipitation reaction of magnesium ions and calcium ions which are slightly dissolved into the solution, specifically:
Mn 2+ +2NH 4 OH→Mn(OH) 2 ↓+2(NH 4 ) +
Ca 2+ +2NH 4 OH→Ca(OH) 2 ↓+2(NH 4 ) +
Mg 2+ +2NH 4 OH→Mg(OH) 2 ↓+2(NH 4 ) +
and 2, pulping and carbonating the manganese hydroxide precipitate.
And (3) pulping deionized water and the manganese hydroxide precipitate according to a liquid-solid ratio (3-5), adding the formula 1 into the slurry, then introducing carbon dioxide into the system until the pH value of the slurry reaches 6.8-7.2, stopping introducing the carbon dioxide, and immediately filtering, wherein a small amount of calcium hydroxide and magnesium hydroxide solids in the manganese hydroxide completely enter a liquid phase at the moment, so that 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+
The acid-soluble manganese hydroxide and manganese sulfate solution deep impurity removal and concentration crystallization method comprises the following steps:
step 1, acid-dissolving manganese hydroxide. Adding the manganese hydroxide prepared in the step three, from which the calcium and the magnesium are removed, 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 ℃; the reaction is as follows:
Mn(OH) 2 +H 2 SO 4 →MnSO 4 +2H 2 O
and 2, deeply purifying the manganese sulfate solution. Adding 0.5-1g/L BaS and 0.5-1g/L BaF into the above solution 2 Stirring for 1-2h to remove residual heavy metal ions and calcium and magnesium ions in the solution; adding 3-5g/L aluminum sulfate or 1-2g/L commercial fluorine removing agent (conventional fluorine removing agent), stirring for 1-2h, and standing for 1-2h; and finally, precisely filtering.
The main reaction is as follows:
BaS+Me 2+ +SO 4 2- →MeS↓+BaSO 4 ↓
2BaF 2 +Ca 2+ +Mg 2+ +2SO 4 2- →2BaSO 4 ↓+BaF 2 ↓+MgF 2 ↓
Al 3+ +3F - →2AlF 3 ↓，Al 3+ +3H 2 O→Al(OH) 3 ↓+3H +
and 3, concentrating and crystallizing the manganese sulfate by adopting MVR and other known technologies to finally obtain the battery-grade manganese sulfate.
Compared with the prior art, the invention has the following advantages:
(1) By adopting a biomass-assisted two-stage leaching process, the recovery rate of manganese ore can be improved, impurity removal is facilitated, and the subsequent impurity removal effect is improved. In addition, straw, corn stalk or corncob biomass waste is waste in other industries, and the waste is applied to a leaching process of manganese ores, so that the purpose of treating waste with waste can be realized; moreover, the biomass waste materials adopted by the invention are rich in components such as cellulose, hemicellulose or crude fiber, and the components are hydrolyzed into saccharide substances with strong reducibility in an acidic environment, so that the reduction of valuable components in manganese ores and slag roasting materials into low-valence elements which are easy to be leached by acid is ensured, and thus, high leaching efficiency can be obtained.
(2) The reducing slag generated in the reducing leaching process is subjected to heat treatment and then reacts with the pickling liquid, so that manganese element in the slag is leached doubly, the comprehensive recovery rate of manganese in pyrolusite is improved, carbon materials with good adsorption effect are generated by heat treatment of carbonaceous components in the reducing slag, and impurities such as organic matters in the leaching liquid can be removed.
(3) The manganese sulfate solution is precipitated by alkali, and the selective separation of soluble impurities (such as N, na and the like), calcium-magnesium and manganese can be realized by further matching with a combined process of the formula 1 and the carbon dioxide. The method of the invention 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.
(4) Small amounts of BaS and BaF 2 In combination with the advanced treatment of manganese sulphate solution, because of BaSO 4 The solubility product of (2) is 1.08X10) -10 (25 ℃) compared with BaF 2 1.84×10 of (2) -7 Is about 3 orders of magnitude lower, thus, while the heavy metals such as Cu, pb, zn, ni, co and the Ca and Mg are deeply removed, other substances are not introducedCationic impurities are a great advantage of the present invention over other known techniques.
Drawings
FIG. 1 is a flow chart of an embodiment of the invention
Detailed Description
The invention will now be further described with reference to the accompanying drawings, without however being limited thereto.
See fig. 1.
The invention provides a method for preparing battery-grade manganese sulfate from low-grade pyrolusite, which comprises the following steps:
step one, high-efficiency reduction leaching of manganese element in pyrolusite;
step two, removing other impurity ions except calcium and magnesium in the pickle liquor;
precipitating manganese with ammonia water and removing calcium and magnesium in manganese hydroxide;
fourthly, acid dissolution of manganese hydroxide, deep impurity removal of manganese sulfate solution and concentration crystallization thereof.
The high-efficiency reduction leaching of manganese element in pyrolusite in the step one refers to wet leaching by taking biomass waste as a reducing agent and sulfuric acid as a leaching agent, and the leaching solution and leaching slag are obtained after filtration, wherein the leaching process comprises the following steps: adding pyrolusite and biomass waste into sulfuric acid solution with concentration of 1-3mol/L according to mass ratio of (1:1) - (3:1), and reacting for 4-10h at 85-95 ℃, wherein the liquid-solid ratio (mL/g) in the reaction system is (3-10): 1. The low-grade pyrolusite refers to manganese dioxide ore with Mn grade of about 20%, and granularity is less than 150um; the biomass waste used as the reducing agent refers to biomass waste rich in cellulose, hemicellulose or crude fiber and the like, wherein the cellulose, the hemicellulose or the crude fiber can be hydrolyzed into reducing sugar under an acidic condition, and preferably any one of straw, corn stalk or corncob with the granularity of 38-74 um.
The first step further comprises deep recovery of manganese element in leaching slag, firstly, heat treatment is carried out on the leaching slag, namely, the slag is placed in a high-temperature furnace isolated from air, the temperature is raised to 850-1000 ℃ at a heating rate of 5-20 ℃/min, then the temperature is kept for 2-4h, the positive pressure range in the high-temperature furnace is maintained to be 0.1-0.2MPa, then the heat treatment slag is added into pickle liquor (the last step) with the temperature maintained to be 50-70 ℃ for continuous stirring reaction, so that the manganese element in the slag is fully dissolved out after the heat treatment, meanwhile, the removal of organic matters in the pickle liquor is realized, and the filtrate obtained through filtration after the stirring reaction is pickle liquor after the removal of the organic matters for 0.5-2 h.
The step two of removing impurity ions except calcium and magnesium in the pickle liquor refers to removing K, na, fe, al, pb, co, ni, cd, as, cu, zn and other elements in the pickle liquor, and the specific steps comprise:
step 1, mn (OH) 2 Adjusting the pH value of the pickle liquor after removing the organic matters to 1.5-2, and adding K into the solution system + 、Na + Fe 40-50 times of the sum of ion masses 2 (SO 4 ) 3 With 8-10 times MnO 2 ，MnO 2 Is added for oxidizing the +2 valent iron ions in the solution to +3 valent iron ions; then heating the solution to above 90 ℃, standing for 1-2h after reacting for 1-2h, at this time, K in the solution + 、Na + Ions enter the precipitate in the form of jarosite and sodium jarosite.
The step three means that the ammonia water is used for precipitating manganese and the removal of calcium and magnesium in manganese hydroxide,
and 1, adding ammonia water to precipitate manganese. Adding ammonia water into the manganese sulfate solution obtained in the second step after removing impurities outside calcium and magnesium, so that manganese in the solution is precipitated in the form of manganese hydroxide, wherein the concentration of the added ammonia water is 6-10mol/L, and the final pH value of the solution after the ammonia water is added is 10-11.5. Because calcium and magnesium ions are difficult to remove in the previous step, the reaction in this step includes precipitation of manganese ions and precipitation of calcium ions that are slightly soluble in the solution with magnesium ions and calcium sulfate.
And 2, pulping and carbonating the manganese hydroxide precipitate.
And (3) pulping deionized water and the manganese hydroxide precipitate according to a liquid-solid ratio (3-5), adding the formula 1 into the slurry, then introducing carbon dioxide into the system until the pH value of the slurry reaches 6.8-7.2, stopping introducing the carbon dioxide, and immediately filtering, wherein a small amount of calcium hydroxide and magnesium hydroxide solids in the manganese hydroxide completely enter a liquid phase at the moment, so that the removal of calcium and magnesium in the manganese hydroxide is realized. The compound of formula 1 is shown as 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 acid-soluble manganese hydroxide and manganese sulfate solution deep impurity removal and concentration crystallization method comprises the following steps:
step 1, acid-dissolving manganese hydroxide. Adding the manganese hydroxide prepared in the third step after removing calcium and magnesium into 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 ℃.
And 2, deeply purifying the manganese sulfate solution. Adding 0.5-1g/L BaS and 0.5-1g/L BaF into the above solution 2 Stirring for 1-2h to remove residual heavy metal ions and calcium and magnesium ions in the solution; then adding 3-5g/L aluminum sulfate or 1-2g/L commercial fluorine removing agent, stirring for 1-2h, and standing for 1-2h; and finally, precisely filtering.
And 3, concentrating and crystallizing the manganese sulfate by adopting MVR and other known technologies to finally obtain the battery-grade manganese sulfate.
Example 1 preparation of Battery grade manganese sulfate from pyrolusite leachate with corncob as biomass reductant
The pyrolusite treated in this example has the characteristics of high content of Ca and Mg, and the content of Ca is 8.51% and the content of Mg is 6.77%.
Step one: and (3) taking corncob as a reducing agent, performing reduction acid leaching in sulfuric acid solution, and filtering to obtain reduction leaching residues and pickle liquor.
(1) Adding 400-mesh (about 38 um) corncob and pyrolusite with granularity less than 150um and Mn grade of 22% into a sulfuric acid solution with the concentration of 3mol/L, wherein the mass ratio of pyrolusite to corncob is 1:1, and the liquid-solid ratio of the solution is 5:1; then, the solution is heated to 90 ℃ and reacts for 4 hours, and water is added for 1 time after the reaction for 1 hour in order to maintain the volume of the solution; filtering after the reaction to obtain pickle liquor and leaching slag;
(2) the leaching slag is subjected to heat treatment in a high-temperature furnace isolated from air, the temperature is raised to 900 ℃ at the heating rate of 10 ℃/min, then the temperature is kept for 3 hours, the positive pressure range in the high-temperature furnace is maintained to be 0.1-0.2MPa, then the heat treatment slag is added into the pickle liquor with the temperature maintained at 60 ℃ for continuous stirring reaction, so that manganese element in the slag is fully dissolved out after the heat treatment, meanwhile, the removal of organic matters in the pickle liquor is realized, and the filtrate obtained after the stirring reaction for 1 hour is filtered to obtain the pickle liquor after the removal of the organic matters.
Step two: aiming at the solution obtained in the step one, the impurity is mainly removed from the pickling solution, such as K, na, fe, al, pb, co, ni, cd, as, cu, zn and the like. Analysis shows that K in pickle liquor + The concentration is 1.81g/L, na + The concentration of the mixed solution is 0.451g/L, and the total weight of the Cu, pb, zn and other heavy metals in the pickle liquor is 45mg/L. In addition, the Mn concentration is 43.97g/L, and the Mn leaching rate in the step one is 99.93 percent.
Step 1, mn (OH) 2 After the pH value of the pickle liquor after removing the organic matters is adjusted to 1.5, fe is added into a solution system 2 (SO 4 ) 3 (40 times of the total amount of sodium ions and potassium ions in the solution), mnO is added 2 (8 times the total amount of sodium and potassium ions in the solution); then, the temperature of the solution was raised to 90℃or higher, and the reaction was allowed to stand for 1 hour and 2 hours.
Step three: and (3) precipitating manganese by ammonia water and removing calcium and magnesium in the manganese hydroxide.
And 1, adding ammonia water to precipitate manganese. Adding ammonia water into the manganese sulfate solution obtained in the second step after removing impurities outside calcium and magnesium, precipitating manganese in the solution in the form of manganese hydroxide, wherein the concentration of the added ammonia water is 8mol/L, the final pH value of the solution after the ammonia water is added is 11, and then filtering to obtain manganese hydroxide precipitate.
And 2, pulping deionized water and the manganese hydroxide precipitate according to a liquid-solid ratio of 3:1, adding the formula 1-A (added according to 12 times of the total amount of calcium and magnesium) into the slurry, then introducing carbon dioxide into the slurry, stopping introducing the carbon dioxide until the pH value of the slurry reaches 7, and filtering, thereby realizing the removal of calcium and magnesium in the manganese hydroxide.
And fourthly, dissolving manganese hydroxide, deeply removing impurities from the manganese sulfate solution, and concentrating and crystallizing.
Step 1, adding the manganese hydroxide prepared in the step three after removing calcium and magnesium into a sulfuric acid solution with the concentration of 50%, controlling the pH value of the end point to be 5.8, and then heating to 80 ℃;
And 3, concentrating and crystallizing the manganese sulfate by adopting MVR and other known technologies to finally obtain the battery-grade manganese sulfate. The following table shows the impurity quality requirement standard of battery grade manganese sulfate and the detection result of the product prepared in this example, and it is obvious that the impurity content in the product prepared by the technology of the present invention is much lower than the quality requirement.
TABLE 1 impurity requirements in Battery grade manganese sulfate and impurity content (ppm) of the product of this example
| Element(s) | ΣFe | K | Na | Ca | Mg | Cu | Zn | Pb | Cd | As | F |
| Standard required content | <10 | <50 | <50 | <50 | <50 | <10 | <10 | <10 | <5 | <1 | <700 |
| The product of this example | 3 | 5.5 | 6.5 | 10 | 9 | 1.5 | 1.2 | - | - | - | 5 |
Example 2
Compared with example 1, the treatment process of the first step is adjusted, and the first difference is that:
reducing and acid leaching with straw as reducing agent in sulfuric acid solution, and filtering to obtain reduced leaching residue and pickle liquor.
(1) Adding 400-mesh (about 38 um) straw and pyrolusite with granularity less than 150um and Mn grade of 22% into a sulfuric acid solution with a concentration of 3mol/L, wherein the mass ratio of pyrolusite to corncob is 1:1, and the liquid-solid ratio of the solution is 5:1; then, the solution is heated to 90 ℃ and reacts for 4 hours, and water is added for 1 time after the reaction for 1 hour in order to maintain the volume of the solution; filtering after the reaction to obtain pickle liquor and leaching slag;
(2) the leaching slag is subjected to heat treatment in a high-temperature furnace isolated from air, the temperature is raised to 1000 ℃ at a heating rate of 15 ℃/min, then the temperature is kept for 3 hours, the positive pressure range in the high-temperature furnace is maintained to be 0.1-0.2MPa, then the heat treatment slag is added into pickle liquor with the temperature maintained to be 50-70 ℃ for continuous stirring reaction, so that manganese element in the slag is fully dissolved out after heat treatment, meanwhile, the removal of organic matters in the pickle liquor is realized, and the filtrate obtained after stirring reaction for 2 hours is filtered to obtain pickle liquor after the removal of the organic matters.
Other operations and parameters were the same as in example 1.
The composition characteristics of the obtained manganese sulfate solution are shown in Table 2:
TABLE 2 impurity requirements in Battery grade manganese sulfate and impurity content (ppm) of the product of this example
| Element(s) | ΣFe | K | Na | Ca | Mg | Cu | Zn | Pb | Cd | As | F |
| Standard required content | <10 | <50 | <50 | <50 | <50 | <10 | <10 | <10 | <5 | <1 | <700 |
| The product of this example | 2.6 | 5.3 | 6.6 | 12 | 11 | 1.2 | 1.1 | - | - | - | 8 |
Example 3
The only difference compared to example 1 is in the regulation of the compound of formula 1 in step 2 of step three, the step 2 of step three being:
and 2, pulping deionized water and the manganese hydroxide precipitate according to a liquid-solid ratio of 3:1, adding the formula 1-B (15 times of the total amount of calcium and magnesium) into the slurry, then introducing carbon dioxide into the slurry, stopping introducing the carbon dioxide until the pH value of the slurry reaches 7, and immediately filtering to remove calcium and magnesium in the manganese hydroxide.
Other operations and parameters were the same as in example 1.
The composition of the resulting battery grade manganese sulfate solution is shown in table 3.
TABLE 3 impurity requirements in battery grade manganese sulfate and impurity levels (ppm) for the products of this example
| Element(s) | ΣFe | K | Na | Ca | Mg | Cu | Zn | Pb | Cd | As | F |
| Standard required content | <10 | <50 | <50 | <50 | <50 | <10 | <10 | <10 | <5 | <1 | <700 |
| The product of this example | 2.8 | 4.3 | 6.4 | 11.7 | 12 | 1.6 | 1.3 | - | - | - | 5 |
Comparative example 1
The difference compared with example 1 is that in the first step (1), no corncob is added, and Mn is contained in the total leachate obtained in the first step 2+ The concentration was only 17.92g/L, and the leaching rate of Mn was only 40.72% as calculated. The leaching rate of manganese is significantly reduced.
Comparative example 2
The difference compared with example 1 is that in step 2 of the third step, the compound of formula 1-A is not added, and other steps and parameters are the same as in example 1.
The impurity element content of the manganese sulfate crystal product obtained after concentrating and crystallizing the manganese sulfate by the MVR technology is shown in Table 4.
TABLE 4 impurity requirements in Battery grade manganese sulfate and impurity content (ppm) of the product of this example
| Element(s) | ΣFe | K | Na | Ca | Mg | Cu | Zn | Pb | Cd | As | F |
| Standard required content | <10 | <50 | <50 | <50 | <50 | <10 | <10 | <10 | <5 | <1 | <700 |
| The product of this example | 3.3 | 3.4 | 5.8 | 1127 | 907 | 3.2 | 1.5 | - | - | - | 9 |
Obviously, the addition of the substance of the formula 1 is canceled, so that the Ca and Mg contents in the final product are too high to meet the production requirement of manganese sulfate. Mn in manganese sulfate solution finally obtained by the whole process 2+ The concentration of (C) was 43.28g/L, and the recovery rate of Mn was 98.36% as calculated.
Comparative example 3
The difference compared with example 1 is that in step 2 of the third step, the compound of formula 2 is replaced with the same amount of the compound of formula 1-A, and the other steps and parameters are the same as in example 1.
The impurity element content of the manganese sulfate crystal product obtained after the manganese sulfate is concentrated and crystallized by the MVR technology is shown in the table 5.
TABLE 5 impurity requirements in battery grade manganese sulfate and impurity levels (ppm) for the products of this example
| Element(s) | ΣFe | K | Na | Ca | Mg | Cu | Zn | Pb | Cd | As | F |
| Standard required content | <10 | <50 | <50 | <50 | <50 | <10 | <10 | <10 | <5 | <1 | <700 |
| The product of this example | 1.1 | 4.6 | 5.1 | 1141 | 885 | 4.4 | 2.3 | - | - | - | 8.5 |
Obviously, the addition of the substance of the formula 1 is canceled, so that the Ca and Mg contents in the final product are too high to meet the production requirement of manganese sulfate. Mn in manganese sulfate solution finally obtained by the whole process 2+ The concentration of (C) is 43.22g/L, and the Mn recovery rate is 98.22 percent
Comparative example 4
The difference from example 1 is that carbon dioxide is not introduced in step 2 of the third step, and other steps and parameters are the same as those of example 1.
The impurity element content of the manganese sulfate crystal product obtained after concentrating and crystallizing the manganese sulfate by the MVR technology is shown in Table 6.
TABLE 6 impurity requirements in battery grade manganese sulfate and impurity levels (ppm) for the products of this example
| Element(s) | ΣFe | K | Na | Ca | Mg | Cu | Zn | Pb | Cd | As | F |
| Standard required content | <10 | <50 | <50 | <50 | <50 | <10 | <10 | <10 | <5 | <1 | <700 |
| The product of this example | 2.6 | 3.1 | 2.3 | 1324 | 1032 | 3.2 | 1.5 | - | - | - | 9.3 |
Obviously cancel CO 2 The addition of the catalyst leads the content of Ca and Mg in the final product to be too high, and can not meet the production requirement of manganese sulfate. Mn in the finally obtained manganese sulfate solution 2+ The concentration of (C) was 43.21g/L, and the Mn recovery rate was 98.20%.
Claims (47)
1. The method for preparing the battery-grade manganese sulfate from the manganese oxide ore is characterized by comprising the following steps of:
step (1): two stage leaching
Carrying out first-stage leaching on manganese oxide ores, biomass and sulfuric acid, and then carrying out solid-liquid separation to obtain first-stage leaching liquid and leaching slag;
roasting leaching residues in an oxygen-free atmosphere, mixing the obtained roasting material with the first-stage leaching solution, carrying out second-stage leaching, and separating to obtain leaching solution;
step (2): first stage impurity removal
Adding ferric sulfate and manganese oxidant into the leaching solution, heating to perform primary precipitation reaction of sodium and/or potassium, then adding sulfide into the system, performing secondary precipitation reaction of heavy metal, and then separating to obtain first-stage impurity-removing solution;
step (3): second stage impurity removal
Carrying out manganese precipitation treatment on the first-stage impurity removal liquid to obtain manganese hydroxide precipitate, dispersing the precipitate and the compound shown in the formula 1 in a solvent to obtain slurry, introducing carbon dioxide into the slurry, carrying out second-stage impurity removal, and carrying out solid-liquid separation to obtain purified manganese hydroxide; the alkali adopted in the manganese precipitation treatment stage is at least one of ammonia water, sodium hydroxide and potassium 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 + ；
Step (4): third stage of impurity removal
Dissolving the purified manganese hydroxide with sulfuric acid, and then adding BaS and BaF 2 Finally, adding aluminum sulfate or a defluorinating agent, and carrying out solid-liquid separation after treatment to obtain the battery-grade manganese sulfate solution.
2. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the manganese oxide ore is at least one of pyrolusite, pyrolusite and pyrolusite.
3. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 2, wherein the particle size of the manganese oxide ore is controlled to be less than 150 μm.
4. The method of producing battery grade manganese sulfate from manganese oxide ore of claim 1, wherein the biomass is biomass waste comprising at least one of cellulose, hemicellulose, or crude fiber.
5. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 4, wherein the biomass is at least one of straw, corn stalk or corncob.
6. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 4, wherein the particle size of the biomass is controlled between 38 μm and 74 μm.
7. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the mass ratio of manganese oxide ore to biomass waste is (1:1) - (3:1).
8. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the concentration of sulfuric acid is 1-3mol/L.
9. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the first leaching stage has a liquid-to-solid ratio of (3-10): 1 (mL/g).
10. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the temperature of the first leaching stage is 85-95 ℃.
11. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the first leaching stage is for 4 to 10 hours.
12. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the roasting temperature is 850-1000 ℃.
13. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the roasting time is 2-4 hours.
14. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the second leaching stage is at a temperature of 50-70 ℃.
15. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the time of the second leaching stage is 0.5-2 hours.
16. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1,
in the step (2), the pH of the initial solution of the first-stage precipitation reaction is 1.5-2.
17. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 16, wherein manganese hydroxide is used to regulate the pH.
18. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the amount of ferric sulfate is 40 to 50 times of the total amount of sodium ions and potassium ions in the leachate.
19. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the manganese-based oxidant is a positive tetravalent or higher valent manganese oxide.
20. The method for preparing battery grade manganese sulfate from manganese oxide ore of claim 19, wherein the manganese-based oxidizer is manganese dioxide.
21. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 19, wherein the amount of the manganese-based oxidant is 8-10 times of the total mass of sodium ions and potassium ions in the leaching solution.
22. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the temperature of the one-stage precipitation reaction is greater than or equal to 90 ℃.
23. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 22, wherein the reaction time is 1 to 2 hours.
24. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 22, wherein the reaction is followed by standing for 1-2 hours.
25. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1,
in the step (2), the pH of the initial solution of the two-stage precipitation reaction is 5.5-6.
26. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 25,
in the step (2), manganese hydroxide is adopted to regulate and control the pH.
27. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1,
the sulfide is sodium thiram.
28. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the amount of sulfide is 15-20 times of the total mass of heavy metals in the solution system.
29. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the time of the secondary precipitation reaction is 1-2 hours.
30. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the first-stage impurity removal liquid is obtained by standing for 1-2 hours after the second-stage precipitation reaction and then performing solid-liquid separation.
31. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein in the step (3), the alkali used in the manganese precipitation treatment stage is ammonia water.
32. The method for preparing battery grade manganese sulfate from manganese oxide ore of claim 31, wherein the concentration of aqueous ammonia is 6-10mol/L.
33. The method for preparing battery grade manganese sulfate from manganese oxide ore of claim 31, wherein the endpoint pH of the manganese precipitation reaction is between 10 and 11.5.
34. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the alkyl group is a C1-C10 linear alkyl group.
35. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein 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.
36. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein R is H, C-C4 alkyl, hydroxyl-substituted C1-C4 alkyl or phenyl-substituted C1-C4 alkyl.
37. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the compound of formula 1 is not less than the theoretical reaction amount.
38. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the compound of formula 1 is 1 to 2 times the theoretical reaction molar amount.
39. The method for preparing battery-grade manganese sulfate from manganese oxide ore 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 C1-C4 alcohol.
40. The method for preparing battery-grade manganese sulfate from manganese oxide ore 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.
41. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the end point pH of the introduced carbon dioxide is 6.5-7.5 in the second stage of impurity removal.
42. The method for preparing battery grade manganese sulfate from manganese oxide ore of claim 41, wherein the endpoint of carbon dioxide introduction during the second stage of impurity removal is 6.8-7.2.
43. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the concentration of sulfuric acid in step (4) is 50-70%.
44. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the temperature of the acid dissolution stage is 70-95 ℃.
45. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the pH of the acid-dissolved manganese sulfate solution is 5.5-6.
46. The method for preparing battery-grade manganese sulfate from manganese oxide ore according to claim 1, wherein the BaS is added at a concentration of 0.5-1g/L;
BaF 2 the addition concentration of (2) is 0.5-1g/L.
47. The method for preparing battery grade manganese sulfate from manganese oxide ore according to claim 1, wherein the aluminum sulfate is applied at a concentration of 3-5g/L; the application concentration of the defluorinating agent is 1-2g/L.
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