CN116798760B - Method and flux for preparing soft magnetic manganese zinc ferrite composite material by utilizing manganese anode slime and zinc slime - Google Patents
Method and flux for preparing soft magnetic manganese zinc ferrite composite material by utilizing manganese anode slime and zinc slime Download PDFInfo
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- CN116798760B CN116798760B CN202310850486.7A CN202310850486A CN116798760B CN 116798760 B CN116798760 B CN 116798760B CN 202310850486 A CN202310850486 A CN 202310850486A CN 116798760 B CN116798760 B CN 116798760B
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- manganese
- zinc
- sulfate
- slime
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 85
- 239000011572 manganese Substances 0.000 title claims abstract description 85
- 239000011701 zinc Substances 0.000 title claims abstract description 68
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 65
- 230000004907 flux Effects 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 34
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 51
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 51
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 51
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 51
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 45
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 45
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000000746 purification Methods 0.000 claims abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 6
- 229920002472 Starch Polymers 0.000 claims abstract description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 6
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019698 starch Nutrition 0.000 claims abstract description 6
- 239000008107 starch Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 35
- 239000012535 impurity Substances 0.000 claims description 34
- 239000013049 sediment Substances 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 30
- 239000007790 solid phase Substances 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000008213 purified water Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- OWSZUKMVEBFJMZ-UHFFFAOYSA-N benzene-1,2,3,4,5,6-hexamine Chemical compound NC1=C(N)C(N)=C(N)C(N)=C1N OWSZUKMVEBFJMZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims description 5
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- LNRYQGINUXUWLV-UHFFFAOYSA-N [Mn].[Fe].[Zn] Chemical compound [Mn].[Fe].[Zn] LNRYQGINUXUWLV-UHFFFAOYSA-N 0.000 abstract 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 abstract 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002893 slag Substances 0.000 description 15
- 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 11
- 238000002386 leaching Methods 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 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 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/342—Oxides
- H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for preparing a soft magnetic manganese zinc ferrite composite material by using manganese anode slime and zinc slime and a flux thereof, wherein the flux is prepared from 30 to 50 percent of KZrF 5 And 70-50% K 3 AlF 6 Composition is prepared. The manganese anode slime and the zinc slime are recycled in a distribution way to obtain manganese sulfate four-time purifying liquid and zinc sulfate four-time purifying liquid; mixing the two purifying solutions according to the manganese-zinc-iron ratio required by the manganese-zinc ferrite, adding ferrous sulfate, ammonium bicarbonate for coprecipitation, washing, then decomposing the coprecipitated starch into ferric oxide, manganous oxide and zinc oxide in a decomposing furnace, and roasting to obtain the manganese-zinc ferrite composite material. The purification steps are more thorough, the purities of the manganese sulfate four-time purifying liquid and the zinc sulfate four-time purifying liquid can reach more than 99.5%, and the manganese sulfate four-time purifying liquid is a high-quality raw material for preparing high-end manganese zinc ferrite.
Description
Technical Field
The invention belongs to the field of recycling of industrial wastes, and particularly relates to a method and a flux for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese anode slime and zinc slime.
Background
In the production process of electrolytic manganese metal, a large amount of anode slime is inevitably produced in the anode region of the electrolytic tank, and 0.05-0.08 ton of anode slime is produced per 1 ton of electrolytic manganese. Manganese in the anode slime mainly exists in the forms of manganese, divalent manganese, tetravalent manganese and the like, is a good manganese resource, and main impurities are sulfur, calcium, magnesium, aluminum, silicon, lead, tin, antimony and the like, so that the electrolytic manganese anode slime is complex in composition. The manganese sulfate is generally used as a pyrolusite raw material in industry and is produced by adopting an iron powder reduction method, a ferrous sulfate reduction leaching method, a two-ore roasting water leaching method or a two-ore one-step method. However, no matter what method is adopted, the solid reducing agent is added, so that the impurity removal difficulty of the manganese leaching is high, and the recovery cost is high. Therefore, at present, domestic manufacturers generally store dangerous waste residues, make steel additives or sell the dangerous waste residues at low cost, are not well developed and comprehensively utilized, not only waste resources, but also cause considerable environmental pollution due to improper treatment.
At present, the technology for industrially treating the manganese-containing waste residue and realizing the comprehensive utilization of the manganese-containing waste residue mainly adopts a fire method, a wet method and biological leaching. Wherein, the wet reduction treatment of the manganese waste residue is the treatment technology with the highest leaching rate, and is widely applied to large-scale industrial production. Because manganese dioxide in manganese waste residue is difficult to acidolysis, a reducing agent is needed to reduce manganese dioxide into low-price manganese, however, the existing extraction and reduction process for treating manganese waste residue by wet reduction still has partial defects. In order to fully reduce manganese dioxide in manganese waste residue, the fineness requirement on a reduced sample is very high (CN 1037785C), and a great amount of time and energy are consumed in the excessively fine grinding process; the molten salt fusion leaching method can remove a large amount of impurities in the manganese waste residue, and can effectively improve the leaching efficiency of manganese, but the high eutectic temperature of the existing molten salt system causes high energy consumption, and still cannot meet the clean production requirements of low carbon and environmental protection.
The industrial zinc-containing waste zinc mud generally contains a large amount of metallic element zinc, and provides possibility for preparing the manganese-zinc ferrite by recycling the industrial waste. The manganese-zinc ferrite is prepared by utilizing the solid waste rich in zinc, so that the zinc in the solid waste can be recycled, the potential hazard of the solid waste to the environment and human health can be eliminated, and the requirements of correctly treating the ecological environment protection and development relation are met. Although the recycling of related industrial wastes is expanded to various solid wastes as metal sources of the manganese-zinc ferrite, the method still has a plurality of technical problems of unsatisfactory purifying effect, environmental pollution of purifying agents, difficult source, serious main element loss caused by low purifying efficiency, high labor intensity, high energy consumption and high production cost, and the product performance is seriously affected by the agglomeration phenomenon formed by the manganese-zinc ferrite composite powder caused by coprecipitation impurity removal, so that the development requirements of electronic devices cannot be met.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a flux, and the second aim is to provide a method for preparing a soft magnetic manganese zinc ferrite composite material by using manganese anode slime and zinc slime, which can realize that the manganese anode slime and the zinc slime are prepared into the soft magnetic manganese zinc ferrite composite material, thereby achieving the aim of waste utilization and having low recovery cost.
To achieve the first object, the present invention is realized by the following technical solutions: a flux, characterized in that: consists of 30 to 50 weight percent of KZrF 5 And 70-50% K 3 AlF 6 Composition is prepared.
The second object of the present invention is achieved by: a method for preparing a soft magnetic manganese zinc ferrite composite material by using manganese anode slime and zinc slime is characterized by comprising the following steps of:
1) Recovery of manganese from electrolytic manganese anode slime
Crushing electrolytic manganese anode slime until the particle diameter is less than or equal to 5mm, drying, adding the flux according to the mass of the electrolytic manganese anode slime, uniformly mixing, wherein the mass ratio of the addition amount of the flux to the manganese-containing waste residue is 10-2: 1, placing the material into an electric furnace, heating to 390 ℃, starting to flow the material, and continuously heating to 950-1050 ℃ for roasting for 30-45 min, so as to generate solid-liquid layering; after solid-liquid separation, the solid phase sediment is fully cleaned by purified water to remove the soluble salt remained in the solid phase sediment; adding water into the solid-phase sediment to prepare slurry after cleaning, sieving the slurry with a 120-mesh sieve, putting the slurry into a reaction kettle with a cooling device, adding excessive sulfuric acid according to the manganese content in the solid-phase sediment, reducing manganese dioxide in the manganese slurry into low-valence manganese by adding a reducing agent under the protection of vacuum or inert gas at normal temperature, quickly reacting the low-valence manganese with the excessive sulfuric acid to convert all manganese into a manganese sulfate solution, and filtering to remove impurities to obtain a manganese sulfate primary purification solution; adding a flocculating agent to remove a small amount of residual aluminum and silicon in the manganese sulfate primary purification solution, and filtering to obtain a manganese sulfate secondary purification solution; adding ammonia water to adjust the pH value of the manganese sulfate solution to 5-7, obtaining manganese sulfate three-time purifying solution after filter pressing and separation, adding ammonium sulfide of 1-2 per mill (1-2 per mill of the mass of the manganese sulfate three-time purifying solution, the same shall apply hereinafter), continuously removing the rest metal ions in the manganese sulfate three-time purifying solution, and filtering to obtain high-purity manganese sulfate four-time purifying solution;
3) Recovery of zinc from zinc sludge
Crushing zinc mud until the particle diameter is less than or equal to 5mm, fully and uniformly mixing the zinc mud with a flux after drying, putting the mixture into a muffle furnace, heating the mixture to 390 ℃, starting melting the flux, gradually penetrating zinc-containing waste residues, continuously heating the mixture to 950-1050 ℃ and keeping the mixture for 30-45 min, removing a molten body fluid phase part, washing solid-phase sediment with purified water, adding excessive sulfuric acid according to the content of zinc oxide in the solid-phase sediment to obtain a zinc sulfate solution, and filtering to remove impurities to obtain a primary zinc sulfate purification solution; adding a flocculating agent to remove a small amount of aluminum and silicon remained in the primary zinc sulfate purifying solution, and filtering to obtain a secondary zinc sulfate purifying solution; adding ammonia water to adjust the pH value of the manganese sulfate solution to 5-7, and obtaining zinc sulfate three-time purifying solution after filter pressing and separation; adding ammonium sulfide of 1-2 per mill (1-2 per mill of the mass of the zinc sulfate three-time purifying solution, the same shall apply hereinafter), continuously removing metal ions in the zinc sulfate three-time purifying solution, and filtering to obtain high-purity zinc sulfate four-time purifying solution;
3) Mixing the manganese sulfate four-time purifying liquid and the zinc sulfate four-time purifying liquid according to the manganese-zinc ratio required by the manganese-zinc ferrite, adding ferrous sulfate with the iron ratio required by the manganese-zinc ferrite, coprecipitating the purifying mixed liquid and ammonium bicarbonate, washing, then decomposing coprecipitated starch into ferric oxide, manganic oxide and zinc oxide in a decomposing furnace, and roasting to obtain the manganese-zinc ferrite composite material.
In the scheme, the method comprises the following steps: the mass ratio of the zinc mud to the flux is 1:2 to 10.
In the scheme, the method comprises the following steps: the reducing agent is one of aniline, diaminobenzene, triaminobenzene, phenol, benzenediol, benzenetriol and aminophenol. The reduction time is 5-10 min.
In the scheme, the method comprises the following steps: the reducing agent is trialdehyde phloroglucinol or hexaminobenzene, the addition of the reducing agent is 20-50% of the manganese slurry, and the reduction time is 3-5 min.
In the scheme, the method comprises the following steps: in the step 1), the ratio of the adding amount of sulfuric acid to the molar amount of manganese is 1.8-2.2: 1, a step of;
in the step 2), the ratio of the addition amount of sulfuric acid to the molar amount of zinc is 1.8-2.2: 1.
in the scheme, the method comprises the following steps: the concentration of sulfuric acid is 400g/L.
In the scheme, the method comprises the following steps: in the steps 1) and 2), the drying is carried out at 100-120 ℃.
In the scheme, the method comprises the following steps: the flocculant is polyacrylamide. The addition amount is 1-3 per mill of the mass of the solution.
The electrolytic manganese anode slime and the zinc slime contain impurity elements such as silicon, aluminum, potassium, sodium and the like to different degrees, especially silicon and aluminum are generally in tetrahedral structures in the electrolytic manganese anode slime and the zinc slime, the content is generally high, and the difficulty in removing the impurities after acid leaching is high. After the mixed flux is mixed with the electrolytic manganese anode slime and the zinc slime, KZrF 5 Can be melted at 390 ℃ so as to drive the roasting material to flow, and KF generated by decomposing ionic molten salt is rapidly dissociated to form free K along with the rise of temperature + And F - Thereby accelerating the melting of the roasting material, destroying the internal structure of the electrolytic manganese anode slime and the zinc slime, releasing insoluble impurities such as aluminum, silicon and the like, and increasing the melting temperature to 950-1050 ℃ to be in a molten state K 3 AlF 6 Continuously extracting impurities such as silicon, aluminum, potassium, sodium and the like in electrolytic manganese anode slime and zinc slime, wherein the impurities exist in a liquid phase form on an upper layer of molten salt, and metal elements such as manganese, zinc, iron, lead, calcium, magnesium, nickel, titanium, tin and the like exist in a solid phase sediment form on a lower layer of molten salt. Electrolytic manganese anode slime and zinc slime removal by solid-liquid separationA large amount of impurity components such as silicon, aluminum, potassium, sodium and the like.
Since manganese in electrolytic manganese anode slime mainly exists in the form of manganese dioxide, reduction treatment is needed after melting treatment to implement subsequent acidification procedures. Compared with the prior art, the hexaminobenzene or the trialdehyde phloroglucinol has strong reducing capability, can thoroughly reduce manganese dioxide and can accelerate the reducing speed of manganese dioxide. Meanwhile, under the protection of vacuum or inert gas, oxygen in the air is prevented from entering, the reduction efficiency is further improved, and the manganese in the electrolytic manganese anode slime and the zinc in the zinc slime can be thoroughly converted into manganese sulfate and zinc sulfate in the subsequent sulfuric acid acidification process.
The beneficial effects are that:
(1) By adopting the technical scheme, a large amount of impurities such as silicon, aluminum, potassium, sodium and the like in the electrolytic manganese anode slime and the zinc slime are removed simultaneously by using a melting method, and the structures of the electrolytic manganese anode slime and the zinc slime are destroyed by melting, so that the difficulty of subsequent acid dissolution and impurity removal is reduced, and the acid leaching efficiency is improved.
(2) Compared with the prior art, the roasting time is shortened by 15-20 min, and the energy consumption for recovering manganese and zinc from electrolytic manganese anode slime and zinc slime is reduced.
(3) Compared with the prior art, the technical scheme has the advantages that the mutual influence of external factors is avoided in the impurity removal process by step-by-step impurity removal, the impurity removal is more thorough, and the purities of the manganese sulfate four-time purifying liquid and the zinc sulfate four-time purifying liquid can reach more than 99.5%.
Detailed Description
The present invention will be further described with reference to examples.
Example 1
1. Recovery of manganese from manganese anode slime
Crushing the manganese anode slime to below 5mm, and drying at 100-120 ℃ to constant weight.
Uniformly mixing the dried manganese anode slime with a mixed flux according to a ratio of 1:10, wherein the flux is composed of 40% of KZrF 5 And 60% K 3 AlF 6 . Is arranged atWhen the temperature is raised to 390 ℃ in the electric furnace, the roasting material starts to flow, and then the roasting material is continuously heated to 1000 ℃ for 40min, so that solid-liquid delamination occurs. Impurities such as silicon, aluminum, sodium, potassium and the like enter the liquid phase layer in the form of molten salt, and metal compounds such as manganese, iron, lead, magnesium and the like exist in the solid phase sediment.
Removing liquid phase components by solid-liquid separation, cleaning solid phase sediment by purified water, pulping by adding water, sieving with 120 mesh sieve, and placing into a reaction kettle with a cooling device.
Adding 2 times (molar ratio) of sulfuric acid according to the content of manganese dioxide in the solid-phase sediment, vacuumizing the reaction kettle at normal temperature to prevent oxygen residues in the air from affecting the reduction efficiency of the subsequent manganese dioxide, adding a reducing agent of trialdehyde phloroglucinol for reduction (added according to 20% of the molar amount of manganese), reducing the manganese dioxide into low-valence manganese, reacting the reduced low-valence manganese with excessive sulfuric acid to generate manganese sulfate, and filtering to remove impurities such as calcium, lead, barium and the like existing in sulfate sediment to obtain a primary purified solution of the manganese sulfate.
Adding polyacrylamide flocculant (the addition amount is 1 per mill of the mass of the solution) to remove a small amount of residual aluminum and silicon, and filtering and removing impurities to obtain a manganese sulfate secondary purification solution.
Ammonia water is adopted to adjust the pH value of the solution to 5-7, and the three-time purifying solution of manganese sulfate is obtained through filter pressing and separation.
Adding 1%o ammonium sulfide into the manganese sulfate tertiary purifying solution, removing impurities and filtering to obtain high-purity manganese sulfate quaternary purifying solution.
2. Zinc sludge recovery zinc
Crushing the recovered zinc of the hot-dip galvanized slag (the particle diameter is less than or equal to 5 mm), drying the hot-dip galvanized slag in an oven at the temperature of 100-120 ℃ and fully and uniformly mixing the hot-dip galvanized slag with a flux, wherein the mass ratio of the zinc slag to the flux is 1:2, flux is composed of 30% of KZrF 5 And 70% K 3 AlF 6 Composition is prepared.
Heating to 390 ℃ in a muffle furnace, melting flux, gradually penetrating hot-dip zinc slag, continuously heating to 1050 ℃ and keeping for 30min, removing liquid phase part of the melt, washing solid phase sediment with purified water, adding 400g/L of excessive sulfuric acid (the molar ratio of zinc to sulfuric acid is 1:1.8) according to the content of zinc oxide in the solid phase sediment to obtain zinc sulfate solution, filtering, and removing impurities such as calcium, lead, barium and the like existing in sulfate sediment to obtain zinc sulfate primary purification solution. Adding polyacrylamide (the addition amount is 1 per mill of the mass of the solution) to remove a small amount of aluminum and silicon remained in the primary purification solution of zinc sulfate, and filtering to obtain a secondary purification solution of zinc sulfate; adding ammonia water to regulate the pH value of the manganese sulfate solution to 5-7, and obtaining the zinc sulfate three-time purifying solution after filter pressing and separation. Adding 1%o ammonium sulfide, continuously removing metal ions in the zinc sulfate three-time purifying solution, and filtering to obtain high-purity zinc sulfate four-time purifying solution.
3 preparing Mn-Zn ferrite composite material
Mixing the manganese sulfate four-time purifying liquid and the zinc sulfate four-time purifying liquid according to the required manganese-zinc ratio in the manganese-zinc ferrite, adding the required iron ratio ferrous sulfate, coprecipitating the purifying mixed liquid and ammonium bicarbonate, washing, then decomposing the coprecipitated starch into ferric oxide, manganic oxide and zinc oxide in a decomposing furnace, and roasting to obtain the manganese-zinc ferrite composite material. The decomposition procedure was prepared as described in CN 115894050.
Example 2
1. Recovery of manganese from manganese anode slime
Crushing the manganese anode slime to below 5mm, and drying at 100-120 ℃ to constant weight.
Uniformly mixing the dried manganese anode slime with a mixed flux according to a ratio of 1:2, wherein the flux is composed of 50% of KZrF 5 And 50% K 3 AlF 6 . And (3) placing the materials in an electric furnace, heating to 390 ℃, starting to flow the materials, and continuously heating to 950 ℃ for roasting for 45min, so that solid-liquid delamination occurs. Impurities such as silicon, aluminum, sodium, potassium and the like enter the liquid phase layer in the form of molten salt, and metal compounds such as manganese, iron, lead, magnesium and the like exist in the solid phase sediment.
Removing liquid phase components by solid-liquid separation, cleaning solid phase sediment by purified water, pulping by adding water, sieving with 120 mesh sieve, and placing into a reaction kettle with a cooling device.
Adding 2.2 times (molar ratio) of sulfuric acid according to the content of manganese dioxide in the solid-phase sediment, vacuumizing the reaction kettle at normal temperature to prevent oxygen residues in the air from affecting the reduction efficiency of the subsequent manganese dioxide, adding a reducing agent hexaaminobenzene for reduction (adding according to 30% of the molar amount of manganese), reducing the manganese dioxide into low-valence manganese, reacting the reduced low-valence manganese with excessive sulfuric acid to generate manganese sulfate, and filtering to remove impurities such as calcium, lead, barium and the like in sulfate sediment to obtain a manganese sulfate primary purification solution.
Adding polyacrylamide flocculant (the addition amount is 1 per mill of the mass of the solution) to remove a small amount of residual aluminum and silicon, and filtering and removing impurities to obtain a manganese sulfate secondary purification solution.
Ammonia water is adopted to adjust the pH value of the solution to 5-7, and the three-time purifying solution of manganese sulfate is obtained through filter pressing and separation.
Adding 1%o ammonium sulfide into the manganese sulfate tertiary purifying solution, removing impurities and filtering to obtain high-purity manganese sulfate quaternary purifying solution.
2. Zinc sludge recovery zinc
Crushing the recovered zinc of the hot-dip galvanized slag (the particle diameter is less than or equal to 5 mm), drying the hot-dip galvanized slag in an oven at the temperature of 100-120 ℃ and fully and uniformly mixing the hot-dip galvanized slag with a flux, wherein the mass ratio of the zinc slag to the flux is 1:5, flux is composed of 40% of KZrF 5 And 60% K 3 AlF 6 Composition is prepared.
Heating to 390 ℃ in a muffle furnace, melting flux, gradually penetrating hot-dip zinc slag, continuously heating to 1000 ℃ and keeping for 40min, removing liquid phase part of the melt, washing solid phase sediment with purified water, adding 400g/L of excessive sulfuric acid (the molar ratio of zinc to sulfuric acid is 1:2.2) according to the content of zinc oxide in the solid phase sediment to obtain zinc sulfate solution, filtering, and removing impurities such as calcium, lead, barium and the like existing in sulfate sediment to obtain zinc sulfate primary purification solution. Adding polyacrylamide (the addition amount is 2 per mill of the mass of the solution) to remove a small amount of aluminum and silicon remained in the primary purification solution of zinc sulfate, and filtering to obtain a secondary purification solution of zinc sulfate; adding ammonia water to regulate the pH value of the manganese sulfate solution to 5-7, and obtaining the zinc sulfate three-time purifying solution after filter pressing and separation. Adding 1%o ammonium sulfide, continuously removing metal ions in the zinc sulfate three-time purifying solution, and filtering to obtain high-purity zinc sulfate four-time purifying solution.
3 preparing Mn-Zn ferrite composite material
Mixing the manganese sulfate four-time purifying liquid and the zinc sulfate four-time purifying liquid according to the required manganese-zinc ratio in the manganese-zinc ferrite, adding the required iron ratio ferrous sulfate, coprecipitating the purifying mixed liquid and ammonium bicarbonate, washing, then decomposing the coprecipitated starch into ferric oxide, manganic oxide and zinc oxide in a decomposing furnace, and roasting to obtain the manganese-zinc ferrite composite material. The decomposition procedure was prepared as described in CN 115894050.
Example 3
1. Recovery of manganese from manganese anode slime
Crushing the manganese anode slime to below 5mm, and drying at 100-120 ℃ to constant weight.
Uniformly mixing the dried manganese anode slime with a mixed flux according to a ratio of 1:5, wherein the flux is composed of 30% of KZrF 5 And 70% K 3 AlF 6 . And (3) when the material is heated to 390 ℃ in an electric furnace, the material starts to flow, and then the material is continuously heated to 1050 ℃ and baked for 40min, so that solid-liquid delamination occurs. Impurities such as silicon, aluminum, sodium, potassium and the like enter the liquid phase layer in the form of molten salt, and metal compounds such as manganese, iron, lead, magnesium and the like exist in the solid phase sediment.
Removing liquid phase components by solid-liquid separation, cleaning solid phase sediment by purified water, pulping by adding water, sieving with 120 mesh sieve, and placing into a reaction kettle with a cooling device.
Adding 2 times (molar ratio) of sulfuric acid according to the content of manganese dioxide in the solid-phase sediment, vacuumizing the reaction kettle at normal temperature to prevent oxygen residues in the air from affecting the reduction efficiency of the subsequent manganese dioxide, adding a reducing agent hexaaminobenzene for reduction (adding 30% of the molar amount of manganese), reducing the manganese dioxide into low-valence manganese, reacting the reduced low-valence manganese with excessive sulfuric acid to generate manganese sulfate, and filtering to remove impurities such as calcium, lead, barium and the like in sulfate sediment to obtain a manganese sulfate primary purification solution.
Adding polyacrylamide flocculant (the addition amount is 3 per mill of the mass of the solution) to remove a small amount of residual aluminum and silicon, and filtering and removing impurities to obtain a manganese sulfate secondary purification solution.
Ammonia water is adopted to adjust the pH value of the solution to 5-7, and the three-time purifying solution of manganese sulfate is obtained through filter pressing and separation.
Adding 1%o ammonium sulfide into the manganese sulfate tertiary purifying solution, removing impurities and filtering to obtain high-purity manganese sulfate quaternary purifying solution.
2. Zinc sludge recovery zinc
Crushing the recovered zinc of the hot-dip galvanized slag (the particle diameter is less than or equal to 5 mm), drying the hot-dip galvanized slag in an oven at the temperature of 100-120 ℃ and fully and uniformly mixing the hot-dip galvanized slag with a flux, wherein the mass ratio of the zinc slag to the flux is 1:10, flux is composed of 40% of KZrF 5 And 60% K 3 AlF 6 Composition is prepared.
Heating to 390 ℃ in a muffle furnace, melting flux, gradually penetrating hot-dip zinc slag, continuously heating to 1000 ℃ and keeping for 40min, removing liquid phase part of the melt, washing solid phase sediment with purified water, adding 400g/L of excessive sulfuric acid (the molar ratio of zinc to sulfuric acid is 1:2.2) according to the content of zinc oxide in the solid phase sediment to obtain zinc sulfate solution, filtering, and removing impurities such as calcium, lead, barium and the like existing in sulfate sediment to obtain zinc sulfate primary purification solution. Adding polyacrylamide (the addition amount is 2 per mill of the mass of the solution) to remove a small amount of aluminum and silicon remained in the primary purification solution of zinc sulfate, and filtering to obtain a secondary purification solution of zinc sulfate; adding ammonia water to regulate the pH value of the manganese sulfate solution to 5-7, and obtaining the zinc sulfate three-time purifying solution after filter pressing and separation. Adding 1%o ammonium sulfide, continuously removing metal ions in the zinc sulfate three-time purifying solution, and filtering to obtain high-purity zinc sulfate four-time purifying solution.
3 preparing Mn-Zn ferrite composite material
Mixing the manganese sulfate four-time purifying liquid and the zinc sulfate four-time purifying liquid according to the required manganese-zinc ratio in the manganese-zinc ferrite, adding the required iron ratio ferrous sulfate, coprecipitating the purifying mixed liquid and ammonium bicarbonate, washing, then decomposing the coprecipitated starch into ferric oxide, manganic oxide and zinc oxide in a decomposing furnace, and roasting to obtain the manganese-zinc ferrite composite material. The decomposition procedure was prepared as described in CN 115894050.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for preparing a soft magnetic manganese zinc ferrite composite material by using manganese anode slime and zinc slime is characterized by comprising the following steps of:
1) Recovery of manganese from electrolytic manganese anode slime
Crushing electrolytic manganese anode slime until the particle diameter is less than or equal to 5mm, drying, adding a flux according to the mass of the electrolytic manganese anode slime, and uniformly mixing, wherein the flux is composed of 30-50% of KZrF 5 And 70-50% K 3 AlF 6 Composition; the mass ratio of the addition amount of the flux to the manganese-containing waste residue is 10-2: 1, placing the material into an electric furnace, heating to 390 ℃, starting to flow the material, and continuously heating to 950-1050 ℃ for roasting for 30-45 min, so as to generate solid-liquid layering; after solid-liquid separation, the solid phase sediment is fully cleaned by purified water to remove the soluble salt remained in the solid phase sediment; adding water into the solid-phase sediment to prepare slurry after cleaning, sieving the slurry with a 120-mesh sieve, putting the slurry into a reaction kettle with a cooling device, adding excessive sulfuric acid according to the manganese content in the solid-phase sediment, reducing manganese dioxide in the manganese slurry into low-valence manganese by adding a reducing agent under the protection of vacuum or inert gas at normal temperature, quickly reacting the low-valence manganese with the excessive sulfuric acid to convert all manganese into a manganese sulfate solution, and filtering to remove impurities to obtain a manganese sulfate primary purification solution; adding a flocculating agent to remove a small amount of residual aluminum and silicon in the manganese sulfate primary purification solution, and filtering to obtain a manganese sulfate secondary purification solution; adding ammonia water to adjust the pH value of the manganese sulfate solution to 5-7, obtaining manganese sulfate three-time purifying solution after filter pressing and separation, adding 1-2 permillage ammonium sulfide, continuously removing the rest metal ions in the manganese sulfate three-time purifying solution, and filtering to obtain high-purity manganese sulfate four-time purifying solution;
2) Recovery of zinc from zinc sludge
Crushing zinc mud until the particle diameter is less than or equal to 5mm, drying and fully and uniformly mixing with a flux, wherein the flux is composed of 30-50% of KZrF 5 And 70% to50% of K 3 AlF 6 Composition; heating to 390 ℃ in a muffle furnace, melting flux, gradually penetrating zinc-containing waste residues, continuously heating to 950-1050 ℃ and keeping for 30-45 min, removing a molten liquid phase part, washing solid phase sediment with purified water, adding excessive sulfuric acid according to the content of zinc oxide in the solid phase sediment to obtain zinc sulfate solution, and filtering to remove impurities to obtain a primary zinc sulfate purification solution; adding a flocculating agent to remove a small amount of aluminum and silicon remained in the primary zinc sulfate purifying solution, and filtering to obtain a secondary zinc sulfate purifying solution; adding ammonia water to adjust the pH value of the manganese sulfate solution to 5-7, and obtaining zinc sulfate three-time purifying solution after filter pressing and separation; adding 1-2 per mill ammonium sulfide, continuously removing metal ions in the zinc sulfate three-time purifying solution, and filtering to obtain high-purity zinc sulfate four-time purifying solution;
3) Mixing the manganese sulfate four-time purifying liquid and the zinc sulfate four-time purifying liquid according to the manganese-zinc ratio required by the manganese-zinc ferrite, adding ferrous sulfate with the iron ratio required by the manganese-zinc ferrite, coprecipitating the purifying mixed liquid and ammonium bicarbonate, washing, then decomposing coprecipitated starch into ferric oxide, manganic oxide and zinc oxide in a decomposing furnace, and roasting to obtain the manganese-zinc ferrite composite material.
2. The method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese anode slime and the zinc slime according to claim 1, which is characterized in that: the mass ratio of the zinc mud to the flux is 1:2 to 10.
3. The method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese anode slime and the zinc slime according to any one of claims 1 to 2, which is characterized in that: the reducing agent is one of aniline, diaminobenzene, triaminobenzene, phenol, benzenediol, benzenetriol and aminophenol.
4. A method for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese anode slime and zinc slime according to claim 3, which is characterized in that: the reducing agent is trialdehyde phloroglucinol or hexaminobenzene, the addition of the reducing agent is 20-50% of the manganese slurry, and the reduction time is 3-5 min.
5. The method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese anode slime and the zinc slime according to claim 4, which is characterized in that:
in the step 1), the ratio of the adding amount of sulfuric acid to the molar amount of manganese is 1.8-2.2: 1, a step of;
in the step 2), the ratio of the addition amount of sulfuric acid to the molar amount of zinc is 1.8-2.2: 1.
6. the method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese anode slime and the zinc slime according to claim 5, which is characterized in that: the concentration of sulfuric acid is 400g/L.
7. The method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese anode slime and the zinc slime according to claim 1, which is characterized in that: in the steps 1) and 2), the drying is carried out at 100-120 ℃.
8. The method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese anode slime and the zinc slime according to claim 7, which is characterized in that: the flocculant is polyacrylamide.
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