CN115028204B - Preparation method of feed-grade manganese sulfate - Google Patents
Preparation method of feed-grade manganese sulfate Download PDFInfo
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- CN115028204B CN115028204B CN202210735489.1A CN202210735489A CN115028204B CN 115028204 B CN115028204 B CN 115028204B CN 202210735489 A CN202210735489 A CN 202210735489A CN 115028204 B CN115028204 B CN 115028204B
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- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 124
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 124
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 124
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000002002 slurry Substances 0.000 claims abstract description 72
- 238000002386 leaching Methods 0.000 claims abstract description 63
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 35
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012045 crude solution Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 239000012452 mother liquor Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- OKVGBKABWITJQA-UHFFFAOYSA-L manganese dithionate Chemical group [Mn+2].[O-]S(=O)(=O)S([O-])(=O)=O OKVGBKABWITJQA-UHFFFAOYSA-L 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 14
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 14
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
- 229910052749 magnesium Inorganic materials 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 235000010755 mineral Nutrition 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 235000013350 formula milk Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 230000035764 nutrition Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- -1 Zn2+ Chemical class 0.000 description 1
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229940126585 therapeutic drug Drugs 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002699 waste material 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of feed-grade manganese sulfate, which comprises the following steps: 1) Preparing sulfur dioxide gas; 2) Preparing slurry: grinding pyrolusite as a raw material into powder; mixing a proper amount of powder with water to obtain slurry A, and mixing another proper amount of powder with sulfuric acid solution to obtain slurry B; 3) Leaching manganese sulfate: introducing sulfur dioxide gas obtained in the step 1) into the slurry A for preliminary reaction, stopping introducing gas after the reaction is completed, continuously adding the slurry B into the slurry after the preliminary reaction is completed for re-leaching, and filtering the slurry which generates precipitation after the re-leaching is completed, wherein the filtered filtrate is manganese sulfate crude solution; 4) Purifying: 5) And (3) crystallization: heating the manganese sulfate purifying liquid to 100-150 ℃, filtering to obtain mother liquor, further concentrating the mother liquor, evaporating and drying to obtain feed-grade manganese sulfate. The method has the advantages of less impurities, low energy consumption, high purity of the obtained feed-grade product and stable quality in the production process.
Description
Technical Field
The invention relates to the technical field of manganese sulfate preparation, in particular to a preparation method of feed-grade manganese sulfate.
Background
Manganese sulfate is widely used in the fields of industry, agriculture, food and medicine, and can be used as a nutrition enhancer and a dietary supplement in the food industry, and is used for pregnant and lying-in women formula milk powder, infant formula milk powder, older infant formula milk powder, children nutrition formula milk powder and the like; in the pharmaceutical industry, manganese sulfate can be used as a daily health product and a therapeutic drug, has the function of preventing atherosclerosis, and can be used for patients with long-term intravenous high nutrition support. In addition, manganese sulfate is used as a major carrier for supplementing trace element manganese for animals and crops as a feed additive and trace fertilizer.
Domestic feed-grade manganese sulfate leaching processes can be classified into a manganese ore pre-reduction leaching method and a manganese ore direct acid leaching method according to different processes. The manganese ore pre-reduction leaching method is mainly used as a coal roasting-sulfuric acid leaching method and a two-ore roasting-sulfuric acid leaching method, and the direct acid leaching method comprises a two-ore acid adding method and an SO2 reduction leaching method; the manganese sulfate crude solution leached by the two methods must be deeply purified to obtain the standard feed-grade manganese sulfate, and the purification operation process and method also determine the quality of the final product.
How to obtain a method which is high-efficiency in leaching and can ensure that the product meets the quality standard of feed-grade manganese sulfate becomes the difficulty and the key point of research. Chinese patent CN921126735 describes a method for preparing high purity manganese sulfate solution in high yield, which takes low grade manganese carbonate containing potassium as raw material, completes leaching process in two stages in two leaches separated from each other, removes potassium, and then prepares manganese sulfate, which has high production cost, complex process steps, and low purity of produced manganese sulfate. In the conventional manganese sulfate leaching process, if sulfur dioxide is used as a reducing agent, about 30% of byproduct manganese dithionate is produced in the leaching reaction process, and new impurities are introduced in subsequent treatment, so that the impurity removal difficulty is increased, the product quality and the product stability are affected, meanwhile, manganese dithionate can turn yellow light pink manganese sulfate, and the feed quality is accelerated after manganese dithionate contained in feed-grade manganese sulfate is used as an additive to enter feed, so that improvement is needed.
Disclosure of Invention
The technical problem solved by the invention is to provide a preparation method of feed-grade manganese sulfate, which has the advantages of less leaching impurities, high product purity, stable quality and lower energy consumption, so as to solve the problems in the background technology.
The technical problems solved by the invention are realized by adopting the following technical scheme:
a preparation method of feed-grade manganese sulfate comprises the following steps:
1) Preparing sulfur dioxide gas: burning sulfur and air to generate sulfur dioxide gas;
2) Preparing slurry: grinding pyrolusite as a raw material into powder; mixing a proper amount of powder with water to obtain slurry A, and mixing another proper amount of powder with sulfuric acid solution to obtain slurry B;
3) Leaching manganese sulfate: introducing sulfur dioxide gas obtained in the step 1) into the slurry A at a flow rate of 2-10 m/s and a bubble diameter of less than 100 mu m for preliminary reaction, stopping introducing gas after the reaction is finished, continuously adding the slurry B into the slurry after the preliminary reaction is finished for re-leaching, adding a neutralizer after the re-leaching is finished to precipitate the slurry after the re-leaching reaction is finished, and filtering the precipitated slurry, wherein the filtered filtrate is manganese sulfate crude solution;
4) Purifying: adding sulfide into the manganese sulfate crude solution to remove impurities, and filtering to obtain manganese sulfate purifying liquid; s2-reacts with impurity ions such as Zn2+, cu2+, ni2+ and the like in the solution to produce sulfide precipitate, and most impurities in the solution can be removed by filtration;
5) And (3) crystallization: heating the manganese sulfate purifying liquid to 100-150 ℃, filtering to obtain mother liquor, further concentrating the mother liquor, evaporating and drying to obtain feed-grade manganese sulfate.
Further, in the step 1), the concentration of sulfur dioxide in the sulfur dioxide gas is 1-99%.
Further, in the step 2), the pyrolusite is ground into powder having a particle size of 1 to 1000 μm, more preferably 0 to 500 μm; the solid-to-liquid ratio of the powder ground from pyrolusite to water is 1:1-10, and more preferably 1:2-6; the solid-to-liquid ratio of the powder ground from pyrolusite to the sulfuric acid solution is 1 to 10, and the concentration of the sulfuric acid solution is more preferably 1mol/L, and is still more preferably 1:2 to 6.
Further, in the step 3), in the preliminary reaction process, the reaction pH value is 1-5, the reaction temperature is 1-200 ℃, and more preferably 50-150 ℃; the reaction time is 1 to 72 hours, more preferably 1 to 48 hours; in the re-leaching process, the reaction pH value is 0.01-5, the reaction temperature is 1-150 ℃, and the further preferable temperature is 50-130 ℃; the reaction time is 1 to 24 hours, more preferably 2 to 20 hours.
Further, in the step 3), the mass percentage of the slurry B added in the re-leaching process and the slurry A added in the preliminary reaction is 10-60%.
Further, in the step 3), the manganese dithionate residual amount of the manganese sulfate crude solution is less than 5g/L.
Further, in the step 4), the sulfide includes one or more of sodium sulfide, barium sulfide, sodium hydrosulfide and ammonium sulfide.
Further, in step 5), the bome degree of the mother liquor is 20-50 before evaporation.
Further, in step 5), the purity of the feed grade manganese sulfate is greater than 98%.
The beneficial effects are that: the method of the feed-grade manganese sulfate of the invention comprises the steps of introducing sulfur dioxide gas obtained by preparation into pyrolusite pulp at a given speed and bubble diameter for primary leaching reaction, introducing a proper amount of pulp for re-leaching reaction after the primary leaching reaction is completed, and in the re-leaching reaction process, mnS 2 O 6 The thermal stability of pyrolusite is deteriorated, and manganese dioxide, which is a main component of pyrolusite, reacts with manganese dithionate under strong acidic conditions. The whole reaction process is rapid and thorough, high temperature is not needed, energy consumption is low, manganese dioxide can be selectively and efficiently leached, the residual quantity of manganese dithionate byproducts in the manganese sulfate crude solution obtained after the reaction is lower than 5g/L, and the subsequent purification and impurity removal pressure is reduced. The invention combines the subsequent purification and recrystallization treatment processes to obtain the feed-grade manganese sulfate with high purification, uniform particle size and high quality and stability.
The pyrolusite contains a certain amount of elements such as calcium, magnesium and the like, and the elements such as the calcium, the magnesium and the like contained in the pyrolusite are difficult to remove in the purifying and impurity removing process. And the manganese sulfate purifying liquid is crystallized after being heated, and the crystal can be used for further preparing battery-grade manganese sulfate. Because the mother solution takes away most of calcium and magnesium elements, the content of the calcium and magnesium elements in crystals is reduced, and the battery-grade manganese sulfate has strict requirements on the calcium and magnesium elements, the technical scheme of the invention can be favorable for further processing to obtain battery-grade manganese sulfate products with higher purity and better quality. And the utilization rate of manganese element can be effectively improved.
Detailed Description
In order that the manner in which the invention is attained, as well as the features and advantages thereof, will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
The pyrolusite used in this example had a manganese content of 30%, an iron content of 25%, a calcium content of 700ppm and a magnesium content of 100ppm.
The method for preparing the feed-grade manganese sulfate comprises the following steps of:
1) Preparing sulfur dioxide gas: burning 100g of sulfur with air to generate sulfur dioxide gas; collecting the gas generated after combustion for later use;
2) Preparing slurry: grinding pyrolusite serving as a raw material into powder with the particle size smaller than 1000um, and mixing 100g of mineral powder with 800ml of water to prepare slurry A for later use; in addition, 100g of mineral powder is weighed and mixed with 400mL of sulfuric acid solution (1 mol/L) to prepare slurry B for standby;
3) Leaching manganese sulfate: introducing the gas obtained in the step 1) into the slurry A at a flow rate of 3m/s and a bubble diameter of less than 100 mu m for leaching reaction, wherein the reaction pH value is 3.5, the reaction temperature is 70 ℃, the reaction time is 4 hours, and stopping gas introduction after the reaction is completed; continuously adding the slurry B into the slurry after the primary reaction is finished for re-leaching; the pH value of the re-leaching reaction is 3.5, the reaction temperature is 40 ℃ and the reaction time is 4 hours, 0.4g of calcium carbonate is added to adjust the pH value to 5 after the reaction is completed, the slurry after the re-leaching reaction is completed is precipitated, the mixture is stood for 1 hour, the slurry which generates the precipitate is filtered, the filtered filtrate is manganese sulfate crude solution, and the residual quantity of manganese dithionate in the manganese sulfate crude solution is shown in table 1.
4) Purifying: weighing 0.3g of sodium sulfide, adding the sodium sulfide into the manganese sulfate crude liquid, stirring and reacting for 1h, standing for 1h, and filtering to obtain manganese sulfate purified liquid;
5) And (3) crystallization: and heating the manganese sulfate purifying liquid to 140 ℃, filtering to obtain mother liquor, further concentrating, evaporating and drying the mother liquor to obtain feed-grade manganese sulfate, wherein the relevant index parameters of the feed-grade manganese sulfate are shown in table 2.
Example 2
Of the pyrolusite used in this example, manganese ore 2: 35% of manganese, 15% of iron, 650ppm of calcium and 200ppm of magnesium.
The method for preparing the feed-grade manganese sulfate comprises the following steps of:
1) Preparing sulfur dioxide gas: burning 120g of sulfur with air to generate sulfur dioxide gas; collecting the gas generated after combustion for later use;
2) Preparing slurry: grinding pyrolusite serving as a raw material into powder with the particle size smaller than 1000um, and mixing 200g of mineral powder with 800ml of water to prepare slurry A for later use; in addition, 100g of mineral powder is weighed and mixed with 400mL of sulfuric acid solution (1 mol/L) to prepare slurry B for standby;
3) Leaching manganese sulfate: introducing the gas obtained in the step 1) into the slurry A at a flow rate of 3m/s and a bubble diameter of less than 100 mu m for leaching reaction, wherein the reaction pH value is 4.5, the reaction temperature is 70 ℃, the reaction time is 4 hours, and stopping gas introduction after the reaction is completed; continuously adding the slurry B into the slurry after the primary reaction is finished for re-leaching; the pH value of the re-leaching reaction is 4.5, the reaction temperature is 60 ℃ and the reaction time is 4 hours, 0.4g of calcium carbonate is added to adjust the pH value to 5 after the reaction is completed, the slurry after the re-leaching reaction is completed is precipitated, the mixture is stood for 1 hour, the slurry which generates the precipitate is filtered, the filtered filtrate is manganese sulfate crude solution, and the residual quantity of manganese dithionate in the manganese sulfate crude solution is shown in table 1.
4) Purifying: weighing 0.4g of sodium sulfide, adding the sodium sulfide into the manganese sulfate crude liquid, stirring and reacting for 1h, standing for 1h, and filtering to obtain manganese sulfate purified liquid;
5) And (3) crystallization: and heating the manganese sulfate purifying liquid to 140 ℃, filtering to obtain mother liquor, further concentrating, evaporating and drying the mother liquor to obtain feed-grade manganese sulfate, wherein the relevant index parameters of the feed-grade manganese sulfate are shown in table 2.
Example 3
In the pyrolusite used in this example, the manganese content was 40%, the iron content was 5%, the calcium content was 900ppm, and the magnesium content was 400ppm.
The method for preparing the feed-grade manganese sulfate comprises the following steps of:
1) Preparing sulfur dioxide gas: burning 140g of sulfur with air to generate sulfur dioxide gas; collecting the gas generated after combustion for later use;
2) Preparing slurry: grinding pyrolusite serving as a raw material into powder with the particle size smaller than 1000um, and mixing 200g of mineral powder with 800ml of water to prepare slurry A for later use; in addition, 100g of mineral powder is weighed and mixed with 400mL of sulfuric acid solution (1 mol/L) to prepare slurry B for standby;
3) Leaching manganese sulfate: introducing the gas obtained in the step 1) into the slurry A at a flow rate of 3m/s and a bubble diameter of less than 100 mu m for leaching reaction, wherein the reaction pH value is 2.5, the reaction temperature is 70 ℃, the reaction time is 4 hours, and stopping gas introduction after the reaction is completed; continuously adding the slurry B into the slurry after the primary reaction is finished for re-leaching; the pH value of the re-leaching reaction is 2.5, the reaction temperature is 80 ℃ and the reaction time is 4 hours, 0.4g of calcium carbonate is added to adjust the pH value to 5 after the reaction is completed, the slurry after the re-leaching reaction is completed is precipitated, the mixture is stood for 1 hour, the slurry which generates the precipitate is filtered, the filtered filtrate is manganese sulfate crude solution, and the residual quantity of manganese dithionate in the manganese sulfate crude solution is shown in table 1.
4) Purifying: weighing 0.5g of sodium sulfide, adding the sodium sulfide into the manganese sulfate crude liquid, stirring and reacting for 1h, standing for 1h, and filtering to obtain manganese sulfate purified liquid;
5) And (3) crystallization: and heating the manganese sulfate purifying liquid to 140 ℃, filtering to obtain mother liquor, further concentrating, evaporating and drying the mother liquor to obtain feed-grade manganese sulfate, wherein the relevant index parameters of the feed-grade manganese sulfate are shown in table 2.
Comparative example 1
The pyrolusite used in this example had a manganese content of 30%, an iron content of 25%, a calcium content of 700ppm and a magnesium content of 100ppm.
The method for preparing the feed-grade manganese sulfate comprises the following steps of:
1) Preparing sulfur dioxide gas: burning 100g of sulfur with air to generate sulfur dioxide gas; collecting the gas generated after combustion for later use;
2) Preparing slurry: grinding pyrolusite serving as a raw material into powder with the particle size smaller than 1000um, and mixing 100g of mineral powder with 800ml of water to prepare slurry A for later use;
3) Leaching manganese sulfate: introducing the gas obtained in the step 1) into the slurry A at a flow rate of 3m/s and a bubble diameter of less than 100 mu m for leaching reaction, wherein the reaction pH value is 2.5, the reaction temperature is 70 ℃, the reaction time is 4 hours, and stopping gas introduction after the reaction is completed; 0.4g of calcium carbonate is added to adjust the pH to 5, so that the slurry is precipitated, the slurry is stood for 1h, the precipitated slurry is filtered, the filtered filtrate is a manganese sulfate crude solution, and the residual quantity of manganese dithionate in the manganese sulfate crude solution is shown in table 1.
4) Purifying: weighing 0.3g of sodium sulfide, adding the sodium sulfide into the manganese sulfate crude liquid, stirring and reacting for 1h, standing for 1h, and filtering to obtain manganese sulfate purified liquid;
5) And (3) crystallization: and heating the manganese sulfate purifying liquid to 140 ℃, filtering to obtain mother liquor, further concentrating, evaporating and drying the mother liquor to obtain feed-grade manganese sulfate, wherein the relevant index parameters of the feed-grade manganese sulfate are shown in table 2.
Comparative example 2
The pyrolusite used in this example had a manganese content of 30%, an iron content of 25%, a calcium content of 700ppm and a magnesium content of 100ppm.
The method for preparing the feed-grade manganese sulfate comprises the following steps of:
1) Preparing sulfur dioxide gas: burning 100g of sulfur with air to generate sulfur dioxide gas; collecting the gas generated after combustion for later use;
2) Preparing slurry: grinding pyrolusite serving as a raw material into powder with the particle size smaller than 1000um, and mixing 100g of mineral powder with 800ml of water to prepare slurry A for later use;
3) Leaching manganese sulfate: introducing the gas obtained in the step 1) into the slurry A for leaching reaction at the reaction temperature of 70 ℃ for 4 hours; after the reaction, 0.4g of calcium carbonate is added to adjust the pH to 5, so that the slurry is precipitated, the slurry is stood for 1h, the precipitated slurry is filtered, the filtered filtrate is a manganese sulfate crude solution, and the residual amount of manganese dithionate in the manganese sulfate crude solution is shown in Table 1.
4) Purifying: weighing 0.3g of sodium sulfide, adding the sodium sulfide into the manganese sulfate crude liquid, stirring and reacting for 1h, standing for 1h, and filtering to obtain manganese sulfate purified liquid;
5) And (3) crystallization: and heating the manganese sulfate purifying liquid to 140 ℃, filtering to obtain mother liquor, further concentrating, evaporating and drying the mother liquor to obtain feed-grade manganese sulfate, wherein the relevant index parameters of the feed-grade manganese sulfate are shown in table 2.
In this comparative example, sulfur dioxide gas was introduced into slurry a at one time to effect the reaction, resulting in the production of more manganese dithionate and more impurities.
Comparative example 3
The pyrolusite used in this example had a manganese content of 30%, an iron content of 25%, a calcium content of 700ppm and a magnesium content of 100ppm.
The method of battery-grade manganese sulfate of the embodiment comprises the following steps:
1) Preparing sulfur dioxide gas: burning 100g of sulfur with air to generate sulfur dioxide gas; collecting the gas generated after combustion for later use;
2) Preparing slurry: grinding pyrolusite serving as a raw material into powder with the particle size smaller than 1000um, and mixing 100g of mineral powder with 800ml of water to prepare slurry A for later use; in addition, 100g of mineral powder is weighed and mixed with 400mL of sulfuric acid solution (1 mol/L) to prepare slurry B for standby;
3) Leaching manganese sulfate: introducing the gas obtained in the step 1) into the slurry A at a flow rate of 3m/s and a bubble diameter of less than 100 mu m for leaching reaction, wherein the reaction pH value is 7, the reaction temperature is 70 ℃, the reaction time is 4 hours, and stopping gas introduction after the reaction is completed; continuously adding the slurry B into the slurry after the primary reaction is finished for re-leaching; the pH value of the re-leaching reaction is 7, the reaction temperature is 10 ℃, the reaction time is 4 hours, 0.4g of neutralizer is added after the reaction is completed to adjust the pH value to 5, the slurry after the re-leaching reaction is completed is precipitated, the mixture is stood for 1 hour, the slurry which generates the precipitate is filtered, the filtered filtrate is manganese sulfate crude solution, and the residual quantity of manganese dithionate in the manganese sulfate crude solution is shown in table 1.
4) Purifying: weighing 0.3g of sodium sulfide, adding the sodium sulfide into the manganese sulfate crude liquid, stirring and reacting for 1h, standing for 1h, and filtering to obtain manganese sulfate purified liquid;
5) And (3) crystallization: and heating the manganese sulfate purifying liquid to 140 ℃, filtering to obtain mother liquor, further concentrating, evaporating and drying the mother liquor to obtain feed-grade manganese sulfate, wherein the relevant index parameters of the feed-grade manganese sulfate are shown in table 2.
In the comparative example, manganese dithionate was hardly converted under the conditions of the primary leaching and the re-leaching at a higher pH, and manganese bivalence would generate a small amount of manganese hydroxide precipitate, and further manganese oxyhydroxide was generated, so that impurities were more generated.
TABLE 1 comparison of residual amount of impurity manganese dithionate in crude manganese sulfate solution
As can be seen from table 1, the manganese dithionate residue in the obtained manganese sulfate crude solution was significantly reduced by the treatment of the re-leaching method, thereby further improving the purity of the final product. The addition mode of sulfur dioxide gas and the parameter conditions of the re-leaching process have great influence on the generation and final content of impurity manganese dithionate.
TABLE 2 feed grade manganese sulfate HG/T4823-2015 grade index and example related parameter Table
As is clear from Table 2, the content of feed-grade manganese sulfate obtained by the technology of the invention is more than 98% calculated by MnSO4.H2O, 31.99%, 32.02% and 32.07% calculated by Mn respectively, which are far higher than the standard of qualified products, and the content of calcium element and magnesium element are far higher than the content of calcium element and magnesium element in common feed-grade manganese sulfate. The whole process has rapid and thorough reaction, no need of high temperature and low energy consumption, and the obtained feed-grade manganese sulfate product has high purification, uniform particle size and stable quality.
In step 5) of examples 1 to 3, the purified manganese sulfate solution was heated to 140 ℃ to produce crystals and a mother liquor, which was prepared into feed-grade manganese sulfate by the method of the present invention. And further recrystallizing the crystal to prepare the battery-grade manganese sulfate. And calculating the utilization rate of manganese element in pyrolusite leaching solution according to the content of manganese element in the obtained battery-grade manganese sulfate and feed-grade manganese sulfate. The results are shown in Table 3, and illustrate that the utilization rate of manganese element in pyrolusite leaching solution can be remarkably improved when the technology is adopted to prepare the feed-grade manganese sulfate, so that the waste of manganese element is avoided.
TABLE 3 utilization of manganese element in pyrolusite leachate
| Project | Example 1 | Example 2 | Example 3 |
| Before feed-grade manganese sulfate is prepared | 79.47 | 79.56 | 79.48 |
| After preparing feed-grade manganese sulfate | 99.34 | 99.46 | 99.35 |
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The preparation method of the feed-grade manganese sulfate is characterized by comprising the following steps of:
1) Preparing sulfur dioxide gas: burning sulfur and air to generate sulfur dioxide gas;
2) Preparing slurry: grinding pyrolusite as a raw material into powder; mixing a proper amount of powder with water to obtain slurry A, and mixing another proper amount of powder with sulfuric acid solution to obtain slurry B;
3) Leaching manganese sulfate: introducing sulfur dioxide gas obtained in the step 1) into the slurry A at a flow rate of 2-10 m/s and a bubble diameter of less than 100 mu m for preliminary reaction, stopping introducing gas after the reaction is finished, continuously adding the slurry B into the slurry after the preliminary reaction is finished for re-leaching, adding a neutralizer after the re-leaching is finished to precipitate the slurry after the re-leaching reaction is finished, and filtering the precipitated slurry, wherein the filtered filtrate is manganese sulfate crude solution;
in the primary reaction process, the pH value of the reaction is 1-5, and in the re-leaching process, the pH value of the reaction is 0.01-5;
4) Purifying: adding sulfide into the manganese sulfate crude solution to remove impurities, and filtering to obtain manganese sulfate purifying liquid;
5) And (3) crystallization: heating the manganese sulfate purifying liquid to 100-150 ℃, filtering to obtain mother liquor, further concentrating the mother liquor, evaporating and drying to obtain feed-grade manganese sulfate.
2. The method of producing feed grade manganese sulfate according to claim 1, wherein in step 1) the sulfur dioxide concentration in the sulfur dioxide gas is 1 to 99%.
3. The method for preparing feed-grade manganese sulfate according to claim 1, wherein in the step 2), pyrolusite is ground into powder with a particle size of less than 1000um, the solid-to-liquid ratio of pyrolusite ground powder to water is 1:1-10, the solid-to-liquid ratio of pyrolusite ground powder to sulfuric acid solution is 1-10, and the concentration of sulfuric acid solution is 1mol/L.
4. The method for preparing feed-grade manganese sulfate according to claim 1, wherein in the step 3), the reaction temperature is 1-200 ℃ and the reaction time is 1-72 h in the preliminary reaction process, and the reaction temperature is 1-150 ℃ and the reaction time is 1-24 h in the re-leaching process.
5. The method for preparing feed-grade manganese sulfate according to claim 1, wherein in the step 3), the mass percentage of the slurry B added in the re-leaching process and the slurry a added in the preliminary reaction is 10-60%.
6. The method of producing feed grade manganese sulfate according to claim 1, wherein in step 3), the manganese dithionate residue of the crude manganese sulfate solution is less than 5g/L.
7. The method for preparing feed-grade manganese sulfate according to claim 1, wherein in step 4), the sulfide includes one or more of sodium sulfide, barium sulfide, sodium hydrosulfide, and ammonium sulfide.
8. The method of preparing feed grade manganese sulfate according to claim 1, wherein in step 5), the mother liquor has a baume of 20-50 before evaporation.
9. The method of producing feed grade manganese sulfate according to claim 8, wherein in step 5), the purity of the feed grade manganese sulfate is greater than 98%.
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