CN117423831A - Zero-emission recycling method for electrolytic manganese slag - Google Patents
Zero-emission recycling method for electrolytic manganese slag Download PDFInfo
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- CN117423831A CN117423831A CN202311356449.7A CN202311356449A CN117423831A CN 117423831 A CN117423831 A CN 117423831A CN 202311356449 A CN202311356449 A CN 202311356449A CN 117423831 A CN117423831 A CN 117423831A
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- Prior art keywords
- manganese slag
- solid
- electrolytic manganese
- manganese
- slag
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- 239000011572 manganese Substances 0.000 title claims abstract description 174
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 164
- 239000002893 slag Substances 0.000 title claims abstract description 160
- 238000004064 recycling Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 70
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 60
- 238000011084 recovery Methods 0.000 claims abstract description 59
- 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 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 239000000706 filtrate Substances 0.000 claims abstract description 39
- 239000002244 precipitate Substances 0.000 claims abstract description 36
- 239000010405 anode material Substances 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 229940099596 manganese sulfate Drugs 0.000 claims description 26
- 239000011702 manganese sulphate Substances 0.000 claims description 26
- 235000007079 manganese sulphate Nutrition 0.000 claims description 26
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 18
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 17
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 17
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- 238000006479 redox reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 229960003638 dopamine Drugs 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 27
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 36
- 239000002184 metal Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000012535 impurity Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 9
- 238000009423 ventilation Methods 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 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
- 238000010304 firing Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- -1 iron ion Chemical class 0.000 description 4
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 208000012868 Overgrowth Diseases 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 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
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229960004838 phosphoric acid Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
The invention relates to the technical field of electrolytic manganese slag recycling, and discloses a zero-emission recycling method for electrolytic manganese slag, which comprises a solid recovery stage and a liquid recovery stage, wherein the solid recovery stage comprises the steps of sequentially carrying out wet ball milling, redox treatment and solid-liquid separation on the electrolytic manganese slag to obtain solid manganese slag and filtrate I; roasting the solid manganese slag to obtain harmless solid manganese slag; and (II) the liquid recovery stage comprises the steps of carrying out precipitation treatment on the filtrate I to obtain mixed precipitate, and then carrying out sulfuric acid dissolution treatment, hydrothermal reaction treatment and roasting treatment on the obtained mixed precipitate in sequence to obtain the carbon-coated doped lithium manganese iron phosphate anode material. According to the scheme, harmless solid manganese slag and anode materials are obtained through the electrolytic manganese slag treatment, various metal ions in the electrolytic manganese slag are fully recycled, and the recycling effect of the electrolytic manganese slag is improved; and the scheme also realizes zero emission treatment of electrolytic manganese slag, and effectively reduces environmental pollution.
Description
Technical Field
The invention relates to the technical field of electrolytic manganese slag resource utilization, in particular to a zero-emission resource utilization method of electrolytic manganese slag.
Background
The electrolytic manganese slag or the manganese slag contains a large amount of heavy metal ions such as manganese, nickel, iron, copper, zinc, cadmium, lead and the like, and the heavy metal ions are directly stored in the environment, so that waste liquid with high manganese content and acid residue can be generated due to the scouring of rainwater, and the direct discharge of the waste liquid can cause great pollution to the environment.
At present, manganese sulfate and ammonium sulfate in electrolytic manganese slag are mainly converted into purified sulfuric acid products and ammonia water for recycling, so that the recycling utilization rate of the electrolytic manganese slag is improved. As in the prior art CN114538804, a self-circulation method for recovering manganese, sulfuric acid and ammonia water by using electrolytic manganese waste residues is disclosed, namely, manganese sulfate and ammonium sulfate in electrolytic manganese residues are dissolved and produced into products for sale in a sulfuric acid leaching mode. However, the following problems still exist in the prior art: (1) The electrolytic manganese slag not only contains manganese sulfate and ammonium sulfate, but also contains metal ions such as iron, magnesium, calcium and the like, only the ammonium sulfate and the manganese sulfate are recovered in the prior art, and other resources are wasted along with the discharge of wastewater; (2) In the prior art, the amount of sulfuric acid solution added in each stage is larger, more wastewater is generated, and the energy consumption in the post-treatment process is higher. (3) The traditional method for treating electrolytic manganese slag by CaO method can be due to CaSO 4 The formation of sediment blocks the delivery pipe, resulting in low treatment efficiency and high treatment costs.
Therefore, the development of the zero-emission recycling method for the electrolytic manganese slag not only effectively makes up the defects of the prior art, but also fully recovers resources in the electrolytic manganese slag, reduces environmental pollution, and has important significance for recycling the electrolytic manganese slag.
Disclosure of Invention
The invention aims to provide a zero-emission recycling method for electrolytic manganese slag, which aims to solve the technical problem that only ammonium sulfate and manganese sulfate are recovered and the rest resources are wasted along with wastewater discharge in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme: the zero-emission recycling method of electrolytic manganese slag comprises a solid recovery stage, wherein the solid recovery stage comprises the steps of sequentially carrying out wet ball milling treatment, oxidation-reduction reaction treatment and solid-liquid separation treatment on the electrolytic manganese slag to obtain solid manganese slag and filtrate I; roasting the solid manganese slag to obtain harmless solid manganese slag; and (II) a liquid recovery stage, which comprises the steps of carrying out precipitation treatment on filtrate I to obtain mixed precipitate, and then carrying out sulfuric acid dissolution treatment, hydrothermal reaction treatment and roasting treatment on the obtained mixed precipitate in sequence to obtain the carbon-coated doped lithium manganese iron phosphate anode material.
The principle and the advantages of the scheme are as follows:
compared with the prior art that only ammonium sulfate and manganese sulfate are recycled and other resources are wasted along with waste water discharge, the method has the advantages that harmless solid manganese slag and carbon-coated doped lithium iron manganese phosphate anode materials are obtained after electrolytic manganese slag is subjected to a series of treatment, various metal ions in the electrolytic manganese slag are fully recycled, and the recycling effect is improved; and the scheme also realizes zero emission treatment of electrolytic manganese slag, and effectively reduces environmental pollution. Specifically, the electrolytic manganese slag is subjected to wet ball milling, so that metal ions in the electrolytic manganese slag can be fully mixed with an oxidant for reaction; and then mixing the ball-milled electrolytic manganese slag (liquid) with an oxidant, carrying out solid-liquid separation after oxidation-reduction reaction, so that metal ions are recycled in a stable valence state, and the pollution to the environment is reduced.
In addition, the obtained solid manganese slag is roasted at a high temperature, so that metal elements such as manganese, iron and the like are further oxidized into stable oxides with higher valence states, harmless solid manganese slag is obtained, the harmless solid manganese slag can be directly put into business, metal ions in the electrolytic manganese slag are effectively and primarily recovered, and the recycling efficiency of metals is improved.
Furthermore, this scheme carries out precipitation through the filtrate I that will contain multiple metal ion, all deposits multiple metal ion and forms mixed precipitation, effectively promotes the recycle effect of various metal ions in the filtrate I. And then carrying out sulfuric acid dissolution treatment, hydrothermal reaction treatment and roasting treatment on the obtained mixed precipitate in sequence to obtain the carbon-coated doped lithium iron manganese phosphate anode material, finally realizing commercial conversion application of various metal ions and improving the recycling effect of electrolytic manganese slag.
Preferably, the (a) solids recovery stage comprises the steps of:
step (1), fully ball-milling electrolytic manganese slag and deionized water to obtain ball-milling electrolytic manganese slag, adding an oxidant into the ball-milling electrolytic manganese slag for full oxidation-reduction reaction and solid-liquid separation, and washing with deionized water to obtain solid manganese slag and filtrate I;
and (2) circularly treating the solid manganese slag obtained in the step (1) for 3-5 times in the mode of the step (1), then sending the solid manganese slag into a high-temperature atmosphere furnace for roasting, and introducing gas to obtain harmless solid manganese slag.
The beneficial effects are that: by adopting the steps, the scheme effectively realizes zero emission recycling utilization of electrolytic manganese slag. Specifically, in the step (1), the electrolytic manganese slag is subjected to wet ball milling firstly, so that metal ions in the electrolytic manganese slag can be fully mixed with an oxidant for reaction; then mixing the electrolytic manganese slag (liquid) after ball milling with an oxidant, and carrying out solid-liquid separation after oxidation-reduction reaction; in the step (2), high-temperature roasting is adopted to effectively remove impurities in the solid manganese slag and convert metal ions in the solid manganese slag into stable metal oxides with higher valence states, so that harmless solid manganese slag is obtained, and preliminary recycling of the solid manganese slag is realized.
Preferably, the (two) liquid recovery stage comprises the steps of:
step (3), adding a precipitator containing carbonate ions into the filtrate I obtained in the step (1) and the step (2), reacting, washing with deionized water for 3-5 times, drying to obtain mixed precipitate, and mixing the washing water with the filtrate I to obtain filtrate II;
the mixed precipitate comprises precipitates of manganese carbonate, nickel carbonate, cobalt carbonate, calcium carbonate and the like, and the formation of the mixed precipitate comprises the following reaction equation:
Mn 4+ +2CO 3 2- →Mn(CO 3 ) 2 ；
Ni 2+ +CO 3 2- →NiCO 3 ；
Co 2+ +CO 3 2- →CoCO 3 ；
Mg 2+ +CO 3 2- →MgCO 3
Fe 2+ +3OH - →Fe(OH) 3 。
adding deionized water into the mixed precipitate for mixing, adding concentrated sulfuric acid into the mixed precipitate for stirring and dissolving, and filtering to remove a small amount of solid manganese slag impurities which do not react with the concentrated sulfuric acid, thereby obtaining manganese sulfate solution doped with metal ions such as iron, magnesium, calcium and the like;
step (5), dissolving phosphoric acid in diethylene glycol, dissolving lithium hydroxide monohydrate in deionized water, mixing a phosphoric acid solution and the lithium hydroxide monohydrate to form a mixed solution, and adjusting the volume of the mixed solution to the volume required by the reaction by utilizing a filtrate II, so that the reaction filtrate is effectively recycled; dropwise adding the manganese sulfate solution obtained in the step (4) into the mixed solution, and then performing hydrothermal reaction to obtain doped lithium iron manganese phosphate; the reaction equation that occurs is as follows:
Mn 4+ +Fe 3+ +Co 2+ +Ni 2+ +Mg 2+ +H 3 PO 4 +LiOH→LiMn(Fe、Co、Ni、Mg)PO 4 。
step (6), after the doped lithium manganese iron phosphate obtained in the step (5) is ultrasonically dispersed, fully mixing the doped lithium manganese iron phosphate with a carbon source solution, and filtering the mixture to obtain a carbon source coated doped lithium manganese iron phosphate precursor;
and (7) roasting the carbon source coated doped lithium iron manganese phosphate precursor obtained in the step (6) under the protection of argon to obtain the carbon coated doped lithium iron manganese phosphate anode material.
The beneficial effects are that: by adopting the steps, the scheme effectively realizes zero emission recycling utilization of electrolytic manganese slag. In the step (3), firstly, metal ions such as manganese, nickel, cobalt, iron, calcium, magnesium and the like in the filtrate I are all precipitated by adopting a precipitator containing carbonate radicals to obtain mixed precipitation (wherein, the iron is precipitated in the form of ferric hydroxide), so that the recovery effect of various metal ions in the filtrate is further improved. In the step (4), the reaction characteristic of concentrated sulfuric acid and mixed carbonate is utilized to obtain mixed sulfate solution, a small amount of solid matters which do not participate in the reaction and solid manganese slag residues are removed through filtration, and the obtained filtrate is the mixed sulfate solution with higher purity. In the step (5), phosphoric acid, lithium hydroxide monohydrate and the mixed sulfate solution obtained in the step (4) are used as raw materials for preparing doped manganese phosphate, the filtrate II obtained in the step (3) is added into the mixed solution, the volume of the reaction solution is regulated, and the doped lithium iron manganese phosphate anode material is obtained after hydrothermal reaction; the filtrate in the previous stage can not only make the reaction better, but also realize the zero emission of the whole production process. In the step (6), the doped lithium manganese iron phosphate is dispersed by ultrasonic, so that the lithium manganese iron phosphate is convenient to fully contact with carbon sources such as citric acid, glucose, dopamine and the like, and the conductivity and the performance of the anode material of the lithium manganese iron phosphate anode material coated by carbon are improved.
Preferably, in the step (1), the mass ratio of the electrolytic manganese slag to the deionized water in the wet ball milling is 1:0.2-1; the oxidant is hydrogen peroxide and sulfuric acid; the mass ratio of the ball-milling electrolytic manganese slag to the hydrogen peroxide and the sulfuric acid is 1:0.01-0.2:0.01-0.5; the mass ratio of the solid manganese slag to the water is kept at 1:1-2 during cleaning, and the temperature of the mixed substances is kept at 25-70 ℃ during mixing.
The beneficial effects are that: by adopting the arrangement, the recycling rate of various metal elements in the electrolytic manganese slag is conveniently improved. Through long-term researches, the applicant finds that excessive water consumption in wet ball milling can lead to outflow of solid manganese slag without reaching a ball milling effect, so that the recovery efficiency of metal ions in the solid manganese slag is reduced; too little water can lead to insufficient ball milling of the solid manganese slag. The inventor experiments find that when the consumption of the oxidant is excessive, the metal recycling effect of the step cannot be improved, the oxidant is wasted, and the recycling effect of metal ions is influenced by the oxidant serving as a new impurity; however, if the consumption of the oxidant is too small, most metal ions in the electrolytic manganese slag cannot be recovered, so that the primary metal recovery and utilization effect is reduced. The excessive precipitation of metal in the manganese slag can be caused by the excessive high hydrogen peroxide content or only hydrogen peroxide, and the incomplete precipitation of impurity metal in the manganese slag can be caused by the excessive low hydrogen peroxide content or only sulfuric acid, so that the metal recycling rate is reduced. Furthermore, the amount of water used in cleaning the solid manganese slag can affect the purity of the resulting solid manganese slag. Specifically, the water content is too low, impurities in the solid manganese slag cannot be cleaned, so that the subsequent application of the solid manganese slag is affected, and the water content is too high, so that the amount of filtrate I is increased, and the preparation effect of the subsequent positive electrode material is affected. Finally, the temperature of the mixed substances is kept in the mixing process, so that side reactions of impurity metals in the electrolytic manganese slag at high temperature are effectively avoided, and the recovery effect of metals in the electrolytic manganese slag is further affected. Specifically, if the temperature is too high, other side reactions of the metal oxide occur and energy is wasted, and if the temperature is too low, the metal ions in the manganese slag cannot form stable metal oxide with higher valence state, so that the stable metal oxide cannot be recovered.
Preferably, in the step (2), the roasting temperature is 700-1100 ℃, and the roasting time is 240-720 min; the gas introduced during roasting is oxygen or oxygen-argon mixed gas; the flow rate of the gas is kept between 10 and 15mL/min.
The beneficial effects are that: by adopting the arrangement, the method is convenient for fully calcining the solid manganese slag and obtaining harmless solid manganese slag. The applicant has found through long-term experiments that when the roasting temperature is too low or too high, insufficient reaction of manganese slag or other side reactions can occur. And when in calcination, gas is introduced, so that combustion is effectively assisted, and the calcination effect is improved. The flow rate of the gas is limited, so that the roasting temperature can be effectively ensured, and the influence of side reaction of metal oxides in the manganese slag on the recovery effect of metals in the manganese slag caused by the fact that the roasting temperature exceeds 1100 ℃ due to the too fast ventilation is avoided, and the insufficient roasting of the manganese slag is caused if the ventilation is too slow, so that the environment is polluted by the circulation.
Preferably, in the step (3), the precipitant is any one of sodium carbonate, sodium bicarbonate, ammonium carbonate and other carbonate containing carbonate, and the precipitant is added in such a ratio that Mn 2+ With CO 3 2- The molar ratio of (2) is 1:1-2.
The beneficial effects are that: by adopting the arrangement, the metal ions in the filtrate I can be precipitated as much as possible, so that the capture and full recycling of various metal ions are realized. And too much carbonate can lead to further reaction to generate bicarbonate compounds or decompose into carbon dioxide and water, and too little carbonate can lead to incomplete precipitation of part of metal ions, so that the recycling rate of the metal ions is reduced.
Preferably, in the step (4), the mass ratio of the mixed precipitate to the deionized water is 1:3-5, the addition amount of the concentrated sulfuric acid is 0.5-0.8 times of the mass of the mixed precipitate, and the concentration of the concentrated sulfuric acid is 98%.
The beneficial effects are that: by adopting the arrangement, the mixed precipitate is convenient to sufficiently clean and sufficiently dissolve, and the redissolution of metal ions in the precipitate is realized, so that the subsequent reaction is convenient to carry out. If the deionized water is too much, part of metal ions are filtered out, and if the deionized water is too little, the metal ions are precipitated and cannot be fully mixed and dissolved; if the added amount of the sulfuric acid is too large, the originally insoluble precipitate is partially dissolved, and if the added amount of the sulfuric acid is too small, the mixed precipitate reacted with the sulfuric acid can be filtered out as solid manganese slag impurities because the mixed precipitate is not completely reacted with the concentrated sulfuric acid.
Preferably, in the step (5), the concentration of phosphoric acid in the diethylene glycol is 0.3-3 mol/L, and the concentration of lithium hydroxide monohydrate in the deionized water is 2-5 mol/L; mixing a phosphoric acid solution and a lithium hydroxide monohydrate solution according to the proportion of 1:1-3 to form a mixed solution; the volume ratio of the manganese sulfate solution to the mixed solution is 1:1-2; the speed of dripping the manganese sulfate solution into the mixed solution is 5-10 mL/min; the hydrothermal reaction is carried out for 600-960 min at 160-200 ℃.
The beneficial effects are that: the manganese sulfate solution obtained in the scheme has the contents of manganese, iron, magnesium and calcium of about 0.1415mol/L and 0.01163 multiplied by 10 respectively -6 The scheme adopts the above arrangement, so that manganese sulfate, phosphoric acid and lithium hydroxide monohydrate can be hydrothermally formed into LiMn (Fe, mg, ca) PO 4 . And the applicant has found through long-term experiments that if the content of phosphoric acid in the phosphoric acid solution is too high, the phosphoric acid solution can further react to generate HPO 4 - Too low an ionic compound may result in incomplete reaction; excessive solute concentration in lithium hydroxide monohydrate solution results in LiMn (Fe, mg, ca) PO 4 The lower Mn ratio forms other crystal phases, and the insufficient reaction is caused by too low Mn ratio; the manganese sulfate solution can generate hydrothermal reaction when being dripped into the mixed solution, so that the agglomeration phenomenon can be caused if the dripping speed is too high, and the two solutions can not be fully mixed if the dripping speed is too low; finally, if the reaction temperature is too high, each ion in the slurry is quickly crystallized, a serious overgrowth phenomenon occurs, and if the temperature is too low, uneven particle distribution is caused, so that the synthesis effect of lithium manganese iron phosphate is reduced.
Preferably, in step (6), the carbon source is any one of citric acid, glucose, and dopamine; the molar mass ratio of the lithium iron manganese phosphate to the carbon source is 1-5:1.
Preferably, in the step (7), the firing is performed at a temperature of 600 to 900 ℃ and an argon gas flow rate of 5 to 10mL/min for 480 to 720min.
The beneficial effects are that: by adopting the arrangement, impurities in the doped lithium manganese iron phosphate precursor can be combusted fully, so that the carbon-coated doped lithium manganese phosphate anode material with higher purity and excellent performance is obtained. The applicant experiment shows that the carbon-coated doped lithium iron manganese phosphate positive electrode material prepared by the scheme has excellent cycle performance, specific discharge capacity and coulombic efficiency performance, effectively improves the performance, and realizes the recycling effect of various metal ions in electrolytic manganese slag.
Drawings
FIG. 1 is a schematic process flow diagram of a zero-emission recycling method for electrolytic manganese slag in an embodiment of the invention.
FIG. 2 is an XRD pattern of a carbon-coated doped lithium manganese phosphate positive electrode material prepared according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. Unless otherwise indicated, the technical means used in the following examples and experimental examples are conventional means well known to those skilled in the art, and the materials, reagents and the like used are all commercially available. The technical means used in the following examples are conventional means well known to those skilled in the art unless otherwise indicated.
Example 1
The scheme provides a zero-emission recycling method for electrolytic manganese slag, and the process flow is basically as shown in figure 1: the method comprises a solid recovery stage, wherein the solid recovery stage comprises the steps of sequentially carrying out wet ball milling treatment, oxidation-reduction reaction treatment and solid-liquid separation treatment on electrolytic manganese slag to obtain solid manganese slag and filtrate I; roasting the solid manganese slag to obtain harmless solid manganese slag; and (II) a liquid recovery stage, which comprises the steps of carrying out precipitation treatment on filtrate I to obtain mixed precipitate, and then sequentially carrying out sulfuric acid dissolution treatment, hydrothermal reaction treatment and roasting treatment on the obtained mixed precipitate to obtain the carbon-coated doped lithium manganese phosphate anode material, wherein XRD (X-ray diffraction) of the carbon-coated doped lithium manganese phosphate anode material is shown in figure 2.
The method specifically comprises the following steps:
solid recovery stage
Step (1), mixing electrolytic manganese slag and deionized water in a mass ratio of 1:0.2-1 (namely, the dosage of the deionized water is 0.2-1 times of the mass of the electrolytic manganese slag), fully ball-milling to obtain ball-milled electrolytic manganese slag, adding oxidant hydrogen peroxide and sulfuric acid into the ball-milled electrolytic manganese slag, wherein the adding amount is such that the mass ratio of the ball-milled electrolytic manganese slag to the hydrogen peroxide and the sulfuric acid is 1:0.01-0.2:0.01-0.5 (namely, the dosage of the hydrogen peroxide is 0.01-0.2 times of the mass of the ball-milled electrolytic manganese slag and the dosage of the sulfuric acid is 0.01-0.5 times of the mass of the ball-milled electrolytic manganese slag); solid-liquid separation is carried out after full oxidation-reduction reaction, solid manganese slag and filtrate are obtained, deionized water with the volume of 1-2 times is used for cleaning the solid manganese slag (namely, the mass ratio of the solid manganese slag to water is kept at 1:1-2 during cleaning), and cleaning water and the filtrate are combined to obtain filtrate I; in this step, the temperature of the mixed substance is maintained at 25 to 70℃during all the mixing.
Specifically, 1000g of electrolytic manganese slag is treated according to the scheme, wherein the manganese ion content is 24.502%, the magnesium ion content is 0.961%, the calcium ion content is 3.861%, and the iron ion content is 0.21%.
Step (2), circularly treating the solid manganese slag obtained in the step (1) for 3-5 times in a mode of the step (1), and then delivering the solid manganese slag into a high-temperature atmosphere furnace for roasting at a roasting temperature of 700-1100 ℃ for 240-720 min; oxygen or oxygen-argon mixed gas is introduced at the speed of 10-15 mL/min during roasting, so as to obtain harmless solid manganese slag; specifically, oxygen is introduced under the condition that the temperature is lower than 600 ℃; introducing oxygen-argon mixed gas at the temperature higher than 600 ℃, wherein the mixing ratio of oxygen to argon in the mixed gas is 1-2:1-3.
And detecting harmless solid manganese slag, wherein all metal ions exist in the form of metal highest valence stable ions, wherein the manganese content is 33.183%, the magnesium content is 0.816%, the calcium content is 0.798%, the iron content is 0.11% and the like, and most of the metal ions are primarily recovered.
The metal recovery rate was calculated as follows: metal recovery% = recovered manganese slag/electrolytic manganese slag 100%.
Examples 1 to 9 and comparative examples 1 to 11 are basically shown in the steps of example 1, wherein examples 1 to 9 show the effect of treating electrolytic manganese slag by taking values within the protection scope of the scheme; comparative examples 1 to 11 show the effect of treating electrolytic manganese slag at values outside the protection range of the scheme, and the differences and results of the parameter values in examples 1 to 9 and comparative examples 1 to 11 are shown in Table 1.
Experimental data show that the electrolytic manganese slag is treated by taking the value within the protection range of the scheme, and the higher harmless solid manganese slag yield can be obtained in the solid recovery stage, so that the higher recovery rate of metals in the manganese slag is achieved. In particular, as in example 1, the mass ratio of electrolytic manganese slag to deionized water in the wet ball milling was 1:0.5; the mass ratio of the ball-milling electrolytic manganese slag to the hydrogen peroxide and the sulfuric acid is 1:0.15, and 1:0.2; the mass ratio of the solid manganese slag to the water is kept at 1:2, and the metal recovery rate is as high as 90.4% when the temperature of the mixed substances is kept at 40 ℃ in the mixing process.
By analyzing the relation between the metal recovery rate in the electrolytic manganese slag and each process step, the applicant finds that the factors such as the wet ball milling water consumption, the hydrogen peroxide consumption, the concentrated sulfuric acid consumption, the mixing temperature, the roasting ventilation type, the roasting ventilation speed and the like are all critical to the preliminary recovery of the metal.
First, too low an amount of wet ball milling water results in insufficient ball milling of the solid manganese slag and a reduction in metal recovery in the solid manganese slag (e.g., only 78.6% in comparative example 1).
Secondly, too high/too low hydrogen peroxide or concentrated sulfuric acid is used as an oxidant, and the precipitation process of the manganese slag oxidant is also influenced, so that the metal recycling rate is reduced. If the dosage of hydrogen peroxide is too low in comparative example 2, the impurity metal in the manganese slag cannot be completely precipitated, so that the metal recycling rate is reduced (only 73.5%); the too low hydrogen peroxide consumption in comparative example 3 causes excessive precipitation of metals in the manganese slag, so that the recycling value of the recycled metals is reduced, and the recycling effect of the metals is affected (the recycling rate is reduced to 81.3%); in contrast, in comparative example 4, too much concentrated sulfuric acid was used as an oxidizing agent, so that the impurity metals in the manganese slag could not be completely precipitated, thereby reducing the metal recovery rate (only 76.9%).
Furthermore, the mixing temperature is too low, so that the metal ions in the manganese slag cannot form stable metal oxides with higher valence, the recycling rate is reduced (for example, the metal recovery rate is only 76.2% in comparative example 5), and the recycling effect is also affected;
finally, the metal recovery rate is reduced by the type and speed of aeration during the roasting, whether the roasting temperature is too high or too low, or the roasting time is too long or too short, or both. Specifically, compared with example 1, the roasting temperature in comparative example 6 is too low, and the manganese slag is not sufficiently reacted, so that the metal recycling rate is reduced (only 79.2%); too high a firing temperature in comparative example 7 would lead to decomposition of the manganese slag, thereby reducing the metal recovery rate (only 80.2%); the oxygen content of the latter half of the roasting in comparative example 8 is too low to affect the roasting effect, but the roasting effect (the metal recovery rate in comparative example 8 is 81.1%) can be properly compensated for by prolonging the roasting time; however, in comparative example 9, the aeration rate was too low, and even if the aeration rate was high, the roasting effect was still affected, but since the roasting time was prolonged, the combustion effect was properly made up (the metal recovery rate was 81.7% in comparative example 9); in comparative example 10, the ventilation speed is too high, so that the roasting temperature exceeds 1100 ℃ to decompose metal oxides in manganese slag, thereby reducing the metal recovery utilization rate (only 78.2%), and even if the roasting time is shortened, the loss cannot be compensated; the ventilation speed in comparative example 11 was too high, and even if the firing temperature was set to be far lower than 1100 ℃, the temperature was rapidly saved to be higher than 1100 ℃ during firing, so that the metal oxide in the manganese slag was decomposed, thereby reducing the metal recovery rate (only 73.5%).
Example 10
The scheme of the zero-emission recycling method for electrolytic manganese slag further comprises the following steps:
(II) liquid recovery stage
Step (3), adding a precipitant containing carbonate ions to the filtrate I obtained in the step (1) and the step (2) in the embodiment 1, wherein the precipitant is any one of sodium carbonate, sodium bicarbonate, ammonium carbonate and other carbonate containing carbonate, and the adding ratio of the precipitant is that Mn is as follows 2+ With CO 3 2- The molar ratio of (2) is 1:1-2; filtering out the precipitate, washing the precipitate with deionized water for 3-5 times, drying to obtain mixed precipitate, and mixing the washing water with the filtrate I to obtain filtrate II; the filtrate II is used for carrying out hydrothermal reaction in the step (5), so that waste liquid is fully recycled, and zero emission treatment is realized.
Adding deionized water 3-5 times of the mixed precipitate into the mixed precipitate for mixing (i.e. the mass ratio of the mixed precipitate to the deionized water is 1:3-5), adding 98% concentrated sulfuric acid 0.5-0.8 times of the mixed precipitate after mixing, stirring for dissolving, and filtering to obtain manganese sulfate solution doped with metal ions such as iron, magnesium, calcium and the like; through detection, the manganese ion content ratio of the manganese sulfate solution doped with metal ions such as iron, magnesium, calcium and the like is 55.04%, the magnesium ion content ratio is 38.23%, the calcium ion content ratio is 2.88%, and the iron ion content ratio is 4.61 multiplied by 10 -6 % and the like.
Step (5), dissolving phosphoric acid in diethylene glycol to form a phosphoric acid solution with the concentration of 0.3-3 mol/L; dissolving lithium hydroxide monohydrate in deionized water to form a lithium hydroxide monohydrate solution with the concentration of 2-5 mol/L; mixing a phosphoric acid solution and a lithium hydroxide monohydrate solution according to the proportion of 1:1-3 to form a mixed solution, and dropwise adding the manganese sulfate solution obtained in the step (4) into the mixed solution for hydrothermal reaction to obtain doped lithium iron manganese phosphate;
wherein the volume ratio of the manganese sulfate solution to the mixed solution is 1:1-2; the speed of dripping the manganese sulfate solution into the mixed solution is 5-10 mL/min; the hydrothermal reaction is carried out for 600-960 min at 160-200 ℃.
After the doped lithium iron manganese phosphate obtained in the step (6) and the ultrasonic dispersion step (5) is fully mixed and filtered with a carbon source (specifically, citric acid, glucose or dopamine is selected), so as to obtain a carbon source coated doped lithium iron manganese phosphate precursor;
and (7) roasting the doped lithium iron manganese phosphate precursor obtained in the step (6) at 600-900 ℃ for 480-720 min under the protection condition that the argon gas flow rate is 5-10 mL/min, so as to obtain the carbon-coated doped lithium iron manganese phosphate anode material.
Examples 10 to 28 and comparative examples 12 to 25 are basically shown in the steps above, wherein examples 10 to 28 show the effect of treating electrolytic manganese slag by taking values within the scope of the present invention; comparative examples 12 to 25 show the effect of treating electrolytic manganese slag by taking values outside the protection range of the scheme, and the differences of the values of the parameters in examples 10 to 28 and comparative examples 12 to 25 are shown in Table 2 in detail; the detection results are shown in Table 3.
Experimental data show that the filtrate I obtained in the solid recovery stage of the electrolytic manganese slag is treated by taking values in the protection range of the scheme, and the carbon-coated doped lithium iron manganese phosphate anode material with excellent discharge specific capacity and coulomb efficiency performance can be obtained in the liquid recovery stage, and has higher recovery utilization rate of metal ions in the manganese slag.
TABLE 3 detection results in examples 10 to 28, comparative examples 12 to 25
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Experimental data shows that the process parameters selected in example 9 of the scheme are combined according to the process steps of the schemeThe metal ions in the filtrate I obtained in the solid recovery stage of the electrolytic manganese slag are recycled, and the prepared carbon-coated doped lithium iron manganese phosphate anode material has the best performance. The selection of each technological parameter is specifically as follows: when Mn is 2+ With CO 3 2- The molar ratio of (2) is 1:1.5; the consumption of the concentrated sulfuric acid is 0.6 times, and the concentration of the phosphoric acid solution is 1mol/L; the concentration of the lithium hydroxide monohydrate solution is 3.5mol/L; the mixing ratio of the phosphoric acid solution and the lithium hydroxide monohydrate solution is 1:3; the volume ratio of the manganese sulfate solution to the mixed solution is 1:1.5; the dropping speed of the manganese sulfate solution is 8mL/min; the hydrothermal reaction temperature is 180 ℃; the hydrothermal reaction time is 720min; roasting at 750 ℃; roasting time is 720min; when the ventilation speed of the roasting protective gas is 7.5mL/min, not only can manganese ions up to 89.35 percent, magnesium ions 89.66 percent, calcium ions 88.48 percent and iron ions 90.03 percent be recovered, but also the carbon-coated doped lithium iron manganese phosphate anode material with the discharge specific capacity of 117.2mAh/g can be prepared; and the reaction speed and the reaction time can be taken into account, zero emission is achieved, better production benefits and environmental protection benefits are achieved, and the method is convenient to popularize and apply widely.
The applicant finds Mn by analyzing the relation between the metal recovery utilization rate in electrolytic manganese slag and each process step 2+ With CO 3 2- The molar ratio, the consumption of concentrated sulfuric acid, the concentration and the consumption of a phosphoric acid solution, the dropping speed of a manganese sulfate solution, the hydrothermal reaction temperature, the roasting temperature and the ventilation speed of roasting protective gas all affect the recovery rate of metal ions in filtrate I and the performance (mainly specific capacity) of the produced carbon-coated doped lithium manganese iron phosphate anode material.
Firstly, the use amount of carbonate directly causes the precipitation effect of metal ions in the filtrate I, thereby affecting the recovery rate; if the carbonate consumption is too low in comparative example 12, partial metal ions cannot be completely precipitated, the metal ion recovery and utilization rate (manganese 80.49%, magnesium 82.42%, calcium 83.54% and iron 84.14%) is reduced, and the specific capacity (only 102.1 mAh/g) of the prepared carbon-coated doped lithium iron manganese phosphate anode material is also reduced; however, too high a carbonate content in comparative example 13 would lead to further reaction to produce bicarbonate compound or to decomposition into carbon dioxide and water, so that part of the precipitated metal ions would instead be redissolved in filtrate i to reduce the content of metal ions entering the subsequent reaction in precipitated form, thereby reducing the recycling rate (83.92% manganese, 80.09% magnesium, 80.32% calcium, 84.103% iron) and reducing the specific capacity (only 94.3 mAh/g) of the prepared carbon-coated doped lithium iron manganese phosphate cathode material.
Secondly, the recovery rate of metal ions can be influenced by the consumption and delivery speed of the concentrated sulfuric acid of the redissolution mixed precipitate. For example, in comparative example 14, too little concentrated sulfuric acid can cause mixed precipitation capable of reacting with sulfuric acid to be filtered out as solid manganese slag impurities because of incomplete reaction with concentrated sulfuric acid, thereby reducing the metal ion recycling rate and also reducing the specific capacity (only 98.9 mAh/g) of the prepared carbon-coated doped lithium manganese iron phosphate positive electrode material; the excessive concentrated sulfuric acid in comparative example 15 results in partial dissolution of the originally insoluble precipitate, and also reduces the metal ion recovery and utilization rate and the specific capacity (only 98.7 mAh/g) of the prepared carbon-coated doped lithium iron manganese phosphate positive electrode material; in contrast, in comparative example 16, too slow concentrated sulfuric acid dropping speed is adopted, so that the preparation of the carbon-coated doped lithium iron manganese phosphate anode material is affected due to the fact that two solutions cannot be fully mixed, and the specific capacity is only 98.5mAh/g; the adoption of too fast concentrated sulfuric acid dropping speed in comparative example 17 can cause agglomeration phenomenon, thereby influencing the subsequent reaction, and reducing the recovery rate of metal ions and the specific capacity of the carbon-coated doped lithium iron manganese phosphate anode material.
Furthermore, the temperature of the hydrothermal reaction and the phosphoric acid content in the hydrothermal reaction can influence the recovery of metal ions, and if the temperature of the hydrothermal reaction is too low in comparative example 18, the particle distribution is uneven, so that the subsequent reaction is influenced, and the recovery of metal ions and the specific capacity of the carbon-coated doped lithium manganese iron phosphate positive electrode material are also reduced; the use of too high a reaction temperature in comparative example 19 resulted in rapid crystallization of each ion in the slurry, and a serious overgrowth phenomenon occurred, thereby affecting the progress of the subsequent reaction and reducing the recovery rate of metal ions and the specific capacity of the carbon-coated doped lithium manganese iron phosphate cathode material. In comparative example 20, the amount of phosphoric acid solution was reduced by increasing the relative proportion of the lithium hydroxide monohydrate solution in the mixed solution, while the amount of phosphorus was too lowThe acid content can cause incomplete reaction, and the content of the metal ion synthesized carbon coated doped lithium manganese iron phosphate anode material is reduced, so that the recovery rate of metal ions is reduced; in comparative example 21, the phosphoric acid in the mixed solution was excessively increased relative to the manganese sulfate solution (i.e., the phosphoric acid content was excessively high) by increasing the amount of the mixed solution, and further reacted to form HPO-containing solution 4 - The content of the metal ion synthesized carbon coated doped lithium manganese iron phosphate anode material is reduced by the ionic compound, so that the recovery rate of the metal ions is reduced;
finally, the roasting temperature and the ventilation speed of the protective gas of the carbon-coated doped lithium manganese iron phosphate anode material also influence the recovery rate of metal ions and the performance of the carbon-coated doped lithium manganese iron phosphate anode material by influencing the content or valence state of the metal ions in the finished product. Too low a firing temperature as in comparative example 22 would decrease the stability of metal ions in the carbon-coated doped lithium iron manganese phosphate positive electrode material, thereby decreasing the content of metal ions in the finished positive electrode material and thus decreasing the recovery rate of metal ions; and the too high roasting temperature of the comparative example 23 can cause the peroxidation of metal ions in the carbon-coated doped lithium manganese iron phosphate positive electrode material, so that the content of the metal ions in the finished positive electrode material is reduced, and the recovery rate of the metal ions is reduced.
The foregoing is merely exemplary of the present invention, and specific technical solutions and/or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present invention, and these should also be regarded as the protection scope of the present invention, which does not affect the effect of the implementation of the present invention and the practical applicability of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (10)
1. A zero-emission recycling method for electrolytic manganese slag is characterized by comprising the following steps of: the method comprises a solid recovery stage, wherein the solid recovery stage comprises the steps of sequentially carrying out wet ball milling treatment, oxidation-reduction reaction treatment and solid-liquid separation treatment on electrolytic manganese slag to obtain solid manganese slag and filtrate I; roasting the solid manganese slag to obtain harmless solid manganese slag; and (II) a liquid recovery stage, which comprises the steps of carrying out precipitation treatment on filtrate I to obtain mixed precipitate, and then carrying out sulfuric acid dissolution treatment, hydrothermal reaction treatment and roasting treatment on the mixed precipitate in sequence to obtain the carbon-coated doped lithium manganese iron phosphate anode material.
2. The zero-emission recycling method for electrolytic manganese slag according to claim 1, which is characterized by comprising the following steps: the solid recovery stage comprises the steps of:
step (1), fully ball-milling electrolytic manganese slag and deionized water to obtain ball-milling electrolytic manganese slag, adding an oxidant into the ball-milling electrolytic manganese slag for full oxidation-reduction reaction and solid-liquid separation, and washing with deionized water to obtain solid manganese slag and filtrate I;
and (2) circularly treating the solid manganese slag obtained in the step (1) for 3-5 times in the mode of the step (1), then sending the solid manganese slag into a high-temperature atmosphere furnace for roasting, and introducing gas to obtain harmless solid manganese slag.
3. The electrolytic manganese slag zero-emission recycling method according to claim 1 or 2, which is characterized by comprising the following steps: the (two) liquid recovery stage comprises the following steps:
step (3), adding a precipitator containing carbonate ions into the filtrate I obtained in the step (1) and the step (2), reacting, washing with deionized water for 3-5 times, drying to obtain mixed precipitate, and mixing the washing water with the filtrate I to obtain filtrate II;
adding deionized water into the mixed precipitate for mixing, adding concentrated sulfuric acid into the mixed precipitate for stirring and dissolving, and filtering to obtain manganese sulfate solution doped with metal ions such as iron, magnesium, calcium and the like;
step (5), dissolving phosphoric acid in diethylene glycol, dissolving lithium hydroxide monohydrate in deionized water, mixing a phosphoric acid solution and the lithium hydroxide monohydrate solution to form a mixed solution, dropwise adding the manganese sulfate solution obtained in the step (4) into the mixed solution, and performing hydrothermal reaction to obtain doped lithium manganese iron phosphate;
step (6), after the doped lithium manganese iron phosphate obtained in the step (5) is ultrasonically dispersed, fully mixing the doped lithium manganese iron phosphate with a carbon source solution, and filtering the mixture to obtain a carbon source coated doped lithium manganese iron phosphate precursor;
and (7) roasting the carbon source coated doped lithium iron manganese phosphate precursor obtained in the step (6) under the protection of argon to obtain the carbon coated doped lithium iron manganese phosphate anode material.
4. The zero-emission recycling method for electrolytic manganese slag according to claim 2, which is characterized by comprising the following steps: in the step (1), the mass ratio of electrolytic manganese slag to deionized water in the wet ball milling is 1:0.2-1; the oxidant is hydrogen peroxide and sulfuric acid; the mass ratio of the ball-milling electrolytic manganese slag to the hydrogen peroxide and the sulfuric acid is 1:0.01-0.2:0.01-0.5; the mass ratio of the solid manganese slag to the water is kept at 1:1-2 during cleaning, and the temperature of the mixed substances is kept at 25-70 ℃ during mixing.
5. The zero-emission recycling method for electrolytic manganese slag according to claim 2, which is characterized by comprising the following steps: in the step (2), the roasting temperature is 700-1100 ℃, and the roasting time is 240-720 min; the gas introduced during roasting is oxygen or oxygen-argon mixed gas; the flow rate of the gas is kept between 10 and 15mL/min.
6. The electrolytic manganese slag zero-emission recycling method according to claim 3, which is characterized by comprising the following steps of: in the step (3), the precipitant is any one of sodium carbonate, sodium bicarbonate, ammonium carbonate and other carbonate containing carbonate groups, and the precipitant is added in a proportion such that Mn 2+ With CO 3 2- The molar ratio of (2) is 1:1-2.
7. The electrolytic manganese slag zero-emission recycling method according to claim 3, which is characterized by comprising the following steps of: in the step (4), the mass ratio of the mixed precipitate to the deionized water is 1:3-5, the addition amount of the concentrated sulfuric acid is 0.5-0.8 times of the mass of the mixed precipitate, and the concentration of the concentrated sulfuric acid is 98%.
8. The electrolytic manganese slag zero-emission recycling method according to claim 3, which is characterized by comprising the following steps of: in the step (5), the concentration of phosphoric acid in diethylene glycol is 0.3-3 mol/L, and the concentration of lithium hydroxide monohydrate in deionized water is 2-5 mol/L; mixing a phosphoric acid solution and a lithium hydroxide monohydrate solution according to the proportion of 1:1-3 to form a mixed solution; the volume ratio of the manganese sulfate solution to the mixed solution is 1:1-2; the speed of dripping the manganese sulfate solution into the mixed solution is 5-10 mL/min; the hydrothermal reaction is carried out for 600-960 min at 160-200 ℃.
9. The electrolytic manganese slag zero-emission recycling method according to claim 3, which is characterized by comprising the following steps of: in the step (6), the carbon source is any one of citric acid, glucose and dopamine; the molar mass ratio of the lithium iron manganese phosphate to the carbon source is 1-5:1.
10. The electrolytic manganese slag zero-emission recycling method according to claim 3, which is characterized by comprising the following steps of: in the step (7), the roasting is performed for 480-720 min under the conditions of the temperature of 600-900 ℃ and the argon gas flow rate of 5-10 mL/min.
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