CN117228727A - Method for removing calcium and magnesium from manganese sulfate at low cost - Google Patents
Method for removing calcium and magnesium from manganese sulfate at low cost Download PDFInfo
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- CN117228727A CN117228727A CN202311140306.2A CN202311140306A CN117228727A CN 117228727 A CN117228727 A CN 117228727A CN 202311140306 A CN202311140306 A CN 202311140306A CN 117228727 A CN117228727 A CN 117228727A
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- fluorine
- manganese
- manganese sulfate
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- magnesium
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 152
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 151
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 151
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 149
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000011575 calcium Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 43
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 41
- 239000011777 magnesium Substances 0.000 title claims abstract description 41
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 41
- 239000011737 fluorine Substances 0.000 claims abstract description 339
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 339
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 330
- 239000007788 liquid Substances 0.000 claims abstract description 92
- 239000002893 slag Substances 0.000 claims abstract description 83
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 55
- -1 aluminum compound Chemical class 0.000 claims abstract description 44
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 230000020477 pH reduction Effects 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000004537 pulping Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 31
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 18
- 229910001424 calcium ion Inorganic materials 0.000 claims description 18
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 16
- 238000002386 leaching Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims description 10
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- ZJOKNSFTHAWVKK-UHFFFAOYSA-K aluminum octadecanoate sulfate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].S(=O)(=O)([O-])[O-] ZJOKNSFTHAWVKK-UHFFFAOYSA-K 0.000 claims description 8
- 235000006748 manganese carbonate Nutrition 0.000 claims description 7
- 239000011656 manganese carbonate Substances 0.000 claims description 7
- 229940093474 manganese carbonate Drugs 0.000 claims description 7
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 7
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 3
- POBNOKAZPBNXAU-UHFFFAOYSA-J magnesium manganese(2+) disulfate Chemical compound [Mg+2].[Mn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O POBNOKAZPBNXAU-UHFFFAOYSA-J 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 12
- 239000010941 cobalt Substances 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 9
- 229910018626 Al(OH) Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 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 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The application discloses a method for removing calcium and magnesium from manganese sulfate with low cost. The method comprises the following steps: (1) Mixing the manganese sulfate crude liquid, a fluorine source and a manganese-containing pH regulator so as to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution; (2) Mixing the fluorine-containing manganese sulfate solution, an aluminum compound and the manganese-containing pH regulator to obtain the fluorine-containing filter residue and manganese sulfate solution, and returning the fluorine-containing filter residue to the step (1); (3) And (3) mixing the fluorine-containing mixed slag with water for pulping, adding acid for acidification to obtain the regenerated fluorine liquid and fluorine-containing calcium magnesium slag, and returning the regenerated fluorine liquid to the step (1). The method can fully utilize fluorine-containing filter residues, not only reduces the use amount of aluminum compounds, but also greatly reduces the use amount of fluorine sources, obviously reduces the production cost, and realizes the harmless treatment of fluorine-containing calcium magnesium residues.
Description
Technical Field
The application belongs to the technical field of fine chemical engineering, and particularly relates to a method for removing calcium and magnesium from manganese sulfate at low cost.
Background
With the rapid development of new energy batteries, ternary lithium batteries, lithium iron manganese phosphate batteries and future sodium ion batteries can all use battery-grade manganese sulfate or battery-grade manganese sulfate derivatives, and the main technology for producing battery-grade manganese sulfate at low cost is direct leaching purification and impurity removal by an ore method, and the most difficult point in the purification and impurity removal process is calcium and magnesium removal. The most effective calcium and magnesium ion removal method of the battery-grade manganese sulfate is a fluorination method at present, and due to low-concentration chemical reaction kinetics, more than 99% of calcium and magnesium ions in the manganese sulfate solution are precipitated and separated from the manganese sulfate solution, a large amount of surplus fluoride ions are necessarily remained in the manganese sulfate solution, fluoride actually consumed in industrial practice is more than 2.5 times of theoretical consumption, most of fluorine enters the manganese sulfate solution in the form of fluoride ions, and is adsorbed by a defluorinating agent and forms defluorinating slag separation in a defluorinating process, so that the method has important practical significance and industrial value on how to recycle defluorinating slag is realized and the fluoride consumption is reduced.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present application is to propose a method for low-cost removal of calcium and magnesium from manganese sulphate. The method can fully utilize fluorine-containing filter residues, not only reduces the use amount of aluminum compounds, but also greatly reduces the use amount of fluorine sources, obviously reduces the production cost, and realizes the harmless treatment of fluorine-containing calcium magnesium residues.
In one aspect of the application, the application provides a method for removing calcium and magnesium from manganese sulfate at low cost. According to an embodiment of the application, the method comprises:
(1) Mixing the manganese sulfate crude liquid, a fluorine source and a manganese-containing pH regulator so as to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution;
(2) Mixing the fluorine-containing manganese sulfate solution, an aluminum compound and the manganese-containing pH regulator to obtain the fluorine-containing filter residue and manganese sulfate solution, and returning the fluorine-containing filter residue to the step (1);
(3) And (3) mixing the fluorine-containing mixed slag with water for pulping, adding acid for acidification to obtain the regenerated fluorine liquid and fluorine-containing calcium magnesium slag, and returning the regenerated fluorine liquid to the step (1).
According to the method for removing calcium and magnesium from manganese sulfate with low cost, disclosed by the embodiment of the application, the manganese sulfate crude liquid, the fluorine source and the manganese-containing pH regulator are mixed, and calcium ions in the manganese sulfate crude liquidAnd magnesium ions and fluoride ions to generate calcium fluoride and magnesium fluoride precipitates, and then filtering to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution; mixing a fluorine-containing manganese sulfate solution, an aluminum compound and a manganese-containing pH regulator, wherein the aluminum compound is used for removing fluorine ions in the fluorine-containing manganese sulfate solution, and the specific reactions are as follows: al (Al) 3+ +3H 2 O＝Al(OH) 3 +3H + (pH≥5)；Al(OH) 3 +XF - ＝Al(OH) 3-X F X ↓+X(OH) - (pH. Gtoreq.5), and then filtering to obtain a fluorine-containing residue (Al (OH) 3-X F X ) And manganese sulfate solution, and returning fluorine-containing filter residues to the step (1); the inventor finds that the fluorine-containing filter residue returns to the step (1), namely, manganese sulfate crude liquid, a fluorine source, a manganese-containing pH regulator and the fluorine-containing filter residue are mixed, the fluorine-containing filter residue can be used as a sedimentation-assisting filter aid, calcium ions and magnesium ions can be promoted to form sediment, and the use amount of fluorine ions is reduced, so that the use amount of aluminum compounds in the subsequent working procedures is reduced. Mixing the fluorine-containing mixed slag with water to form slurry, wherein the fluorine-containing mixed slag is acidified by adding acid because the fluorine-containing mixed slag returns to the step (1), so that the fluorine-containing filtered slag (Al (OH) 3-X F X ) The fluorine ions in the catalyst are dissociated, and the specific reactions are as follows: al (OH) 3-X F X +0.5XH 2 SO 4 ＝Al(OH) 3-X (SO 4 ) 0.5X +xhf; and filtering to obtain regenerated fluorine liquid and fluorine-containing calcium magnesium slag, and returning the regenerated fluorine liquid to the step (1), namely, mixing and reacting the manganese sulfate crude liquid, the fluorine source, the manganese-containing pH regulator, the fluorine-containing filter residue and the regenerated fluorine liquid, wherein the regenerated fluorine liquid contains fluorine ions and can replace part of the fluorine source. On one hand, the addition amount of the fluorine source is reduced, so that the consumption of the fluorine source is close to the theoretical consumption of the calcium-magnesium-removed fluorine source, and more than half of the consumption of the fluorine source is saved; on the other hand, the full utilization of fluorine-containing filter residues is realized, the emission of fluorine-containing mixed residues is reduced, and the harmless treatment of fluorine-containing calcium magnesium residues is realized. Therefore, the method can fully utilize the fluorine-containing filter residues, not only reduces the use amount of aluminum compounds, but also greatly reduces the use amount of fluorine sources, obviously reduces the production cost, and realizes the harmless treatment of fluorine-containing calcium magnesium residues.
In addition, the method for removing calcium and magnesium from manganese sulfate with low cost according to the embodiment of the application can also have the following technical characteristics:
in some embodiments of the application, in step (1), the manganese content in the manganese sulfate crude liquid is 100g/L to 180g/L.
In some embodiments of the application, in step (1), the content of heavy metals other than calcium and magnesium ions in the manganese sulfate crude liquid is not more than 5ppm.
In some embodiments of the application, in step (1), the manganese-containing pH adjuster comprises at least one of manganese carbonate and manganese metal powder.
In some embodiments of the application, in step (1), the fluorine source comprises at least one of hydrofluoric acid and manganese fluoride.
In some embodiments of the present application, after the fluorine-containing filter residue is returned to step (1) and the regenerated fluorine liquid is returned to step (1), in step (1), the pH of the mixed system of the manganese sulfate raw liquid, the fluorine source, the manganese-containing pH adjustor, the fluorine-containing filter residue, and the regenerated fluorine liquid is 4.5 to 7. Therefore, the calcium and magnesium in the manganese sulfate solution can be reduced to the qualified requirement.
In some embodiments of the present application, after the fluorine-containing filter residue is returned to the step (1) and the regenerated fluorine liquid is returned to the step (1), in the step (1), the reaction temperature of the mixed system of the manganese sulfate crude liquid, the regenerated fluorine liquid, the fluorine-containing filter residue, the fluorine source and the manganese-containing pH adjuster is 40 ℃ to 95 ℃ and the reaction time is 1h to 8h. Therefore, calcium and magnesium ions can be effectively removed, and the production energy consumption is reduced.
In some embodiments of the application, in step (1), the calcium and magnesium content of the fluorine-containing manganese sulfate solution are each independently no greater than 20ppm. Thus, it was demonstrated that calcium and magnesium in the fluorine-containing manganese sulfate solution were removed as much as possible.
In some embodiments of the application, in step (1), the fluorine content of the fluorine-containing manganese sulfate solution is not greater than 1000ppm. This means that the amount of fluorine source is controlled within the range actually required.
In some embodiments of the application, in step (2), the aluminum compound is added in an amount of 20g/L to 80g/L based on the volume of the fluorine-containing manganese sulfate solution. Thereby facilitating the removal of fluoride ions from the fluorine-containing manganese sulfate solution.
In some embodiments of the application, in step (2), the aluminum compound comprises at least one of aluminum sulfate octadecanoate, aluminum nitrate, aluminum chloride, aluminum dihydrogen phosphate.
In some embodiments of the application, in step (2), the reaction temperature of the mixed system of the fluorine-containing manganese sulfate solution, the aluminum compound and the manganese-containing pH regulator is 40-95 ℃ and the reaction time is 1-8 h. Thereby facilitating the removal of fluoride ions from the fluorine-containing manganese sulfate solution.
In some embodiments of the application, the endpoint pH of the mixed system of the magnesium-fluoride-containing manganese sulfate solution, the aluminum compound, and the manganese-containing pH adjuster is between 4.5 and 7. Thereby facilitating the removal of fluoride ions from the fluorine-containing manganese sulfate solution.
In some embodiments of the application, the fluorine content of the manganese sulfate solution is no greater than 25ppm. This indicates that fluoride ions in the manganese sulfate solution have been removed as much as possible.
In some embodiments of the application, in step (3), the pH of the regenerated fluorine liquid is between 0.5 and 3. Thereby, the yield of the regenerated fluorine liquid can be improved.
In some embodiments of the present application, in step (3), the content of fluoride ions in the regenerated fluorine liquid is 0.5wt% to 5wt%.
In some embodiments of the application, in step (3), the manganese content in the regenerated fluorine liquid is not less than 60g/L.
In some embodiments of the application, in step (3), the mass ratio of the fluorine-containing mixed slag to the water is (1-3): 1 when the fluorine-containing mixed slag is slurried with the water. Thus, fluorine can be separated from the fluorine-containing mixed slag well, and the reaction can be performed normally without causing expansion of the water system.
In some embodiments of the application, in step (3), the acid comprises hydrochloric acid or sulfuric acid.
In some embodiments of the application, in step (3), the concentration of the acid is 1mol/L to 12mol/L. Thereby being beneficial to acidification of the fluorine-containing mixed slag.
In some embodiments of the application, in step (3), the acidification time is between 1h and 8h. Thereby being beneficial to acidification of the fluorine-containing mixed slag.
In some embodiments of the application, in step (3), the mass ratio of the fluorine-containing calcium magnesium slag to the fluorine-containing mixed slag is no greater than 0.6. Therefore, the emission of the fluorine-containing mixed slag is reduced, and the harmless treatment of the fluorine-containing calcium magnesium slag is realized.
In some embodiments of the application, in step (3), the fluoride ion content of the leachate after leaching the fluorine-containing calcium magnesium slag with 20 times of water is not more than 100ppm. Thus, the harmless treatment of the fluorine-containing calcium magnesium slag is realized.
In some embodiments of the present application, after the fluorine-containing filter residue returns to the step (1) and the regenerated fluorine liquid returns to the step (1), the addition amount of the fluorine source is 0.9 to 1.3 times of the theoretical amount of the fluorine source added when the manganese sulfate crude liquid removes calcium and magnesium.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow chart of a method for removing calcium and magnesium from manganese sulfate at low cost according to an embodiment of the application.
Detailed Description
The following detailed description of the embodiments of the application is intended to be illustrative of the application and is not to be taken as limiting the application.
In one aspect of the application, the application provides a method for removing calcium and magnesium from manganese sulfate at low cost. Referring to fig. 1, according to an embodiment of the present application, the method includes:
s100: mixing the manganese sulfate crude liquid, fluorine source and manganese-containing pH regulator
In the step, manganese sulfate crude liquid, a fluorine source and a manganese-containing pH regulator are mixed, the pH of the mixed system is regulated to be 4.5-7, the reaction temperature of the mixed system is 40-90 ℃ and the reaction time is 1-8 h. Calcium ions, magnesium ions and fluoride ions generate calcium fluoride and magnesium fluoride precipitates, and then the precipitates are filtered, so that fluorine-containing mixed slag and fluorine-containing manganese sulfate solution are obtained.
The manganese sulfate crude liquid is a manganese sulfate solution obtained by leaching feed-grade manganese sulfate or manganese ore with sulfuric acid to remove heavy metals. Wherein the manganese content in the manganese sulfate crude liquid is 100 g/L-180 g/L; the content of other heavy metals except calcium and magnesium ions in the manganese sulfate crude liquid is not more than 5ppm, wherein the heavy metals comprise iron, nickel and the like. The fluorine source and the manganese-containing pH adjuster are materials conventional in the art, and may be selected according to the actual practice by those skilled in the art, for example, the manganese-containing pH adjuster includes at least one of manganese carbonate and manganese metal powder, and the fluorine source includes at least one of hydrofluoric acid and manganese fluoride.
S200: mixing the fluorine-containing manganese sulfate solution, the aluminum compound and the manganese-containing pH regulator
In the step, the fluorine-containing manganese sulfate solution, the aluminum compound and the manganese-containing pH regulator obtained in the step S100 are mixed, the reaction temperature of the mixed system is 40-95 ℃, the reaction time is 1-8 h, and the end point pH of the mixed system is 4.5-7. The aluminum compound is used for removing fluoride ions in the fluorine-containing manganese sulfate solution, and specific reactions are as follows: al (Al) 3+ +3H 2 O＝Al(OH) 3 +3H + (pH≥4.5)；Al(OH) 3 +XF - ＝Al(OH) 3-X F X ↓+X(OH) - (pH. Gtoreq. 4.5), and then filtering to obtain a fluorine-containing residue (Al (OH) 3-X F X ) And manganese sulfate solution, and returning the fluorine-containing filter residue to the step S100. The inventor finds that the fluorine-containing filter residue returns to the step S100, namely, manganese sulfate crude liquid, a fluorine source, a manganese-containing pH regulator and the fluorine-containing filter residue are mixed, the fluorine-containing filter residue can be used as a sedimentation-assisting filter aid, calcium ions and magnesium ions can be promoted to form sediment, and the use amount of fluorine ions is reduced, so that the use amount of aluminum compounds in the subsequent working procedures is reduced.
According to an embodiment of the present application, the aluminum compound is added in an amount of 20g/L to 80g/L based on the volume of the fluorine-containing manganese sulfate solution. The inventor finds that the fluorine of the manganese sulfate solution obtained after defluorination is higher and the requirement of the qualified solution is difficult to reach based on the volume of the fluorine-containing manganese sulfate solution; if the amount of the aluminum compound added is too large, aluminum remains in the solution after defluorination, and the consumption is large. Therefore, the addition amount of the aluminum compound is 20 g/L-80 g/L based on the volume of the fluorine-containing manganese sulfate solution, which is favorable for removing fluorine ions in the fluorine-containing manganese sulfate solution and reducing the fluorine content in the manganese sulfate solution. Further, the fluorine content in the manganese sulfate solution is not more than 25ppm, indicating that fluorine ions in the manganese sulfate solution have been removed as much as possible. The aluminum compound is a material conventional in the art, for example, the aluminum compound includes at least one of aluminum sulfate octadecanoate, aluminum nitrate, aluminum chloride, aluminum dihydrogen phosphate.
S300: mixing fluorine-containing mixed slag with water to slurry, and adding acid to acidify
In this step, the fluorine-containing mixed slag is slurried with water, and since the fluorine-containing residue in S200 is returned to S100, the fluorine-containing residue is present in the fluorine-containing mixed slag, and the fluorine-containing mixed slag is acidified by adding an acid to acidify the fluorine-containing residue (Al (OH) 3-X F X ) The fluorine ions in the catalyst are dissociated, and the specific reactions are as follows: al (OH) 3-X F X +0.5XH 2 SO 4 ＝Al(OH) 3-X (SO 4 ) 0.5X +xhf; and filtering to obtain regenerated fluorine liquid and fluorine-containing calcium magnesium slag, returning the regenerated fluorine liquid to the S100, and further reacting, wherein the fluorine-containing filter residue in the S200 is simultaneously returned to the S100, namely, the manganese sulfate crude liquid, the fluorine source, the manganese-containing pH regulator, the fluorine-containing filter residue and the regenerated fluorine liquid are mixed for reaction, and part of fluorine sources can be replaced because fluorine ions are contained in the regenerated fluorine liquid. On one hand, the addition amount of the fluorine source is reduced, so that the consumption of the fluorine source is close to the theoretical consumption of the calcium and magnesium removal fluorine source, and particularly, the addition amount of the fluorine source is 0.9-1.3 times of the theoretical consumption of the fluorine source added when the calcium and magnesium removal is carried out on the manganese sulfate crude liquid, thereby saving more than half of the consumption of the fluorine source; on the other hand, the full utilization of the fluorine-containing filter residue is realized, and the content of fluorine is reducedThe discharge amount of the fluorine mixed slag realizes the harmless treatment of the fluorine-containing calcium magnesium slag. Specifically, the mass ratio of the fluorine-containing calcium magnesium slag to the fluorine-containing mixed slag is not more than 0.6. After the fluorine-containing calcium magnesium slag is leached by water which is 20 times, the fluorine ion content of the leaching solution is not more than 100ppm. Further illustrates that the fluorine-containing calcium magnesium slag realizes harmless treatment.
According to the embodiment of the application, when the fluorine-containing mixed slag and water are mixed and pulped, the mass ratio of the fluorine-containing mixed slag to the water is (1-3): 1. The inventor finds that the mass ratio of the fluorine-containing mixed slag to the water is too large, so that the fluorine separation effect is poor and stirring is difficult; when the mass ratio of the fluorine-containing mixed slag to water is too small, the water consumption is large, and the water system expands. Thus, the mass ratio of the fluorine-containing mixed slag to water is (1-3): 1, fluorine can be separated from the fluorine-containing mixed slag well, and the reaction can be carried out normally without causing expansion of the water system. Further, the concentration of the acid is 1mol/L to 12mol/L, the pH end point of the mixed slurry can be adjusted to 0.5 to 3 in the above range, and the regeneration and separation of fluoride ions can be realized without water expansion. Specifically, the acid includes hydrochloric acid or sulfuric acid.
According to an embodiment of the application, the acidification time is 1-8 h. The inventor finds that the acidification time is too short, so that the fluoride ion regeneration and separation effect is poor; if the acidification time is too long, the process efficiency is low and the regeneration and separation of fluoride ions are not improved. Therefore, the acidification time adopted by the application is 1-8 hours, so that the acidification efficiency of the fluorine-containing mixed slag is improved. Further, the content of fluoride ions in the regenerated fluorine liquid is 0.5-5 wt%. The pH of the regenerated fluorine liquid is 0.5-3. The manganese content in the regenerated fluorine liquid is not less than 60g/L.
According to the embodiment of the application, after the fluorine-containing filter residue is returned to S100 and the regenerated fluorine liquid is returned to S100, the reaction temperature of a mixed system of the manganese sulfate crude liquid, a fluorine source, a manganese-containing pH regulator and the fluorine-containing filter residue and the regenerated fluorine liquid is 40-95 ℃ and the reaction time is 1-8 h. The inventor finds that the reaction temperature of the mixed system is too low and the reaction time is too short, so that the effect of removing calcium and magnesium is poor; the reaction temperature of the mixed system is too high and the reaction time is too long, so that the production energy consumption is high and the efficiency is low. Therefore, the application adopts a mixed system with the reaction temperature of 40-95 ℃ and the reaction time of 1-8 hours, can effectively remove calcium and magnesium ions, and reduces the production energy consumption. Further, after the fluorine-containing filter residue is returned to S100 and the regenerated fluorine liquid is returned to S100, the pH of a mixed system of the manganese sulfate crude liquid, the fluorine source, the manganese-containing pH regulator and the fluorine-containing filter residue and the regenerated fluorine liquid is 4.5-7, so that calcium and magnesium in the manganese sulfate solution can be reduced to the qualified requirement.
According to the embodiment of the application, after the fluorine-containing filter residue is returned to S100 and the regenerated fluorine liquid is returned to S100, the manganese sulfate crude liquid, the fluorine source, the manganese-containing pH regulator, the fluorine-containing filter residue and the regenerated fluorine liquid are mixed to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution, and the contents of calcium and magnesium in the fluorine-containing manganese sulfate solution are respectively and independently not more than 20ppm, which indicates that the calcium and magnesium in the fluorine-containing manganese sulfate solution are removed as much as possible. The fluorine content in the fluorine-containing manganese sulfate solution is not more than 1000ppm, which means that the fluorine source dosage in S100 is controlled in the range of practical application.
Therefore, the method can fully utilize the fluorine-containing filter residues, not only reduces the use amount of aluminum compounds, but also greatly reduces the use amount of fluorine sources, obviously reduces the production cost, and realizes the harmless treatment of fluorine-containing calcium magnesium residues.
The application will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
(1) Selecting an experimental sample, and measuring and concentrating 2.5 liters of heavy metal manganese sulfate crude liquid, wherein the components comprise 120g/L of manganese, 4.1ppm of iron, 2.01ppm of cobalt, 2.34ppm of nickel, 1.35ppm of zinc, 402.2ppm of calcium, 1540.7ppm of magnesium, 7.26ppm of potassium, 26.15ppm of sodium, 14.31ppm of aluminum and pH6.2;
(2) Mixing 18.75g of manganese sulfate crude liquid, 18.75g of hydrofluoric acid (solute mass fraction 40%) and 20g of manganese metal powder in the step (1), adjusting the pH value of the mixed system to 5, and obtaining fluorine-containing mixed slag and fluorine-containing manganese sulfate solution after the reaction is carried out at 70 ℃ for 3 hours;
(3) Mixing the fluorine-containing manganese sulfate solution in the step (2), 32g of aluminum sulfate octadecanoate and 8g of manganese metal powder, wherein the pH of the reaction end point of the mixed system is 5, the reaction temperature of the mixed system is 85 ℃, the reaction time is 2 hours, and obtaining fluorine-containing filter residues and manganese sulfate solution, and the mass of the fluorine-containing filter residues is 55g;
(4) Returning the fluorine-containing filter residue in the step (3) to the step (2), and repeating the reaction of the step (2) to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution, wherein the mass of the fluorine-containing mixed slag is 75g;
(5) Mixing the fluorine-containing mixed slag in the step (4) with water of the same weight, pulping, acidifying and leaching with concentrated sulfuric acid at normal temperature, wherein the concentration of the concentrated sulfuric acid is 12mol/L, the acidification time is 1h, the pH of the final leaching solution is 3, leaching filtrate (regenerated fluorine liquid) returns to the step (2), the obtained fluorine-containing calcium magnesium slag is washed three times with water of 3:1 liquid-solid ratio, the regenerated fluorine liquid is 200ml, and the components are 80.08 g/L of manganese and 3.1wt% of fluorine;
(6) Repeating the process operation, returning the fluorine-containing filter residues in the step (3) to the step (2) and the regenerated fluorine liquid in the step (5), adding 8 g/L of metal manganese powder and 7.5 g/L of hydrofluoric acid (solute mass fraction 40%) to mix and react according to 2.5 liters of manganese sulfate crude liquid, reacting at 40 ℃ for 2 hours, wherein the pH value of a mixed system is 6, and filtering to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution, wherein the fluorine-containing manganese sulfate solution is 2.3L, and the components of the fluorine-containing mixed slag and the fluorine-containing manganese sulfate solution are manganese 129.33g/L, iron 2.23ppm, cobalt 3.73ppm, nickel 3.9ppm, zinc 2.3ppm, potassium 2.91ppm, sodium 2.1ppm, calcium 19ppm, magnesium 17.83ppm, aluminum 70ppm, fluorine 814ppm and pH value of the fluorine-containing mixed slag and the fluorine-containing manganese sulfate solution is 6.2;
(7) Adding water with the same weight into the fluorine-containing mixed slag in the step (6), leaching the mixed slag with concentrated sulfuric acid at normal temperature to ensure that the final leaching pH value is 3, obtaining 300mL of regenerated fluorine liquid and fluorine-containing calcium magnesium slag, returning the regenerated fluorine liquid to the next calcium and magnesium removal process, washing the fluorine-containing calcium magnesium slag for three times with water with a liquid-solid ratio of 3:1, wherein the regenerated fluorine liquid comprises 91 g/L of manganese and 2.2wt% of fluorine, the dry weight of the fluorine-containing mixed slag is 75g, and the dry weight of the fluorine-containing calcium magnesium slag is 42 g;
(8) Adding 12.5 g of metal manganese powder and 50 g of aluminum sulfate octadecanoate into the fluorine-containing manganese sulfate solution in the step (6), wherein the reaction temperature is 85 ℃, the reaction time is 2 hours, the end point pH value is 4.5, the fluorine-containing filter residue and manganese sulfate solution are obtained after filtering, the manganese sulfate solution is 2.1 liters, and the components of the fluorine-containing filter residue and manganese sulfate solution are 139.74 g/liter, 2.11ppm of iron, 3.2ppm of nickel, 1.7ppm of zinc, 3.18ppm of cobalt, 3.61ppm of potassium, 2.42ppm of sodium, 18.95ppm of calcium, 11.12ppm of magnesium, 64.41ppm of aluminum and 24.7ppm of fluorine, and the fluorine-containing filter residue returns to the next calcium and magnesium removal process.
In example 1, 18.75g (40% hydrofluoric acid-solute mass fraction 40%) of a fluorine source was used to remove calcium and magnesium ions from 2.5 liters of a manganese sulfate crude liquid.
Comparative example 1
(1) Selecting an experimental sample, and measuring and concentrating 2.5 liters of heavy metal manganese sulfate crude liquid, wherein the components comprise 120g/L of manganese, 4.1ppm of iron, 2.01ppm of cobalt, 2.34ppm of nickel, 1.35ppm of zinc, 402.2ppm of calcium, 1540.7ppm of magnesium, 7.26ppm of potassium, 26.15ppm of sodium, 14.31ppm of aluminum and pH6.2;
(2) Mixing 56.25g of manganese sulfate crude liquid, 56.25g of hydrofluoric acid (solute mass fraction 40%) and 35g of manganese metal powder in the step (1), adjusting the pH of the mixed system to 6, reacting at 40 ℃ for 2 hours to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution, wherein 2.2L of fluorine-containing manganese sulfate solution comprises 125.33g/L of manganese, 2.8ppm of iron, 4.73ppm of cobalt, 3.5ppm of nickel, 3.3ppm of zinc, 3.91ppm of potassium, 6.1ppm of sodium, 3.5ppm of calcium, 20.63ppm of magnesium, 60ppm of aluminum, 1100ppm of fluorine and pH6;
(3) Mixing the fluorine-containing manganese sulfate solution in the step (2), 99g of aluminum sulfate octadecanoate and 24.5g of manganese metal powder, wherein the pH of the reaction end point is 4.5, the reaction temperature of the mixed system is 85 ℃, the reaction time is 2 hours, and fluorine-containing filter residues and manganese sulfate solution are obtained, and 2.16 liters of manganese sulfate solution are obtained, wherein the components of the fluorine-containing manganese sulfate solution comprise 135.74 g/liter, 3.11ppm of iron, 4.2ppm of nickel, 1.9ppm of zinc, 2.18ppm of cobalt, 4.61ppm of potassium, 2.8ppm of sodium, 24.5ppm of calcium, 21.12ppm of magnesium, 64.41ppm of aluminum and 40ppm of fluorine.
Comparative example 1 a 2.5 liter crude manganese sulfate solution was treated using conventional techniques using 56.25g (40% hydrofluoric acid-solute mass fraction 40%) of a fluorine source.
Example 2
(1) Selecting an experimental sample, and measuring and concentrating 5 liters of heavy metal manganese sulfate crude liquid, wherein the components of the manganese sulfate crude liquid comprise 140g/L of manganese, 2.1ppm of iron, 3.01ppm of cobalt, 2.8ppm of nickel, 2.35ppm of zinc, 800.2ppm of calcium, 3000.7ppm of magnesium, 5.26ppm of potassium, 18.15ppm of sodium, 20.31ppm of aluminum and pH5.8;
(2) Mixing the manganese sulfate crude liquid in the step (1), 75g of manganese fluoride and 80g of manganese carbonate powder, adjusting the pH value of the mixed system to 6, and obtaining fluorine-containing mixed slag and fluorine-containing manganese sulfate solution, wherein the reaction temperature is 80 and the reaction time is 4;
(3) Mixing the fluorine-containing manganese sulfate solution in the step (2), 65g of aluminum sulfate octadecanoate and 18g of manganese metal powder, adjusting the pH value of the mixed system to 4.5, and reacting at 85 ℃ for 2 hours to obtain fluorine-containing filter residues and manganese sulfate solution, wherein the mass of the fluorine-containing filter residues is 76g;
(4) Returning the fluorine-containing filter residue in the step (3) to the step (2), and repeating the reaction of the step (2) to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution, wherein the mass of the fluorine-containing mixed slag is 100g;
(5) Mixing the fluorine-containing mixed slag in the step (4) with water of the same weight, pulping, acidifying and leaching with concentrated sulfuric acid at normal temperature, wherein the concentration of the concentrated sulfuric acid is 5mol/L, the acidification time is 1h, the pH of the final leaching solution is 3, leaching filtrate (regenerated fluorine liquid) returns to the step (2), the obtained fluorine-containing calcium magnesium slag is washed three times with water of 3:1 liquid-solid ratio, the regenerated fluorine liquid is 600ml, and the components are 91.08 g/L of manganese and 2.1wt% of fluorine;
(6) Repeating the process operation, returning the fluorine-containing filter residues in the step (3) to the step (2) and the regenerated fluorine liquid in the step (5), adding 16 g/L manganese carbonate powder and 15 g/L manganese fluoride according to 5 liters of manganese sulfate crude liquid, mixing and reacting at the reaction temperature of 95 ℃ for 4 hours, wherein the pH value of a mixed system is 5.5, filtering to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution, wherein the fluorine-containing manganese sulfate solution is 4.7L, and the components of the fluorine-containing mixed slag and the fluorine-containing manganese sulfate solution are manganese 120.43g/L, iron 3.23ppm, cobalt 2.73ppm, nickel 3.2ppm, zinc 3.3ppm, potassium 8.91ppm, sodium 10.1ppm, calcium 16.5ppm, magnesium 18.83ppm, aluminum 56ppm, fluorine 910ppm and pH5.8;
(7) Adding water with the same weight into the fluorine-containing mixed slag in the step (6), leaching the mixed slag with concentrated sulfuric acid at normal temperature to ensure that the final leaching pH value is 1, obtaining 800mL of regenerated fluorine liquid and fluorine-containing calcium magnesium slag, returning the regenerated fluorine liquid to the next calcium and magnesium removal process, washing the fluorine-containing calcium magnesium slag for three times with water with a liquid-solid ratio of 3:1, wherein the components of the regenerated fluorine liquid are 72 g/L manganese and 1.8wt% fluorine, the dry weight of the fluorine-containing mixed slag is 160 g, and the dry weight of the fluorine-containing calcium magnesium slag is 89 g;
(8) Adding 9.8 g/L manganese carbonate powder, 20g/L aluminum sulfate octadecabydrate into the fluorine-containing manganese sulfate solution in the step (6), wherein the reaction temperature is 50 ℃, the reaction time is 4 hours, the end point pH value is 5.5, the fluorine-containing filter residue and manganese sulfate solution are obtained after filtering, the manganese sulfate solution is 4.4 liters, and the components of the fluorine-containing filter residue and manganese sulfate solution are 139.74 g/liter, 3.11ppm of iron, 1.2ppm of nickel, 2.7ppm of zinc, 2.18ppm of cobalt, 2.61ppm of potassium, 7.42ppm of sodium, 13.95ppm of calcium, 16.12ppm of magnesium, 30.41ppm of aluminum and 27.7ppm of fluorine, and the fluorine-containing filter residue returns to the next calcium and magnesium removal process.
In example 2, 5 liters of calcium and magnesium ions in the crude manganese sulfate solution were removed, and 75g of a fluorine source (manganese fluoride) was used.
Comparative example 2
(1) Selecting an experimental sample, and measuring and concentrating 5 liters of heavy metal manganese sulfate crude liquid, wherein the components of the manganese sulfate crude liquid comprise 140g/L of manganese, 2.1ppm of iron, 3.01ppm of cobalt, 2.8ppm of nickel, 2.35ppm of zinc, 800.2ppm of calcium, 3000.7ppm of magnesium, 5.26ppm of potassium, 18.15ppm of sodium, 20.31ppm of aluminum and pH5.8;
(2) Mixing the manganese sulfate crude liquid in the step (1), 255g of manganese fluoride and 175g of manganese carbonate powder, adjusting the pH of the mixed system to 6, reacting at 95 ℃ for 4 hours to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution, wherein the fluorine-containing manganese sulfate solution is 4.5L, and the components of the fluorine-containing mixed slag and the fluorine-containing manganese sulfate solution are 120.33g/L of manganese, 2.2ppm of iron, 4.1ppm of cobalt, 3.9ppm of nickel, 4.3ppm of zinc, 3.1ppm of potassium, 16.1ppm of sodium, 28.5ppm of calcium, 30.13ppm of magnesium, 80ppm of aluminum, 980ppm of fluorine and pH6.2;
(3) Mixing the fluorine-containing manganese sulfate solution in the step (2), 396g of aluminum sulfate octadecanoate and 94.5g of manganese metal powder, wherein the pH of the reaction end point is 5, the reaction temperature of the mixed system is 50 ℃, the reaction time is 4 hours, and 4.3 liters of fluorine-containing filter residues and manganese sulfate solution are obtained, and the components of the manganese sulfate solution are 145.74 g/liter, 2.11ppm of iron, 3.2ppm of nickel, 4.9ppm of zinc, 3.18ppm of cobalt, 14.61ppm of potassium, 12.8ppm of sodium, 28ppm of calcium, 31.2ppm of magnesium, 60.41ppm of aluminum and 35ppm of fluorine.
In comparative example 2, 255g of a fluorine source (manganese fluoride) was used to remove calcium and magnesium ions from 5 liters of the manganese sulfate crude liquid.
Comparative example 1 a 2.5L crude manganese sulphate solution was treated by conventional techniques using 56.25g (40% hydrofluoric acid-solute mass fraction 40%) of a fluorine source to remove calcium and magnesium ions and bring the calcium and magnesium content to standard. Whereas example 1 used the process of the present application to remove calcium and magnesium ions from 2.5 liters of crude manganese sulfate, 18.75g (40% hydrofluoric acid-solute mass fraction) of fluorine source was used. Comparative example 2 calcium and magnesium ions were removed from 5 liters of the crude manganese sulfate solution, and 255g of a fluorine source (manganese fluoride) was used. Example 2 calcium and magnesium ions were removed from 5 liters of a crude manganese sulfate solution, and 75g of a fluorine source (manganese fluoride) was used. It can be seen that the amount of fluorine source used is significantly reduced after the process of the present application compared to the amount of fluorine source used in the prior art, indicating that the cost can be significantly saved by employing the process of the present application.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (10)
1. A method for removing calcium and magnesium from manganese sulfate at low cost, comprising the steps of:
(1) Mixing the manganese sulfate crude liquid, a fluorine source and a manganese-containing pH regulator so as to obtain fluorine-containing mixed slag and fluorine-containing manganese sulfate solution;
(2) Mixing the fluorine-containing manganese sulfate solution, an aluminum compound and the manganese-containing pH regulator to obtain the fluorine-containing filter residue and manganese sulfate solution, and returning the fluorine-containing filter residue to the step (1);
(3) And (3) mixing the fluorine-containing mixed slag with water for pulping, adding acid for acidification to obtain the regenerated fluorine liquid and fluorine-containing calcium magnesium slag, and returning the regenerated fluorine liquid to the step (1).
2. The method according to claim 1, wherein in the step (1), the manganese content in the manganese sulfate crude liquid is 100g/L to 180g/L;
optionally, the content of other heavy metals except calcium and magnesium ions in the manganese sulfate crude liquid is not more than 5ppm;
optionally, the manganese-containing pH adjuster comprises at least one of manganese carbonate and manganese metal powder;
optionally, the fluorine source comprises at least one of hydrofluoric acid and manganese fluoride.
3. The method according to claim 1, wherein after the return of the fluorine-containing filter residue to step (1) and the return of the regenerated fluorine liquid to step (1), the pH of the mixed system of the manganese sulfate raw liquid, the fluorine source, the manganese-containing pH adjustor, the fluorine-containing filter residue and the regenerated fluorine liquid is 4.5 to 7 in step (1);
optionally, the reaction temperature of the mixed system of the manganese sulfate crude liquid, the regenerated fluorine liquid, the fluorine-containing filter residue, the fluorine source and the manganese-containing pH regulator is 40-95 ℃ and the reaction time is 1-8 h.
4. The method of claim 1, wherein in step (1), the calcium and magnesium content of the fluorine-containing manganese sulfate solution are each independently not more than 20ppm;
optionally, the fluorine content of the fluorine-containing manganese sulfate solution is not more than 1000ppm.
5. The method according to claim 1, wherein in the step (2), the aluminum compound is added in an amount of 20g/L to 80g/L based on the volume of the fluorine-containing manganese sulfate solution;
optionally, the aluminum compound comprises at least one of aluminum sulfate octadecanoate, aluminum nitrate, aluminum chloride, aluminum dihydrogen phosphate.
6. The method according to claim 1, wherein in the step (2), the reaction temperature of the mixed system of the fluorine-containing manganese sulfate solution, the aluminum compound and the manganese-containing pH adjuster is 40 ℃ to 95 ℃ and the reaction time is 1h to 8h;
optionally, the end point pH of the mixed system of the fluorine-containing magnesium manganese sulfate solution, the aluminum compound and the manganese-containing pH regulator is 4.5-7;
optionally, the fluorine content in the manganese sulfate solution is no greater than 25ppm.
7. The method according to claim 1, wherein in the step (3), the pH of the regenerated fluorine liquid is 0.5 to 3;
optionally, the content of fluoride ions in the regenerated fluorine liquid is 0.5-5 wt%;
optionally, the manganese content in the regenerated fluorine liquid is not less than 60g/L.
8. The method according to claim 1, wherein in the step (3), when the fluorine-containing mixed slag is slurried with the water, the mass ratio of the fluorine-containing mixed slag to the water is (1-3): 1;
optionally, the acid comprises hydrochloric acid or sulfuric acid;
optionally, the concentration of the acid is 1mol/L to 12mol/L;
optionally, the acidification time is 1 to 8 hours.
9. The method according to claim 1, wherein in step (3), the mass ratio of the fluorine-containing calcium magnesium slag to the fluorine-containing mixed slag is not more than 0.6;
optionally, after the fluorine-containing calcium magnesium slag is leached with 20 times of water, the fluorine ion content of the leaching solution is not more than 100ppm.
10. The method according to claim 1, wherein after the fluorine-containing filter residue is returned to the step (1) and the regenerated fluorine liquid is returned to the step (1), the fluorine source is added in an amount which is 0.9 to 1.3 times the theoretical amount of the fluorine source added when the calcium and magnesium are removed from the manganese sulfate crude liquid.
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