CN107188149A - A kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate - Google Patents
A kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate Download PDFInfo
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- CN107188149A CN107188149A CN201710635752.9A CN201710635752A CN107188149A CN 107188149 A CN107188149 A CN 107188149A CN 201710635752 A CN201710635752 A CN 201710635752A CN 107188149 A CN107188149 A CN 107188149A
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- Prior art keywords
- acid
- purity
- organic phase
- phosphoric acid
- ferric 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 58
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 57
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 55
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 85
- 239000012074 organic phase Substances 0.000 claims abstract description 74
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000005406 washing Methods 0.000 claims abstract description 61
- 238000000605 extraction Methods 0.000 claims abstract description 45
- 239000003350 kerosene Substances 0.000 claims abstract description 44
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006227 byproduct Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 19
- 239000001038 titanium pigment Substances 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 239000003643 water by type Substances 0.000 claims abstract description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 239000000706 filtrate Substances 0.000 claims description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 58
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000008346 aqueous phase Substances 0.000 claims description 32
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 21
- AIJDCDQXDPERNG-UHFFFAOYSA-N azanium;bis(2-ethylhexyl) phosphate Chemical compound [NH4+].CCCCC(CC)COP([O-])(=O)OCC(CC)CCCC AIJDCDQXDPERNG-UHFFFAOYSA-N 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004568 cement Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005292 vacuum distillation Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 12
- 238000010348 incorporation Methods 0.000 claims description 12
- 235000014413 iron hydroxide Nutrition 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- OWVGDMONTGJBRI-UHFFFAOYSA-N bis(2-ethylhexyl) hydrogen phosphate iron Chemical compound [Fe].CCCCC(CC)COP(O)(=O)OCC(CC)CCCC OWVGDMONTGJBRI-UHFFFAOYSA-N 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- -1 Ethylhexyl Chemical group 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001728 nano-filtration Methods 0.000 claims description 6
- 235000021110 pickles Nutrition 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 238000005201 scrubbing Methods 0.000 claims description 6
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002912 waste gas Substances 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims 2
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 abstract 1
- 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 abstract 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 68
- 229910052493 LiFePO4 Inorganic materials 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000016804 zinc Nutrition 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 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 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000000414 obstructive effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 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
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
Abstract
The present invention discloses a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate.It includes by-product of white titanium pigment and improves pH and add iron powder to carry out impurity and purification solution, then reoxidize ferrous oxidation into ferric iron, then the pH of ferric sulfate is adjusted, using two (2 ethylhexyl) phosphoric acid extraction ferric ions therein, using the extraction of 56 stage countercurrents and 56 stage countercurrent acid solution washes and 23 stage countercurrent pure waters, organic phase after being washed, sulfonated kerosene is distilled off, by the organic phase mixed catalyst after distillation, reacted 34 hours at 300 320 DEG C, dried after reacted material is added into ethanol washing, obtain high-purity nm ferric phosphate.A kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate of the present invention, by by-product of white titanium pigment, can prepare high-purity nm ferric phosphate, and obtained ferric phosphate purity is high, fine size, and specific surface area is big, and ferrophosphorus ratio is 0.995 1.01, and waste water yield is few.
Description
Technical field
The present invention relates to a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate, belong to new energy battery material field.
Background technology
Ferric phosphate, also known as high ferric phosphate, ferric orthophosphate, molecular formula is FePO4, is a kind of white, canescence monoclinic crystal
Powder.It is the salt of iron salt solutions and sodium phosphate effect, iron therein is positive trivalent.Its main application is to manufactureLiFePO4 electricity PondMaterial, catalyst and ceramics etc..
The phosphate dihydrate iron of high-purityColorFor near-white or shallow (light) yellowWhitePowder, with the loss of the crystallization water,
Color gradually turns yellow, and pure anhydride is in yellow-white powder.Outward appearance is in canescence or dull gray when phosphorus (P) is exceeded in two water thing ferric phosphates
White；As being in dark yellow when iron is exceeded.Ferrophosphorus ratio is the index for weighing ferric phosphate quality most critical, is also to determine LiFePO4 product
The factor of matter most critical.Such as exist in ferric phosphate substantial amounts of ferrous iron orSodium、Potassium、Sulfate radical、Ammonium ionWhen, phosphate dihydrate iron
It is in then furvous or canescence.Tap density：1.13~1.59g/cm3,0.75~0.97g/cm3 of apparent density.During heatingEasily It is moltenInHydrochloric acid, but be insoluble in other acid, be practically insoluble in water,Acetic acid、Alcohol。
With the large-scale use of ferric phosphate lithium cell, ferric phosphate as lithium iron phosphate positive material primary raw material, its
Demand is greatly improved, it is contemplated that annual demand is more than 50,000 tons.
But present ferric phosphate prepares the general technique using ferrous salt, oxidant and phosphate reaction, but exist
The problem of be：1. because ferric ion is particularly easy to hydrolytic precipitation, so during ferric phosphate is prepared, easily producing hydrogen-oxygen
Changing the impurity such as iron causes ferric phosphate purity not high；2. the purification of ferrous iron solution, manganese particularly therein, magnesium, nickel, sodium plasma,
It is difficult to be removed with relatively low cost, so the iron material of high-purity must be used, such as high-purity iron powder, high-purity phosphoric acid ferrous iron comes
Prepare, cause cost high；3. there is particle diameter too in liquid-phase precipitation, and use the methods such as colloidal sol to prepare to prepare ferric phosphate
Superfine iron phosphate there is the shortcomings of impurity is not easy to wash off.
Simultaneously for byproduct ferrous sulfate of titanium dioxide, annual yield reaches million tons, and it recycles general use
Make water purification agent etc. low value-added, due to wherein containing the foreign ion such as substantial amounts of magnesium, manganese, zinc, high-end recycled for its
Very big obstructive action.
The content of the invention
In view of this, the invention provides a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate, by by-product of white titanium pigment,
High-purity nm ferric phosphate can be prepared, obtained ferric phosphate purity is high, fine size, specific surface area is big, ferrophosphorus ratio is 0.995-
1.01, waste water yield is few.
The present invention solves above-mentioned technical problem by following technological means：
A kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate of the present invention, is following steps：
(1) by-product of white titanium pigment is dissolved in water, it is 30-50g/l to be dissolved to all iron content in solution, adds iron hydroxide
The mixture of mud and iron powder, in 50-70 DEG C of reaction, the terminal pH of regulation solution is 4.5-5.5,0.5-1 is reacted at this ph small
When, filtering obtains the first filter residue and the first filtrate；
(2) it is 1-1.5 the first filtrate to be added into acid for adjusting pH, then passes to air oxidation, while acid maintains the pH of solution
For the 1-1.5, [Fe into solution2+] in 3-5g/l, then it is further continued for standing 1-1.5 hours at this ph, filters, obtain second
Filter residue and the second filtrate；
(3) the second filtrate is added into acid, the pH of regulation solution is 0.1-0.2, activated carbon powder is added, using nanofiltration device
Depth-type filtration is carried out, the 3rd filtrate is obtained, di-(2-ethylhexyl)phosphoric acid is washed with the mixed acid of phosphoric acid and sulfuric acid, washed
After washing use pure water, by after washing di-(2-ethylhexyl)phosphoric acid add sulfonated kerosene, di-(2-ethylhexyl)phosphoric acid with
The volume ratio of sulfonated kerosene is 0.9-1.1：10, then with ammoniacal liquor stirring mixing 30-50 minute, di-(2-ethylhexyl)phosphoric acid and
The mol ratio of ammonia is 2.05-2.1:1, stand addition ultrasonic wave simultaneously and be layered, the di-(2-ethylhexyl)phosphoric acid after layering
Ammonium adds pure water, and electrical conductivity ＜ 10 the μ S/cm, pH of washing to washings are 6.8-7.5, by two (2- ethyls after washing
Hexyl) ammonium phosphate carries out the extraction of 5-6 stage countercurrents and 5-6 stage countercurrents acid solution wash with the 3rd filtrate and 2-3 stage countercurrent pure water is washed
Wash, the organic phase after being washed；
(4) organic phase after step (3) is washed passes through vacuum distillation, and sulfonated kerosene is distilled off, treated in organic phase
The mass fraction of sulfonated kerosene is less than 0.5%, by the organic phase mixed catalyst after distillation, reacts 3-4 at 300-320 DEG C small
When, dried after reacted material is added into ethanol washing, obtain high-purity nm ferric phosphate.
First filter residue adds 1-2mol/l sulfuric acid scrubbing after 700-750 DEG C is calcined 1-2 hours, and filter residue is dried
To Ti content ＞ 30% slag, return to titanium dioxide producer and use, the mass ratio of hydroxide iron cement and iron powder is 1:8-10.
Second filter residue is mainly iron hydroxide, and return to step (1) is used as hydroxide iron cement.
Acid in the step (3) is sulfuric acid or hydrochloric acid solution, and the mass ratio of activated carbon and the second filtrate is 1-2:1,
The granularity of activated carbon is 0.1-0.2mm, micro porous filtration or secondary filter is used during depth-type filtration, the aperture of filter medium is
150-250nm, di-(2-ethylhexyl)phosphoric acid and sulfonated kerosene are technical pure, phosphoric acid and sulphur in the mixed acid of phosphoric acid and sulfuric acid
The mol ratio of acid is 1:3-4, the hydrogen ion total mole number of mixed acid is 1-1.1mol/l.
In the step (3) in extraction process, the volume flow ratio of organic phase and aqueous phase is 3-5:1, extraction stirring mixing,
By the droplet distribution of di-(2-ethylhexyl)phosphoric acid ammonium it is the diameter that particle diameter is 0.1-0.2mm during stirring, aqueous phase is continuous phase, extraction
The temperature mixed when taking per one-level is 40-45 DEG C, and mixing speed is 150-200r/min, extraction time 5-10min, settling time
For 30-35min, during acid solution wash, the volume flow ratio of organic phase and acid solution is 6-10:1, wash agitation is mixed
Close, acid solution be 1-1.2mol/l hydrochloric acid solution, during stirring by the droplet distribution of di-(2-ethylhexyl)phosphoric acid iron be particle diameter
For 0.05-0.1mm diameter, aqueous phase is continuous phase, and the temperature that acid solution wash is mixed per one-level is 35-40 DEG C, mixing speed
For 200-300r/min, incorporation time 2-5min, settling time is 30-35min, during pure water, organic phase with it is pure
The volume flow ratio of water is 1-1.2:1, wash agitation mixing, during stirring by pure water droplet distribution be that particle diameter is 0.4-0.5mm
Diameter, organic phase is continuous phase, and the temperature that pure water is mixed per one-level is 40-50 DEG C, and mixing speed is 120-150r/
Min, incorporation time 2-5min, settling time is 30-35min.
Pressure in the step (4) during vacuum distillation is 0.001-0.002Mpa, and temperature is 80-120 DEG C, still-process
Condensate recycling device is added, reclaims and is used in sulfonated kerosene, the sulfonated kerosene return to step (3) of recovery at 30-40 DEG C.
Catalyst in the step (4) is at least one of ammonium persulfate, hydrogenperoxide steam generator, ferrate, is steamed
The mol ratio of organic phase and catalyst after evaporating is 5-6:1, during high-temperature catalytic decomposition reaction, reaction atmosphere is oxygen gas
Atmosphere, pressure is 0.05-0.06Mpa, and the waste gas that reaction is produced is absorbed with alkali lye, and course of reaction observation becomes when the color of material
When omiting powder for white, as reaction terminates, and the mass ratio of the reacted material of washing process and ethanol is 1:4-5, drying is used
Microwave drying, drying to free water content is less than 0.5%.
In the step (3), di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd filtrate after washing carry out counter-current extraction process
In, the ferrous ion of sampling and measuring raffinate and the content of ferric ion, raffinate ferrous ions content and the 3rd filtrate
When ferrous ions content is equal, and during the content ＞ 0.5g/l of ferric ion, the volume flow of reduction organic phase and aqueous phase
Than in raffinate during the content ＜ 0.5g/l of ferric ion, or raffinate ferrous ions content is less than the 3rd filtrate Central Asia
During iron ion content, the volume flow ratio of organic phase and aqueous phase is improved.
The equal return to step of water washing liquor (1) that the pickle and pure water that acid elution is produced in the step (3) are produced
Dissolve by-product of white titanium pigment.
The present invention uses byproduct ferrous sulfate of titanium dioxide for raw material, and the component of by-product of white titanium pigment is as follows：
From the point of view of data, by-product of white titanium pigment comparison of ingredients is complicated, and impurity content is higher for Mg, Ti, Mn plasma, together
The jelly such as heavy metal and silicic acid such as Shi Hanyou cobalt nickel zincs, conventional technique precipitates titanium, silicon etc. to pass through flocculation sediment
Afterwards, add sulfide or heavy metal chelating agent carrys out precipitation of heavy metals, add fluoride and carry out removing calcium and magnesium, then to prepare ferric phosphate,
But have that long flow path, cost be high, waste water yield is few, the low shortcoming of the rate of recovery of iron.
And the present invention can improve the pH of solution, while iron powder and copper by the way of hydroxide iron cement and iron powder is added
Ion, lead ion and a small amount of cobalt nickel ion etc. replace, be translated into metal simple-substance and precipitate, at the same by titanium, chromium, aluminium,
Silicon etc. is deposited in slag, by filtering, precipitation is separated with solution, using hydroxide iron cement and the mixture of iron powder, can be dropped
The consumption of low iron powder, reduces cost, while improving the pH speed of solution faster, production efficiency is high, while hydroxide iron cement can be with
Obtained when being aoxidized by second step, further reduce cost, improve the rate of recovery of iron.
In pH1-1.5 oxidations, ferric hydrolytic precipitation after oxidation can be avoided, while turn avoid too low pH causes
Oxidation efficiency reduction, then oxidation finish, add the pH0.1-0.2 of acid-conditioning solution, sulfuric acid can be improved under this pH
The stability of iron, while di-(2-ethylhexyl)phosphoric acid can farthest extract ferric iron at this ph, while also avoiding
Zinc, the extraction of manganese plasma, can both improve the utilization rate of iron, turn avoid the extraction of other ions, improve the pure of iron
Degree.
Using the mixing of di-(2-ethylhexyl)phosphoric acid and ammoniacal liquor, di-(2-ethylhexyl)phosphoric acid extraction iron can be improved
Capacity, improves production efficiency, and the di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd filtrate after washing carry out the extraction of 5-6 stage countercurrents and 5-
6 stage countercurrent acid solution washes and 2-3 stage countercurrent pure waters, can obtain the pure di-(2-ethylhexyl)phosphoric acid iron of comparison,
In extraction and acid elution process, it is continuous phase to control aqueous phase, while controlling the size droplet diameter of organic phase, can preferably improve extraction
The efficiency with acid elution is taken, while it also avoid the entrainment of aqueous phase in organic phase, the purity of organic phase is improved, and washed in pure water
Process is washed, using organic phase as continuous phase, organic phase can be farthest reclaimed, improve the rate of recovery of organic phase, it is to avoid
A large amount of entrainments of organic phase in washings.
Obtained pure di-(2-ethylhexyl)phosphoric acid iron is decomposed by high-temperature catalytic, by 2- ethylhexyls official therein
It can roll into a ball and resolve into carbon dioxide and water by high-temperature oxydation, the speed for controlling it to decompose by temperature, catalytic amount and pressure
Degree, so as to obtain high-purity nano ferric phosphate, due to decomposing the impact of the carbon dioxide produced and vapor, causes loose
Loose structure, ferric phosphate specific surface area of the invention is big, and purity is high.Because the poorly conductive of lithium iron phosphate positive material,
The electric conductivity for improving LiFePO4 is general by reducing the granularity of LiFePO4 and two kinds of approach of cladding of conductive material, and reduces
The granularity of LiFePO4, which is generally required, first reduces the granularity of its presoma ferric phosphate, thus the present invention can nano ferric phosphate just
This requirement is met well.The ferric phosphate specific surface area of the present invention is big simultaneously, and activity is high, with lithium salts mixed process, pyroreaction
Temperature is low, and reaction is abundant, and the reaction time is short, and obtained LiFePO4 primary particle size is small, and activity is high, and chemical property is good.
The synthetically produced waste water of liquid-phase precipitation is avoided simultaneously, wastewater flow rate is substantially reduced, and technological process is short.
Sulfonated kerosene is distilled off using vacuum distillation, recycled, it is possible to decrease cost.
The ferric phosphate index finally given is as follows：
The beneficial effects of the invention are as follows：
1. preparing high-purity nm ferric phosphate using by-product of white titanium pigment, cost is low, and flow is short.
2. wastewater discharge is few, the waste water that the saponification liquor and raffinate only produced in extraction process is produced, compare
Wastewater flow rate is substantially reduced for liquid-phase precipitation, and liquid-phase precipitation ferric phosphate per ton produces 100 tons or so of waste water, and the present invention is only only
Produce 10-20 tons.
3. the present invention is decomposed using catalysis oxidation, nano ferric phosphate can be prepared, obtained ferric phosphate purity is high, granularity
Carefully, specific surface area is big, and ferrophosphorus ratio is 0.995-1.01.
Embodiment
Below with reference to specific embodiment, the present invention is described in detail, a kind of LITHIUM BATTERY high-purity nm of the present embodiment
The technique of ferric phosphate, is following steps：
(1) by-product of white titanium pigment is dissolved in water, it is 30-50g/l to be dissolved to all iron content in solution, adds iron hydroxide
The mixture of mud and iron powder, in 50-70 DEG C of reaction, the terminal pH of regulation solution is 4.5-5.5,0.5-1 is reacted at this ph small
When, filtering obtains the first filter residue and the first filtrate；
(2) it is 1-1.5 the first filtrate to be added into acid for adjusting pH, then passes to air oxidation, while acid maintains the pH of solution
For the 1-1.5, [Fe into solution2+] in 3-5g/l, then it is further continued for standing 1-1.5 hours at this ph, filters, obtain second
Filter residue and the second filtrate；
(3) the second filtrate is added into acid, the pH of regulation solution is 0.1-0.2, activated carbon powder is added, using nanofiltration device
Depth-type filtration is carried out, the 3rd filtrate is obtained, di-(2-ethylhexyl)phosphoric acid is washed with the mixed acid of phosphoric acid and sulfuric acid, washed
After washing use pure water, by after washing di-(2-ethylhexyl)phosphoric acid add sulfonated kerosene, di-(2-ethylhexyl)phosphoric acid with
The volume ratio of sulfonated kerosene is 0.9-1.1：10, then with ammoniacal liquor stirring mixing 30-50 minute, di-(2-ethylhexyl)phosphoric acid and
The mol ratio of ammonia is 2.05-2.1:1, stand addition ultrasonic wave simultaneously and be layered, the di-(2-ethylhexyl)phosphoric acid after layering
Ammonium adds pure water, and electrical conductivity ＜ 10 the μ S/cm, pH of washing to washings are 6.8-7.5, by two (2- ethyls after washing
Hexyl) ammonium phosphate carries out the extraction of 5-6 stage countercurrents and 5-6 stage countercurrents acid solution wash with the 3rd filtrate and 2-3 stage countercurrent pure water is washed
Wash, the organic phase after being washed；
(4) organic phase after step (3) is washed passes through vacuum distillation, and sulfonated kerosene is distilled off, treated in organic phase
The mass fraction of sulfonated kerosene is less than 0.5%, by the organic phase mixed catalyst after distillation, reacts 3-4 at 300-320 DEG C small
When, dried after reacted material is added into ethanol washing, obtain high-purity nm ferric phosphate.
First filter residue adds 1-2mol/l sulfuric acid scrubbing after 700-750 DEG C is calcined 1-2 hours, and filter residue is dried
To Ti content ＞ 30% slag, return to titanium dioxide producer and use, the mass ratio of hydroxide iron cement and iron powder is 1:8-10.
Second filter residue is mainly iron hydroxide, and return to step (1) is used as hydroxide iron cement.
Acid in the step (3) is sulfuric acid or hydrochloric acid solution, and the mass ratio of activated carbon and the second filtrate is 1-2:1,
The granularity of activated carbon is 0.1-0.2mm, micro porous filtration or secondary filter is used during depth-type filtration, the aperture of filter medium is
150-250nm, di-(2-ethylhexyl)phosphoric acid and sulfonated kerosene are technical pure, phosphoric acid and sulphur in the mixed acid of phosphoric acid and sulfuric acid
The mol ratio of acid is 1:3-4, the hydrogen ion total mole number of mixed acid is 1-1.1mol/l.
In the step (3) in extraction process, the volume flow ratio of organic phase and aqueous phase is 3-5:1, extraction stirring mixing,
By the droplet distribution of di-(2-ethylhexyl)phosphoric acid ammonium it is the diameter that particle diameter is 0.1-0.2mm during stirring, aqueous phase is continuous phase, extraction
The temperature mixed when taking per one-level is 40-45 DEG C, and mixing speed is 150-200r/min, extraction time 5-10min, settling time
For 30-35min, during acid solution wash, the volume flow ratio of organic phase and acid solution is 6-10:1, wash agitation is mixed
Close, acid solution be 1-1.2mol/l hydrochloric acid solution, during stirring by the droplet distribution of di-(2-ethylhexyl)phosphoric acid iron be particle diameter
For 0.05-0.1mm diameter, aqueous phase is continuous phase, and the temperature that acid solution wash is mixed per one-level is 35-40 DEG C, mixing speed
For 200-300r/min, incorporation time 2-5min, settling time is 30-35min, during pure water, organic phase with it is pure
The volume flow ratio of water is 1-1.2:1, wash agitation mixing, during stirring by pure water droplet distribution be that particle diameter is 0.4-0.5mm
Diameter, organic phase is continuous phase, and the temperature that pure water is mixed per one-level is 40-50 DEG C, and mixing speed is 120-150r/
Min, incorporation time 2-5min, settling time is 30-35min.
Pressure in the step (4) during vacuum distillation is 0.001-0.002Mpa, and temperature is 80-120 DEG C, still-process
Condensate recycling device is added, reclaims and is used in sulfonated kerosene, the sulfonated kerosene return to step (3) of recovery at 30-40 DEG C.
Catalyst in the step (4) is at least one of ammonium persulfate, hydrogenperoxide steam generator, ferrate, is steamed
The mol ratio of organic phase and catalyst after evaporating is 5-6:1, during high-temperature catalytic decomposition reaction, reaction atmosphere is oxygen gas
Atmosphere, pressure is 0.05-0.06Mpa, and the waste gas that reaction is produced is absorbed with alkali lye, and course of reaction observation becomes when the color of material
When omiting powder for white, as reaction terminates, and the mass ratio of the reacted material of washing process and ethanol is 1:4-5, drying is used
Microwave drying, drying to free water content is less than 0.5%.
In the step (3), di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd filtrate after washing carry out counter-current extraction process
In, the ferrous ion of sampling and measuring raffinate and the content of ferric ion, raffinate ferrous ions content and the 3rd filtrate
When ferrous ions content is equal, and during the content ＞ 0.5g/l of ferric ion, the volume flow of reduction organic phase and aqueous phase
Than in raffinate during the content ＜ 0.5g/l of ferric ion, or raffinate ferrous ions content is less than the 3rd filtrate Central Asia
During iron ion content, the volume flow ratio of organic phase and aqueous phase is improved.
The equal return to step of water washing liquor (1) that the pickle and pure water that acid elution is produced in the step (3) are produced
Dissolve by-product of white titanium pigment.
Embodiment 1
(1) by-product of white titanium pigment is dissolved in water, it is 45.5g/l to be dissolved to all iron content in solution, adds iron hydroxide
The mixture of mud and iron powder, in 60 DEG C of reactions, the terminal pH of regulation solution is 5.2, is reacted 0.6 hour at this ph, and filtering is obtained
To the first filter residue and the first filtrate；
(2) it is 1.25 the first filtrate to be added into acid for adjusting pH, then passes to air oxidation, while the pH of acid maintenance solution is
The 1.25, [Fe into solution2+] in 3.5g/l, be then further continued for standing 1 hour at this ph, filter, obtain the second filter residue and
Second filtrate；
(3) the second filtrate is added into acid, the pH of regulation solution is 0.12, adds activated carbon powder, enters using nanofiltration device
Row depth-type filtration, obtains the 3rd filtrate, and di-(2-ethylhexyl)phosphoric acid is washed with the mixed acid of phosphoric acid and sulfuric acid, washing
Pure water is used afterwards, and the di-(2-ethylhexyl)phosphoric acid after washing is added into sulfonated kerosene, di-(2-ethylhexyl)phosphoric acid and sulphur
The volume ratio for changing kerosene is 1.0：10, then with ammoniacal liquor stirring mixing 45 minutes, mole of di-(2-ethylhexyl)phosphoric acid and ammonia
Than for 2.08:1, stand addition ultrasonic wave simultaneously and be layered, the di-(2-ethylhexyl)phosphoric acid ammonium after layering adds pure water and washed
Wash, electrical conductivity ＜ 10 the μ S/cm, pH of washing to washings are 7.1, by the di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd after washing
Filtrate carries out the extraction of 5 stage countercurrents and 6 stage countercurrent acid solution washes and 3 stage countercurrent pure waters, the organic phase after being washed；
(4) organic phase after step (3) is washed passes through vacuum distillation, and sulfonated kerosene is distilled off, treated in organic phase
The mass fraction of sulfonated kerosene is less than 0.5%, and the organic phase mixed catalyst after distillation reacts 3.5 hours at 310 DEG C, will
Reacted material is dried after adding ethanol washing, obtains high-purity nm ferric phosphate.
First filter residue adds 1.2mol/l sulfuric acid scrubbing after 720 DEG C are calcined 1.5 hours, and filter residue drying obtains titanium
Content ＞ 30% slag, returns to titanium dioxide producer and uses, and the mass ratio of hydroxide iron cement and iron powder is 1:8.5.
Second filter residue is mainly iron hydroxide, and return to step (1) is used as hydroxide iron cement.
Acid in the step (3) is sulfuric acid or hydrochloric acid solution, and the mass ratio of activated carbon and the second filtrate is 1.5:1,
The granularity of activated carbon is 0.15mm, micro porous filtration is used during depth-type filtration, the aperture of filter medium is 220nm, two (2- ethyl hexyls
Base) phosphoric acid and sulfonated kerosene be technical pure, and the mol ratio of phosphoric acid and sulfuric acid is 1 in the mixed acid of phosphoric acid and sulfuric acid:3.5, mix
The hydrogen ion total mole number for closing acid is 1.05mol/l.
In the step (3) in extraction process, the volume flow ratio of organic phase and aqueous phase is 4.5:1, extraction stirring mixing,
By the droplet distribution of di-(2-ethylhexyl)phosphoric acid ammonium it is the diameter that particle diameter is 0.15mm during stirring, aqueous phase is continuous phase, extraction
When per one-level mix temperature be 42 DEG C, mixing speed is 180r/min, and extraction time 8min, settling time is 32min, in acid
In solution washing process, the volume flow ratio of organic phase and acid solution is 8:1, wash agitation mixing, acid solution is 1.15mol/l
Hydrochloric acid solution, by the droplet distribution of di-(2-ethylhexyl)phosphoric acid iron be the diameter that particle diameter is 0.08mm during stirring, aqueous phase is
Continuous phase, the temperature that acid solution wash is mixed per one-level is 38 DEG C, and mixing speed is 250r/min, incorporation time 2.5min, clear
The clear time is 33min, during pure water, and the volume flow ratio of organic phase and pure water is 1.15:1, wash agitation mixing,
During stirring by pure water droplet distribution be diameter that particle diameter is 0.45mm, organic phase is continuous phase, and pure water is mixed per one-level
Temperature be 42 DEG C, mixing speed is 130r/min, and incorporation time 3.2min, settling time is 32min.
Pressure in the step (4) during vacuum distillation is 0.0018Mpa, and temperature is 110 DEG C, and still-process adds condensation
Retracting device, reclaims at 35 DEG C and is used in sulfonated kerosene, the sulfonated kerosene return to step (3) of recovery.
Catalyst in the step (4) is ammonium persulfate, and the mol ratio of organic phase and catalyst after distillation is 5.5:
1, during high-temperature catalytic decomposition reaction, reaction atmosphere is oxygen atmosphere, and pressure is 0.052Mpa, and the waste gas that reaction is produced is used
Alkali lye is absorbed, and course of reaction observation is when the color of material is changed into white slightly powder, and as reaction terminates, washing process reaction
Material and the mass ratio of ethanol afterwards is 1:4.3, drying uses microwave drying, and drying to free water content is less than 0.5%.
In the step (3), di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd filtrate after washing carry out counter-current extraction process
In, the ferrous ion of sampling and measuring raffinate and the content of ferric ion, raffinate ferrous ions content and the 3rd filtrate
When ferrous ions content is equal, and during the content ＞ 0.5g/l of ferric ion, the volume flow of reduction organic phase and aqueous phase
Than in raffinate during the content ＜ 0.5g/l of ferric ion, or raffinate ferrous ions content is less than the 3rd filtrate Central Asia
During iron ion content, the volume flow ratio of organic phase and aqueous phase is improved.
The equal return to step of water washing liquor (1) that the pickle and pure water that acid elution is produced in the step (3) are produced
Dissolve by-product of white titanium pigment.
The ferric phosphate index finally given is as follows：
| Index | Iron content | Ferrophosphorus mol ratio | D10 | D50 | D90 |
| Numerical value | 28.95% | 0.998 | 18nm | 75nm | 130nm |
| BET | Ca | Mg | Na | Ni | Co |
| 105m2/g | 8ppm | 4ppm | 3ppm | 1.5ppm | 0.18ppm |
| Mn | Zn | Cu | Ti | Al | Si |
| 8ppm | 8ppm | 0.4ppm | 0.37ppm | 1.5ppm | 1.2ppm |
Embodiment 2
(1) by-product of white titanium pigment is dissolved in water, it is 45.5g/l to be dissolved to all iron content in solution, adds iron hydroxide
The mixture of mud and iron powder, in 60 DEG C of reactions, the terminal pH of regulation solution is 5.4, is reacted 0.6 hour at this ph, and filtering is obtained
To the first filter residue and the first filtrate；
(2) it is 1.25 the first filtrate to be added into acid for adjusting pH, then passes to air oxidation, while the pH of acid maintenance solution is
The 1.25, [Fe into solution2+] in 3.5g/l, be then further continued for standing 1 hour at this ph, filter, obtain the second filter residue and
Second filtrate；
(3) the second filtrate is added into acid, the pH of regulation solution is 0.12, adds activated carbon powder, enters using nanofiltration device
Row depth-type filtration, obtains the 3rd filtrate, and di-(2-ethylhexyl)phosphoric acid is washed with the mixed acid of phosphoric acid and sulfuric acid, washing
Pure water is used afterwards, and the di-(2-ethylhexyl)phosphoric acid after washing is added into sulfonated kerosene, di-(2-ethylhexyl)phosphoric acid and sulphur
The volume ratio for changing kerosene is 1.0：10, then with ammoniacal liquor stirring mixing 45 minutes, mole of di-(2-ethylhexyl)phosphoric acid and ammonia
Than for 2.08:1, stand addition ultrasonic wave simultaneously and be layered, the di-(2-ethylhexyl)phosphoric acid ammonium after layering adds pure water and washed
Wash, electrical conductivity ＜ 10 the μ S/cm, pH of washing to washings are 7.1, by the di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd after washing
Filtrate carries out the extraction of 6 stage countercurrents and 6 stage countercurrent acid solution washes and 2 stage countercurrent pure waters, the organic phase after being washed；
(4) organic phase after step (3) is washed passes through vacuum distillation, and sulfonated kerosene is distilled off, treated in organic phase
The mass fraction of sulfonated kerosene is less than 0.5%, and the organic phase mixed catalyst after distillation reacts 3.5 hours at 300 DEG C, will
Reacted material is dried after adding ethanol washing, obtains high-purity nm ferric phosphate.
First filter residue adds 1.2mol/l sulfuric acid scrubbing after 720 DEG C are calcined 1.5 hours, and filter residue drying obtains titanium
Content ＞ 30% slag, returns to titanium dioxide producer and uses, and the mass ratio of hydroxide iron cement and iron powder is 1:8.5.
Second filter residue is mainly iron hydroxide, and return to step (1) is used as hydroxide iron cement.
Acid in the step (3) is sulfuric acid or hydrochloric acid solution, and the mass ratio of activated carbon and the second filtrate is 1.5:1,
The granularity of activated carbon is 0.15mm, micro porous filtration is used during depth-type filtration, the aperture of filter medium is 220nm, two (2- ethyl hexyls
Base) phosphoric acid and sulfonated kerosene be technical pure, and the mol ratio of phosphoric acid and sulfuric acid is 1 in the mixed acid of phosphoric acid and sulfuric acid:3.5, mix
The hydrogen ion total mole number for closing acid is 1.05mol/l.
In the step (3) in extraction process, the volume flow ratio of organic phase and aqueous phase is 4.5:1, extraction stirring mixing,
By the droplet distribution of di-(2-ethylhexyl)phosphoric acid ammonium it is the diameter that particle diameter is 0.15mm during stirring, aqueous phase is continuous phase, extraction
When per one-level mix temperature be 42 DEG C, mixing speed is 180r/min, and extraction time 8min, settling time is 32min, in acid
In solution washing process, the volume flow ratio of organic phase and acid solution is 8:1, wash agitation mixing, acid solution is 1.15mol/l
Hydrochloric acid solution, by the droplet distribution of di-(2-ethylhexyl)phosphoric acid iron be the diameter that particle diameter is 0.08mm during stirring, aqueous phase is
Continuous phase, the temperature that acid solution wash is mixed per one-level is 38 DEG C, and mixing speed is 250r/min, incorporation time 2.5min, clear
The clear time is 33min, during pure water, and the volume flow ratio of organic phase and pure water is 1.15:1, wash agitation mixing,
During stirring by pure water droplet distribution be diameter that particle diameter is 0.45mm, organic phase is continuous phase, and pure water is mixed per one-level
Temperature be 42 DEG C, mixing speed is 130r/min, and incorporation time 3.2min, settling time is 32min.
Pressure in the step (4) during vacuum distillation is 0.0018Mpa, and temperature is 110 DEG C, and still-process adds condensation
Retracting device, reclaims at 35 DEG C and is used in sulfonated kerosene, the sulfonated kerosene return to step (3) of recovery.
Catalyst in the step (4) is hydrogenperoxide steam generator, and the mol ratio of organic phase and catalyst after distillation is
5.4:1, during high-temperature catalytic decomposition reaction, reaction atmosphere is oxygen atmosphere, and pressure is 0.052Mpa, and it is useless that reaction is produced
Gas is absorbed with alkali lye, and course of reaction observation is when the color of material is changed into white slightly powder, and as reaction terminates, washing process
The mass ratio of reacted material and ethanol is 1:4.3, drying uses microwave drying, and drying to free water content is less than 0.5%
.
In the step (3), di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd filtrate after washing carry out counter-current extraction process
In, the ferrous ion of sampling and measuring raffinate and the content of ferric ion, raffinate ferrous ions content and the 3rd filtrate
When ferrous ions content is equal, and during the content ＞ 0.5g/l of ferric ion, the volume flow of reduction organic phase and aqueous phase
Than in raffinate during the content ＜ 0.5g/l of ferric ion, or raffinate ferrous ions content is less than the 3rd filtrate Central Asia
During iron ion content, the volume flow ratio of organic phase and aqueous phase is improved.
The equal return to step of water washing liquor (1) that the pickle and pure water that acid elution is produced in the step (3) are produced
Dissolve by-product of white titanium pigment.
The ferric phosphate index finally given is as follows：
| Index | Iron content | Ferrophosphorus mol ratio | D10 | D50 | D90 |
| Numerical value | 29.2% | 1.005 | 17nm | 79nm | 130nm |
| BET | Ca | Mg | Na | Ni | Co |
| 117m2/g | 8ppm | 4.9ppm | 4ppm | 1.8ppm | 0.3ppm |
| Mn | Zn | Cu | Ti | Al | Si |
| 7ppm | 8ppm | 0.45ppm | 0.43ppm | 1.7ppm | 1.2ppm |
Embodiment 3
(1) by-product of white titanium pigment is dissolved in water, it is 45.5g/l to be dissolved to all iron content in solution, adds iron hydroxide
The mixture of mud and iron powder, in 60 DEG C of reactions, the terminal pH of regulation solution is 5.4, is reacted 0.6 hour at this ph, and filtering is obtained
To the first filter residue and the first filtrate；
(2) it is 1.15 the first filtrate to be added into acid for adjusting pH, then passes to air oxidation, while the pH of acid maintenance solution is
The 1.25, [Fe into solution2+] in 4.0g/l, be then further continued for standing 1 hour at this ph, filter, obtain the second filter residue and
Second filtrate；
(3) the second filtrate is added into acid, the pH of regulation solution is 0.12, adds activated carbon powder, enters using nanofiltration device
Row depth-type filtration, obtains the 3rd filtrate, and di-(2-ethylhexyl)phosphoric acid is washed with the mixed acid of phosphoric acid and sulfuric acid, washing
Pure water is used afterwards, and the di-(2-ethylhexyl)phosphoric acid after washing is added into sulfonated kerosene, di-(2-ethylhexyl)phosphoric acid and sulphur
The volume ratio for changing kerosene is 1.0：10, then with ammoniacal liquor stirring mixing 45 minutes, mole of di-(2-ethylhexyl)phosphoric acid and ammonia
Than for 2.08:1, stand addition ultrasonic wave simultaneously and be layered, the di-(2-ethylhexyl)phosphoric acid ammonium after layering adds pure water and washed
Wash, electrical conductivity ＜ 10 the μ S/cm, pH of washing to washings are 7.2, by the di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd after washing
Filtrate carries out the extraction of 6 stage countercurrents and 6 stage countercurrent acid solution washes and 3 stage countercurrent pure waters, the organic phase after being washed；
(4) organic phase after step (3) is washed passes through vacuum distillation, and sulfonated kerosene is distilled off, treated in organic phase
The mass fraction of sulfonated kerosene is less than 0.5%, and the organic phase mixed catalyst after distillation reacts 3.5 hours at 310 DEG C, will
Reacted material is dried after adding ethanol washing, obtains high-purity nm ferric phosphate.
First filter residue adds 1.2mol/l sulfuric acid scrubbing after 720 DEG C are calcined 1.5 hours, and filter residue drying obtains titanium
Content ＞ 30% slag, returns to titanium dioxide producer and uses, and the mass ratio of hydroxide iron cement and iron powder is 1:8.5.
Second filter residue is mainly iron hydroxide, and return to step (1) is used as hydroxide iron cement.
Acid in the step (3) is sulfuric acid or hydrochloric acid solution, and the mass ratio of activated carbon and the second filtrate is 1.5:1,
The granularity of activated carbon is 0.12mm, micro porous filtration is used during depth-type filtration, the aperture of filter medium is 220nm, two (2- ethyl hexyls
Base) phosphoric acid and sulfonated kerosene be technical pure, and the mol ratio of phosphoric acid and sulfuric acid is 1 in the mixed acid of phosphoric acid and sulfuric acid:3.5, mix
The hydrogen ion total mole number for closing acid is 1.05mol/l.
In the step (3) in extraction process, the volume flow ratio of organic phase and aqueous phase is 4.5:1, extraction stirring mixing,
By the droplet distribution of di-(2-ethylhexyl)phosphoric acid ammonium it is the diameter that particle diameter is 0.15mm during stirring, aqueous phase is continuous phase, extraction
When per one-level mix temperature be 42 DEG C, mixing speed is 180r/min, and extraction time 8min, settling time is 32min, in acid
In solution washing process, the volume flow ratio of organic phase and acid solution is 8:1, wash agitation mixing, acid solution is 1.15mol/l
Hydrochloric acid solution, by the droplet distribution of di-(2-ethylhexyl)phosphoric acid iron be the diameter that particle diameter is 0.06mm during stirring, aqueous phase is
Continuous phase, the temperature that acid solution wash is mixed per one-level is 38 DEG C, and mixing speed is 250r/min, incorporation time 2.5min, clear
The clear time is 33min, during pure water, and the volume flow ratio of organic phase and pure water is 1.15:1, wash agitation mixing,
During stirring by pure water droplet distribution be diameter that particle diameter is 0.45mm, organic phase is continuous phase, and pure water is mixed per one-level
Temperature be 42 DEG C, mixing speed is 130r/min, and incorporation time 3.2min, settling time is 32min.
Pressure in the step (4) during vacuum distillation is 0.0018Mpa, and temperature is 110 DEG C, and still-process adds condensation
Retracting device, reclaims at 35 DEG C and is used in sulfonated kerosene, the sulfonated kerosene return to step (3) of recovery.
Catalyst in the step (4) is hydrogenperoxide steam generator, and the mol ratio of organic phase and catalyst after distillation is
5.4:1, during high-temperature catalytic decomposition reaction, reaction atmosphere is oxygen atmosphere, and pressure is 0.050Mpa, and it is useless that reaction is produced
Gas is absorbed with alkali lye, and course of reaction observation is when the color of material is changed into white slightly powder, and as reaction terminates, washing process
The mass ratio of reacted material and ethanol is 1:4.3, drying uses microwave drying, and drying to free water content is less than 0.5%
.
In the step (3), di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd filtrate after washing carry out counter-current extraction process
In, the ferrous ion of sampling and measuring raffinate and the content of ferric ion, raffinate ferrous ions content and the 3rd filtrate
When ferrous ions content is equal, and during the content ＞ 0.5g/l of ferric ion, the volume flow of reduction organic phase and aqueous phase
Than in raffinate during the content ＜ 0.5g/l of ferric ion, or raffinate ferrous ions content is less than the 3rd filtrate Central Asia
During iron ion content, the volume flow ratio of organic phase and aqueous phase is improved.
The equal return to step of water washing liquor (1) that the pickle and pure water that acid elution is produced in the step (3) are produced
Dissolve by-product of white titanium pigment.
The ferric phosphate index finally given is as follows：
| Index | Iron content | Ferrophosphorus mol ratio | D10 | D50 | D90 |
| Numerical value | 29.01% | 1.001 | 13nm | 75nm | 138nm |
| BET | Ca | Mg | Na | Ni | Co |
| 112m2/g | 7ppm | 4.5ppm | 3.5ppm | 1.85ppm | 0.14ppm |
| Mn | Zn | Cu | Ti | Al | Si |
| 7ppm | 6.2ppm | 0.35ppm | 0.42ppm | 1.2ppm | 1.2ppm |
Ferric phosphate product mix lithium carbonate in embodiment 1,2,3 is sintered and prepares LiFePO4, while using normal
The particle diameter of the liquid phase synthesis of rule is sintered for 1-3um two kinds of ferric phosphate mixed carbonic acid lithiums and prepares LiFePO4, its performance pair
Than as follows：
From the point of view of experimental data, ferric phosphate of the invention is thin due to particle, and activity is high, and specific surface area is big, so relatively low
Temperature and can prepare LiFePO4 in shorter time, LiFePO4 specific surface area is big obtained from, fine size,
It is simultaneously higher than existing common LiFePO4 on discharging efficiency first, 0.1C initial charges and discharge capacity.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to skill of the invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (9)
1. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate, it is characterised in that be following steps：
(1) by-product of white titanium pigment is dissolved in water, it is 30-50g/l to be dissolved in solution all iron content, add hydroxide iron cement and
The mixture of iron powder, in 50-70 DEG C of reaction, the terminal pH of regulation solution is 4.5-5.5, is reacted 0.5-1 hours at this ph, mistake
Filter, obtains the first filter residue and the first filtrate；
(2) it is 1-1.5 the first filtrate to be added into acid for adjusting pH, then passes to air oxidation, while acid maintains the pH of solution to be 1-
The 1.5, [Fe into solution2+] in 3-5g/l, then it is further continued for standing 1-1.5 hours at this ph, filters, obtain the second filter residue
With the second filtrate；
(3) the second filtrate is added into acid, the pH of regulation solution is 0.1-0.2, adds activated carbon powder, is carried out using nanofiltration device
Depth-type filtration, obtains the 3rd filtrate, di-(2-ethylhexyl)phosphoric acid is washed with the mixed acid of phosphoric acid and sulfuric acid, after washing
With pure water, the di-(2-ethylhexyl)phosphoric acid after washing is added into sulfonated kerosene, di-(2-ethylhexyl)phosphoric acid and sulfonation
The volume ratio of kerosene is 0.9-1.1：10, then with ammoniacal liquor stirring mixing 30-50 minutes, di-(2-ethylhexyl)phosphoric acid and ammonia
Mol ratio is 2.05-2.1:1, stand addition ultrasonic wave simultaneously and be layered, the di-(2-ethylhexyl)phosphoric acid ammonium after layering adds
Enter pure water, electrical conductivity ＜ 10 the μ S/cm, pH of washing to washings are 6.8-7.5, by two (2- ethylhexyls) after washing
Ammonium phosphate and the 3rd filtrate carry out the extraction of 5-6 stage countercurrents and 5-6 stage countercurrents acid solution wash and 2-3 stage countercurrent pure waters, obtain
Organic phase after to washing；
(4) organic phase after step (3) is washed passes through vacuum distillation, and sulfonated kerosene is distilled off, sulfonation in organic phase is treated
The mass fraction of kerosene is less than 0.5%, and the organic phase mixed catalyst after distillation reacts 3-4 hours at 300-320 DEG C, will
Reacted material is dried after adding ethanol washing, obtains high-purity nm ferric phosphate.
2. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate according to claim 1, it is characterised in that：First filter residue is passed through
After crossing 700-750 DEG C of roasting 1-2 hour, 1-2mol/l sulfuric acid scrubbing is added, filter residue drying obtains Ti content ＞ 30% slag,
Return to titanium dioxide producer to use, the mass ratio of hydroxide iron cement and iron powder is 1:8-10.
3. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate according to claim 1, it is characterised in that：Second filter
Slag is mainly iron hydroxide, and return to step (1) is used as hydroxide iron cement.
4. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate according to claim 1, it is characterised in that：The step
(3) acid in is sulfuric acid or hydrochloric acid solution, and the mass ratio of activated carbon and the second filtrate is 1-2:1, the granularity of activated carbon is
0.1-0.2mm, uses micro porous filtration or secondary filter, the aperture of filter medium is 150-250nm, two (2- during depth-type filtration
Ethylhexyl) phosphoric acid and sulfonated kerosene be technical pure, and the mol ratio of phosphoric acid and sulfuric acid is 1 in the mixed acid of phosphoric acid and sulfuric acid:
3-4, the hydrogen ion total mole number of mixed acid is 1-1.1mol/l.
5. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate according to claim 1, it is characterised in that：The step
(3) in extraction process, the volume flow ratio of organic phase and aqueous phase is 3-5:1, extraction stirring mixing, by two (2- second during stirring
Base hexyl) droplet distribution of ammonium phosphate is diameter that particle diameter is 0.1-0.2mm, aqueous phase is continuous phase, is mixed during extraction per one-level
Temperature be 40-45 DEG C, mixing speed is 150-200r/min, and extraction time 5-10min, settling time is 30-35min,
During acid solution wash, the volume flow ratio of organic phase and acid solution is 6-10:1, wash agitation mixing, acid solution is 1-
1.2mol/l hydrochloric acid solution, by the droplet distribution of di-(2-ethylhexyl)phosphoric acid iron is that particle diameter is 0.05-0.1mm's during stirring
Diameter, aqueous phase is continuous phase, and the temperature that acid solution wash is mixed per one-level is 35-40 DEG C, and mixing speed is 200-300r/min,
Incorporation time 2-5min, settling time is 30-35min, during pure water, and the volume flow ratio of organic phase and pure water is
1-1.2:1, wash agitation mixing, during stirring by pure water droplet distribution be diameter that particle diameter is 0.4-0.5mm, organic phase is connects
Continuous phase, the temperature that pure water is mixed per one-level is 40-50 DEG C, and mixing speed is 120-150r/min, incorporation time 2-5min,
Settling time is 30-35min.
6. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate according to claim 1, it is characterised in that：The step
(4) pressure in during vacuum distillation is 0.001-0.002Mpa, and temperature is 80-120 DEG C, and still-process adds condensation and reclaims dress
Put, reclaim and used in sulfonated kerosene, the sulfonated kerosene return to step (3) of recovery at 30-40 DEG C.
7. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate according to claim 1, it is characterised in that：The step
(4) catalyst in is at least one of ammonium persulfate, hydrogenperoxide steam generator, ferrate, and the organic phase after distillation is with urging
The mol ratio of agent is 5-6:1, during high-temperature catalytic decomposition reaction, reaction atmosphere is oxygen atmosphere, and pressure is 0.05-
0.06Mpa, the waste gas that reaction is produced is absorbed with alkali lye, and course of reaction is observed when the color of material is changed into white slightly powder,
As reaction terminates, and the mass ratio of the reacted material of washing process and ethanol is 1:4-5, drying uses microwave drying, dries
It is less than 0.5% to free water content.
8. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate according to claim 1, it is characterised in that：The step
(3) in, di-(2-ethylhexyl)phosphoric acid ammonium and the 3rd filtrate after washing are carried out during counter-current extraction, sampling and measuring raffinate
Ferrous ion and ferric ion content, raffinate ferrous ions content is equal with the 3rd filtrate ferrous ions content
When, and during the content ＞ 0.5g/l of ferric ion, the volume flow ratio of reduction organic phase and aqueous phase, in raffinate ferric iron from
Son content ＜ 0.5g/l when, or raffinate ferrous ions content be less than the 3rd filtrate ferrous ions content when, raising has
The volume flow ratio of machine phase and aqueous phase.
9. a kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate according to claim 1, it is characterised in that：The step
(3) the equal return to step of water washing liquor (1) the dissolving by-product of white titanium pigment that the pickle and pure water that acid elution is produced in are produced.
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| CN108046229A (en) * | 2017-12-14 | 2018-05-18 | 瓮福（集团）有限责任公司 | A kind of method of battery-grade anhydrous iron phosphate synthesis desulfurating |
| CN108083330A (en) * | 2017-12-08 | 2018-05-29 | 蒋央芳 | A kind of preparation of the ferric phosphate of doped nano titanium dioxide |
| CN108306003A (en) * | 2018-01-29 | 2018-07-20 | 蒋央芳 | A kind of preparation method of iron manganese phosphate |
| CN108455547A (en) * | 2018-02-11 | 2018-08-28 | 衢州华友钴新材料有限公司 | A kind of low impurity high ferro phosphorus is than greatly than the preparation method of table battery-grade iron phosphate |
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| CN108821255A (en) * | 2018-07-11 | 2018-11-16 | 方嘉城 | A kind of preparation method of ferric phosphate |
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| CN108083330A (en) * | 2017-12-08 | 2018-05-29 | 蒋央芳 | A kind of preparation of the ferric phosphate of doped nano titanium dioxide |
| CN108083330B (en) * | 2017-12-08 | 2019-10-25 | 蒋央芳 | A kind of preparation method of the ferric phosphate of doped nano titanium dioxide |
| CN108046229A (en) * | 2017-12-14 | 2018-05-18 | 瓮福（集团）有限责任公司 | A kind of method of battery-grade anhydrous iron phosphate synthesis desulfurating |
| CN108557792B (en) * | 2018-01-29 | 2019-10-25 | 蒋央芳 | A kind of preparation method of cladded type iron manganese phosphate |
| CN108306003A (en) * | 2018-01-29 | 2018-07-20 | 蒋央芳 | A kind of preparation method of iron manganese phosphate |
| CN108557792A (en) * | 2018-01-29 | 2018-09-21 | 蒋央芳 | A kind of preparation method of cladded type iron manganese phosphate |
| CN108455547A (en) * | 2018-02-11 | 2018-08-28 | 衢州华友钴新材料有限公司 | A kind of low impurity high ferro phosphorus is than greatly than the preparation method of table battery-grade iron phosphate |
| CN108455547B (en) * | 2018-02-11 | 2019-09-03 | 衢州华友钴新材料有限公司 | A kind of preparation method of low impurity high-speed rail phosphorus than bigger serface battery-grade iron phosphate |
| CN108821255A (en) * | 2018-07-11 | 2018-11-16 | 方嘉城 | A kind of preparation method of ferric phosphate |
| CN109368612A (en) * | 2018-11-30 | 2019-02-22 | 乳源东阳光磁性材料有限公司 | Method for preparing battery-grade iron phosphate by using iron phosphate production wastewater and iron phosphate prepared by method |
| CN110562946A (en) * | 2019-08-08 | 2019-12-13 | 安徽昶源新材料股份有限公司 | Battery-grade anhydrous iron phosphate with sheet structure and preparation method thereof |
| CN111106302A (en) * | 2019-11-25 | 2020-05-05 | 深圳市卓能新能源股份有限公司 | Cylindrical lithium ion battery and preparation method thereof |
| CN112850679A (en) * | 2021-02-23 | 2021-05-28 | 云南航开科技有限公司 | Method for preparing iron phosphate by using waste acid |
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