CN116875827B - Method for preparing soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in production of perillaldehyde - Google Patents
Method for preparing soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in production of perillaldehyde Download PDFInfo
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- CN116875827B CN116875827B CN202310850490.3A CN202310850490A CN116875827B CN 116875827 B CN116875827 B CN 116875827B CN 202310850490 A CN202310850490 A CN 202310850490A CN 116875827 B CN116875827 B CN 116875827B
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- Prior art keywords
- manganese
- zinc
- containing waste
- waste residues
- sulfate
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- 239000002699 waste material Substances 0.000 title claims abstract description 85
- 239000011701 zinc Substances 0.000 title claims abstract description 73
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 72
- 239000011572 manganese Substances 0.000 title claims abstract description 72
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- RUMOYJJNUMEFDD-UHFFFAOYSA-N perillyl aldehyde Chemical compound CC(=C)C1CCC(C=O)=CC1 RUMOYJJNUMEFDD-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 70
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 39
- 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 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 49
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 49
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 49
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 49
- 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 38
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 230000004907 flux Effects 0.000 claims abstract description 31
- 238000000746 purification Methods 0.000 claims abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 17
- 230000008018 melting Effects 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 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
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000359 iron(II) sulfate Inorganic materials 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 52
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 48
- 239000013049 sediment Substances 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 31
- 239000007790 solid phase Substances 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000008213 purified water Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000008394 flocculating agent Substances 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 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 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
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 5
- 229960001553 phloroglucinol Drugs 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 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
- 239000011261 inert gas Substances 0.000 claims description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 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
- 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 12
- 239000011133 lead Substances 0.000 description 10
- NDTYTMIUWGWIMO-UHFFFAOYSA-N perillyl alcohol Chemical compound CC(=C)C1CCC(CO)=CC1 NDTYTMIUWGWIMO-UHFFFAOYSA-N 0.000 description 10
- 238000002386 leaching Methods 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229930007631 (-)-perillyl alcohol Natural products 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 235000005693 perillyl alcohol Nutrition 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 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 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000003205 fragrance Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000004537 pulping 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 235000007421 Mentha citrata Nutrition 0.000 description 1
- 244000024873 Mentha crispa Species 0.000 description 1
- 235000014749 Mentha crispa Nutrition 0.000 description 1
- 235000002899 Mentha suaveolens Nutrition 0.000 description 1
- 241000234479 Narcissus Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 235000004347 Perilla Nutrition 0.000 description 1
- 244000124853 Perilla frutescens Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 235000019693 cherries Nutrition 0.000 description 1
- 239000001926 citrus aurantium l. subsp. bergamia wright et arn. oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling 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
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in the production of perillaldehyde, which comprises the steps of crushing and drying the manganese-containing waste residues of the perillaldehyde, adding a flux, heating to 390 ℃, melting the whole molten salt system, and then continuously heating to 750 ℃ for 30-45 min, so as to generate solid-liquid layering; then removing impurities in multiple steps to obtain high-purity manganese sulfate four-time purifying liquid; the zinc slag is subjected to melting impurity removal, and then a multi-step impurity removal process is carried out to obtain a high-purity 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 four-time purification liquid of manganese sulfate and the purification liquid of zinc sulfate can reach more than 99.5%, and the purification 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 for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in the production of perillaldehyde.
Background
The perillaldehyde is naturally existing in perilla oil, lotus leaf tung and bergamot oil, has faint scent, cherry and oil fragrance, and can be used for preparing flower fragrance type daily chemical essence such as jasmine, narcissus and the like, and apple, orange and spearmint fragrance type edible essence. The industrial production of perillaldehyde in China mainly adopts a perillyl alcohol oxidation method, namely, an oxidant is used for oxidizing the perillyl alcohol into the perillyl aldehyde, wherein the oxidant is usually electrolytic manganese dioxide. In the oxidation process of the perillyl alcohol, a large amount of manganese dioxide is reduced into divalent manganese (mainly in the form of solid manganese monoxide) by the perillyl alcohol, and the divalent manganese is mixed with unreduced manganese dioxide to form manganese-containing waste residues, wherein the manganese content is 90-92%, and other residues are aluminum oxide, silicon oxide, ferric oxide, potassium salt, sodium salt, organic residues and the like.
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.
Industrial wastes such as zinc sludge, hot-dip galvanized slag, zinc ash and the like generally contain a large amount of metal element zinc, and the method provides possibility for preparing the manganese-zinc ferrite by recycling the industrial wastes. 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 method for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in the production of perillaldehyde, which can realize the preparation of the soft magnetic manganese zinc ferrite composite material by utilizing the manganese-containing waste residues generated in the production of perillaldehyde and industrial zinc-containing waste residues, thereby achieving the aim of waste utilization and having low recovery cost.
In order to achieve the above purpose, the invention is realized by the following technical scheme: a method for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in the production of perillaldehyde is characterized by recycling and preparing according to the following steps:
1) Crushing manganese-containing waste residues generated by perillaldehyde until the particle diameter is less than or equal to 5mm, drying, adding a flux according to the mass of the perillaldehyde waste residues, heating in an electric furnace, heating to 390 ℃, starting melting of the whole molten salt system, and then continuously heating to 750 ℃ for 30-45 min 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 manganese sulfate solution, and filtering to remove impurities to obtain 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;
2) Crushing zinc-containing waste residues until the particle diameter is less than or equal to 5mm, fully and uniformly mixing the zinc-containing waste residues with a flux after drying, putting the mixture into a muffle furnace, heating the muffle furnace to 390 ℃, starting melting the flux, gradually penetrating the zinc-containing waste residues, continuously heating the mixture to 750 ℃ and keeping the temperature 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 a zinc sulfate solution, and filtering to remove impurities to obtain a primary zinc sulfate purifying 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 the rest metal ions in the zinc sulfate three-time purifying solution, and filtering to obtain high-purity zinc sulfate four-time purifying solution; the flux comprises the following components in percentage by weight: 30% -50% of KZrF 5 And 70% -50% NaAlF 4 。
3) Mixing the manganese sulfate four-time purifying liquid with the zinc sulfate four-time purifying liquid according to the manganese-zinc ratio required by the manganese-zinc ferrite, adding ferrous sulfate according to 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 perillaldehyde manganese-containing waste residue to the flux is 1:2.
in the scheme, the method comprises the following steps: the zinc-containing waste residue is at least one of zinc mud, hot-dip zinc slag and zinc ash, and the mass ratio of the zinc-containing waste residue to the flux is 1: (2-10).
In the scheme, the method comprises the following steps: the reducing agent is one of aniline, diaminobenzene, triaminobenzene, phenol, benzenediol, benzenetriol and aminophenol. The reducing agent is the reducing agent conventionally used at present, and the reducing 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 addition amount of sulfuric acid to the molar amount of manganese is 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 1.2-2.0 according to the molar ratio: 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 to 3 per mill of the mass of the solution.
Both the manganese-containing waste slag and the zinc-containing waste slag inevitably contain constant impurity components such as silicon, aluminum and the like, and the impurities are extremely difficult to remove under the acidic condition. KZrF in flux 5 Although the melting point is 475 ℃, the melting point starts to be eutectic at 390 ℃, and as the temperature rises, the melting is accelerated, and the formed KF is dissociated in the molten salt to generate strong corrosive K + And F - The melting of the manganese slag and the zinc-containing slag is accelerated, thereby releasing metal ions. When the temperature reaches 750 ℃, naAlF 4 And at the moment, impurities such as aluminum, silicon, sodium, potassium and the like in the manganese-containing waste residues and the zinc-containing waste residues are melted into the upper layer of the liquid-phase molten salt, and impurities such as iron, lead, calcium, magnesium, nickel, titanium, tin and the like in the manganese-containing waste residues and the zinc-containing waste residues exist in the lower layer of the molten salt in the form of solid-phase sediment. Therefore, on one hand, the above operation damages the mineral structure of the manganese-containing waste slag and the zinc-containing waste slag, so that the metal elements such as manganese, zinc, iron and the like are released; on the other hand, the difficultly treated impurity groups in the manganese-containing waste residues and the zinc-containing waste residues are effectively removedParts by weight.
In the process of preparing perillyl aldehyde from perillyl alcohol, although part of manganese dioxide is reduced to divalent manganese, part of manganese still exists in the form of manganese dioxide, and the form of manganese is not changed during the melting treatment. In order to thoroughly dissolve manganese in the subsequent acid leaching process, manganese dioxide in the solid-phase sediment obtained after solid-liquid separation is required to be reduced into divalent manganese, and compared with a reducing agent adopted in the prior art, hexaaminobenzene and trialdehyde phloroglucinol have stronger reduction characteristics, and can rapidly and efficiently reduce manganese dioxide into divalent manganese. After the addition of sulfuric acid, other metal ions including manganese, iron and the like are present in the form of sulfate solutions, except that calcium, magnesium and lead are present as precipitates. Removing impurities such as calcium, magnesium, lead and the like through filtration; ammonia water is adopted to adjust the acidity of the solution, and impurity elements such as tin, antimony and the like are filtered and removed in the form of hydroxide precipitation; adding ammonium sulfide to precipitate further to precipitate heavy metal ion to purify the manganese sulfate solution. And for the zinc-containing waste residue, which does not involve the reduction of zinc ions, only sulfuric acid leaching and impurity removal, ammonia water acidity adjustment and impurity removal and ammonium sulfide precipitation and impurity removal are adopted, so that the purification process of zinc sulfate is completed.
The beneficial effects are that:
(1) By adopting the technical scheme, the structure of the manganese-containing waste residue and the zinc-containing waste residue is damaged, the efficiency of extracting and leaching manganese and zinc from the manganese-containing waste residue and the zinc-containing waste residue is high, the stability is good, and the leaching rates of manganese and zinc are above 99.0%.
(2) By adopting the technical scheme, compared with the prior art, the highest roasting temperature is reduced by 150-200 ℃, the roasting time is shortened by 15-20 min, and the energy consumption is reduced.
(3) Compared with the prior art, the technical scheme has the advantages that the step-by-step impurity removal is more thorough, the purities of the four-time manganese sulfate purifying liquid and the zinc sulfate purifying liquid can reach more than 99.5%, and the method is a high-quality raw material for preparing high-end manganese zinc ferrite.
Detailed Description
The present invention will be further described with reference to examples.
Example 1
1. Recovering manganese from the perillaldehyde waste residue:
crushing the waste residue of perillaldehyde (the content of manganese monoxide and manganese dioxide is 92%) to below 5mm, and drying at 100-120 ℃ to constant weight.
Adding 2 times of flux according to the mass of the perillaldehyde waste residue, wherein the flux consists of 50% of KZrF according to the mass 5 And 50% NaAlF 4 Composition is prepared.
Heating in an electric furnace, melting the whole molten salt system when the temperature is raised to 390 ℃, and then continuously raising the temperature to 750 ℃ and keeping for 30-45 min, so that solid-liquid delamination occurs. Impurities such as silicon, aluminum, sodium, potassium and the like in the manganese-containing waste residues 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 (400 g/L) 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 ratio 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 the 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 to remove impurities to obtain manganese sulfate secondary purifying liquid.
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.
Ammonium sulfide (the addition amount is 1 per mill of the mass of the solution) is added into the manganese sulfate tertiary purifying liquid, and the high-purity manganese sulfate quaternary purifying liquid is obtained after filtration and impurity removal.
2. Recovery of zinc from hot-dip zinc slag
Crushing zinc recovered from hot-dip galvanized slag (particle diameter is less than or equal to 5 mm), drying in an oven at 100-120 ℃ and filling with fluxUniformly mixing, wherein the mass ratio of zinc slag to flux is 1:5, flux is composed of 50% of KZrF 5 And 50% NaAlF 4 Composition is prepared.
Heating to 390 ℃ in a muffle furnace, melting flux, gradually penetrating hot-dip zinc slag, continuously heating to 750 ℃ and keeping for 30-45 min, removing a molten liquid phase part, washing solid phase sediment with purified water, adding 400g/L of excessive sulfuric acid (the molar ratio of zinc to sulfuric acid is 1:2.0) 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 a flocculating agent 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 ammonium sulfide (the addition amount is 1 per mill of the mass of the solution), 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 with the zinc sulfate four-time purifying liquid according to the manganese-zinc ratio required by the manganese-zinc ferrite, adding ferrous sulfate according to 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. The decomposition procedure was prepared as described in CN 115894050.
Example 2
1. Recovering manganese from the perillaldehyde waste residue:
crushing the waste residue of perillaldehyde (the content of manganese monoxide and manganese dioxide is 92%) to below 5mm, and drying at 100-120 ℃ to constant weight.
Adding 2 times of flux according to the mass of the perillaldehyde waste residue, wherein the flux consists of 30% of KZrF according to the mass 5 And 70% NaAlF 4 Composition is prepared.
Heating in an electric furnace, melting the whole molten salt system when the temperature is raised to 390 ℃, and then continuously raising the temperature to 750 ℃ and keeping for 30-45 min, so that solid-liquid delamination occurs. Impurities such as silicon, aluminum, sodium, potassium and the like in the manganese-containing waste residues 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 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, filtering and removing impurities to obtain the manganese sulfate primary purifying 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 ammonium sulfide (the addition amount is 1 per mill of the mass of the solution) into the manganese sulfate tertiary purification solution, and filtering and removing impurities to obtain high-purity manganese sulfate quaternary purification solution.
2. Zinc ash recovery zinc
Crushing zinc ash (particle diameter is less than or equal to 5 mm), drying in an oven at 100-120 ℃ and fully and uniformly mixing with flux, wherein the mass ratio of the zinc ash to the flux is 1:10, flux is composed of 30% of KZrF 5 And 70% NaAlF 4 Composition is prepared.
Heating to 390 ℃ in a muffle furnace, melting flux, gradually penetrating zinc ash, continuously heating to 750 ℃ and keeping for 30-45 min, removing a liquid phase part of the molten liquid, 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 a flocculating agent 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 ammonium sulfide (the addition amount is 2 per mill of the mass of the solution), 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 with the zinc sulfate four-time purifying liquid according to the manganese-zinc ratio required by the manganese-zinc ferrite, adding ferrous sulfate according to 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. The decomposition procedure was prepared as described in CN 115894050.
Example 3
1. Recovery of manganese from perillaldehyde waste residue
Crushing the waste residue of perillaldehyde (the content of manganese monoxide and manganese dioxide is 91%) to below 5mm, and drying at 100-120 ℃ to constant weight.
Adding 2 times of flux according to the mass of the perillaldehyde waste residue, wherein the flux consists of 40% of KZrF according to the mass 5 And 60% NaAlF 4 Composition is prepared.
Heating in an electric furnace, melting the whole molten salt system when the temperature is raised to 390 ℃, and then continuously raising the temperature to 750 ℃ and keeping for 30-45 min, so that solid-liquid delamination occurs. Impurities such as silicon, aluminum, sodium, potassium and the like in the manganese-containing waste residues 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 50% 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, filtering and removing impurities to obtain the manganese sulfate primary purifying 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, filtering and removing impurities to obtain a manganese sulfate secondary purifying 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 ammonium sulfide (the addition amount is 1 per mill of the mass of the solution) into the manganese sulfate tertiary purification solution, and filtering and removing impurities to obtain high-purity manganese sulfate quaternary purification solution.
2. Recovery of zinc from hot-dip zinc slag
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 40% of KZrF 5 And 60% NaAlF 4 Composition is prepared.
Heating to 390 ℃ in a muffle furnace, melting flux, gradually penetrating hot-dip zinc slag, continuously heating to 750 ℃ and keeping for 30-45 min, removing a molten liquid phase part, washing solid phase sediment with purified water, adding 400g/L of excessive sulfuric acid (the molar ratio of zinc to sulfuric acid is 1:1.5) 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 a flocculating agent 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 ammonium sulfide (the addition amount is 1 per mill of the mass of the solution), 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 with the zinc sulfate four-time purifying liquid according to the manganese-zinc ratio required by the manganese-zinc ferrite, adding ferrous sulfate according to 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. 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 (9)
1. A method for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in the production of perillaldehyde is characterized by recycling and preparing according to the following steps:
1) Crushing manganese-containing waste residues generated by perillaldehyde until the particle diameter is less than or equal to 5mm, drying, adding a flux according to the mass of the perillaldehyde waste residues, heating in an electric furnace, heating to 390 ℃, starting melting of the whole molten salt system, and then continuously heating to 750 ℃ for 30-45 min 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 manganese sulfate solution, and filtering to remove impurities to obtain manganese sulfate primary purification solution; adding a flocculating agent to remove a small amount of residual aluminum and silicon flocculating agents 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) Crushing zinc-containing waste residues until the particle diameter is less than or equal to 5mm, fully and uniformly mixing the zinc-containing waste residues with a flux after drying, putting the mixture into a muffle furnace, heating the muffle furnace to 390 ℃, starting melting the flux, gradually penetrating the zinc-containing waste residues, continuously heating the mixture to 750 ℃ and keeping the temperature 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 a zinc sulfate solution, and filtering to remove impurities to obtain a primary zinc sulfate purifying 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; ammonium sulfide with the addition of 1-2 per mill of the solution mass is added, the rest metal ions in the zinc sulfate three-time purifying solution are continuously removed, and the high-purity zinc sulfate four-time purifying solution is obtained by filtering; the fluxes of step 1) and step 2) are each composed of the following components in weight percent: 30% -50% of KZrF 5 And 70% -50% NaAlF 4 ；
3) Mixing the manganese sulfate four-time purifying liquid with the zinc sulfate four-time purifying liquid according to the manganese-zinc ratio required by the manganese-zinc ferrite, adding ferrous sulfate according to 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-containing waste residues and the zinc-containing waste residues generated in the production of the perillaldehyde according to claim 1, which is characterized in that: the mass ratio of the perillaldehyde manganese-containing waste residue to the flux is 1:2.
3. the method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese-containing waste residues and the zinc-containing waste residues generated in the production of the perillaldehyde according to claim 1, which is characterized in that: the zinc-containing waste residue is at least one of zinc mud, hot-dip zinc slag and zinc ash, and the mass ratio of the zinc-containing waste residue to the flux is 1:2-10.
4. A method for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in the production of perillaldehyde according to any one of claims 1 to 3, which is characterized in that: the reducing agent is one of aniline, diaminobenzene, triaminobenzene, phenol, benzenediol, benzenetriol and aminophenol.
5. A method for preparing a soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in the production of perillaldehyde according to any one of claims 1 to 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.
6. The method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese-containing waste residues and the zinc-containing waste residues generated in the production of the perillaldehyde according to claim 5, which is characterized in that:
in the step 1), the ratio of the addition amount of sulfuric acid to the molar amount of manganese is 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 1.2-2.0 according to the molar ratio: 1.
7. the method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese-containing waste residues and the zinc-containing waste residues generated in the production of the perillaldehyde according to claim 6, which is characterized in that: the concentration of sulfuric acid is 400g/L.
8. The method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese-containing waste residues and the zinc-containing waste residues generated in the production of the perillaldehyde according to claim 7, which is characterized in that: in the steps 1) and 2), the drying is carried out at 100-120 ℃.
9. The method for preparing the soft magnetic manganese zinc ferrite composite material by utilizing the manganese-containing waste residues and the zinc-containing waste residues generated in the production of the perillaldehyde according to claim 8, which is characterized in that: the flocculant is polyacrylamide.
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