CN110668502A - Method for preparing manganese sulfate by purification - Google Patents
Method for preparing manganese sulfate by purification Download PDFInfo
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- CN110668502A CN110668502A CN201911050591.2A CN201911050591A CN110668502A CN 110668502 A CN110668502 A CN 110668502A CN 201911050591 A CN201911050591 A CN 201911050591A CN 110668502 A CN110668502 A CN 110668502A
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- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 102
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 102
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 102
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000000746 purification Methods 0.000 title description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 178
- 239000011572 manganese Substances 0.000 claims abstract description 124
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 110
- 239000000843 powder Substances 0.000 claims abstract description 100
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 21
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 21
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 21
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 21
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000007885 magnetic separation Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims description 106
- 230000008025 crystallization Effects 0.000 claims description 106
- 239000000706 filtrate Substances 0.000 claims description 59
- 238000001914 filtration Methods 0.000 claims description 58
- 239000013078 crystal Substances 0.000 claims description 56
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 229910052745 lead Inorganic materials 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of manganese sulfate, and particularly discloses a method for purifying and preparing manganese sulfate, wherein manganese ore is used as a raw material, and manganese in the manganese ore can be recovered through crushing, grinding and magnetic separation to obtain refined manganese ore powder; adding fine manganese ore powder into a sulfuric acid solution, so that manganese ions can be dissolved in the sulfuric acid solution to obtain a manganese sulfate solution; adding manganese dioxide into manganese sulfate solution to make Fe in manganese sulfate solution2+Is oxidized into Fe3+(ii) a Then, after the pH value of the solution is adjusted, manganese carbonate is added, and manganese ions are replaced with calcium ions in a manganese sulfate solution to generate calcium carbonate precipitates which can remove calcium; and adding MnS, and removing heavy metal ions such as Mg, Fe, Cu, Pb, Zn, Cd, Co, Ti and the like by adopting the MnS, so that the purity of the manganese sulfate is improved, and the quality of the manganese sulfate is improved. The method provided by the invention is suitable for preparing manganese sulfate by taking various manganese ores as raw materials, improves the recovery rate of manganese in manganese ore powder, and improves the quality of manganese sulfate.
Description
Technical Field
The invention relates to the field of manganese sulfate, in particular to a method for purifying and preparing manganese sulfate.
Background
The reserves of manganese resources in China are abundant, the use method of manganese is continuously developed, and the wide use of manganese sulfate is the best embodiment. At present, the domestic manganese sulfate production scale is large, the annual output exceeds 15 million tons, and China becomes a main manganese sulfate producing country and a supplying country in the world. However, the existing manganese sulfate production process in China, whether a wet method or a fire method, is simple, impurities cannot be effectively removed, the detection results of Ca, Mg and Fe are high, and particularly, a high-quality manganese sulfate product is difficult to obtain by taking common manganese sulfate as a material.
Disclosure of Invention
In view of the above, the invention aims to provide a method for purifying and preparing manganese sulfate, which can improve the quality of manganese sulfate.
In order to achieve the above purpose, the invention provides the following technical scheme:
the method for purifying and preparing manganese sulfate comprises the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 10-50 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder obtained in the step a) into a sulfuric acid solution, reacting for 3-5 h, and filtering to obtain a manganese sulfate solution;
b) standing the manganese sulfate solution obtained in the step a) for 3-5 hours, filtering the obtained filtrate, adding manganese dioxide into the filtrate to react for 2-3 hours at 50-80 ℃, filtering, standing the filtrate for 3-5 hours at 50-80 ℃, and filtering;
c) adjusting the pH value of the filtrate obtained in the step b) to 4-6, adding manganese carbonate, stirring and reacting for 3-4 h at the temperature of 50-60 ℃, and filtering;
d) adding MnS into the filtrate obtained in the step c), stirring and reacting for 3-4 h at the temperature of 80-100 ℃, and filtering;
e) carrying out primary crystallization on the filtrate obtained in the step d) at the temperature of 60-80 ℃ under the pressure of 3-5 MPa; adding a dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 5-10 MPa and the temperature of 80-120 ℃; adding a dilute sulfuric acid solution into the precipitated crystal, and carrying out tertiary crystallization at the pressure of 10-15 MP and the temperature of 120-150 ℃;
f) cooling the crystal obtained in the step e) to room temperature, adding deionized water, adjusting the pH to 6-7, and performing primary crystallization at the temperature of 60-80 ℃; adding deionized water into the precipitated crystal, and performing secondary crystallization at the pressure of 5-10 MPa and the temperature of 80-120 ℃; and adding a dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization under the pressure of 10-15 MP and the temperature of 120-150 ℃, and drying the precipitated crystals to obtain the manganese sulfate.
Further, in the step a), the mass concentration of sulfuric acid in the sulfuric acid solution is 30-50 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 200-400 g/L.
Further, in the step b), the mass ratio of manganese dioxide to fine manganese ore powder is (0.03-0.05): 1.
further, in the step c), the mass ratio of the manganese carbonate to the fine manganese ore powder is (0.02-0.04): 1.
further, in the step d), the mass ratio of MnS to the fine manganese ore powder is (0.01-0.02): 1.
further, in the step e), the concentration of dilute sulfuric acid in the third crystallization is 0.5-1 mol/L; the ratio of the mass of the crystals to the volume of the dilute sulfuric acid solution is 1: (10-12).
Further, in step f), the ratio of the mass of the crystals to the volume of the deionized water is 1: (10-12).
Further, in step c) and step f), Mn (OH) is used2The powder adjusted the pH of the solution.
The invention provides a method for purifying and preparing manganese sulfate, which takes manganese ore as a raw material, and can recover manganese in the manganese ore through crushing, grinding and magnetic separation to obtain refined manganese ore powder; adding fine manganese ore powder into a sulfuric acid solution, so that manganese ions can be dissolved in the sulfuric acid solution to obtain a manganese sulfate solution; adding manganese dioxide into manganese sulfate solution to make Fe in manganese sulfate solution2+Is oxidized into Fe3+(ii) a Then, after the pH value of the solution is adjusted, manganese carbonate is added, and manganese ions are replaced with calcium ions in a manganese sulfate solution to generate calcium carbonate precipitates which can remove calcium; and adding MnS, and removing heavy metal ions such as Mg, Fe, Cu, Pb, Zn, Cd, Co, Ti and the like by adopting the MnS, so that the purity of the manganese sulfate is improved, and the quality of the manganese sulfate is improved. The method provided by the invention is suitable for preparing manganese sulfate by taking various manganese ores as raw materials, improves the recovery rate of manganese in manganese ore powder, and improves the quality of manganese sulfate.
Detailed Description
The invention provides a method for purifying and preparing manganese sulfate, which comprises the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 10-50 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder obtained in the step a) into a sulfuric acid solution, reacting for 3-5 h, and filtering to obtain a manganese sulfate solution;
b) standing the manganese sulfate solution obtained in the step a) for 3-5 hours, filtering the obtained filtrate, adding manganese dioxide into the filtrate to react for 2-3 hours at 50-80 ℃, filtering, standing the filtrate for 3-5 hours at 50-80 ℃, and filtering;
c) adjusting the pH value of the filtrate obtained in the step b) to 4-6, adding manganese carbonate, stirring and reacting for 3-4 h at the temperature of 50-60 ℃, and filtering;
d) adding MnS into the filtrate obtained in the step c), stirring and reacting for 3-4 h at the temperature of 80-100 ℃, and filtering;
e) carrying out primary crystallization on the filtrate obtained in the step d) at the temperature of 60-80 ℃ under the pressure of 3-5 MPa; adding a dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 5-10 MPa and the temperature of 80-120 ℃; adding a dilute sulfuric acid solution into the precipitated crystal, and carrying out tertiary crystallization at the pressure of 10-15 MP and the temperature of 120-150 ℃;
f) cooling the crystal obtained in the step e) to room temperature, adding deionized water, adjusting the pH to 6-7, and performing primary crystallization at the temperature of 60-80 ℃; adding deionized water into the precipitated crystal, and performing secondary crystallization at the pressure of 5-10 MPa and the temperature of 80-120 ℃; and adding a dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization under the pressure of 10-15 MP and the temperature of 120-150 ℃, and drying the precipitated crystals to obtain the manganese sulfate.
The method provided by the invention has no limitation on the source of the manganese ore, and is suitable for various manganese ores; recovering the recovery rate of manganese in the manganese ore powder through magnetic separation; adding fine manganese ore powder obtained through magnetic separation into a sulfuric acid solution, reacting for 3-5 h, and filtering to obtain a manganese sulfate solution.
In the embodiment of the invention, the mass concentration of sulfuric acid in the sulfuric acid solution is 30-50 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 200-400 g/L. It should be noted that the addition of sulfuric acid is based on the condition that the addition of sulfuric acid exceeds the upper surface of fine manganese ore powder by 1-2 cm.
Wherein, the fine manganese ore powder also contains substances which are insoluble in sulfuric acid solutionStanding the manganese sulfate solution for 3-5 hours, and filtering to obtain a substance insoluble in the sulfuric acid solution; adding manganese dioxide into the filtrate to react for 2-3 h at 50-80 ℃, wherein the addition of manganese dioxide can enable Fe in the manganese sulfate solution2+Is oxidized into Fe3+Filtering to remove manganese dioxide which does not participate in the reaction; standing the filtrate for 3-5 h at 50-80 ℃ to precipitate manganese dioxide floating in the filtrate, so as to be convenient for removal.
In the embodiment of the invention, the mass ratio of manganese dioxide to fine manganese ore powder is (0.03-0.05): 1.
adjusting the pH value of the filtrate to 4-6, adding manganese carbonate, stirring and reacting for 3-4 h at the temperature of 50-60 ℃, and filtering; the manganese ions are replaced with calcium ions in the manganese sulfate solution to generate calcium carbonate precipitates, and the calcium ions can be removed. In the embodiment of the invention, the mass ratio of the manganese carbonate to the fine manganese ore powder is (0.02-0.04): 1.
Adding MnS into the filtrate obtained in the step b), stirring and reacting for 3-4 hours at the temperature of 80-100 ℃, and filtering; MnS is adopted to remove heavy metal ions such as Fe, Cu, Pb, Zn, Cd, Co, Ti and the like, and the purity of manganese sulfate is improved.
In the embodiment of the invention, the mass ratio of MnS to the fine manganese ore powder is (0.01-0.02): 1.
adjusting the pH value of the filtrate again to 4-6, and performing primary crystallization at a temperature of 60-80 ℃ under the primary crystallization pressure of 3-5 MPa; adding a dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 5-10 MPa and the temperature of 80-120 ℃; adding a dilute sulfuric acid solution into the precipitated crystal, and carrying out tertiary crystallization at the pressure of 10-15 MP and the temperature of 120-150 ℃; and the third crystallization is used for further improving the purity of the manganese sulfate.
In the embodiment of the invention, the concentration of the dilute sulfuric acid solution adopted in the secondary crystallization and the third crystallization is 0.5-1 mol/L, the addition amount of the dilute sulfuric acid solution in the secondary crystallization and the third crystallization is the same, and the mass ratio of the addition volume of the dilute sulfuric acid solution to the fine manganese ore powder is (5-6): 1.
cooling the crystal to room temperature, adding deionized water, adjusting the pH to 6-7, and performing primary crystallization at the temperature of 60-80 ℃; adding deionized water into the precipitated crystal, and performing secondary crystallization at the pressure of 5-10 MPa and the temperature of 80-120 ℃; adding a dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization under the pressure of 10-15 MP and the temperature of 120-150 ℃, and drying the precipitated crystals to obtain manganese sulfate; the steps are used for removing redundant sulfuric acid and improving the purity of manganese sulfate.
In the embodiment of the invention, the deionized water is used in the same amount in the first crystallization, the second crystallization and the third crystallization, and the volume ratio of the fine manganese ore powder to the deionized water is 1: (5-6).
In step c) and step f), Mn (OH) is used2The powder adjusted the pH of the solution.
In order to further illustrate the present invention, the following examples are provided to describe the method for purifying manganese sulfate according to the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
The method for purifying and preparing manganese sulfate comprises the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 10-50 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder obtained in the step a) into a sulfuric acid solution, reacting for 3 hours, and filtering to obtain a manganese sulfate solution; the mass concentration of sulfuric acid in the sulfuric acid solution is 30 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 200 g/L;
b) standing the manganese sulfate solution obtained in the step a) for 3h, filtering the obtained filtrate, adding manganese dioxide into the filtrate, reacting for 2h at 50 ℃, filtering, standing the filtrate for 3h at 50 ℃, and filtering; the mass ratio of manganese dioxide to the fine manganese ore powder is 0.03: 1;
c) adjusting the pH value of the filtrate obtained in the step b) to 4, adding manganese carbonate, stirring and reacting for 3 hours at the temperature of 50 ℃, and filtering; the mass ratio of the manganese carbonate to the fine manganese ore powder is 0.02: 1; in which Mn (OH) is used2Adjusting the pH value of the solution to 4 by using the powder;
d) adding MnS into the filtrate obtained in the step c), stirring and reacting for 3 hours at the temperature of 80 ℃, and filtering; the mass ratio of MnS to the fine manganese ore powder is 0.01: 1;
e) carrying out primary crystallization on the filtrate obtained in the step d) at the temperature of 60 ℃ and the pressure of 3 MPa; adding dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 5MPa and the temperature of 80 ℃; adding dilute sulfuric acid solution into the precipitated crystal, and performing tertiary crystallization at the pressure of 10MP and the temperature of 120 ℃; the concentration of the dilute sulfuric acid solution adopted in the secondary crystallization and the third crystallization is 0.5mol/L, the addition amount of the dilute sulfuric acid solution in the secondary crystallization and the third crystallization is the same, and the mass ratio of the addition volume of the dilute sulfuric acid solution to the fine manganese ore powder is 5: 1;
f) cooling the crystals obtained in step e) to room temperature, adding deionized water and Mn (OH) simultaneously2Adjusting the pH value of the powder to 6, and carrying out primary crystallization at the temperature of 60 ℃; adding deionized water into the precipitated crystal, and performing secondary crystallization at a pressure of 5MPa and a temperature of 80 ℃; adding dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization at the pressure of 10MP and the temperature of 120 ℃, and drying the precipitated crystals to obtain manganese sulfate;
the usage amount of the deionized water for the primary crystallization, the secondary crystallization and the tertiary crystallization is the same, and the volume ratio of the refined manganese ore powder to the deionized water is 1: 5.
example 2
The method for purifying and preparing manganese sulfate comprises the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 20-40 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder obtained in the step a) into a sulfuric acid solution, reacting for 5 hours, and filtering to obtain a manganese sulfate solution; the mass concentration of sulfuric acid in the sulfuric acid solution is 50 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 400 g/L;
b) standing the manganese sulfate solution obtained in the step a) for 5 hours, filtering the obtained filtrate, adding manganese dioxide into the filtrate, reacting for 3 hours at the temperature of 80 ℃, filtering, standing the filtrate for 5 hours at the temperature of 80 ℃, and filtering; the mass ratio of manganese dioxide to fine manganese ore powder is 0.05: 1;
c) adjusting the pH value of the filtrate obtained in the step b) to 6, adding manganese carbonate, stirring and reacting for 4 hours at the temperature of 60 ℃, and filtering; the mass ratio of the manganese carbonate to the fine manganese ore powder is 0.04: 1; in which Mn (OH) is used2Adjusting the pH value of the solution to 6 by using the powder;
d) adding MnS into the filtrate obtained in the step c), stirring and reacting for 4 hours at the temperature of 100 ℃, and filtering; the mass ratio of MnS to the fine manganese ore powder is 0.02: 1;
e) carrying out primary crystallization on the filtrate obtained in the step d) at the temperature of 80 ℃ and the pressure of 5 MPa; adding dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 10MPa and the temperature of 120 ℃; adding dilute sulfuric acid solution into the precipitated crystal, and performing tertiary crystallization at the pressure of 15MP and the temperature of 150 ℃; the concentration of the dilute sulfuric acid solution adopted in the secondary crystallization and the third crystallization is 1mol/L, the addition amount of the dilute sulfuric acid solution in the secondary crystallization and the third crystallization is the same, and the mass ratio of the addition volume of the dilute sulfuric acid solution to the fine manganese ore powder is 6: 1;
f) cooling the crystals obtained in step e) to room temperature, adding deionized water and Mn (OH) simultaneously2Adjusting the pH value of the powder to 7, and carrying out primary crystallization at the temperature of 80 ℃; adding deionized water into the precipitated crystal, and performing secondary crystallization at a pressure of 10MPa and a temperature of 120 ℃; adding dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization under the pressure of 15MP and the temperature of 150 ℃, and drying the precipitated crystals to obtain manganese sulfate;
the usage amount of the deionized water for the primary crystallization, the secondary crystallization and the tertiary crystallization is the same, and the volume ratio of the refined manganese ore powder to the deionized water is 1: 6.
example 3
The method for purifying and preparing manganese sulfate comprises the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 20-40 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder obtained in the step a) into a sulfuric acid solution, reacting for 4 hours, and filtering to obtain a manganese sulfate solution; the mass concentration of sulfuric acid in the sulfuric acid solution is 40 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 300 g/L;
b) standing the manganese sulfate solution obtained in the step a) for 4h, filtering the obtained filtrate, adding manganese dioxide into the filtrate, reacting for 2.5h at the temperature of 60 ℃, filtering, standing the filtrate for 4h at the temperature of 60 ℃, and filtering; the mass ratio of manganese dioxide to the fine manganese ore powder is 0.04: 1;
c) adjusting the pH value of the filtrate obtained in the step b) to 5, adding manganese carbonate, stirring and reacting for 3.5h at the temperature of 55 ℃, and filtering; the mass ratio of the manganese carbonate to the fine manganese ore powder is 0.03: 1; in which Mn (OH) is used2Adjusting the pH value of the solution to 5 by using the powder;
d) adding MnS into the filtrate obtained in the step c), stirring and reacting for 3.5h at the temperature of 90 ℃, and filtering; the mass ratio of MnS to the fine manganese ore powder is 0.015: 1;
e) carrying out primary crystallization on the filtrate obtained in the step d) at the temperature of 70 ℃ under the pressure of 4 MPa; adding dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 8MPa and the temperature of 100 ℃; adding dilute sulfuric acid solution into the precipitated crystal, and performing tertiary crystallization at the pressure of 12MP and the temperature of 140 ℃; the concentration of the dilute sulfuric acid solution adopted in the secondary crystallization and the third crystallization is 0.8mol/L, the addition amount of the dilute sulfuric acid solution in the secondary crystallization and the third crystallization is the same, and the mass ratio of the addition volume of the dilute sulfuric acid solution to the fine manganese ore powder is 5.5: 1;
f) cooling the crystals obtained in step e) to room temperature, adding deionized water and Mn (OH) simultaneously2Adjusting the pH value of the powder to 6.5, and carrying out primary crystallization at the temperature of 70 ℃; adding deionized water into the precipitated crystal, and performing secondary crystallization at a pressure of 8MPa and a temperature of 1000 ℃; adding dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization under the pressure of 12MP and the temperature of 130 ℃, and drying the precipitated crystals to obtain manganese sulfate;
the usage amount of the deionized water for the primary crystallization, the secondary crystallization and the tertiary crystallization is the same, and the volume ratio of the refined manganese ore powder to the deionized water is 1: 5.5.
comparative example 1
The method for purifying and preparing manganese sulfate comprises the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 20-40 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder obtained in the step a) into a sulfuric acid solution, reacting for 4 hours, and filtering to obtain a manganese sulfate solution; the mass concentration of sulfuric acid in the sulfuric acid solution is 40 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 300 g/L;
b) standing the manganese sulfate solution obtained in the step a) for 4h, filtering the obtained filtrate, adding manganese dioxide into the filtrate, reacting for 2.5h at the temperature of 60 ℃, filtering, standing the filtrate for 4h at the temperature of 60 ℃, and filtering; the mass ratio of manganese dioxide to the fine manganese ore powder is 0.04: 1;
c) adjusting the pH value of the filtrate obtained in the step b) to 5, adding manganese carbonate, stirring and reacting for 3.5h at the temperature of 55 ℃, and filtering; the mass ratio of the manganese carbonate to the fine manganese ore powder is 0.03: 1; in which Mn (OH) is used2Adjusting the pH value of the solution to 5 by using the powder;
d) adding MnS into the filtrate obtained in the step c), stirring and reacting for 3.5h at the temperature of 90 ℃, and filtering; the mass ratio of MnS to the fine manganese ore powder is 0.015: 1;
e) carrying out primary crystallization on the filtrate obtained in the step d) at the temperature of 70 ℃ under the pressure of 4 MPa; adding dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 8MPa and the temperature of 100 ℃; adding dilute sulfuric acid solution into the precipitated crystal, and performing tertiary crystallization at the pressure of 12MP and the temperature of 140 ℃; drying the precipitated crystals to obtain manganese sulfate;
the concentration of the dilute sulfuric acid solution adopted in the secondary crystallization and the third crystallization is 0.8mol/L, the addition amount of the dilute sulfuric acid solution in the secondary crystallization and the third crystallization is the same, and the mass ratio of the addition volume of the dilute sulfuric acid solution to the fine manganese ore powder is 5.5: 1.
comparative example 2
The method for purifying and preparing manganese sulfate comprises the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 20-40 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder obtained in the step a) into a sulfuric acid solution, reacting for 4 hours, and filtering to obtain a manganese sulfate solution; the mass concentration of sulfuric acid in the sulfuric acid solution is 40 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 300 g/L;
b) standing the manganese sulfate solution obtained in the step a) for 4h, filtering the obtained filtrate, adding manganese dioxide into the filtrate, reacting for 2.5h at the temperature of 60 ℃, filtering, standing the filtrate for 4h at the temperature of 60 ℃, and filtering; the mass ratio of manganese dioxide to the fine manganese ore powder is 0.04: 1;
c) adjusting the pH value of the filtrate obtained in the step b) to 5, adding manganese carbonate, stirring and reacting for 3.5h at the temperature of 55 ℃, and filtering; the mass ratio of the manganese carbonate to the fine manganese ore powder is 0.03: 1; in which Mn (OH) is used2Adjusting the pH value of the solution to 5 by using the powder;
d) adding MnS into the filtrate obtained in the step c), stirring and reacting for 3.5h at the temperature of 90 ℃, and filtering; the mass ratio of MnS to the fine manganese ore powder is 0.015: 1;
e) using Mn (OH) as the filtrate obtained in the step d)2Adjusting the pH value of the powder to 6.5, and carrying out primary crystallization at the temperature of 70 ℃ under the pressure of 4 MPa; adding deionized water into the precipitated crystal, and performing secondary crystallization at a pressure of 8MPa and a temperature of 1000 ℃; adding dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization under the pressure of 12MP and the temperature of 130 ℃, and drying the precipitated crystals to obtain manganese sulfate;
the usage amount of the deionized water for the primary crystallization, the secondary crystallization and the tertiary crystallization is the same, and the volume ratio of the refined manganese ore powder to the deionized water is 1: 5.5.
comparative example 3
The method for purifying and preparing manganese sulfate comprises the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 20-40 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder obtained in the step a) into a sulfuric acid solution, reacting for 4 hours, and filtering to obtain a manganese sulfate solution; the mass concentration of sulfuric acid in the sulfuric acid solution is 40 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 300 g/L;
b) standing the manganese sulfate solution obtained in the step a) for 4 hours, filtering the obtained filtrate, and addingAdding manganese dioxide into the filtrate, reacting at 60 deg.C for 2.5h, filtering, standing the filtrate at 60 deg.C for 4h, and filtering; the mass ratio of manganese dioxide to the fine manganese ore powder is 0.04: 1; in which Mn (OH) is used2Adjusting the pH value of the solution to 5 by using the powder;
c) adjusting the pH value of the filtrate obtained in the step b) to 5, adding manganese carbonate, stirring and reacting for 3.5h at the temperature of 55 ℃, and filtering; the mass ratio of the manganese carbonate to the fine manganese ore powder is 0.03: 1;
d) carrying out primary crystallization on the filtrate obtained in the step c) at the temperature of 70 ℃ under the pressure of 4 MPa; adding dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 8MPa and the temperature of 100 ℃; adding dilute sulfuric acid solution into the precipitated crystal, and performing tertiary crystallization at the pressure of 12MP and the temperature of 140 ℃; the concentration of the dilute sulfuric acid solution adopted in the secondary crystallization and the third crystallization is 0.8mol/L, the addition amount of the dilute sulfuric acid solution in the secondary crystallization and the third crystallization is the same, and the mass ratio of the addition volume of the dilute sulfuric acid solution to the fine manganese ore powder is 5.5: 1;
e) cooling the crystal obtained in the step d) to room temperature, adding deionized water, and simultaneously adopting Mn (OH)2Adjusting the pH value of the powder to 6.5, and carrying out primary crystallization at the temperature of 70 ℃; adding deionized water into the precipitated crystal, and performing secondary crystallization at a pressure of 8MPa and a temperature of 1000 ℃; adding dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization under the pressure of 12MP and the temperature of 130 ℃, and drying the precipitated crystals to obtain manganese sulfate;
the usage amount of the deionized water for the primary crystallization, the secondary crystallization and the tertiary crystallization is the same, and the volume ratio of the refined manganese ore powder to the deionized water is 1: 5.5.
the manganese sulfate prepared in examples 1 to 3 and comparative examples 1 to 3 was tested, and the results are shown in table 1.
TABLE 1 test results of examples 1 to 3 and comparative examples 1 to 3
The previous description is provided to enable any person skilled in the art to make or use the present disclosure, and is provided in the context of a computer-implemented process. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The method for purifying and preparing manganese sulfate is characterized by comprising the following steps:
a) crushing and grinding manganese ore to obtain manganese ore powder with the particle size of 10-50 mu m; carrying out magnetic separation on manganese ore powder to obtain refined manganese ore powder; adding the fine manganese ore powder into a sulfuric acid solution, reacting for 3-5 h, and filtering to obtain a manganese sulfate solution;
b) standing the manganese sulfate solution obtained in the step a) for 3-5 hours, filtering the obtained filtrate, adding manganese dioxide into the filtrate to react for 2-3 hours at 50-80 ℃, filtering, standing the filtrate for 3-5 hours at 50-80 ℃, and filtering;
c) adjusting the pH value of the filtrate obtained in the step b) to 4-6, adding manganese carbonate, stirring and reacting for 3-4 h at the temperature of 50-60 ℃, and filtering;
d) adding MnS into the filtrate obtained in the step c), stirring and reacting for 3-4 h at the temperature of 80-100 ℃, and filtering;
e) carrying out primary crystallization on the filtrate obtained in the step d) at the temperature of 60-80 ℃ under the pressure of 3-5 MPa; adding a dilute sulfuric acid solution into the precipitated crystal, and performing secondary crystallization at the pressure of 5-10 MPa and the temperature of 80-120 ℃; adding a dilute sulfuric acid solution into the precipitated crystal, and carrying out tertiary crystallization at the pressure of 10-15 MP and the temperature of 120-150 ℃;
f) cooling the crystal obtained in the step e) to room temperature, adding deionized water, adjusting the pH to 6-7, and performing primary crystallization at the temperature of 60-80 ℃; adding deionized water into the precipitated crystal, and performing secondary crystallization at the pressure of 5-10 MPa and the temperature of 80-120 ℃; and adding a dilute sulfuric acid solution into the precipitated crystals, carrying out three-time crystallization under the pressure of 10-15 MP and the temperature of 120-150 ℃, and drying the precipitated crystals to obtain the manganese sulfate.
2. The method for purifying and preparing manganese sulfate according to claim 1, wherein in the step a), the mass concentration of sulfuric acid in the sulfuric acid solution is 30-50 wt%, and the concentration of manganese sulfate in the manganese sulfate solution is 200-400 g/L.
3. The method for purifying and preparing manganese sulfate according to claim 1, wherein in the step b), the mass ratio of manganese dioxide to fine manganese ore powder is (0.03-0.05): 1.
4. the method for purifying and preparing manganese sulfate according to claim 1, wherein in the step c), the mass ratio of manganese carbonate to fine manganese ore powder is (0.02-0.04): 1.
5. the method for purifying and preparing manganese sulfate according to claim 1, wherein in the step d), the mass ratio of MnS to the fine manganese ore powder is (0.01-0.02): 1.
6. the method for purifying and preparing manganese sulfate according to claim 1, wherein in step e), the concentration of the dilute sulfuric acid solution used in the secondary crystallization and the concentration of the dilute sulfuric acid solution used in the tertiary crystallization are both 0.5-1 mol/L, the addition amount of the dilute sulfuric acid solution used in the secondary crystallization and the addition amount of the dilute sulfuric acid solution used in the tertiary crystallization are the same, and the mass ratio of the dilute sulfuric acid solution to the fine manganese ore powder is (5-6): 1.
7. the method for purifying and preparing manganese sulfate according to claim 1, wherein in step f), the amounts of deionized water for primary crystallization, secondary crystallization and tertiary crystallization are the same, and the volume ratio of the refined manganese ore powder to the deionized water is 1: (5-6).
8. The method for purifying manganese sulfate as claimed in claim 1, wherein Mn (OH) is used in step c) and step f)2The powder adjusted the pH of the solution.
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