CN119100342A - Method for preparing iron phosphate by recycling renewable phosphorus resources - Google Patents
Method for preparing iron phosphate by recycling renewable phosphorus resources Download PDFInfo
- Publication number
- CN119100342A CN119100342A CN202411382271.8A CN202411382271A CN119100342A CN 119100342 A CN119100342 A CN 119100342A CN 202411382271 A CN202411382271 A CN 202411382271A CN 119100342 A CN119100342 A CN 119100342A
- Authority
- CN
- China
- Prior art keywords
- iron
- phosphorus
- phosphate
- phosphoric acid
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000011574 phosphorus Substances 0.000 title claims abstract description 67
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 67
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 229910000398 iron phosphate Inorganic materials 0.000 title claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 178
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 140
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 89
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 74
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 73
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 73
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical group [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 claims abstract description 46
- 238000002386 leaching Methods 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000002308 calcification Effects 0.000 claims abstract description 16
- 229940043430 calcium compound Drugs 0.000 claims abstract description 16
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002910 solid waste Substances 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims description 152
- 239000000243 solution Substances 0.000 claims description 127
- 239000007788 liquid Substances 0.000 claims description 111
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000002893 slag Substances 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000001914 filtration Methods 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000003825 pressing Methods 0.000 claims description 27
- 239000001506 calcium phosphate Substances 0.000 claims description 22
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 21
- 239000000920 calcium hydroxide Substances 0.000 claims description 21
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 21
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 21
- 239000011790 ferrous sulphate Substances 0.000 claims description 20
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 20
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 20
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000001488 sodium phosphate Substances 0.000 claims description 20
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 20
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 235000011010 calcium phosphates Nutrition 0.000 claims description 16
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 15
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 16
- 239000011777 magnesium Substances 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 description 67
- 239000012065 filter cake Substances 0.000 description 41
- 239000012535 impurity Substances 0.000 description 41
- 239000011347 resin Substances 0.000 description 38
- 229920005989 resin Polymers 0.000 description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 28
- 235000011121 sodium hydroxide Nutrition 0.000 description 21
- 229960001714 calcium phosphate Drugs 0.000 description 15
- -1 iron magnesium aluminum calcium Chemical compound 0.000 description 15
- 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 13
- 229910021529 ammonia Inorganic materials 0.000 description 13
- 238000001354 calcination Methods 0.000 description 13
- 238000006477 desulfuration reaction Methods 0.000 description 13
- 230000023556 desulfurization Effects 0.000 description 13
- 238000005086 pumping Methods 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 239000010440 gypsum Substances 0.000 description 12
- 229910052602 gypsum Inorganic materials 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 11
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 235000019691 monocalcium phosphate Nutrition 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229960005069 calcium Drugs 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- 238000005273 aeration Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 150000004683 dihydrates Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229910001448 ferrous ion Inorganic materials 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 8
- 229910001414 potassium ion Inorganic materials 0.000 description 8
- 229960004887 ferric hydroxide Drugs 0.000 description 7
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000002367 phosphate rock Substances 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010626 work up procedure Methods 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229940116007 ferrous phosphate Drugs 0.000 description 3
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010936 aqueous wash Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000005347 demagnetization Effects 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229940062993 ferrous oxalate Drugs 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to the field of resource recycling, and particularly relates to a method for preparing ferric phosphate by recycling renewable phosphorus resources. The invention takes phosphorus-containing solid waste as a raw material, and prepares a phosphorus-calcium compound and iron-containing waste residue through alkaline leaching and calcification, the phosphorus-calcium compound reacts with concentrated sulfuric acid and water to obtain a phosphoric acid solution, and the iron-containing waste residue or phosphorus-iron residue as a raw material reacts with the phosphoric acid solution or ammonia water to prepare the ferric phosphate. The method utilizes extremely low-cost solid waste phosphorus resources to prepare high-purity phosphoric acid by recycling, produces high-purity high-value ferric phosphate, effectively reduces the waste of the phosphoric acid resources, realizes the efficient recycling of phosphorus, effectively reduces the cost of the phosphoric acid and the ferric phosphate, has stronger cost advantage, has relatively simple whole process flow, can recycle the generated wastewater after phosphorus recovery and decalcification magnesium, and is beneficial to environmental protection.
Description
Technical Field
The invention belongs to the field of resource recycling, and particularly relates to a method for preparing ferric phosphate by recycling renewable phosphorus resources.
Background
Ferric phosphate, also known as ferric phosphate and ferric orthophosphate, is an inorganic compound with a chemical formula of FePO 4 and is white or light red crystalline powder, and orthophosphate is generated by the reaction of ferric oxide and phosphoric acid solution, wherein the iron is orthotrivalent. The method is mainly used for producing the anode material, the catalyst, the ceramic and the like of the lithium iron phosphate battery. The iron phosphate used in the manufacture of the lithium iron phosphate cathode material is referred to as battery grade iron phosphate (purity >99.7%, iron to phosphorus ratio 0.985±0.2).
Currently, iron phosphate production processes mainly include an iron method (main raw materials are high-purity phosphoric acid and an iron source), a sodium method (main raw materials are industrial grade phosphoric acid, liquid alkali and an iron source), and an ammonium method (main raw materials are industrial grade phosphoric acid, synthetic ammonia and an iron source), and phosphorus is an extremely important raw material in any of the methods. The demand of phosphorite is increased under the influence of rapid development of new energy automobiles and energy storage industry, but the exploitation scale of phosphorite is not further increased under the influence of policies and environmental protection, so that the supply capacity of phosphorite is weakened to a certain extent, the contradiction between industry supply and demand is aggravated, the phosphorite has non-renewable and non-recyclable properties, and the service life of the phosphorite is estimated to be 2042 years by the normal line Zengqun in the Ningde era of the new energy automobile meeting in 2024 world, and the battery produced globally is half used for recovering lithium and half is used for mineral, so that the social demand can be met. Thus, in the iron phosphate production process, the phosphorus source occupies the first place (the proportion exceeds 53%), the iron phosphate market competition is the competition of phosphorus, and how to obtain and efficiently utilize the low-cost renewable phosphorus source is the cost life line of battery-grade iron phosphate.
The recovery treatment of the lithium battery refers to the centralized recovery of the scrapped lithium battery, the battery is recycled through physical, chemical and other recovery treatment processes or metal elements with utilization value in the battery such as lithium, cobalt, nickel and the like are extracted, the phosphorus iron slag after the lithium extraction of the lithium iron phosphate is basically not concerned in the market, and the existing lithium iron phosphate lithium extraction phosphorus iron slag mass storage is limited by the lithium iron phosphate pole piece black powder lithium extraction process equipment, so that a large amount of phosphorus and iron elements are in an idle state. How to recycle the renewable iron phosphorus element becomes an industry problem.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing ferric phosphate by recycling renewable phosphorus resources, which not only solves the problems of calcium phosphate sludge generated by dephosphorization of tailings, phosphorus and iron slag remained by extracting lithium after disassembling a lithium battery and sewage, but also reduces the production cost of ferric phosphate.
The method for preparing ferric phosphate by recycling renewable phosphorus resources comprises the steps of preparing a phosphoric acid solution and preparing ferric phosphate, wherein the process for preparing the phosphoric acid solution comprises the following steps:
(1-1) alkaline leaching and calcification are carried out on the phosphorus-containing solid waste to obtain phosphorus-calcium compound and iron-containing waste residue;
(1-2) adding concentrated sulfuric acid and water into a phosphorus calcium compound for reaction, and performing post-treatment I to obtain a phosphoric acid solution;
The phosphorus-containing solid waste is ferrophosphorus slag or calcium phosphate sludge. The phosphorus iron slag is a black mixture of residual iron phosphate and graphite after lithium extraction from lithium iron phosphate positive electrode black powder, the calcium phosphate sludge is a byproduct rich in phosphate generated by chemical dephosphorization or sewage dephosphorization, and the dry basis content of phosphorus pentoxide is more than 30%, and the main components are high-iron calcium phosphate, high-magnesium calcium phosphate and high-organic calcium phosphate.
The specific process of the alkaline leaching is that the phosphorus-containing solid waste is mixed with liquid alkali for reaction. In the alkaline leaching process, the phosphorus-containing solid waste is liquid alkali=1 (6-9), the liquid alkali is 15-25% sodium hydroxide aqueous solution by mass fraction, the alkaline leaching temperature is 60-95 ℃, and the alkaline leaching time is 0.5-3h. And after the alkaline leaching is finished, filter pressing and hot water washing are carried out to obtain a filter cake, filtrate and washing liquid. Typically, the sodium content of the filter cake after washing is less than 0.05% by four times with hot water at 90 ℃ or as the specific process conditions. The primary water washing uses the last secondary washing liquid, the secondary water washing uses the last tertiary washing liquid, the tertiary water washing uses clear water, and the fourth water washing uses clear water. The resulting low-strength aqueous wash solution can be concentrated to a high-strength wash solution for use in replenishing the evaporated water during alkaline leaching. The filtrate and primary wash liquor enter the subsequent process flow.
If the solid waste containing phosphorus is ferrophosphorus slag, ferric phosphate reacts with sodium hydroxide to generate ferric hydroxide and sodium phosphate, and the sodium phosphate exists in filtrate and water washing liquid, especially primary water washing liquid, and the filter cake is mainly ferric hydroxide and graphite, which is called ferrocarbon slag.
If the phosphorus-containing solid waste is high-impurity calcium phosphate, the components in the phosphorus-containing solid waste react with sodium hydroxide to generate sodium phosphate, calcium hydroxide, magnesium hydroxide and ferric hydroxide, the sodium phosphate exists in filtrate and water washing liquid, especially primary water washing liquid, and calcium hydroxide, magnesium hydroxide and ferric hydroxide are mainly formed in filter cakes, and the filter cakes are called calcium iron slag.
And (3) absorbing and decoloring the filtrate obtained by alkaline leaching and the primary washing liquid by using active carbon to obtain transparent colorless decolored sodium phosphate solution, and entering a calcification procedure.
The calcification is specifically carried out by adding calcium hydroxide (calcium carbonate content is less than 0.5%, pH of 10g calcium hydroxide dissolved in 200 g water is not lower than 12) into decolorized sodium phosphate solution, reacting at normal temperature and pressure for 1h, filtering, washing with hot water, and obtaining filter cake, filtrate and washing liquid. Sodium phosphate solution, calcium hydroxide=1 (0.055-0.095). The reaction that occurs in this process is the reaction of sodium phosphate with calcium hydroxide to produce calcium phosphate, monocalcium phosphate and sodium hydroxide. The filter cake is a phosphocalcic compound (calcium phosphate and calcium dihydrogen phosphate mixture), and the main component of the filtrate and the water washing liquid is sodium hydroxide.
In the calcification process, the water is generally washed with hot water for 7 times (three times of washing with the last time, four times of washing with the second time, five times of washing with the third time, six times of washing with the fourth time, six times of washing with the fifth time, six times of washing with the last time, six times of washing with clear water and seven times of washing with clear water), until the sodium hydroxide content is less than 0.05%, and the number of times of washing depends on the specific technological condition. Mixing the filtrate, primary washing liquid and secondary washing liquid, removing impurities (dealuminating and calcium, removing aluminum by sodium silicate, removing calcium by sodium carbonate, adding an aluminum-calcium impurity remover according to the detection value of the filtrate and the theoretical amount), pumping the low-concentration sodium hydroxide solution after impurity removal into an evaporation concentration system to evaporate into sodium hydroxide solution with the content of 20%, and returning distilled water to a pure water tank for standby.
Adding concentrated sulfuric acid and water into the calcified phosphorus-calcium compound to react to obtain phosphoric acid. The mass ratio of the phosphorus-calcium compound to the concentrated sulfuric acid is that the water=1:1-1.2:4-5, the reaction temperature is 75-160 ℃, and the reaction time is 1-3h.
The concentration of phosphoric acid obtained at 75-95 deg.C is 20-25%, the concentration of phosphoric acid obtained at 100-130 deg.C is 25-33%, the concentration of phosphoric acid obtained at 130-160 deg.C is 33-40%, and the reaction pressure is 0-0.5MPa (under the condition that the steam pressure is not reached, compressed air is used for supplementing pressure).
The molecular formula of the dihydrate gypsum is CaSO 4·2H2 O, the chemical structure of the dihydrate gypsum is calcium sulfate crystal with 2 crystal water, and the crystal water is easy to be separated out in the heating treatment under different conditions, so that the dihydrate gypsum and the anhydrous gypsum of various crystals are formed.
When heated at 65 ℃, the dihydrate gypsum begins to release crystal water, but the dewatering rate is relatively slow. When the water vapor pressure reaches 971mmHg at about 107 ℃, the dehydration rate becomes fast. As the temperature continues to rise, the dehydration is more accelerated, and at l 70-l90 ℃, the anhydrite dehydrates at a rapid rate to become alpha-hemihydrate or beta-hemihydrate. And when the temperature is continuously increased to 220 ℃ and 320-360 ℃, the semi-hydrated gypsum is continuously dehydrated to become alpha-soluble anhydrous gypsum. But the anhydrous gypsum produced under 220 ℃ conditions is relatively easy to absorb water in the air to become semi-hydrated gypsum. The volume of the dihydrate gypsum is larger than that of the hemihydrate gypsum, if less water is added, the water absorption of the gypsum is converted into the dihydrate gypsum, so that the slurry thickens, the stirring difficulty is increased, and the concentration of phosphoric acid is regulated and controlled by controlling the crystal water form of the gypsum through temperature.
The post-treatment I comprises the steps of filtering, hot water washing, desulfurizing, impurity removing, resin column filtering and active carbon decoloring.
After the reaction is completed, filtering and washing with hot water are carried out to obtain a filter cake, filtrate and washing liquid. Typically, the filter cake is washed 3-5 times with hot water at 90 ℃ until the phosphorus content of the filter cake is less than 0.5%. And combining the filtrate and the water washing solution, and sequentially carrying out coarse desulfurization, fine desulfurization, impurity removal, resin column filtration and active carbon decolorization to obtain a phosphoric acid solution.
The specific process of the coarse desulfurization is that the phosphorus-calcium mixture is added into the filtrate and the water washing liquid for filter pressing to obtain the coarse desulfurization filtrate, and the dosage of the phosphorus-calcium mixture is determined by taking the detection value of sulfur as the reference.
Adding barium carbonate into the coarse desulfurization filtrate until no bubbles are generated, reacting sulfuric acid with the barium carbonate to generate barium sulfate, reacting calcium with carbon dioxide to generate calcium carbonate, heating to a boiling state for 30-60 minutes after the reaction is finished to enable residual magnesium carbonate calcium carbonate to be heated and separated out, and then performing filter pressing and water washing for three times to obtain the fine desulfurization filtrate.
The specific process of impurity removal comprises the steps of detecting the content of iron magnesium aluminum calcium impurity ions in desulfurization filtrate, adding oxalic acid or oxalic acid salt (sodium oxalate and ammonium oxalate) into the desulfurization filtrate for reaction for 1-3 hours at 60 ℃ to generate ferrous oxalate and divalent metal oxalate precipitates such as magnesium oxalate, calcium oxalate, aluminum oxalate, ferrous oxalate and the like, and after the reaction is finished, carrying out filter pressing and water washing for three times to obtain impurity removal filtrate and water washing liquid.
The specific process of the resin column filtration comprises mixing the impurity-removed filtrate and the first water washing solution, evaporating and concentrating to 20-25% concentration, filtering by a 5-level resin column to remove divalent metal ions, and reducing sodium potassium ions and divalent metal ions to below 0.005% to obtain resin column filtration filtrate. After saturation of the resin, the resin was regenerated and reduced with a 5% sulfuric acid solution and washed with water to ph=7, the sulfur content of the wash being below 0.005%. The resin is T-42H resin or T-62H resin or a mixture of T-42H resin and T-62H resin (T-42H resin: T-62H resin=6:4 by volume ratio)
And decolorizing the filtrate of the resin column filtration by adopting active carbon to obtain phosphoric acid solution, and pumping the phosphoric acid solution to a phosphoric acid storage tank for standby.
And adding a proper amount of calcium hydroxide or calcium oxide into the phosphorus-containing washing liquid obtained in the reaction and post-treatment process to generate calcium dihydrogen phosphate to recycle the phosphorus component, wherein the calcium dihydrogen phosphate is returned to the phosphoric acid preparation process for recycling. And (5) recycling the reclaimed water, and discharging the redundant reclaimed water after precipitation.
In the preparation process of the ferric phosphate, the adopted raw materials can be ferrophosphorus slag or ferrocarbon slag or ferrocalcium slag generated in the preparation process of the phosphoric acid.
When the ferrophosphorus slag or the carbon iron slag obtained in the step (1-1) is used as a raw material to prepare the ferric phosphate, the specific process is as follows:
(2-1) reacting the iron-containing slag with iron powder and phosphoric acid solution, and performing post-treatment II to obtain ferrophosphorus liquid and carbon slag;
The mass ratio of the iron-containing slag to the iron powder to the phosphoric acid solution=1 (0.01-0.04) to (5-7) is 20%. The reaction time is 10-60min, carbon residue (the main component is graphite) is separated by filter pressing, the carbon residue is washed for 2 times by 90 ℃ hot water, washing liquid is added into filtrate, and main components of ferric phosphate and ferrous phosphate in the filtrate are called as ferrophosphorus liquid crude product. The addition of iron powder also inhibits leaching of aluminum.
The post-treatment II comprises fluoride impurity removal, sulfide impurity removal and sodium and potassium ion adsorption of resin.
The specific process of fluoride impurity removal comprises the steps of detecting the content of aluminum, calcium, magnesium and zinc in the crude ferrophosphorus liquid, adding fluoride into the crude ferrophosphorus liquid, reacting for 30 minutes, heating to 98 ℃ and keeping for 1 hour, and evaporating to remove residual hydrogen fluoride. The fluoride is selected from any one of potassium fluoride, sodium fluoride, ammonium bifluoride, ferric fluoride and ferrous fluoride.
The specific process of sulfide impurity removal comprises the steps of detecting the content of manganese, copper, nickel, chromium and lead in the liquid after fluoride impurity removal, adding sulfide, reacting for 30 minutes, heating to 98 ℃ and keeping for 1 hour to evaporate and remove residual hydrogen sulfide. The sulfide is selected from any one of potassium sulfide, sodium sulfide, ammonium sulfide and ferrous sulfide.
The specific process of adsorbing sodium and potassium ions by the resin comprises the steps of adsorbing sodium and potassium ions by the resin until the sodium and potassium contents in the total content of the liquid are respectively lower than 50ppm, and obtaining the ferrophosphorus liquid, wherein the flow rate of the liquid passing through the resin is 0.5V liter/min (V is the volume of the resin).
(2-2) Detecting the iron-phosphorus ratio in the ferrophosphorus liquid, adding a phosphoric acid solution to the specified iron-phosphorus ratio, oxidizing, heating to 85-95 ℃ after the oxidation is finished, preserving heat, precipitating, press-filtering, washing with water to pH=3.5 to obtain ferric phosphate dihydrate, and carrying out post-treatment III to obtain anhydrous ferric phosphate;
specifically, the content of iron ions and phosphorus ions in the ferrophosphorus liquid is detected, a phosphoric acid solution is added according to the iron-phosphorus ratio (iron: phosphorus) =1:2.6-3.0 to adjust the iron-phosphorus ratio to the specified iron-phosphorus ratio, after the iron-phosphorus ratio is adjusted, hydrogen peroxide (the concentration of hydrogen peroxide is 7.5% -30%) is added to oxidize divalent iron ions into trivalent iron ions (the metal ion online analyzer detects the divalent iron ions < 0.1%), after oxidation is finished, the iron ions are heated to 85-95 ℃ and are kept warm for 3 hours to obtain near-white or pink ferric phosphate dihydrate slurry, the reacted ferric phosphate dihydrate slurry is subjected to filter pressing and then is subjected to hot water washing to pH=3-4, and filtrate and washing liquid are pumped to a phosphate concentrate pretreatment procedure and then are neutralized for recycling as reclaimed water. The dosage of the hydrogen peroxide is generally 1.2 to 1.5 times of the molar quantity of ferrous ions.
The post-treatment III comprises the procedures of drying, calcining and the like.
And (3) conveying the iron phosphate dihydrate filter cake to a flash evaporator, heating to 110-150 ℃ for drying, putting the iron phosphate dihydrate filter cake into an electric heating rotary kiln for calcination after drying and dehydrating until the water content is less than 5%, calcining the iron phosphate in the rotary kiln for 2-4 hours at 550-650 ℃ to generate anhydrous iron phosphate, grinding the anhydrous iron phosphate to 2500-4000 meshes through air separation superfine grinding, and packaging the anhydrous iron phosphate by using a ton bag after electromagnetic removal of magnetic particles.
When the carbon iron slag or the calcium iron slag obtained in the step (1-1) is used as a raw material to prepare the ferric phosphate, the specific process is as follows:
(3-1) reacting the iron-containing slag with concentrated sulfuric acid, carrying out filter pressing and water washing to obtain a filter cake and a filtrate, wherein the main component of the filter cake is calcium sulfate dihydrate or graphite, the main component of the filtrate is ferric sulfate or ferric sulfate and magnesium sulfate, namely a solution containing ferric sulfate, and the iron-containing slag comprises concentrated sulfuric acid=100 (120-200) in terms of mass ratio, and the reaction time is 30-60min.
(3-2) Adding iron powder into the solution containing the ferric sulfate for reaction, performing filter pressing, and performing aftertreatment IV to obtain a ferrous sulfate solution;
In the process, ferric sulfate is reduced into ferrous sulfate, magnesium sulfate is hydrolyzed into ferrous sulfate and magnesium hydroxide, after the hydrolysis is finished, solid-liquid separation is carried out by pressure filtration, the main component of a filter cake is magnesium hydroxide, and the main component of a filtrate is ferrous sulfate. The amount of the iron powder is determined based on the detected amount of the metal ion such as Fe 3+、Al3+、Mg2+.
The post-treatment IV process is the same as the post-treatment II.
(3-3) Mixing ferrous sulfate solution and phosphoric acid solution, blending to a specified iron-phosphorus ratio, heating to 75-80 ℃, aerating (the metal ion online analyzer detects the content of ferrous ions and ferric ions, stopping aerating when the ferrous ions are less than 2%), adding hydrogen peroxide for ending oxidation (the metal ion online analyzer detects the ferrous ions are less than 0.1%), detecting the blended iron-phosphorus ratio to 0.96-0.98, adjusting the pH=1.7-2.2, heating to 90-95 ℃ for reaction for 3-5 hours, press-filtering, and washing with hot water to obtain the ferrophosphorus complex.
Specifically, the phosphorus content in the phosphoric acid solution and the iron content in the ferrous sulfate solution are detected respectively, the iron-phosphorus ratio (0.965-0.985) of the ferric phosphate is generated according to the requirement (the calculation formula X=iron/phosphorus is 0.5545), the phosphoric acid solution and the ferrous sulfate solution are metered respectively, firstly, the quantitative phosphoric acid solution is added into an iron phosphate reaction kettle, then the quantitative ferrous sulfate solution is added, after the addition is finished, the iron-phosphorus ratio of the solution is detected after stirring reaction for 30 minutes, if the iron-phosphorus ratio does not meet the requirement, the ammonium dihydrogen phosphate solution is used for preparing the iron-phosphorus ratio, the reaction solution with the iron-phosphorus ratio finished is heated to 75-80 ℃ for the first time, the aeration fan (500 cubic meters/hour) is maintained to be heated after the temperature reaches the requirement, the ferrous iron solution is aerated for 0.5-6 hours to obtain the ferric iron solution, a small amount of 7.5% hydrogen peroxide is added for final tail-ending oxidation after the aeration is finished, and the iron-phosphorus ratio of the solution is detected after the tail-ending oxidation is finished, and if the iron-phosphorus ratio does not meet the requirement, the phosphoric acid is used for preparing. And regulating the pH value of the solution with the iron-phosphorus ratio to be 1.7-2.2 by using ammonia water, and heating to 90-95 ℃ for reaction for 3-5 hours after the ammonia water is added to obtain the ferrophosphorus complex. Filter-pressing and washing with 80-90deg.C hot water for 5 times until sulfate radical and ammonia content is less than 0.001%, and directly pumping the washing liquid into ammonia synthesis system for preparing ammonia water
(3-4) Aging the ferrophosphorus complex, and performing post-treatment on the ferrophosphorus complex to obtain anhydrous ferric phosphate;
The post-treatment V comprises filtering, water washing, drying, calcining and the like.
Specifically, putting the ferrophosphorus complex filter cake into 10% -15% phosphoric acid solution for aging for 3-5 hours to obtain ferric phosphate dihydrate, filtering and washing with 80 ℃ hot water, pumping the aged primary filtrate to a ferrophosphorus slag acid/carbon iron slag decomposition process for standby after removing impurities through a phosphoric acid resin column, and then collecting all washing liquid into monocalcium phosphate by calcium hydroxide and returning to a phosphoric acid preparation link.
And (3) conveying the aged filter cake into a flash evaporator to be dried and milled at 110-150 ℃, conveying the dry powder of the ferric phosphate dihydrate into a rotary kiln to be electrically heated, calcining 550-700 for 3-4 hours to produce anhydrous ferric phosphate, and packaging the anhydrous ferric phosphate in ton bags after grinding, sorting and demagnetizing.
Compared with the prior art, the invention has the following beneficial effects:
1. The waste or high-impurity phosphorus resources are utilized for recycling to prepare the high-purity phosphoric acid, and the high-purity phosphoric acid is used for manufacturing the ferric phosphate, so that the waste of the phosphoric acid resources is effectively reduced, and the efficient recycling of the phosphorus is realized.
2. The waste or high-impurity phosphorus resource is used for preparing the ferric phosphate, so that the cost of the phosphoric acid is effectively reduced, the extremely low-cost waste or high-impurity phosphorus resource is utilized, a small amount of impurity removing agent is not used in the production process, other agents are not used in addition, a high-purity high-value phosphate product is produced, and the performance equivalent to that of the standard iron method ferric phosphate is realized.
3. The high-impurity calcium phosphate sludge generated by dephosphorization of the tailings after the disassembly and the lithium extraction of the waste lithium batteries and the sewage is fully utilized, so that the pollution of the phosphorus tailings with complex components to the environment is reduced.
4. The whole process flow is relatively simple, and the pH value does not need to be adjusted by adding sodium alkali, so that the complexity of chemical reaction is reduced, and the production efficiency is improved. In addition, the process has small influence on the environment in the production process, almost no exhaust gas is discharged, and the generated wastewater can be recycled after the decalcification magnesium is recovered by phosphorus, thereby being beneficial to environmental protection. The method also has the characteristics of high product purity and high raw material utilization rate, and has unique advantages.
5. The iron phosphate produced by the process has high purity, and the produced finished iron phosphate has a plurality of impurity elements which are not detected.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention;
FIGS. 2-3 show iron phosphate detection reports according to the present invention;
fig. 4-5 are SEM photographs of the iron phosphate according to the present invention.
Detailed Description
Example 1 preparation of phosphoric acid solution Using ferrophosphorus slag as raw Material
The process for preparing the phosphoric acid solution comprises the following steps:
(1-1) alkaline leaching and calcification are carried out on the ferrophosphorus slag to obtain a calcium phosphate compound and carbon iron slag;
The specific process of the alkaline leaching is that the ferrophosphorus slag and liquid alkali are mixed for reaction. In the alkaline leaching process, the mass ratio of the ferrophosphorus slag to the liquid alkali=1:6, wherein the liquid alkali is 25% sodium hydroxide aqueous solution by mass percent, the alkaline leaching temperature is 90 ℃, and the alkaline leaching time is 0.5h. And after the alkaline leaching is finished, filter pressing and hot water washing are carried out to obtain a filter cake, filtrate and washing liquid.
The hot water washing is performed four times by adopting 90 ℃ hot water washing, and the sodium content in a filter cake after the water washing is required to be less than 0.05 percent. The primary water washing uses the last secondary washing liquid, the secondary water washing uses the last tertiary washing liquid, the tertiary water washing uses clear water, and the fourth water washing uses clear water. The resulting low-strength aqueous wash solution can be concentrated to a high-strength wash solution for use in replenishing the evaporated water during alkaline leaching. The filtrate and primary wash liquor enter the subsequent process flow.
In the alkaline leaching process, ferric phosphate reacts with sodium hydroxide to generate ferric hydroxide and sodium phosphate, and the sodium phosphate exists in filtrate and water washing liquid, especially primary water washing liquid, and the filter cake mainly becomes ferric hydroxide and graphite, which are called carbon iron slag.
And (3) absorbing and decoloring the filtrate obtained by alkaline leaching and the primary washing liquid by using active carbon to obtain transparent colorless decolored sodium phosphate solution, and entering a calcification procedure.
The calcification is specifically carried out by adding calcium hydroxide (calcium carbonate content <0.5%, pH of 10 g calcium hydroxide dissolved in 200 g water is not lower than 12) into decolorized sodium phosphate solution, reacting at 25deg.C for 1 hr, filtering, and washing with hot water to obtain filter cake, filtrate and water washing liquid. Sodium phosphate solution, calcium hydroxide=1:0.055 by mass ratio. The sodium phosphate reacts with calcium hydroxide to form calcium phosphate, monocalcium phosphate and sodium hydroxide. The filter cake is a phosphocalcic compound (calcium phosphate and calcium dihydrogen phosphate mixture), and the main component of the filtrate and the water washing liquid is sodium hydroxide.
In the calcification process, 7 times of hot water washing (three times of washing liquid are used for one time, four times of washing liquid are used for two times of washing liquid are used for the last time, five times of washing liquid are used for three times of washing liquid, six times of washing liquid are used for four times of washing liquid, six times of washing liquid are used for five times of washing liquid, and clear water is used for six times and seven times of washing liquid) are used for washing until the sodium hydroxide content is less than 0.15%. Mixing the filtrate, primary washing liquid and secondary washing liquid, removing impurities (dealuminating and calcium, removing aluminum by sodium silicate, removing calcium by sodium carbonate, adding an aluminum-calcium impurity remover according to the detection value of the filtrate and the theoretical amount), pumping the low-concentration sodium hydroxide solution after impurity removal into an evaporation concentration system to evaporate into sodium hydroxide solution with the content of 20%, and returning distilled water to a pure water tank for standby.
(1-2) Adding concentrated sulfuric acid and water into a phosphorus calcium compound for reaction, and performing post-treatment I to obtain a phosphoric acid solution;
adding concentrated sulfuric acid and water into the calcified phosphorus-calcium compound to react to obtain phosphoric acid solution. The reaction temperature is 80 ℃ and the reaction time is 3h according to the mass ratio of ferric phosphate to concentrated sulfuric acid to water=1:1:4. The post-treatment I comprises the steps of filtering, hot water washing, desulfurizing, impurity removing, resin column filtering and active carbon decoloring.
After the reaction is completed, filtering and washing with hot water are carried out to obtain a filter cake, filtrate and washing liquid. Washing with hot water at 90deg.C for 5 times until the phosphorus content of the filter cake is lower than 0.5%. And combining the filtrate and the water washing solution, and then sequentially carrying out desulfurization, impurity removal, resin column filtration and active carbon decolorization to obtain a phosphoric acid solution.
The specific process of desulfurization is that barium carbonate is added until no bubbles are generated, the mixture is heated to a boiling state for 60 minutes, and then the mixture is subjected to filter pressing and water washing for three times, so that desulfurization filtrate is obtained.
Adding oxalic acid into the desulfurization filtrate, heating to 60 ℃ for reaction for 3 hours, reacting impurities such as iron, magnesium, aluminum, calcium and the like with the oxalic acid to generate precipitates respectively, and performing filter pressing and water washing for three times after the reaction is finished to obtain the impurity removal filtrate and water washing liquid.
The specific process of the resin column filtration comprises the steps of mixing the impurity removal filtrate and the first water washing liquid, evaporating and concentrating to 25% concentration, removing divalent metal ions through 5-level resin column filtration, and reducing sodium potassium ions and divalent metal ions to below 0.005% to obtain resin column filtration filtrate. The resin is T-42H resin.
And decolorizing the filtrate of the resin column filtration by adopting active carbon to obtain phosphoric acid solution, and pumping the phosphoric acid solution to a phosphoric acid storage tank for standby.
Example 2 preparation of phosphoric acid solution Using phosphorus-containing Calcific Compound as raw Material
The process for preparing the phosphoric acid solution comprises the following steps:
(1-1) alkaline leaching and calcification of the phosphorus-containing calcium compound to obtain phosphorus-containing calcium compound and calcium iron slag;
The specific process of the alkaline leaching is that the phosphorus-containing solid waste is mixed with liquid alkali for reaction. In the alkaline leaching process, the phosphorus-containing calcium compound is liquid alkali=1:9, the liquid alkali is 15% sodium hydroxide aqueous solution by mass percent, the alkaline leaching temperature is 60 ℃, and the alkaline leaching time is 3 hours. And after the alkaline leaching is finished, filter pressing and hot water washing are carried out to obtain a filter cake, filtrate and washing liquid. And water washing is carried out four times by adopting hot water at 90 ℃, and the sodium content in a filter cake after water washing is required to be less than 0.05 percent. The primary water washing uses the last secondary washing liquid, the secondary water washing uses the last tertiary washing liquid, the tertiary water washing uses clear water, and the fourth water washing uses clear water. The main component of the filtrate and the water washing liquid, especially the primary water washing liquid, is sodium phosphate, and the filter cake is mainly calcium hydroxide, magnesium hydroxide and ferric hydroxide, which are called calcium iron slag.
And (3) absorbing and decoloring the filtrate obtained by alkaline leaching and the primary washing liquid by using active carbon to obtain transparent colorless decolored sodium phosphate solution, and entering a calcification procedure.
The calcification is specifically carried out by adding calcium hydroxide (calcium carbonate content <0.5%, pH of 10g calcium hydroxide dissolved in 200 g water is not lower than 12) into decolorized sodium phosphate solution, reacting at 20deg.C for 0.5h, filtering, and washing with hot water to obtain filter cake, filtrate and washing liquid. Sodium phosphate solution, calcium hydroxide=1:0.095 by mass ratio. The reaction that occurs in this process is the reaction of sodium phosphate with calcium hydroxide to produce calcium phosphate, monocalcium phosphate and sodium hydroxide. The filter cake is a phosphocalcic compound (calcium phosphate and calcium dihydrogen phosphate mixture), and the main component of the filtrate and the water washing liquid is sodium hydroxide.
In the calcification process, 7 times of hot water washing (three times of washing liquid are used for one time, four times of washing liquid are used for two times of washing liquid are used for the last time, five times of washing liquid are used for three times of washing liquid, six times of washing liquid are used for four times of washing liquid, six times of washing liquid are used for five times of washing liquid, and clean water is used for six times and seven times of washing liquid) are used for washing until the sodium hydroxide content is less than 0.15%. Mixing the filtrate, primary washing liquid and secondary washing liquid, removing impurities (dealuminating and calcium, removing aluminum by sodium silicate, removing calcium by sodium carbonate, adding an aluminum-calcium impurity remover according to the detection value of the filtrate and the theoretical amount), pumping the low-concentration sodium hydroxide solution after impurity removal into an evaporation concentration system to evaporate into sodium hydroxide solution with the content of 20%, and returning distilled water to a pure water tank for standby.
(1-2) Adding concentrated sulfuric acid and water into a phosphorus calcium compound for reaction, and performing post-treatment I to obtain a phosphoric acid solution;
adding concentrated sulfuric acid and water into the calcified phosphorus-calcium compound to react to obtain phosphoric acid. The mass ratio of the phosphorus-containing solid waste to the concentrated sulfuric acid is that the water=1:1.2:6, the reaction temperature is 150 ℃, and the reaction time is 1h. The post-treatment I comprises the steps of filtering, hot water washing, desulfurizing, impurity removing, resin column filtering and active carbon decoloring.
After the reaction is completed, filtering and washing with hot water are carried out to obtain a filter cake, filtrate and washing liquid. Washing with 90 deg.c hot water for 3 times until the phosphorus content in the filter cake is lower than 0.5%. The filtrate and the water washing solution are combined and then subjected to desulfurization, impurity removal, resin column filtration and activated carbon decolorization in sequence to obtain a phosphoric acid solution, and the process is the same as in example 1.
Example 3 preparation of iron phosphate Using iron phosphate slag and phosphoric acid solution as raw materials
The specific process for preparing the ferric phosphate comprises the following steps:
(2-1) reacting the ferrophosphorus slag with iron powder and phosphoric acid solution, and performing post-treatment II to obtain ferrophosphorus liquid and carbon slag;
The mass ratio of the ferrophosphorus slag to the iron powder is that the mass ratio of the phosphoric acid solution to the iron powder is=1:0.04:5, and the mass ratio of the phosphoric acid solution is 20%. The reaction time is 60min, the carbon residue is separated by filter pressing, the carbon residue is washed by 90 ℃ hot water for 2 times, the washing liquid is added into the filtrate, and the main components of ferric phosphate and ferrous phosphate in the filtrate are called as a crude ferrophosphorus liquid. The addition of iron powder also inhibits leaching of aluminum.
The post-treatment II comprises fluoride impurity removal, sulfide impurity removal and sodium and potassium ion adsorption of resin.
The specific process of fluoride impurity removal comprises the steps of detecting the content of aluminum, calcium, magnesium and zinc in the crude ferrophosphorus liquid, adding fluoride into the crude ferrophosphorus liquid, reacting for 30 minutes, heating to 98 ℃ and keeping for 1 hour. The fluoride is selected from potassium fluoride.
The specific process of sulfide impurity removal comprises the steps of detecting the content of manganese copper nickel chromium lead in the liquid after fluoride impurity removal, adding sulfide, reacting for 30 minutes, heating to 98 ℃ and keeping for 1 hour. The sulfide is selected from sodium sulfide.
The specific process of adsorbing sodium and potassium ions by the resin comprises the steps of adsorbing sodium and potassium ions by the resin until the sodium and potassium contents in the total content of the liquid are respectively lower than 50ppm, and obtaining the ferrophosphorus liquid, wherein the flow rate of the liquid passing through the resin is 0.5V liter/min (V is the volume of the resin).
(2-2) Detecting the iron-phosphorus ratio in the ferrophosphorus liquid, adding a phosphoric acid solution to the specified iron-phosphorus ratio, oxidizing, heating to 85 ℃ after the oxidation is finished, preserving heat, precipitating, press-filtering, washing with water to pH=3 to obtain ferric phosphate dihydrate, and carrying out post-treatment III to obtain anhydrous ferric phosphate;
Specifically, detecting the content of iron ions and phosphorus ions in the ferrophosphorus liquid, adding a phosphoric acid solution according to the iron-phosphorus ratio (iron: phosphorus) =1:2.6, adding hydrogen peroxide (hydrogen peroxide concentration is 30%) for oxidation, heating to 85 ℃ after the oxidation is finished, preserving heat and precipitating for 3 hours to obtain ferric phosphate dihydrate slurry, filtering the ferric phosphate dihydrate slurry after the reaction is filtered, washing with hot water to pH=3, pumping filtrate and washing liquor to a pre-treatment procedure of phosphate concentrate, and neutralizing treatment to be used as reclaimed water for recycling. The dosage of the hydrogen peroxide is determined according to ferrous ions and is 1.2 times of the molar quantity of the ferrous ions.
The dihydrate ferric phosphate filter cloth is conveyed to a dryer to be heated to 150 ℃ for drying, the powder is crushed to 80-90 meshes by a silt machine after the dehydration is carried out to the water content of 5%, the powder is put into an electric heating rotary kiln for calcination, anhydrous ferric phosphate is generated after the calcination for 4 hours at 550 ℃ by the rotary kiln, and the anhydrous ferric phosphate is crushed by a pair of rollers, screened, ground to the grain size of less than 5 microns by a oversize material air flow mill, mixed and batched, and packaged by a ton bag after electromagnetic demagnetization.
Example 4 preparation of iron phosphate Using carbon iron slag and phosphoric acid solution as raw materials
The specific process for preparing the ferric phosphate comprises the following steps:
(2-1) reacting carbon-iron slag with iron powder and phosphoric acid solution, and performing post-treatment II to obtain ferrophosphorus solution and carbon slag;
Iron-containing slag and phosphoric acid solution=1:0.01:7, wherein the mass fraction of the phosphoric acid solution is 35%. The reaction time is 30min, carbon residue (the main component is graphite) is separated by filter pressing, the carbon residue is washed for 2 times by 90 ℃ hot water, washing liquid is added into filtrate, and main components of ferric phosphate and ferrous phosphate in the filtrate are called as ferrophosphorus liquid crude product.
The work-up II is the same as in example 3.
(2-2) Detecting the iron-phosphorus ratio in the ferrophosphorus liquid, adding a phosphoric acid solution to the specified iron-phosphorus ratio, oxidizing, heating to 95 ℃ after the oxidation is finished, preserving heat, precipitating, press-filtering, washing with water to pH=4 to obtain ferric phosphate dihydrate, and carrying out post-treatment III to obtain anhydrous ferric phosphate;
Specifically, detecting the content of iron ions and phosphorus ions in the ferrophosphorus liquid, adding a phosphoric acid solution according to the iron-phosphorus ratio (iron: phosphorus) =1:3.0, adjusting the iron-phosphorus ratio, adding hydrogen peroxide (the concentration of hydrogen peroxide is 30%), heating to 95 ℃ after oxidation is finished, and carrying out heat preservation and precipitation for 3 hours to obtain near-white or pink ferric phosphate dihydrate slurry, wherein the reacted ferric phosphate dihydrate slurry is subjected to filter pressing and then is washed with hot water until the pH value is=4, and the filtrate and washing liquid are pumped to a pre-treatment procedure of phosphate concentrate and then are subjected to neutralization treatment to be recycled as reclaimed water. The dosage of the hydrogen peroxide is determined according to ferrous ions and is 1.5 times of the molar quantity of the ferrous ions.
The dihydrate ferric phosphate filter cloth is conveyed to a dryer to be heated to 150 ℃ for drying, the powder is crushed to 80-100 meshes by a silt machine after the water content is 10%, the powder is put into an electric heating rotary kiln for calcination, anhydrous ferric phosphate is generated after the calcination for 3 hours at 650 ℃ by the rotary kiln, and the anhydrous ferric phosphate is crushed by a pair of rollers, screened, ground to a particle size of less than 5 microns by a oversize material air flow mill, mixed and batched, and packaged by a ton bag after electromagnetic demagnetization.
Example 5 preparation of iron phosphate Using calcium iron slag and Ammonia Water as raw materials
The specific process for preparing the ferric phosphate comprises the following steps:
(3-1) reacting the calcium iron slag with concentrated sulfuric acid, carrying out filter pressing and water washing to obtain a filter cake and a filtrate, wherein the main component of the filter cake is calcium sulfate dihydrate or graphite, the main component of the filtrate is ferric sulfate or ferric sulfate and magnesium sulfate, namely a solution containing ferric sulfate, and the reaction time is 30min.
(3-2) Adding iron powder into the solution containing the ferric sulfate for reaction, performing filter pressing, and performing aftertreatment IV to obtain a ferrous sulfate solution;
The amount of the iron powder may be determined based on the detected amount of Fe 3+、Al3+、Mg2+ or the like.
The work-up IV procedure is the same as work-up II in example 3.
(3-3) Mixing ferrous sulfate solution and phosphoric acid solution, blending to a specified iron-phosphorus ratio, heating to 75 ℃, aerating, adding hydrogen peroxide with the mass fraction of 7.5% for ending oxidation, detecting the blended iron-phosphorus ratio, adjusting the pH value to be 1.7, heating to 90 ℃ for reacting for 3 hours, press-filtering, and washing with hot water to obtain the ferrophosphorus complex.
Specifically, the phosphorus content in the phosphoric acid solution and the iron content in the ferrous sulfate solution are detected respectively, the iron-phosphorus ratio (0.971) of the ferric phosphate is generated according to the requirement (the calculation formula X=iron/phosphorus is 0.5545), the phosphoric acid solution and the ferrous sulfate solution are metered respectively, and the phosphoric acid solution and the ferrous sulfate solution are added into the ferric phosphate synthesis reaction kettle simultaneously in the same proportion by using an electric valve PID (proportion integration differentiation) control according to the proportion between weighing values;
After the addition is finished, stirring and reacting for 30 minutes, detecting the iron-phosphorus ratio of the solution, wherein the iron-phosphorus ratio does not meet the requirement, preparing the iron-phosphorus ratio by using an ammonium dihydrogen phosphate solution, heating to 75 ℃, maintaining heating after the temperature is reached, starting an aeration fan (500 cubic meters per hour) for aeration for 3 hours to obtain a ferric iron solution, adding a small amount of 7.5% hydrogen peroxide after the aeration is finished, ending and oxidizing, detecting the iron-phosphorus ratio of the solution after the ending and oxidizing is finished, and preparing by using phosphoric acid if the iron-phosphorus ratio does not meet the requirement. And regulating the pH value of the solution with the iron-phosphorus ratio by ammonia water to 1.7, and heating to 95 ℃ for reaction for 3 hours after the ammonia water is added to obtain the ferrophosphorus complex. And (3) carrying out filter pressing and washing with 80 ℃ hot water for 5 times until the sulfate radical and ammonia content are lower than 0.001%, and directly pumping the washing liquid to an ammonia synthesis system for preparing ammonia water.
(3-4) Aging the ferrophosphorus complex, and performing post-treatment on the ferrophosphorus complex to obtain anhydrous ferric phosphate;
The post-treatment V comprises filtering, water washing, drying, calcining and the like.
And (3) putting the ferrophosphorus complex filter cake into 10% phosphoric acid solution for ageing for 3 hours, filtering and washing with 80 ℃ hot water, pumping the primary ageing filtrate to a ferrophosphorus slag acidolysis process for standby after removing impurities through a phosphoric acid resin column, and then collecting washing liquid into monocalcium phosphate by using calcium hydroxide and returning to a phosphoric acid preparation link.
And (3) conveying the aged filter cake into a flash evaporator to be dried and milled at 100 ℃, conveying the dry powder of the ferric phosphate dihydrate into a rotary kiln to be electrically heated, calcining at 550 ℃ for 3 hours to generate anhydrous ferric phosphate, and packaging the anhydrous ferric phosphate in ton bags after grinding, sieving and demagnetizing.
Example 6 preparation of iron phosphate Using carbon iron slag and Ammonia Water as raw materials
The specific process for preparing the ferric phosphate comprises the following steps:
(3-1) reacting the carbon iron slag with concentrated sulfuric acid, carrying out filter pressing and water washing to obtain a filter cake and a filtrate, wherein the main component of the filter cake is calcium sulfate dihydrate or graphite, the main component of the filtrate is ferric sulfate or ferric sulfate and magnesium sulfate, namely a solution containing ferric sulfate, and the reaction time is 60min.
(3-2) Adding iron powder into the solution containing the ferric sulfate for reaction, performing filter pressing, and performing aftertreatment IV to obtain a ferrous sulfate solution;
The amount of the iron powder may be determined based on the detected amount of Fe 3+、Al3+、Mg2+ or the like.
The work-up IV procedure is the same as work-up II in example 3.
And (3-3) mixing a ferrous sulfate solution and a phosphoric acid solution, blending to a specified iron-phosphorus ratio, heating to 80 ℃, aerating, adding 7.5% of hydrogen peroxide by mass fraction for ending oxidation, detecting the blended iron-phosphorus ratio, adjusting pH=2.1, heating to 95 ℃ for reacting for 4 hours, press-filtering, and washing with hot water to obtain the ferrophosphorus complex.
Specifically, the phosphorus content in the phosphoric acid solution and the iron content in the ferrous sulfate solution are detected respectively, the iron-phosphorus ratio (0.968) of the ferric phosphate is generated according to the requirement (the calculation formula X=iron/phosphorus is 0.5545), the phosphoric acid solution and the ferrous sulfate solution are metered respectively, and the phosphoric acid solution and the ferrous sulfate solution are added into the ferric phosphate synthesis reaction kettle simultaneously in the same proportion by using an electric valve PID (proportion integration differentiation) control according to the proportion between weighing values;
After the addition is finished, stirring and reacting for 30 minutes, detecting the iron-phosphorus ratio of the solution, wherein the iron-phosphorus ratio does not meet the requirement, preparing the iron-phosphorus ratio by using an ammonium dihydrogen phosphate solution, heating to 80 ℃, maintaining heating after the temperature is reached, starting an aeration fan (500 cubic meters per hour) for aeration for 2 hours to obtain a ferric iron solution, adding a small amount of 7.5% hydrogen peroxide after the aeration is finished, ending and oxidizing, detecting the iron-phosphorus ratio of the solution after the ending and oxidizing is finished, and preparing by using phosphoric acid if the iron-phosphorus ratio does not meet the requirement. And (3) regulating the pH value of the solution with the iron-phosphorus ratio to 2.1 by using ammonia water, and heating to 95 ℃ for reaction for 3 hours after the ammonia water is added to obtain the ferrophosphorus complex. And (3) carrying out filter pressing and washing with 80 ℃ hot water for 5 times until the sulfate radical and ammonia content are lower than 0.001%, and directly pumping the washing liquid to an ammonia synthesis system for preparing ammonia water.
(3-4) Aging the ferrophosphorus complex, and performing post-treatment on the ferrophosphorus complex to obtain anhydrous ferric phosphate;
The post-treatment V comprises filtering, water washing, drying, calcining and the like.
And (3) putting the ferrophosphorus complex filter cake into 15% phosphoric acid solution for aging for 5 hours, filtering and washing with 80 ℃ hot water, pumping the primary aging filtrate to a ferrophosphorus slag acidolysis process for standby after removing impurities through a phosphoric acid resin column, and then collecting washing liquid into monocalcium phosphate by using calcium hydroxide and returning to a phosphoric acid preparation link.
And (3) conveying the aged filter cake into a flash evaporator to be dried and milled at 120 ℃, conveying the dry powder of the ferric phosphate dihydrate into a rotary kiln to be electrically heated, calcining at 700 ℃ for 3 hours to generate anhydrous ferric phosphate, and packaging the anhydrous ferric phosphate in ton bags after grinding, sieving and demagnetizing.
EXAMPLE 7 Ammonia Synthesis
Adding calcium hydroxide to an ammonium sulfate solution (filtrate and washing liquid) [ from the procedures of filter pressing and hot water washing in the steps (3-3) of the embodiment 5 or 6 ] until the pH=12, reacting for 30 minutes at normal temperature, filter pressing, washing a filter cake with normal temperature water for three times after filter pressing, wherein the filter cake is dihydrate gypsum, pumping the filtrate and the washing liquid into an ammonia still, wherein the ammonia still is of a jacket structure (201 stainless steel inner scraping corrosion resistant putty), introducing steam into the ammonia still to heat to 98 ℃, stirring and heating ammonia water, enabling the ammonia gas to pass through a 6-stage ammonia dissolving still (5 for 1 standby ammonia water to reach concentration and then buffer and utilize) (jacket cooling, 201 stainless steel inner scraping corrosion resistant putty, maintaining the temperature to 25 ℃, circulating cooling water needs to be provided with a cold water tank and a cooler), determining the concentration of the ammonia water in a density detection mode, and switching the ammonia dissolving still after the concentration of the ammonia water reaches 25%. Ammonia gas is adsorbed by active carbon and then used for preparing ammonia water, and the tailing is dihydrate gypsum.
Claims (10)
1. The method for preparing the ferric phosphate by recycling renewable phosphorus resources comprises the steps of preparing a phosphoric acid solution and preparing the ferric phosphate, and is characterized in that the process for preparing the phosphoric acid solution comprises the following steps:
(1-1) alkaline leaching and calcification are carried out on the phosphorus-containing solid waste to obtain phosphorus-calcium compound and iron-containing waste residue;
(1-2) adding concentrated sulfuric acid and water into a phosphorus calcium compound to react to obtain a phosphoric acid solution;
The phosphorus-containing solid waste is ferrophosphorus slag or calcium phosphate sludge.
2. The method for preparing ferric phosphate by recycling renewable phosphorus resources according to claim 1, wherein in the step (1-1), in the alkaline leaching process, phosphorus-containing solid waste is liquid alkali=1 (6-9), the liquid alkali is sodium hydroxide aqueous solution with the mass fraction of 15-25%, the alkaline leaching temperature is 60-95 ℃, and the alkaline leaching time is 0.5-3h.
3. The method for preparing ferric phosphate by recycling renewable phosphorus resources according to claim 1, wherein in the step (1-1), in the calcification process, the sodium phosphate solution is calcium hydroxide=1 (0.055-0.095) in terms of mass ratio, the temperature is 20-25 ℃, and the calcification time is 0.5-1h.
4. The method for preparing ferric phosphate by recycling renewable phosphorus resources according to claim 1, wherein in the step (1-2), the reaction temperature is 75-160 ℃ and the reaction time is 1-3h, wherein the mass ratio of the phosphorus-calcium compound to the concentrated sulfuric acid is 1:1-1.2:4-6.
5. The method for preparing iron phosphate by recycling renewable phosphorus resources according to claim 1, wherein the process for preparing iron phosphate comprises:
(2-1) reacting the iron-containing slag with iron powder and phosphoric acid solution to obtain ferrophosphorus liquid and carbon slag;
(2-2) detecting the iron-phosphorus ratio in the ferrophosphorus liquid, adding a phosphoric acid solution to the specified iron-phosphorus ratio, oxidizing, heating to 85-95 ℃ after the oxidation is finished, preserving heat, precipitating, press-filtering, and washing until the pH value is=3-4 to obtain ferric phosphate dihydrate;
the iron-containing slag is ferrophosphorus slag or the iron-containing slag in the step (1-1).
6. The method for producing iron phosphate by recycling renewable phosphorus resources according to claim 5, wherein in the step (2-1), iron-containing slag is iron powder, phosphoric acid solution=1 (0.01-0.04), 5-7, and the mass fraction of the phosphoric acid solution is 20% -25% in terms of mass ratio.
7. The method for preparing ferric phosphate by recycling renewable phosphorus resources according to claim 4, wherein in the step (2-2), the iron-phosphorus ratio is iron: phosphorus=1:2.6-3.0, and the mass fraction of hydrogen peroxide is 7.5-30% by adopting hydrogen peroxide oxidation.
8. The method for preparing iron phosphate by recycling renewable phosphorus resources according to claim 1, wherein the process for preparing iron phosphate comprises:
(3-1) reacting the iron-containing slag with concentrated sulfuric acid, and performing filter pressing and water washing to obtain a solution containing ferric sulfate;
(3-2) adding iron powder into the solution containing the ferric sulfate for reaction, and performing filter pressing to obtain a ferrous sulfate solution;
(3-3) mixing ferrous sulfate solution and phosphoric acid solution, blending to a specified iron-phosphorus ratio, heating to 75-80 ℃, aerating, oxidizing, detecting the blended iron-phosphorus ratio, adjusting pH to 1.7-2.1, heating to 90-95 ℃ for reaction, press-filtering, and washing with hot water to obtain a phosphorus-iron complex;
(3-4) aging the ferrophosphorus complex to obtain ferric phosphate dihydrate;
The iron-containing slag is the iron-containing slag in the step (1-1).
9. The method for preparing ferric phosphate by recycling renewable phosphorus resources according to claim 7, wherein in the step (3-1), the iron-containing slag comprises concentrated sulfuric acid=100 (120-200) in terms of mass ratio, and the reaction time is 30-60min.
10. The method for producing iron phosphate by recycling renewable phosphorus resources according to claim 7, wherein in the step (3-4), the iron phosphate complex cake is put into 10% -15% phosphoric acid solution and aged for 3-5 hours.
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