CN103496746A - Method for preparing cell-grade high-purity manganese sulfate by low-grade manganese ore high-pressure crystallization - Google Patents
Method for preparing cell-grade high-purity manganese sulfate by low-grade manganese ore high-pressure crystallization Download PDFInfo
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Abstract
The invention discloses a method for preparing cell-grade high-purity manganese sulfate by low-grade manganese ore high-pressure crystallization. The method comprises the following steps of grinding low-grade pyrolusite and pyrite into powder particles, preparing a manganese sulfate solution, mixing the manganese sulfate solution and the pyrolusite powder particles to obtain preliminary pulp, mixing the preliminary pulp, concentrated sulfuric acid and the pyrite powder particles according to a certain ratio, carrying out heating, stirring and manganese impregnation on the mixture, adding a neutralizer into the mixture to adjust a pH value, adding barium sulphide and sodium dimethyldithiocarbamate into the mixture to remove impurities so that a pure manganese sulfate solution is obtained, carrying out heating pressurization stirring on the pure manganese sulfate solution, discharging a supernatant to obtain a manganese sulfate crystal-containing solution, carrying out standing precipitation of the manganese sulfate crystal-containing solution at a normal temperature, carrying out filtration to obtain a high-concentration manganese sulfate solution, adding the high-concentration manganese sulfate solution into a high-pressure autoclave, carrying out crystallization at a high temperature under high pressure, discharging a supernatant after crystallization to obtain manganese sulfate crystal-containing magma, separating the manganese sulfate crystal-containing magma to obtain high-purity manganese sulfate crystals, and drying and crushing the high-purity manganese sulfate crystals to obtain the cell-grade high-purity manganese sulfate.
Description
Technical field
The present invention relates to a kind of method for preparing the cell-grade manganous sulfate, be specially and utilize low-grade manganese to adopt the standby cell-grade high purity manganese sulfate of high pressure crystal legal system.
Background technology
High purity manganese sulfate is compared common manganous sulfate, is that a kind of technology content is higher, production process is controlled very strict a kind of high added value manganese deep processed product, and its purposes mainly contains three fields: industrial circle, food pharmaceutical industries and energy field.High purity manganese sulfate is except in the general industry field, the food pharmaceutical industries has outside the part use, it is mainly to be used as in a large number the raw material of nickle cobalt lithium manganate and lithium manganate, as the nickle cobalt lithium manganate of the positive electrode material of power cell and the production that lithium manganate has been widely used in the power cell of automobile, at present, almost each domestic automobile manufacturing enterprise is in trial-production, what have has released oneself electromobile as BYD, electric automobile is the main development direction of international and domestic automobile industry of coming few decades, and the automobile production enterprise a large amount of common manganous sulfate from foreign procurement specially, then its meticulous purification is obtained to high purity manganese sulfate, the process trouble, and cost is very high.The method of producing at present the manganous sulfate crystal has: 1, normal pressure inspissation, by heated solution make solvent constantly evaporation reach the condensing crystal manganous sulfate, but the method carries out under normal pressure, need to steam a large amount of water, lot of energy; 2, vitriol oil salting-out process, when sulfuric acid exists, the solubleness of manganous sulfate significantly descends, and is mainly due to SO
4 2-common-ion effcet, causes in solid phase having the manganous sulfate crystal and separate out, but the shortcoming of the method is to consume a large amount of sulfuric acid, and large to the corrosion of equipment.These methods generally need take the taste higher manganese ore be raw material, but along with the exhaustion of higher-grade manganese ore totally, in the face of these methods that prepare manganous sulfate of low-grade manganese with regard to aobvious poor effect, shortcoming is many, has greatly increased cost.
Summary of the invention
For the shortcoming of above-mentioned prior art, the invention provides a kind of method of utilizing low-grade manganese to prepare high purity high quality cell-grade manganous sulfate.
The present invention solves the problems of the technologies described above by the following technical solutions: the method for the standby cell-grade high purity manganese sulfate of a kind of low-grade manganese high pressure crystal legal system comprises the following steps:
(1) by low-grade pyrolusite and sulfurous iron ore respectively ball milling become powder;
(2) prepare certain density manganese sulfate solution, itself and described pyrolusite powder are mixed to get to preliminary ore pulp;
(3) after being mixed in proportion, heating, stirring, soaking manganese, described preliminary ore pulp, the vitriol oil and sulfurous iron ore powder obtain the sulfur acid manganese ore slurry;
(4) add the neutralizing agent adjust pH in described sulfur acid manganese ore slurry;
(5) add barium sulphide in the sulfur acid manganese ore slurry after neutralization, reaction is carried out press filtration after for some time, obtains the sulfur acid manganese solution; To heavy metal ion, for example zinc and arsenic have good impurity-eliminating effect to barium sulphide;
(6) add Sodium Dimethyldithiocarbamate in described sulfur acid manganese solution, filtered after reaction for some time, obtain bright sulfur acid manganese solution; To heavy metal ion, for example nickel and cobalt have good impurity-eliminating effect to Sodium Dimethyldithiocarbamate;
(7) described bright sulfur acid manganese solution heating and pressurizing is stirred, and discharge supernatant liquor and obtain containing coarse particles manganous sulfate crystalloid solution, supernatant liquor returns to the batching that participates in described preliminary ore pulp;
(8) staticly settled at normal temperatures containing coarse particles manganous sulfate crystalloid solution described, then filter and obtain the high-concentration sulfuric acid manganese solution;
(9) described high-concentration sulfuric acid manganese solution is put into to autoclave and carry out hydro-thermal reaction, and pass into high-temperature steam in autoclave, and carry out crystallization under High Temperature High Pressure, after finishing, crystallization discharges supernatant liquor, obtain the magma of sulfur acid manganese crystal, supernatant liquor returns to the batching that participates in described preliminary ore pulp;
(10) described magma is separated, obtain respectively high purity manganese sulfate crystal and mother liquor, mother liquor returns and participates in soaking manganese, is conducive to improve the leaching yield of manganese;
(11) by described crystal drying and crushing, obtain the cell-grade high purity manganese sulfate.
As preferably, described in step (1), the particle diameter of powder is 0.01mm～0.05mm, during reaction, fully contacts and is conducive to soak manganese.
As preferably, described in step (2), the manganous sulfate concentration of preparation is 60g/L～80 g/L, improves the leaching yield of manganese.
As preferably, preliminary ore pulp in mass ratio in step (3): the vitriol oil: sulfurous iron ore=1:(0.2～0.3): (0.1～0.15), the time of soaking manganese is 180min, and Heating temperature is 75 ℃～85 ℃, such proportioning, soaks the manganese time and Heating temperature can obtain good leaching result.
As preferably, described in step (4), neutralizing agent is the manganous carbonate breeze, slurry pH after neutralization is 5.8～6.5, make ferric ion in ore pulp precipitate with the form of ironic hydroxide, thereby reach the purpose of deironing, also make the strainability of ore pulp improve, be beneficial to the press filtration operation of follow-up ore pulp; The manganous carbonate breeze is as the ore pulp neutralizing agent, its advantage is: on the one hand, the carbonic acid manganese powder can not gambled the plug filter cloth, can not produce resistance to pressure-filtering process, on the other hand, in manganous carbonate, with the principle of ore pulp, be that manganous carbonate and residual acid react, consume residual acid, improve pH values of pulp, the product of its reaction is manganous sulfate, these extra manganous sulfates enter solution, can improve the concentration of manganous sulfate.
As preferably, add again potassium permanganate and activated carbon after adding Sodium Dimethyldithiocarbamate in step (6), to removal of impurities and the precipitation of the heavy metals such as arsenic in solution.
As preferably, in step (7), Heating temperature is 100 ℃～110 ℃, is pressurised into 1.0Mpa, is conducive to the pre-concentration of manganese sulfate solution.
As preferably, in step (8), the still aging time is 25～30 hours, can obtain the manganese sulfate solution that concentration is higher like this.
As preferably, pressure in step (9) mesohigh still is 11 Mpa～13.0 Mpa, temperature in autoclave is 200 ℃～240 ℃, manganous sulfate supersaturation under High Temperature High Pressure and crystallization can make percent crystallization in massecuite higher under this pressure and temperature, other metallic impurity solubleness that do not reach capacity, stay in solution, then, by follow-up solid-liquid separation, realize separating of manganous sulfate and impurity, reach the removal of impurities purpose again of manganous sulfate production process, finally make manganous sulfate purity higher.
As preferably, in step (10), the concentration of mother liquor is 55g/L～60 g/L, can not cause the waste of manganous sulfate, also is conducive to improve the leaching yield of manganese simultaneously.
The present invention compared with prior art has following advantage: 1) the present invention adopts two ore deposits to add acid system and leaches hydrometallurgy new technology processing low-grade manganese, efficiently solve the technical barrier of low-grade manganese application, also expand the source of manganous sulfate raw material, belonged to the innovation in the technology application, 2) existing process using Wingdale is neutralized, and the characteristic of Wingdale is light weight, easily mill, after ore grinding is processed, its granularity is very little, is easy to stick in the filter cloth hole of pressure filter, stops up filtration channel, destroy the continuity of production process, and the present invention adopts the manganous carbonate breeze to be neutralized, not only overcome the shortcoming that adopts Wingdale to bring, and added extra manganese source, can, so that leach liquor manganous sulfate concentration increases, also increase output when having reduced cost, 3) adopt the high pressure crystal method to produce high purity manganese sulfate, manganous sulfate supersaturation under High Temperature High Pressure and crystallization, other metallic impurity solubleness that do not reach capacity, stay in solution, again by follow-up solid-liquid separation, realize separating of manganous sulfate and impurity, reach the removal of impurities purpose again of manganous sulfate production process, finally make manganous sulfate purity higher, the required energy consumption of the method is low, the manganous sulfate purity of producing is high, both reduced production cost, reduced the pollution to environment, also improved value-added content of product, created high profit, meet national environmental protection and Sustainable development policy fully.
The accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with concrete diagram and embodiment, further set forth the present invention.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
With reference to figure 1, the invention provides the method for the standby cell-grade high purity manganese sulfate of a kind of low-grade manganese high pressure crystal legal system, comprise the following steps: by low-grade pyrolusite and sulfurous iron ore respectively ball milling become powder; Prepare certain density manganese sulfate solution and described pyrolusite powder is mixed to get preliminary ore pulp; After being mixed in proportion, heating, stirring, soaking manganese, described preliminary ore pulp, the vitriol oil and sulfurous iron ore powder obtain the sulfur acid manganese ore slurry; Add the neutralizing agent adjust pH in described sulfur acid manganese ore slurry; Add barium sulphide in the sulfur acid manganese ore slurry after neutralization, reaction is carried out press filtration after for some time, obtains respectively sulfur acid manganese solution and filter residue; Add Sodium Dimethyldithiocarbamate in described sulfur acid manganese solution, filtered after reaction for some time, obtain bright sulfur acid manganese solution; Described bright sulfur acid manganese solution heating and pressurizing is stirred, and discharge supernatant liquor and obtain containing coarse particles manganous sulfate crystalloid solution, supernatant liquor returns to the batching that participates in described preliminary ore pulp; Carry out at normal temperatures still agingly containing coarse particles manganous sulfate crystalloid solution by described, then filter and obtain the high-concentration sulfuric acid manganese solution; Described high-concentration sulfuric acid manganese solution is put into to autoclave, and pass into high-temperature steam in autoclave, carry out crystallization under High Temperature High Pressure, after crystallization finishes, discharge supernatant liquor, obtain the magma of sulfur acid manganese crystal, supernatant liquor returns to the batching that participates in described preliminary ore pulp; Described magma is separated, obtain respectively high purity manganese sulfate crystal and mother liquor, mother liquor returns and participates in soaking manganese; By described crystal drying and crushing, obtain the cell-grade high purity manganese sulfate.
Embodiment 1:
By low-grade pyrolusite and sulfurous iron ore respectively ball milling become the powder that particle diameter is 0.01mm, ore grinding is to leach one of most important link in liquid processed, the too little cost that just increases ore grinding of particle diameter, particle diameter has just reduced too greatly the leaching yield of manganese, and this directly has influence on final production cost, the manganese sulfate solution that compound concentration is 60g/L and pyrolusite powder are mixed to get preliminary ore pulp, the vitriol oil of getting the preliminary ore pulp of 100kg, sulfurous iron ore powder that the 10kg particle diameter is 0.01mm and 20kg is according to the preliminary ore pulp of mass ratio: the ratio batching of the vitriol oil: pyrite=1:0.2:0.1, what the material prepared was put into to band stirs soaks the manganese bucket, temperature in bucket is heated to 75 ℃ and remain at this temperature and soak manganese 180min, such proportioning, soaks the manganese time and Heating temperature can obtain good leaching result, add neutralizing agent manganous carbonate breeze adjust pH to described ore pulp, slurry pH after neutralization is 6.5, make ferric ion in ore pulp precipitate with the form of ironic hydroxide, thereby reach the purpose of deironing, also make the strainability of ore pulp improve, be beneficial to the press filtration operation of follow-up ore pulp, the manganous carbonate breeze is as the ore pulp neutralizing agent, its advantage is: on the one hand, the carbonic acid manganese powder can not gambled the plug filter cloth, can not produce resistance to pressure-filtering process, on the other hand, in manganous carbonate, with the principle of ore pulp, be that manganous carbonate and residual acid react, consume residual acid, improve pH values of pulp, the product of its reaction is manganous sulfate, these extra manganous sulfates enter solution, can improve the concentration of manganous sulfate, add barium sulphide in the sulfur acid manganese ore slurry after neutralization, barium sulphide to heavy metal ion in ore pulp for example zinc and arsenic there is good impurity-eliminating effect, carry out press filtration after reaction for some time, obtain respectively sulfur acid manganese solution and filter residue, add Sodium Dimethyldithiocarbamate in described sulfur acid manganese solution, to heavy metal ion, for example nickel and cobalt have good impurity-eliminating effect to Sodium Dimethyldithiocarbamate, after adding Sodium Dimethyldithiocarbamate, add again potassium permanganate further arsenic in solution to be carried out to removal of impurities, but add again the activated carbon aggregated colloids to reach precipitation, filtered after reaction for some time, obtained bright sulfur acid manganese solution, it is 100 ℃ that described bright sulfur acid manganese solution is heated to temperature, is pressurized to 1.0Mpa and stirs, and is conducive to like this pre-concentration of manganese sulfate solution, and the concentration that has improved manganous sulfate is that follow-up High Temperature High Pressure crystallization is laid a good foundation, then discharge supernatant liquor and obtain containing coarse particles manganous sulfate crystalloid solution, supernatant liquor returns to the batching that participates in described preliminary ore pulp, by described, containing coarse particles manganous sulfate crystalloid solution, carry out at normal temperatures still agingly, the time is 25 hours, then filters and obtains the high-concentration sulfuric acid manganese solution that degree Beaume is 45.7 ° of Be ', described high-concentration sulfuric acid manganese solution is put into to autoclave, and pass into high-temperature steam in autoclave, pressure in autoclave is 11.0 Mpa, temperature in autoclave is 200 ℃, then carry out crystallization, manganous sulfate supersaturation under High Temperature High Pressure and crystallization, under this pressure and temperature, can make percent crystallization in massecuite higher, other metallic impurity solubleness that do not reach capacity, stay in solution, again by follow-up solid-liquid separation, realize separating of manganous sulfate and impurity, reach the removal of impurities purpose again of manganous sulfate production process, finally make manganous sulfate purity higher, after finishing, crystallization discharges supernatant liquor, obtain the magma of sulfur acid manganese crystal, supernatant liquor returns to the batching that participates in described preliminary ore pulp, described magma is separated, obtain respectively high purity manganese sulfate crystal and mother liquor, mother liquor returns and participates in soaking manganese, and the concentration of mother liquor is 55g/L, returns to participate in soaking manganese and can not cause the waste of manganous sulfate, is conducive to improve the leaching yield of manganese, finally, by described crystal drying and crushing, obtain the cell-grade high purity manganese sulfate.
Result of laboratory test is as follows:
Embodiment 2:
By low-grade pyrolusite and sulfurous iron ore respectively ball milling become the powder that particle diameter is 0.03mm, the manganese sulfate solution that compound concentration is 70g/L and pyrolusite powder are mixed to get preliminary ore pulp, get the preliminary ore pulp of 100kg, the sulfurous iron ore powder that the 13kg particle diameter is 0.03mm and the vitriol oil of 25kg are according to the preliminary ore pulp of mass ratio: the ratio batching of the vitriol oil: pyrite=1:0.25:0.13, what the material prepared was put into to band stirs soaks the manganese bucket, temperature in bucket is heated to 80 ℃ and remain at this temperature and soak manganese 180min, add neutralizing agent manganous carbonate breeze adjust pH to described ore pulp, slurry pH after neutralization is 6.1, make ferric ion in ore pulp precipitate with the form of ironic hydroxide, thereby reach the purpose of deironing, to the neutralization after the sulfur acid manganese ore slurry in add barium sulphide, carry out press filtration after reaction for some time, obtain respectively sulfur acid manganese solution and filter residue, add Sodium Dimethyldithiocarbamate in described sulfur acid manganese solution, add again potassium permanganate further arsenic in solution to be carried out to removal of impurities after adding Sodium Dimethyldithiocarbamate, but then add the activated carbon aggregated colloids to reach precipitation, after reaction for some time, filtered, obtain bright sulfur acid manganese solution, it is 105 ℃ that described bright sulfur acid manganese solution is heated to temperature, is pressurized to 1.0Mpa and stirs, and then discharges supernatant liquor and obtains containing coarse particles manganous sulfate crystalloid solution, and supernatant liquor returns to the batching that participates in described preliminary ore pulp, by described, containing coarse particles manganous sulfate crystalloid solution, carry out at normal temperatures still agingly, the time is 28 hours, then filters and obtains the high-concentration sulfuric acid manganese solution that degree Beaume is 47 ° of Be ', described high-concentration sulfuric acid manganese solution is put into to autoclave, and pass into high-temperature steam in autoclave, pressure in autoclave is 12.0Mpa, temperature in autoclave is 220 ℃, carry out crystallization under High Temperature High Pressure, discharge supernatant liquor after crystallization finishes, obtain the magma of sulfur acid manganese crystal, supernatant liquor returns to the batching that participates in described preliminary ore pulp, described magma is separated, obtain respectively high purity manganese sulfate crystal and mother liquor, mother liquor returns and participates in soaking manganese, and the concentration of mother liquor is 57g/L, returns to participate in soaking manganese and can not cause the waste of manganous sulfate, is conducive to improve the leaching yield of manganese, finally, by described crystal drying and crushing, obtain the cell-grade high purity manganese sulfate.
Result of laboratory test is as follows:
Embodiment 3:
By low-grade pyrolusite and sulfurous iron ore respectively ball milling become the powder that particle diameter is 0.05mm, the manganese sulfate solution that compound concentration is 80g/L and pyrolusite powder are mixed to get preliminary ore pulp, get the preliminary ore pulp of 100kg, the sulfurous iron ore powder that the 15kg particle diameter is 0.05mm and the vitriol oil of 30kg are according to the preliminary ore pulp of mass ratio: the ratio batching of the vitriol oil: pyrite=1:0.3:0.15, what the material prepared was put into to band stirs soaks the manganese bucket, temperature in bucket is heated to 85 ℃ and remain at this temperature and soak manganese 180min, add neutralizing agent manganous carbonate breeze adjust pH to described ore pulp, slurry pH after neutralization is 5.8, make ferric ion in ore pulp precipitate with the form of ironic hydroxide, thereby reach the purpose of deironing, to the neutralization after the sulfur acid manganese ore slurry in add barium sulphide, carry out press filtration after reaction for some time, obtain respectively sulfur acid manganese solution and filter residue, add Sodium Dimethyldithiocarbamate in described sulfur acid manganese solution, add again potassium permanganate further arsenic in solution to be carried out to removal of impurities after adding Sodium Dimethyldithiocarbamate, but then add the activated carbon aggregated colloids to reach precipitation, after reaction for some time, filtered, obtain bright sulfur acid manganese solution, it is 110 ℃ that described bright sulfur acid manganese solution is heated to temperature, is pressurized to 1.0Mpa and stirs, and then discharges supernatant liquor and obtains containing coarse particles manganous sulfate crystalloid solution, and supernatant liquor returns to the batching that participates in described preliminary ore pulp, by described, containing coarse particles manganous sulfate crystalloid solution, carry out at normal temperatures still agingly, the time is 30 hours, then filters and obtains the high-concentration sulfuric acid manganese solution that degree Beaume is 48.8 ° of Be ', described high-concentration sulfuric acid manganese solution is put into to autoclave, and pass into high-temperature steam in autoclave, pressure in autoclave is 13.0 Mpa, temperature in autoclave is 240 ℃, carry out crystallization under High Temperature High Pressure, discharge supernatant liquor after crystallization finishes, obtain the magma of sulfur acid manganese crystal, supernatant liquor returns to the batching that participates in described preliminary ore pulp, described magma is separated, obtain respectively high purity manganese sulfate crystal and mother liquor, mother liquor returns and participates in soaking manganese, and the concentration of mother liquor is 60g/L, returns to participate in soaking manganese and can not cause the waste of manganous sulfate, is conducive to improve the leaching yield of manganese, finally, by described crystal drying and crushing, obtain the cell-grade high purity manganese sulfate.
Result of laboratory test is as follows:
Above demonstration and described ultimate principle of the present invention and principal character and advantage of the present invention; the technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and the claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (10)
1. the method for the standby cell-grade high purity manganese sulfate of low-grade manganese high pressure crystal legal system, comprise the following steps:
(1) by low-grade pyrolusite and sulfurous iron ore respectively ball milling become powder;
(2) prepare certain density manganese sulfate solution, itself and described pyrolusite powder are mixed to get to preliminary ore pulp;
(3) after being mixed in proportion, heating, stirring, soaking manganese, described preliminary ore pulp, the vitriol oil and sulfurous iron ore powder obtain the sulfur acid manganese ore slurry;
(4) add the neutralizing agent adjust pH in described sulfur acid manganese ore slurry;
(5) add barium sulphide in the sulfur acid manganese ore slurry after neutralization, reaction is carried out press filtration after for some time, obtains the sulfur acid manganese solution;
(6) add Sodium Dimethyldithiocarbamate in described sulfur acid manganese solution, filtered after reaction for some time, obtain bright sulfur acid manganese solution;
(7) described bright sulfur acid manganese solution heating and pressurizing is stirred, and discharge supernatant liquor and obtain containing coarse particles manganous sulfate crystalloid solution, supernatant liquor returns to the batching that participates in described preliminary ore pulp;
(8) staticly settled at normal temperatures containing coarse particles manganous sulfate crystalloid solution described, then filter and obtain the high-concentration sulfuric acid manganese solution;
(9) described high-concentration sulfuric acid manganese solution is put into to autoclave and carry out hydro-thermal reaction, and pass into high-temperature steam in autoclave, and carry out crystallization under High Temperature High Pressure, after finishing, crystallization discharges supernatant liquor, obtain the magma of sulfur acid manganese crystal, supernatant liquor returns to the batching that participates in described preliminary ore pulp;
(10) described magma is separated, obtain respectively high purity manganese sulfate crystal and mother liquor, mother liquor returns and participates in soaking manganese;
(11) by described crystal drying and crushing, obtain the cell-grade high purity manganese sulfate.
2. method according to claim 1, it is characterized in that: described in step (1), the particle diameter of powder is 0.01mm～0.05mm.
3. method according to claim 1 is characterized in that: described in step (2), the manganous sulfate concentration of preparation is 60g/L～80 g/L.
4. method according to claim 1 is characterized in that: preliminary ore pulp in mass ratio in step (3): the vitriol oil: sulfurous iron ore=1:(0.2～0.3): (0.1～0.15), the time of soaking manganese is 180min, Heating temperature is 75 ℃～85 ℃.
5. method according to claim 1, it is characterized in that: described in step (4), neutralizing agent is the manganous carbonate breeze, the slurry pH after neutralization is 5.8～6.5.
6. method according to claim 1, is characterized in that: after adding Sodium Dimethyldithiocarbamate in step (6), add potassium permanganate and activated carbon again.
7. method according to claim 1 is characterized in that: in step (7), Heating temperature is 100 ℃～110 ℃, is pressurised into 1.0Mpa.
8. method according to claim 1, it is characterized in that: in step (8), the still aging time is 25～30 hours.
9. method according to claim 1, it is characterized in that: the pressure in step (9) mesohigh still is 11 Mpa～13.0 Mpa, the temperature in autoclave is 200 ℃～240 ℃.
10. method according to claim 1 is characterized in that: in step (10), the concentration of mother liquor is 55g/L～60 g/L.
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| CN113684381A (en) * | 2021-08-27 | 2021-11-23 | 昆明理工大学 | Method for preparing high-purity manganese sulfate by microwave-flow field coupling strengthening treatment of pyrolusite |
| CN113860378A (en) * | 2021-11-08 | 2021-12-31 | 田世超 | Method for producing high-purity manganese sulfate by using hydroxyl combined liquid phase reduction treatment manganese oxide ore |
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| CN109136571A (en) * | 2018-09-28 | 2019-01-04 | 中南大学 | Method for extracting valuable metals from lithium ion battery mixed manganese-rich waste leachate |
| CN110143615A (en) * | 2019-06-19 | 2019-08-20 | 贵州红星发展大龙锰业有限责任公司 | The method that electrolytic manganese dioxide and electrolytic manganese dioxide depth remove potassium |
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| CN112591800A (en) * | 2021-01-05 | 2021-04-02 | 广西埃索凯新材料科技有限公司 | Thickening equipment suitable for manganese sulfate high temperature crystallization |
| CN112777641A (en) * | 2021-01-26 | 2021-05-11 | 广西埃索凯新材料科技有限公司 | Method for simultaneously preparing battery-grade manganese sulfate and feed-grade manganese sulfate |
| CN112897599A (en) * | 2021-05-08 | 2021-06-04 | 蜂巢能源科技有限公司 | Crystallization method of nickel sulfate, cobalt sulfate and manganese sulfate |
| CN113684381A (en) * | 2021-08-27 | 2021-11-23 | 昆明理工大学 | Method for preparing high-purity manganese sulfate by microwave-flow field coupling strengthening treatment of pyrolusite |
| CN113860378A (en) * | 2021-11-08 | 2021-12-31 | 田世超 | Method for producing high-purity manganese sulfate by using hydroxyl combined liquid phase reduction treatment manganese oxide ore |
| CN114261990A (en) * | 2022-01-26 | 2022-04-01 | 贵州金瑞新材料有限责任公司 | Method for crystallizing manganese sulfate solution based on sulfuric acid method |
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