CN116409764A - Method for preparing ferric phosphate from refined phosphoric acid - Google Patents
Method for preparing ferric phosphate from refined phosphoric acid Download PDFInfo
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- CN116409764A CN116409764A CN202111651849.1A CN202111651849A CN116409764A CN 116409764 A CN116409764 A CN 116409764A CN 202111651849 A CN202111651849 A CN 202111651849A CN 116409764 A CN116409764 A CN 116409764A
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- iron
- ferrous sulfate
- phosphate
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 117
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 69
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 69
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 63
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 56
- 238000001556 precipitation Methods 0.000 claims abstract description 86
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 76
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 76
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 76
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 76
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 123
- 229910052742 iron Inorganic materials 0.000 claims description 48
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 230000006911 nucleation Effects 0.000 claims description 29
- 238000010899 nucleation Methods 0.000 claims description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims description 28
- 239000011574 phosphorus Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 239000007790 solid phase Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- -1 iron ion Chemical class 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 235000010215 titanium dioxide Nutrition 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 5
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021489 α-quartz Inorganic materials 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 4
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 4
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 103
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 238000004321 preservation Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 238000003801 milling Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 5
- 239000002367 phosphate rock Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000000247 postprecipitation Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 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 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229940007277 combination propanol Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LEAMSPPOALICQN-UHFFFAOYSA-H iron(2+);diphosphate;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEAMSPPOALICQN-UHFFFAOYSA-H 0.000 description 2
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
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
- C01B25/26—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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention provides a method for preparing ferric phosphate from refined phosphoric acid, which comprises the following steps: (1) Mixing ferrous sulfate solution, oxidant and refined phosphoric acid to obtain a pre-precipitation solution; (2) Heating and preserving heat for precipitation of the precipitation precursor liquid to obtain slurry containing ferric phosphate precipitation; and (3) carrying out solid-liquid separation on the slurry to obtain the ferric phosphate. The method forms a preparation method of the ferric phosphate based on phosphoric acid instead of monoamino phosphate, can avoid the problem of large amount of low-concentration ammonium sulfate wastewater in the traditional ferric phosphate preparation process, and opens up a new way for the preparation of the ferric phosphate, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of chemical metallurgy, in particular to a method for preparing ferric phosphate from refined phosphoric acid.
Background
The lithium iron phosphate gradually exceeds the loading capacity of the ternary battery, and the reverse exceeding of the lithium iron phosphate battery is closely related to the raw material price of the power battery and the high safety of the lithium iron phosphate battery. It is predicted that lithium iron phosphate batteries will also have a wide range of applications in the energy storage field.
Preparation process of lithium iron phosphateThere are various, among which the mainstream techniques include three, a solid phase method based on iron phosphate, a solid phase method based on ferrous oxalate, and a liquid phase method based on iron nitrate. Iron phosphate is an important requirement for the development of low cost manufacturing techniques as a core precursor for the first process. The preparation process of the ferric phosphate mainly comprises a one-step method and a two-step method, and the quality of the ferric phosphate can be improved by the two-step method compared with the one-step method, so that the method is a main method adopted in industrial production. The two-step process includes two modes of synthesis, the first mode of synthesis being to first react a ferrous source (e.g. FeSO 4 ·7H 2 O) and a phosphorus source (e.g. (NH) 4 ) 2 HPO 4 ) Adjusting pH to 4-5 with ammonia water, and precipitating to obtain ferrous phosphate octahydrate (Fe) 3 (PO 4 ) 2 ·8H 2 Washing ferrous phosphate octahydrate, stirring with water solution, pulping, adding phosphoric acid and hydrogen peroxide into the slurry, heating the slurry to below 100deg.C to obtain ferric phosphate dihydrate crystal (FePO) 4 ·2H 2 O) the ferric phosphate dihydrate crystals are washed again to increase purity; the second mode of synthesis is to first make the ferrous source (e.g. FeSO 4 ·7H 2 O) and a phosphorus source (e.g. (NH) 4 ) 2 HPO 4 ) Reacting in the presence of oxidant (such as hydrogen peroxide) to form amorphous ferric phosphate precipitate, washing the obtained amorphous ferric phosphate precipitate, adding the washed amorphous ferric phosphate precipitate into phosphoric acid solution, and crystallizing at 85-100deg.C to obtain ferric phosphate dihydrate crystal, which can be washed again to remove entrained free ions.
In addition, CN112390237a discloses a method for preparing nano-structured ferric phosphate, specifically, pumping mixed solution of hydrogen peroxide and phosphate or concentrated phosphoric acid into acidic solution (pH value 0.1-1.0) obtained by dissolving and filtering titanium white byproduct ferrous sulfate, then introducing ammonia water to adjust pH value to 1.0-3.0, stirring at 100 ℃ to prepare white ferric phosphate slurry, and carrying out solid-liquid separation and solid dehydration treatment to obtain anhydrous nano-structured ferric phosphate.
CN104944400B and CN110482512a also adopt ferrous sulfate and phosphoric acid as iron source and phosphorus source respectively to precipitate ferric phosphate, but the pH value of the mixed solution is not adjusted by adding ammonia base or sodium base, but the pH value is increased by adding water for dilution to help ferric phosphate precipitation, the precipitation temperature is below 100 ℃, which is a dilution hydrolysis precipitation method, which can avoid the generation of salt-containing wastewater such as ammonium sulfate, but the water circulation amount is large.
CN102491302B discloses a battery-grade anhydrous ferric phosphate and a preparation method thereof, which takes ferrous sulfate or ferrous chloride as an iron source, phosphoric acid or phosphate as a phosphorus source, prepares a mixed solution of the iron source and the phosphorus source, prepares an alkaline regulator based on ammonium, pumps the mixed solution and the alkaline regulator into a stirring reactor, inputs compressed air, controls the pH to be 0.5-7.5 through the adjustment of liquid materials and air flow, and generates NH 4 Fe 2 (OH)(PO 4 ) 2 ·2H 2 And (3) fully washing the solid and roasting to obtain the battery grade anhydrous ferric phosphate of the orthorhombic crystal form.
However, the above-mentioned documents still have problems of large water circulation amount or generation of ammonia-containing wastewater.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a method for preparing ferric phosphate from refined phosphoric acid, which is based on the thought of being combined with phosphorus chemical enterprises, and develops a method for preparing ferric phosphate by adopting phosphoric acid instead of monoammonia phosphate so as to avoid the problems caused by a large amount of low-concentration ammonium sulfate wastewater in the traditional method for preparing ferric phosphate.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing ferric phosphate from refined phosphoric acid, which comprises the following steps:
(1) Mixing ferrous sulfate solution, oxidant and refined phosphoric acid to obtain a pre-precipitation solution;
(2) Heating and preserving heat for precipitation of the precipitation precursor liquid to obtain slurry containing ferric phosphate precipitation;
(3) And carrying out solid-liquid separation on the slurry to obtain ferric phosphate.
The method for preparing the ferric phosphate from the refined phosphoric acid can be suitable for ferrous sulfate solution containing impurities, and can obtain the ferric phosphate product with higher purity in the follow-up process by directly heating and preserving heat and precipitating the precipitation precursor liquid, thereby avoiding the generation of a large amount of circulating water and ammonia-containing wastewater and realizing the green production of the ferric phosphate by utilizing the characteristics that the ferric phosphate has smaller solubility in an inorganic acid environment or a mixed solvent acid environment and can be crystallized preferentially and inhibit the substitution of the ferric lattice position of the impurities in ferric phosphate lattices.
The mixing steps of the ferrous sulfate solution, the oxidant and the refined phosphoric acid are not particularly limited, and the mixture can be mixed according to any sequence, for example, the mixture is obtained by mixing the ferrous sulfate solution and the refined phosphoric acid uniformly and then mixing the mixture with the ferrous sulfate solution, or the mixture is obtained by oxidizing ferrous ions with the hydrogen peroxide after mixing the ferrous sulfate solution and the refined phosphoric acid uniformly, or the mixture is obtained by oxidizing the ferrous sulfate solution with the hydrogen peroxide and then mixing the refined phosphoric acid; or directly and simultaneously adding the three components into a container for mixing.
Preferably, the preparation of the ferrous sulfate solution in step (1) includes: mixing ferrous sulfate raw material and solvent, mixing iron powder and sulfuric acid solution or mixing ferrous sulfate raw material, iron powder and solvent, dissolving and refining after mixing to obtain ferrous sulfate solution.
Preferably, the ferrous sulfate feedstock comprises any one or a combination of at least two of high purity ferrous sulfate, technical grade ferrous sulfate or ferrous sulfate as a byproduct of acid process titanium dioxide, wherein typical but non-limiting combinations are: a combination of high-purity ferrous sulfate and industrial grade ferrous sulfate, a combination of high-purity ferrous sulfate and ferrous sulfate which is a byproduct of titanium white by an acid method, a combination of industrial grade ferrous sulfate and ferrous sulfate which is a byproduct of titanium white by an acid method, and a combination of high-purity ferrous sulfate, industrial grade ferrous sulfate and ferrous sulfate which is a byproduct of titanium white by an acid method. The method has the advantages of wide sources of raw materials of the ferrous sulfate and low cost, and even if the raw materials contain partial impurities, the purity of the ferric phosphate in the final product is not affected.
Preferably, the iron powder includes any one or a combination of at least two of raw iron powder, reduced iron powder, electrolytic iron powder, hydroxy iron powder, or atomized iron powder, wherein typical but non-limiting combinations are combinations of raw iron powder and reduced iron powder, combinations of raw iron powder and electrolytic iron powder, combinations of electrolytic iron powder and reduced iron powder, combinations of hydroxy iron powder and reduced iron powder, and combinations of raw iron powder and atomized iron powder.
Preferably, the impurities include any one or a combination of at least two of titanium, magnesium, aluminum, calcium, vanadium, chromium, manganese, nickel, cobalt, zinc, lead, sodium, potassium, silicon, or copper, for example, titanium, magnesium, aluminum, calcium, and the like may be contained at the same time.
Preferably, the refined phosphoric acid contains any one or at least two impurities of iron, aluminum, magnesium, manganese, titanium, zinc, calcium, sodium, chromium or vanadium, but the concentration of the iron, the aluminum, the magnesium and the manganese is lower than 0.85g/L, and the concentration of the titanium, the zinc, the calcium, the sodium, the chromium and the vanadium is not higher than 0.35g/L.
Preferably, the solvent comprises water and/or a sulfuric acid solution.
The total iron ion concentration in the ferrous sulfate solution is preferably 0.1 to 2mol/L, and may be, for example, 0.1mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, or 2mol/L, etc., but not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the refining in step (1) comprises: the pH of the solution after dissolution is adjusted to 2 to 10 and solid-liquid separation may be, for example, 2.0, 2.2, 2.5, 2.8, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 8.0, 9.0 or 10.0, etc., but other non-enumerated values within this range are equally applicable. The invention further carries out subsequent precipitation process after refining, thereby further improving the purity of the final ferric phosphate.
Preferably, the substance for adjusting the pH of the solution after dissolution comprises an alkaline substance.
Preferably, the alkaline substance includes any one or a combination of at least two of sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, lime, limestone, slaked lime, metallic calcium, magnesium hydroxide, magnesium oxide, magnesium powder, magnesium dust, ferric hydroxide, ferric oxide, ferric carbonate, iron powder or iron filings, wherein typical but non-limiting combinations are sodium carbonate and sodium hydroxide combinations, potassium hydroxide and sodium hydroxide combinations, sodium carbonate and lime combinations, slaked lime and magnesium hydroxide combinations, metallic calcium and sodium hydroxide combinations, magnesium powder and ferric hydroxide combinations, magnesium powder and magnesium dust combinations, and ferric carbonate and ferric oxide combinations.
Preferably, the oxidizing agent in step (1) comprises hydrogen peroxide.
Preferably, the hydrogen peroxide is used in an amount of 0.5 to 2 times the total molar amount of the ferrous ions in the ferrous sulfate solution, for example, 0.5 times, 1.0 times, 1.5 times, or 2.0 times, but not limited to the recited values, and other non-recited values within the range are equally applicable. The invention further preferably controls the dosage of the hydrogen peroxide in the range, which is more beneficial to guaranteeing the state of iron in the solution before precipitation.
Preferably, the purified phosphoric acid is added in an amount of 0.8 to 1.1:1 molar ratio of iron to phosphorus in the pre-precipitation solution, for example, 0.8:1, 0.9:1, 1.0:1, or 1.1:1, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the concentration of the refined phosphoric acid is 5 to 85wt% P 2 O 5 For example, 5wt% P 2 O 5 、10wt％P 2 O 5 、15wt％P 2 O 5 、20wt％P 2 O 5 、25wt％P 2 O 5 、30wt％P 2 O 5 、35wt％P 2 O 5 、40wt％P 2 O 5 、45wt％P 2 O 5 、50wt％P 2 O 5 、55wt％P 2 O 5 、60wt％P 2 O 5 、65wt％P 2 O 5 、70wt％P 2 O 5 、75wt％P 2 O 5 、80wt％P 2 O 5 Or 85wt% P 2 O 5 And the like, but are not limited to the recited values, and other non-recited values within this range are equally applicable.
The temperature of the thermal precipitation is preferably 60 to 150 ℃, and may be 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or the like, for example, but is not limited to the values recited, and other values not recited in the range are equally applicable. The invention further preferably keeps the temperature of precipitation at 60-150 ℃, can be matched with the concentration of hydrogen ions in the solution before precipitation, an alcohol solvent or a nucleation promoter, better realizes the precipitation of ferric phosphate under strong acid, and can avoid the entrainment of impurities.
Preferably, the thermal insulation precipitation is performed under stirring conditions.
Preferably, the precipitation precursor solution and the sulfuric acid solution are mixed to H before the temperature is raised in the step (2) + The concentration is 1 to 5mol/L, and may be, for example, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 4.0mol/L, or 5.0mol/L, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable. The invention further adjusts the concentration of hydrogen ions in the system before heating and heat-preserving precipitation, and ensures that the system is in a strong acid environment, thereby being beneficial to the subsequent separation of ferric phosphate and impurities and further improving the purity of ferric phosphate.
Preferably, the pre-precipitation solution and the alcohol solvent are mixed before the temperature is raised in step (2). In the invention, an alcohol solvent is further preferably added, so that the precipitation of ferric phosphate precipitates is further enhanced in a strong acid system.
Preferably, the alcoholic solvent includes any one or a combination of at least two of methanol, ethanol, propanol or isopropanol, wherein typical but non-limiting combinations are combinations of methanol and ethanol, combinations of methanol and propanol, combinations of ethanol and propanol, combinations of methanol and isopropanol, combinations of methanol, ethanol and propanol, and the like.
The amount of the alcohol solvent added is preferably 5 to 100% by volume of the liquid before precipitation, and may be, for example, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the pre-precipitation solution and nucleation promoter are mixed prior to the warming in step (2). The invention further preferably adds a nucleation promoter to further enhance the precipitation of ferric phosphate precipitates in a strongly acidic system.
Preferably, the nucleation promoter comprises any one or a combination of at least two of isophosphoric ferromanganese type iron phosphate, monoclinic type iron phosphate, orthorhombic type iron phosphate, alpha-quartz type iron phosphate, monoclinic type iron phosphate dihydrate or orthorhombic iron phosphate dihydrate, wherein the typical but non-limiting combination is a combination of isophosphoric ferromanganese type iron phosphate and monoclinic type iron phosphate, a combination of orthorhombic iron phosphate and monoclinic type iron phosphate, a combination of isophosphoric ferromanganese type iron phosphate and alpha-quartz type iron phosphate, a combination of monoclinic iron phosphate and monoclinic type iron phosphate, and a combination of isophosphoric ferromanganese type iron phosphate and orthorhombic iron phosphate dihydrate.
Preferably, the nucleation promoter is finely ground prior to mixing the nucleation promoter with the pre-precipitation solution. The invention further carries out the grinding treatment of the nucleation promoter, thereby being beneficial to regulating and controlling the particle size and morphology of the ferric phosphate.
The nucleation promoter is preferably added in a molar amount of 0.01 to 10 times the total molar amount of iron in the precipitation precursor solution, and may be, for example, 0.01 times, 0.02 times, 0.05 times, 0.1 times, 0.2 times, 0.5 times, 1.0 times, 2.0 times, 3.0 times, 5.0 times, 7.5 times, 9.0 times, or 10.0 times, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
The acid solution, the alcohol solvent and the nucleation promoter which are supplemented in the invention can be added simultaneously, or one or at least two of the acid solution, the alcohol solvent and the nucleation promoter can be selected to be added simultaneously, preferably the acid solution, the alcohol solvent and the nucleation promoter are added simultaneously, so that the invention has better regulating effect.
Preferably, the solid phase after the solid-liquid separation in step (3) is washed.
Preferably, the washing comprises water washing.
Preferably, the washing in step (3) further comprises: the solid phase is calcined.
Preferably, the calcination is preceded by milling.
Preferably, the milling method comprises any one or a combination of at least two of ball milling, stirring milling or sand milling, wherein typical but non-limiting combinations are combinations of ball milling and stirring milling, combinations of stirring milling and sand milling, and combinations of ball milling and sand milling.
The particle diameters of the fine particles are preferably 20 μm or less, and may be, for example, 20 μm, 19 μm, 18 μm, 16 μm, 15 μm, 12 μm, 10 μm or 8 μm, etc., but are not limited to the values recited, and other values not recited in the range are equally applicable.
The temperature of the calcination in the step (3) is preferably 400 to 900 ℃, and may be, for example, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The calcination time is preferably 0.5 to 12 hours, and may be, for example, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or 12 hours, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
The present invention is not particularly limited in terms of solid-liquid separation, and any means known to those skilled in the art as being applicable to solid-liquid separation may be employed, and may be adjusted according to the actual process, for example, centrifugal separation, filtration separation, sedimentation separation, or the like.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Mixing ferrous sulfate raw materials with a solvent, mixing iron powder with a sulfuric acid solution or mixing ferrous sulfate raw materials, iron powder and a solvent, dissolving after mixing, adjusting the pH value of the dissolved solution to 2-10, and carrying out solid-liquid separation to obtain a ferrous sulfate solution with the total iron ion concentration of 0.1-2 mol/L;
mixing the ferrous sulfate solution, hydrogen peroxide and P with the concentration of 5-85wt% 2 O 5 The consumption of hydrogen peroxide is 0.5-2 times of the total molar quantity of ferrous ions in the ferrous sulfate solution, and the consumption of the refined phosphoric acid is added according to the molar ratio of iron to phosphorus in the solution before precipitation of 0.8-1.1:1, so as to obtain the solution before precipitation;
(2) Adding any one or a combination of at least two of an acidic solution, an alcohol solvent and a nucleation promoter into the precipitation precursor solution, heating to 60-150 ℃, and carrying out heat preservation precipitation under the stirring condition to obtain slurry containing ferric phosphate precipitation;
wherein, when the acid solution is added, the mixture is mixed into the system H + The concentration is 1-5 mol/L; when the alcohol solvent is added, the addition amount of the alcohol solvent is 5-100% of the volume fraction of the liquid before precipitation; when the nucleation promoter is added, the adding molar quantity of the nucleation promoter is 0.01-10 times of the total molar quantity of iron in the precipitation precursor liquid;
(3) And washing the solid phase of the slurry subjected to solid-liquid separation to obtain the ferric phosphate.
Further preferably, the liquid phase obtained by solid-liquid separation of the slurry is distilled to recover an alcohol solvent and an acid solution, and the alcohol solvent can be recycled to the heat preservation precipitation step; the acid solution is circulated to the wet phosphoric acid system for the decomposition of the phosphate rock.
Further preferably, after washing the solid phase obtained by solid-liquid separation of the slurry, the solid phase can be ground into particles with the particle size of below 20 mu m, and then calcined for 0.5 to 12 hours at the temperature of 400 to 900 ℃ to obtain the ferric phosphate. It may be further preferable to control the particle size and product purity of the final iron phosphate.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The method for preparing ferric phosphate from refined phosphoric acid provided by the invention can be suitable for ferrous sulfate and iron powder with wide sources, wherein the purity of ferrous sulfate in ferrous sulfate raw materials can be as low as 82wt%, the purity of iron powder can be as low as 95wt%, the purity requirements on raw materials such as ferrous sulfate and iron powder are relatively low, the method can be combined with phosphorus chemical industry, the operation is simple, the process cost is low, and the production cost is reduced; even if the raw materials containing impurities are adopted, the iron phosphate product with the purity of more than 99.7 percent, preferably more than 99.9 percent can be obtained, the recovery rate of the iron phosphate can reach more than 90 percent under the better condition, and the iron-phosphorus ratio is more than 0.9;
(2) The method for preparing the ferric phosphate from the refined phosphoric acid provided by the invention can be used for directly separating out ferric phosphate precipitate under the condition of strong acid, avoiding the generation of a large amount of circulating water or ammonia-containing wastewater and realizing the low-cost green production of the ferric phosphate.
Drawings
FIG. 1 is a flow chart of a method for preparing iron phosphate from refined phosphoric acid provided by the invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
As one embodiment of the present invention, there is provided a method for preparing iron phosphate from refined phosphoric acid, as shown in fig. 1, comprising the steps of:
(1) Mixing ferrous sulfate raw material with solvent or mixed iron powder and sulfuric acid solution, dissolving, regulating the pH value of the dissolved solution to 2-10, and carrying out solid-liquid separation to obtain ferrous sulfate solution with total iron ion concentration of 0.1-2 mol/L;
mixing the ferrous sulfate solution, hydrogen peroxide and P with the concentration of 5-85wt% 2 O 5 The consumption of hydrogen peroxide is 0.5-2 times of the total molar quantity of ferrous ions in the ferrous sulfate solution, and the consumption of the refined phosphoric acid is added according to the molar ratio of iron to phosphorus in the solution before precipitation of 0.8-1.1:1, so as to obtain the solution before precipitation;
(2) Adding any one or a combination of at least two of an acidic solution, an alcohol solvent or a nucleation promoter into the precipitation precursor solution (the broken line in the figure 1 indicates that one or a combination of at least two of the acidic solution, the alcohol solvent or the nucleation promoter can be added at will), heating to 60-150 ℃, and carrying out heat preservation precipitation under the stirring condition to obtain slurry containing ferric phosphate precipitation;
wherein, when the acid solution is added, the mixture is mixed into the system H + The concentration is 1-5 mol/L; when the alcohol solvent is added, the addition amount of the alcohol solvent is 5-100% of the volume fraction of the liquid before precipitation; when the nucleation promoter is added, the adding molar quantity of the nucleation promoter is 0.01-10 times of the total molar quantity of iron in the precipitation precursor liquid;
(3) And washing the solid phase of the slurry subjected to solid-liquid separation to obtain the ferric phosphate.
Further preferably, in the above specific embodiment, as shown in fig. 1, the liquid phase obtained by solid-liquid separation of the slurry is distilled to recover an alcohol solvent and an acidic solution, and the alcohol solvent may be recycled to the thermal insulation precipitation step; the acid solution is circulated to the wet phosphoric acid system for the decomposition of the phosphate rock.
Further preferably, in the above specific embodiment, as shown in fig. 1, the solid phase obtained by solid-liquid separation of the slurry may be washed, milled to have particle diameters of less than 20 μm, and calcined at 400-900 ℃ for 0.5-12 hours to obtain iron phosphate. It may be further preferable to control the particle size and product purity of the final iron phosphate.
Example 1
This example provides a method of preparing iron phosphate from refined phosphoric acid, the method comprising the steps of:
(1) Mixing ferrous sulfate raw materials (by-product ferrous sulfate of acid titanium white, wherein the content of ferrous sulfate is 87wt%, and the ferrous sulfate contains 0.40wt% of magnesium, 0.10wt% of aluminum, 0.17wt% of silicon, 0.02wt% of potassium, 0.03wt% of calcium, 5.4wt% of titanium, 0.03wt% of vanadium, 0.12wt% of manganese, 0.02wt% of nickel, 0.07wt% of zinc and free water), dissolving, adding ferric hydroxide to adjust the pH value of the dissolved solution to 8, and filtering to obtain ferrous sulfate solution with total iron ion concentration of 0.5 mol/L;
mixing the ferrous sulfate solution, hydrogen peroxide and 50wt% P 2 O 5 The concentration of iron, aluminum, magnesium and manganese in the solution is lower than 0.5g/L, the concentration of titanium, zinc, calcium, sodium, chromium and vanadium in the solution is not higher than 0.2g/L, the dosage of hydrogen peroxide is 0.8 times of the total molar quantity of ferrous ions in the ferrous sulfate solution, and the dosage of the refined phosphoric acid is added according to the molar ratio of iron to phosphorus in the solution before precipitation of 1.0:1, so as to obtain solution before precipitation;
(2) The pre-precipitation solution is placed in a precipitator, and sulfuric acid solution is added into the system H + Adding methanol with the concentration of 1mol/L and the addition amount of 50 percent of the volume fraction of the solution before precipitation, heating to 120 ℃ and carrying out heat preservation precipitation under the stirring condition to obtain slurry containing ferric phosphate precipitation;
(3) The liquid phase obtained by filtering the slurry is distilled to recover an alcohol solvent and an acid solution, and the alcohol solvent can be recycled to the heat preservation precipitation step; the acid solution is circulated to a wet phosphoric acid system for decomposing phosphorite; the solid phase obtained by filtering the slurry can be firstly ground into particles with the particle size of below 20 mu m after being washed, and then the particles are calcined for 10 hours at the temperature of 500 ℃ to obtain the ferric phosphate.
Example 2
This example provides a method of preparing iron phosphate from refined phosphoric acid, the method comprising the steps of:
(1) Mixing ferrous sulfate raw materials (industrial grade ferrous sulfate, wherein the ferrous sulfate content is 91wt%, and the industrial grade ferrous sulfate contains 0.33wt% of magnesium, 0.09wt% of aluminum, 0.30wt% of silicon, 0.20wt% of potassium and 0.24wt% of calcium) and sulfuric acid solution, dissolving, adding scrap iron (the iron content is 97wt%, and the industrial grade ferrous sulfate contains 0.67wt% of magnesium, 0.10wt% of aluminum, 1.05wt% of silicon and 0.12wt% of calcium), adjusting the pH value of the dissolved solution to 2, and filtering to obtain ferrous sulfate solution with the total iron ion concentration of 0.1 mol/L;
mixing the ferrous sulfate solution, hydrogen peroxide and 85wt% P 2 O 5 The concentration of iron, aluminum, magnesium and manganese in the solution is lower than 0.85g/L, the concentration of titanium, zinc, calcium, sodium, chromium and vanadium in the solution is not higher than 0.35g/L, the dosage of hydrogen peroxide is 2 times of the total molar quantity of ferrous ions in the ferrous sulfate solution, and the dosage of the refined phosphoric acid is added according to the molar ratio of iron to phosphorus in the solution before precipitation of 1.1:1, so as to obtain solution before precipitation;
(2) Placing the pre-precipitation solution in a precipitator, adding monoclinic ferric phosphate dihydrate as a nucleation promoter, adding 10 times of the total molar weight of iron in the pre-precipitation solution, adding methanol, wherein the addition of the methanol is 5% of the volume fraction of the pre-precipitation solution, heating to 60 ℃, and carrying out heat preservation precipitation under the stirring condition to obtain slurry containing ferric phosphate precipitate;
(3) The liquid phase obtained by filtering the slurry is distilled to recover an alcohol solvent and an acid solution, and the alcohol solvent can be recycled to the heat preservation precipitation step; the acid solution is circulated to a wet phosphoric acid system for decomposing phosphorite; the solid phase obtained by filtering the slurry can be firstly ground into particles with the particle size of below 20 mu m after being washed, and then the particles are calcined for 12 hours at 400 ℃ to obtain the ferric phosphate.
Example 3
This example provides a method of preparing iron phosphate from refined phosphoric acid, the method comprising the steps of:
(1) Mixing iron powder (the iron content is 99 wt%), ferrous sulfate raw materials (high-purity ferrous sulfate, the ferrous sulfate content is 99 wt%) and sulfuric acid solution, dissolving, adding ferric hydroxide to adjust the pH value of the dissolved solution to 10, and filtering to obtain ferrous sulfate solution with the total iron ion concentration of 2 mol/L;
mixing the ferrous sulfate solution, hydrogen peroxide and P with the concentration of 5wt% 2 O 5 The concentration of iron, aluminum, magnesium and manganese in the solution is lower than 0.05g/L, the concentration of titanium, zinc, calcium, sodium, chromium and vanadium in the solution is not higher than 0.02g/L, the dosage of hydrogen peroxide is 0.5 times of the total molar quantity of ferrous ions in the ferrous sulfate solution, and the dosage of the refined phosphoric acid is added according to the molar ratio of iron to phosphorus in the solution before precipitation of 0.8:1, so as to obtain solution before precipitation;
(2) The pre-precipitation solution is placed in a precipitator, and sulfuric acid solution is added into the system H + Adding monoclinic ferric phosphate with the concentration of 5mol/L as a nucleation promoter, wherein the adding molar quantity of the nucleation promoter is 2 times of the total molar quantity of iron in the solution before precipitation, heating to 150 ℃ and carrying out heat preservation precipitation under the stirring condition to obtain slurry containing ferric phosphate precipitation;
(3) The liquid phase obtained by filtering the slurry is distilled to recover an alcohol solvent and an acid solution, and the alcohol solvent can be recycled to the heat preservation precipitation step; the acid solution is circulated to a wet phosphoric acid system for decomposing phosphorite; after the solid phase obtained by filtering the slurry is washed, the solid phase can be ground into particles with the particle size of less than 18 mu m, and then the solid phase is calcined for 0.5h at 900 ℃ to obtain the ferric phosphate.
Example 4
This example provides a method for producing iron phosphate from refined phosphoric acid, which differs from example 1 only in that: the amount of the refined phosphoric acid in the step (1) is added according to the mole ratio of iron to phosphorus in the solution before precipitation of 0.7:1.
Example 5
This example provides a method for producing iron phosphate from refined phosphoric acid, which differs from example 1 only in that: the amount of the refined phosphoric acid in the step (1) is added according to the mole ratio of iron to phosphorus in the solution before precipitation of 1.3:1.
Example 6
This example provides a method for producing iron phosphate from refined phosphoric acid, which differs from example 1 only in that: adding sulfuric acid solution into the system H in the step (2) + The concentration was 7mol/L.
Example 7
This example provides a method for producing iron phosphate from refined phosphoric acid, which differs from example 1 only in that: in the step (2), no methanol is added, and only sulfuric acid solution is added into the system H + The concentration was 1mol/L.
Example 8
This example provides a method for producing iron phosphate from refined phosphoric acid, which differs from example 1 only in that: and (3) simultaneously adding monoclinic iron phosphate serving as a nucleation promoter into the step (2), wherein the adding molar quantity of the nucleation promoter is 3 times of the total molar quantity of iron in the precipitation precursor solution.
Example 9
This example provides a method for producing iron phosphate from refined phosphoric acid, which differs from example 2 only in that: in the step (2), no methanol is added, and only monoclinic ferric phosphate dihydrate is added.
Example 10
This example provides a method for producing iron phosphate from refined phosphoric acid, which differs from example 1 only in that: in step (3), calcination is not performed.
Comparative example 1
This comparative example provides a method of preparing iron phosphate by hydrolysis, which is example 1 in CN 104944400B.
The comparative example adopts a hydrolysis method to prepare ferric phosphate, water is required to be added for dilution to improve the pH value and help ferric phosphate to precipitate, the circulating amount of water is large, the precipitation efficiency of ferric phosphate is low, and the method is difficult to be suitable for raw materials with impurities.
The testing method comprises the following steps:
the purity of iron phosphate was measured by dissolving iron phosphate in 6mol/L hydrochloric acid, and then analyzing it by ICP-OES, and calculating the recovery rates of iron and phosphorus, respectively, as follows.
The detection method of the mole ratio of phosphorus to iron in the iron phosphate product is ICP-OES analysis, so as to obtain the mass content of iron and phosphorus in the iron phosphate product, and then the mass content is converted into the mole ratio of iron to phosphorus.
The calculation formula of the yield of iron is: 1- (post-precipitation liquid volume x concentration of iron in post-precipitation liquid)/(pre-precipitation liquid volume x concentration of iron in pre-precipitation liquid).
The yield of phosphorus is calculated as: 1- (post-precipitation liquid volume x phosphorus concentration in post-precipitation liquid)/(pre-precipitation liquid volume x phosphorus concentration in pre-precipitation liquid).
The test results of the above examples are shown in Table 1.
TABLE 1
From table 1, the following points can be seen:
(1) Comprehensive examples 1 to 3 show that the method for preparing ferric phosphate from refined phosphoric acid provided by the invention has high purity and high recovery rate of iron and phosphorus, wherein the purity of ferric phosphate is more than or equal to 99.9%, the recovery rate of iron and phosphorus is more than or equal to 90%, and the method avoids the generation of a large amount of low-concentration ammonium sulfate wastewater;
(2) As can be seen from a combination of example 1 and example 6, in example 1, sulfuric acid solution was added to H in the system + At a concentration of 1mol/L, as compared to H in example 6 + The recovery of iron and phosphorus in example 1 was 92% and the recovery of iron and phosphorus in example 6 was only 57% at a concentration of 7mol/L, thus indicating that the present invention prefers to use sulfuric acid solution to recycle H in the system + The concentration is controlled in a specific range, so that the recovery rate can be improved;
(3) It can be seen from the combination of examples 1 and 7 to 8 that the addition of sulfuric acid solution, methanol and monoclinic iron phosphate as nucleation promoters in example 8 is performed at the same time, and the recovery rate of iron and phosphorus in example 8 is as high as 97% and the recovery rate in example 1 is only 92% and the recovery rate in example 7 is more than 87% compared with the addition of no nucleation promoters in example 1 and the addition of only sulfuric acid solution in example 7, and the similar cases are shown in examples 2 and 9, thereby showing that the invention further preferably adds sulfuric acid solution, methanol and monoclinic iron phosphate as nucleation promoters at the same time, and the recovery rate can be improved better;
(4) It can be seen from a combination of examples 1 and 10 that the calcination step was performed in example 1, the purity of iron phosphate in example 1 was 99.9% and the purity of iron phosphate in example 10 was only 99.7% compared to the case where no calcination was performed in example 10, thus indicating that the present invention further improves the purity of iron phosphate by preferably adding the calcination step.
In conclusion, the method for preparing the ferric phosphate from the refined phosphoric acid can be suitable for the refined phosphoric acid and the iron powder containing impurities, the sources of raw materials are wide, the purity of the obtained product is high, the recovery rate is high, and the method is suitable for industrial popularization.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (10)
1. A method of producing iron phosphate from refined phosphoric acid, the method comprising the steps of:
(1) Mixing ferrous sulfate solution, oxidant and refined phosphoric acid to obtain a pre-precipitation solution;
(2) Heating and preserving heat for precipitation of the precipitation precursor liquid to obtain slurry containing ferric phosphate precipitation;
(3) And carrying out solid-liquid separation on the slurry to obtain ferric phosphate.
2. The method of claim 1, wherein the preparation of the ferrous sulfate solution in step (1) comprises: mixing ferrous sulfate raw materials with a solvent, mixing iron powder with a sulfuric acid solution or mixing ferrous sulfate raw materials, iron powder and a solvent, and dissolving and refining after mixing to obtain a ferrous sulfate solution;
preferably, the ferrous sulfate raw material comprises any one or a combination of at least two of high-purity ferrous sulfate, industrial grade ferrous sulfate or ferrous sulfate as a byproduct of acid process titanium white;
preferably, the iron powder comprises any one or a combination of at least two of raw iron powder, reduced iron powder, electrolytic iron powder, hydroxy iron powder or atomized iron powder;
preferably, the solvent comprises water and/or sulfuric acid solution;
preferably, the total iron ion concentration in the ferrous sulfate solution is 0.1-2 mol/L.
3. The method of claim 2, wherein the refining in step (1) comprises: adjusting the pH value of the dissolved solution to 2-10 and carrying out solid-liquid separation;
preferably, the substance for adjusting the pH of the solution after dissolution comprises an alkaline substance.
4. A method according to any one of claims 1 to 3, wherein the oxidant in step (1) comprises hydrogen peroxide;
preferably, the dosage of the hydrogen peroxide is 0.5 to 2 times of the total molar quantity of ferrous ions in the ferrous sulfate solution;
preferably, the use amount of the refined phosphoric acid is added according to the mole ratio of iron to phosphorus in the solution before precipitation of 0.8-1.1:1;
preferably, the concentration of the refined phosphoric acid is 5 to 85wt% P 2 O 5 。
5. The method according to any one of claims 1 to 4, wherein the temperature of the thermal precipitation in step (2) is 60 to 150 ℃;
preferably, the thermal insulation precipitation is performed under stirring conditions.
6. The method according to any one of claims 1 to 5, wherein the precipitation precursor solution and the sulfuric acid solution are mixed to H before the temperature is raised in the step (2) + The concentration is 1-5 mol/L.
7. The method according to any one of claims 1 to 6, wherein the pre-precipitation solution and an alcoholic solvent are mixed before the temperature is raised in step (2);
preferably, the alcohol solvent comprises any one or a combination of at least two of methanol, ethanol, propanol or isopropanol;
preferably, the addition amount of the alcohol solvent is 5-100% of the volume fraction of the liquid before precipitation.
8. The method according to any one of claims 1 to 7, wherein the pre-precipitation solution and nucleation promoter are mixed prior to the warming in step (2);
preferably, the nucleation promoter comprises any one or a combination of at least two of isophosphoric ferromanganese ore type iron phosphate, monoclinic iron phosphate, orthorhombic iron phosphate, alpha-quartz crystal type iron phosphate, monoclinic iron phosphate dihydrate or orthorhombic iron phosphate dihydrate;
preferably, the nucleation promoter is added in a molar amount of 0.01 to 10 times the total molar amount of iron in the precipitation precursor solution.
9. The method according to any one of claims 1 to 8, wherein the washing in step (3) further comprises: calcining the solid phase;
preferably, the calcination is preceded by grinding;
preferably, the particle diameters of the ground particles are all below 20 μm.
10. The method according to claim 9, wherein the temperature of the calcination in step (3) is 400 to 900 ℃;
preferably, the calcination time is 0.5 to 12 hours.
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| CN101913586A (en) * | 2010-08-09 | 2010-12-15 | 中钢集团安徽天源科技股份有限公司 | Preparation method of ferric phosphate and product thereof |
| CN111847416A (en) * | 2020-07-24 | 2020-10-30 | 中南大学 | Method for preparing hydrated iron phosphate from ferrous sulfate serving as titanium dioxide byproduct |
| CN112093785A (en) * | 2020-09-08 | 2020-12-18 | 北京科技大学 | Method for efficiently recycling lithium in lithium iron phosphate cathode waste and preparing iron phosphate for battery |
| CN112479174A (en) * | 2020-11-09 | 2021-03-12 | 湖南雅城新材料有限公司 | Method for synthesizing iron phosphate by using titanium dioxide byproduct ferrous sulfate |
| CN112591726A (en) * | 2020-11-30 | 2021-04-02 | 重庆特瑞新能源材料有限公司 | Preparation method of iron phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913586A (en) * | 2010-08-09 | 2010-12-15 | 中钢集团安徽天源科技股份有限公司 | Preparation method of ferric phosphate and product thereof |
| CN111847416A (en) * | 2020-07-24 | 2020-10-30 | 中南大学 | Method for preparing hydrated iron phosphate from ferrous sulfate serving as titanium dioxide byproduct |
| CN112093785A (en) * | 2020-09-08 | 2020-12-18 | 北京科技大学 | Method for efficiently recycling lithium in lithium iron phosphate cathode waste and preparing iron phosphate for battery |
| CN112479174A (en) * | 2020-11-09 | 2021-03-12 | 湖南雅城新材料有限公司 | Method for synthesizing iron phosphate by using titanium dioxide byproduct ferrous sulfate |
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