CN112408352A - Linkage production process of battery-grade iron phosphate and refined phosphoric acid - Google Patents
Linkage production process of battery-grade iron phosphate and refined phosphoric acid Download PDFInfo
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- CN112408352A CN112408352A CN202011336839.4A CN202011336839A CN112408352A CN 112408352 A CN112408352 A CN 112408352A CN 202011336839 A CN202011336839 A CN 202011336839A CN 112408352 A CN112408352 A CN 112408352A
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- Prior art keywords
- phosphoric acid
- iron phosphate
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- battery
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 303
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 151
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 124
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 122
- 239000000243 solution Substances 0.000 claims abstract description 62
- 239000000047 product Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000012452 mother liquor Substances 0.000 claims abstract description 23
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 21
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 20
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000000605 extraction Methods 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 239000002351 wastewater Substances 0.000 claims description 15
- 239000011790 ferrous sulphate Substances 0.000 claims description 14
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 14
- 238000001223 reverse osmosis Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000008213 purified water Substances 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002367 phosphate rock Substances 0.000 abstract description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011164 primary particle Substances 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 description 111
- 238000003825 pressing Methods 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 229940000489 arsenate Drugs 0.000 description 5
- -1 iron ions Chemical class 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000021110 pickles Nutrition 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- AFSWOABZOLEQMR-UHFFFAOYSA-J iron(4+);hydroxide;phosphate Chemical compound [OH-].[Fe+4].[O-]P([O-])([O-])=O AFSWOABZOLEQMR-UHFFFAOYSA-J 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 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
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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-
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
-
- 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- C01P2006/11—Powder tap density
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- 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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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
The invention relates to a linkage production process of battery-grade iron phosphate and refined phosphoric acid. Taking a ferrous salt solution, an oxidant and a phosphoric acid solution as raw materials, and taking a weak acid salt as a pH value regulator to prepare a crude iron phosphate product; after the iron phosphate crude product is slurried with a phosphoric acid solution uniformly, an iron phosphate product and a conversion mother liquor are formed; the conversion mother liquor enters a phosphoric acid production system, and is mixed and blended with rough phosphoric acid prepared by acid leaching of phosphorite to produce refined phosphoric acid; the content of phosphoric acid in the refined phosphoric acid is 50-85%, the total content of impurities is less than 0.05g/L, and the refined phosphoric acid is used as a raw material for iron phosphate reaction and forms linkage production with iron phosphate. The method can obtain the uniform primary-particle superfine ferric phosphate with high uniformity among product batches and controllable product quality.
Description
Technical Field
The invention relates to the technical field of new energy battery preparation, in particular to a production process of battery-grade iron phosphate.
Background
With the strong support of the country on the lithium battery new energy battery industry, the market scale of the lithium ion battery is expanding by times. The lithium iron phosphate battery has the advantages of wide raw material source, low price, good safety performance, long cycle life and the like, so that the lithium iron phosphate battery becomes an ideal anode material of a new generation of lithium ion battery. The requirement of the 5G base station newly built and modified in 2020 can reach 10 GWH. The method opens up a new market for the application of the lithium iron phosphate battery in the field of standby power supplies of communication base stations. In the field of power automobiles, because of good safety performance, lithium iron phosphate batteries account for about 78% in 2020. Meanwhile, lithium iron phosphate batteries are also widely applied to the field of energy storage. The iron phosphate is an important precursor for preparing the lithium iron phosphate, and the performance of the iron phosphate determines various main performances of the lithium iron phosphate, so that the method has important significance for fully reducing the production cost of the iron phosphate while preparing the iron phosphate with excellent performance and reducing the cost of the whole lithium iron phosphate battery industrial chain.
For the preparation process of the ferric phosphate, a kettle-divided one-step chemical precipitation method is generally adopted at present, namely all raw materials are put into a reaction kettle to directly generate the battery-grade ferric phosphate. The representative technique is described in patent No. CN201110419619.2, etc. Such a processThe product has higher impurity content, wherein impurity elements such as S, Na and the like reach more than 400 ppm; secondly, the components of the wastewater are complex, and the treatment difficulty is high. The waste water contains various components such as sulfuric acid, phosphoric acid, sulfate and the like, and the waste water treatment cost is high and the difficulty is high to obtain a byproduct with higher purity. Thus, a two-step process is developed for iron phosphate production, in which iron and phosphorus raw materials are first synthesized into an intermediate product, hydroxyl iron phosphate, and then reacted with phosphoric acid to convert the hydroxyl iron phosphate into battery-grade iron phosphate. The basic process is described in patent document "a synthesis process of battery-grade iron phosphate" (application No. CN201910875696.5) and patent "a battery-grade iron phosphate and its preparation method" (application No. CN 201410062178.9). The two-step method is subjected to two reactions, the intermediate product is washed, the impurity content of the final product of the ferric phosphate is reduced, and meanwhile, the waste water of the two reactions can be separately treated and is relatively simple. On the product performance, the iron-phosphorus ratio of the two-step product is improved, generally between 0.97 and 0.99, and the tap density reaches 1.0g/cm3The above.
However, the existing two-step method has disadvantages, and mainly adopts a discontinuous production process, so that the product performance difference among different batches is large; in addition, the obtained product has great room for improvement in properties such as granularity and uniformity. Compared with a one-step method, the treatment of the wastewater and the conversion mother liquor of the two-step method becomes relatively easy, but the specific process can be further optimized and upgraded, the treatment cost is reduced, and the utilization rate of raw materials and auxiliary materials is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a linkage production process of battery-grade iron phosphate and refined phosphoric acid, and the method can obtain primary-particle superfine iron phosphate with high uniformity among product batches and controllable and uniform product quality; meanwhile, the conversion mother liquor phosphoric acid generated in the process of preparing the iron phosphate is merged into a refined phosphoric acid production system, and is used as a raw material for producing the iron phosphate after purification.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
step a: preparing a ferrous solution, a weak acid salt solution, an oxidant and a phosphoric acid solution;
step b: injecting a ferrous solution, an oxidant and a phosphoric acid solution into a reaction kettle A in a continuous parallel flow and bottom feeding mode, and controlling the reaction temperature to be 30-70 ℃;
step c: when the feed liquid in the reaction kettle A rises to an overflow port positioned at the upper part of the reaction kettle, the material naturally flows into the reaction kettle B from the overflow port, and the material is injected from a feed port at the middle part of the reaction kettle B; injecting weak acid salt solution into the reaction kettle B, injecting materials from a feed inlet at the middle part of the reaction kettle B, controlling the pH value of the reaction process to be 2.0-3.5, and controlling the reaction temperature to be 40-70 ℃;
step d: when the feed liquid in the reaction kettle B rises to an overflow port positioned at the upper part of the reaction kettle, the material naturally flows into the aging kettle from the overflow port, and the material is subjected to heat preservation and aging for 0.5-1 hour, then filtered and washed to obtain a crude iron phosphate product;
step e: mixing the iron phosphate crude product obtained in the step d with a phosphoric acid solution, and carrying out heat preservation reaction at the temperature of 80-100 ℃ for 1-3 hours to convert the iron phosphate crude product into iron phosphate slurry;
step f: filtering the iron phosphate slurry to obtain an iron phosphate conversion mother solution; washing, drying and calcining the filter cake iron phosphate to obtain battery-grade iron phosphate;
step g: blending and mixing the ferric phosphate conversion mother liquor with rough phosphoric acid produced by a phosphoric acid production system, purifying and purifying to obtain refined phosphoric acid, providing raw materials for the production of the ferric phosphate, and producing the refined phosphoric acid in linkage with the ferric phosphate; wherein (1) adding sulfuric acid into the mixed solution of the ferric phosphate conversion mother liquor and the rough phosphoric acid to prepare a solution with the phosphoric acid content of 10-35%, wherein the adding amount of the sulfuric acid is 0.5-10%; (2) purifying phosphoric acid by a fractional extraction process, adding solvent oil and an extracting agent, wherein the volume concentration of the extracting agent is 10-95%, and the balance is the solvent oil; the extraction stage number is 6-15, the O/A phase ratio is 0.5-5.0, the extraction temperature is 20-60 ℃, and the mixing time of the two phases is 5-20 minutes; (3) performing back extraction, wherein the back extraction agent is deionized water, the O/A ratio is 0.1-10, the back extraction temperature is 20-60 ℃, the two phases are mixed for 1-10 minutes, the water phase is a phosphoric acid solution, and the content of phosphoric acid is 15-85%; (4) and (3) extracting and purifying again, repeating the steps (1) to (3) by using the phosphoric acid obtained in the step (3), and further purifying the phosphoric acid to obtain refined phosphoric acid, wherein the content of the phosphoric acid is 50-85 percent, and the total salt content of impurities is less than 0.1 percent.
Preferably, the concentrations of the ferrous solution, the weak acid salt solution, the oxidant and the phosphoric acid solution in the step a are 0.5-2.5 mol/l; the weak acid salt is one or more of soluble bicarbonate, carbonate and acetate; the oxidant is one or more of sodium hypochlorite, sodium chlorate, hydrogen peroxide, peroxysulfuric acid, oxygen and air; the ferrous iron is ferrous sulfate or ferrous chloride.
Preferably, the molar ratio of the ferrous iron to the oxidant and the phosphoric acid injected into the reaction kettle A in the step b is 1: (0.5-1.5): (0.5 to 1).
Preferably, the concentration of the phosphoric acid solution in the step e is 1.5-2.5 mol/l.
Preferably, the drying temperature in the step f is 80-120 ℃, and the calcining temperature is 500-750 ℃.
Preferably, the crude phosphoric acid in step g is the leachate obtained after the reaction of phosphate ore with sulfuric acid in the phosphoric acid production system, wherein the phosphoric acid concentration is more than 35%.
Preferably, in the step g, kerosene is used as solvent oil, and the extracting agent is one or more of TBP, N235, N-octanol, P204, P507 and MIBK (methyl isobutyl ketone).
Preferably, the wastewater generated by filtering and washing in the step d enters a reverse osmosis membrane concentration-triple effect evaporation crystallization system for treatment; purified water produced by reverse osmosis membrane concentration is reused for production; adding a proper amount of ferric salt into the concentrated water to remove phosphate radical, adjusting the pH value to remove iron, feeding the purified residual liquid into a triple-effect evaporator, concentrating and crystallizing by taking steam as a heat source to obtain a high-purity related salt product, and recycling condensed water.
More preferably, the iron salt is ferric sulfate, ferric chloride or polymeric ferric sulfate, and the addition amount of the iron salt is as follows: p molar ratio (1.05-1.1): 1; and the pH value is 3.0-4.5 in the process of adjusting the pH value to remove iron.
The invention has the following beneficial effects:
1. the battery-grade iron phosphate synthesis reaction section adopts a continuous feeding production process, and the uniformity among product batches is increased in a continuous feeding mode, the equipment capacity is improved, and the equipment investment is reduced.
2. In the battery-grade iron phosphate synthesis reaction section, weak acid salt is used as a pH value regulator, and the acid-base buffering action of weak acid salt solution is utilized to slow down the growth speed of reaction materials, so that the quality of the materials is controllable and uniform; avoids the direct reaction of local high-concentration strong alkaline substances such as NaOH and the like with iron ions to generate an irregular stoichiometric iron ion-hydroxide complex. Along with the reduction of the reaction speed, the growth speed of material particles in the reaction process is reduced, which is beneficial to preparing superfine primary iron phosphate particles, and the size of the primary particles is 50-100 nm.
3. The recovery of the phosphoric acid of the conversion mother liquor and the linkage process of the production of the refined phosphoric acid and the production of the iron phosphate. The components of the conversion mother liquor are mainly phosphoric acid, the total content of impurities is less than 5g/L, and the conversion mother liquor is merged into a refined phosphoric acid production system for recycling and is used as a raw material for producing iron phosphate. After FePO4 and H3PO4 are produced in a linkage manner, the utilization rate of phosphoric acid is improved to more than 95 percent from about 80 percent. In the phosphoric acid extraction and purification section, a two-step extraction method is adopted to purify phosphoric acid, so that the purity of the phosphoric acid meets the quality requirement of linkage production with battery-grade iron phosphate, and meanwhile, the acid consumption and related treatment processes are reduced. The content of phosphoric acid in the refined phosphoric acid is 50-85%, the total content of impurities of all substances except phosphoric acid and water, such as sulfate, arsenate, fluoride and the like, is less than 0.05g/L, and the refined phosphoric acid is used as a raw material for iron phosphate reaction and forms linkage production with iron phosphate.
4. The wastewater generated by filtering and washing the battery-grade iron phosphate synthesis section is mainly related salts, and the concentration of phosphoric acid or phosphate is less than 0.1 g/L. The total salinity of the purified water produced by the concentration of the reverse osmosis membrane is less than 0.1 percent, and the concentration of electrolyte in the concentrated water generated by the concentration of the reverse osmosis membrane is lower than that of crystals, so that the concentrated water needs to be further concentrated; the pure residual liquid after removing phosphorus and removing iron enters a triple-effect evaporator to be concentrated and crystallized into a high-purity salt byproduct, so that the value of the byproduct is improved, and meanwhile, the condensed water is recycled, and the water reuse rate reaches 100%.
Drawings
Fig. 1 is a flow chart of a linkage production process of battery-grade iron phosphate and refined phosphoric acid.
Fig. 2 is an electron microscope scanning image of the ultrafine primary iron phosphate particles.
Detailed Description
Example 1
Step a: preparing ferrous sulfate solution, ammonium carbonate solution, hydrogen peroxide and phosphoric acid solution, wherein the concentration is 0.5 mol/l;
step b: injecting a ferrous sulfate solution, hydrogen peroxide and a phosphoric acid solution into a reaction kettle A in a continuous parallel flow and bottom feeding mode, and controlling the reaction temperature to be 60 ℃; the molar ratio of the ferrous sulfate to the oxidant to the phosphoric acid is 1: 1: 0.9;
step c: when the feed liquid in the reaction kettle A rises to an overflow port positioned at the upper part of the reaction kettle, the material naturally flows into the reaction kettle B from the overflow port, and the material is injected from a feed port at the middle part of the reaction kettle B; injecting an ammonium carbonate solution into the reaction kettle B, injecting a material from a feed inlet in the middle of the reaction kettle B, controlling the pH value of the reaction process to be 2.0, and controlling the reaction temperature to be 50 ℃;
step d: overflowing the reaction material into an aging kettle from a discharge hole of the reaction kettle B, aging the material for 1 hour under heat preservation, and then entering a filter pressing washing system through a pressing pump to generate synthetic reaction wastewater and a crude iron phosphate product; the synthetic reaction wastewater enters a reverse osmosis membrane concentration-triple effect evaporation crystallization system for treatment; the total salt content of purified water produced by concentration of the reverse osmosis membrane is 0.1 percent, and the purified water is reused for production; adding 108% of polymeric ferric sulfate contained in phosphorus into the concentrated water, removing phosphate radicals, adjusting the pH value of the filtered clear solution to 4.5, precipitating to remove iron ions, removing phosphorus and iron from the concentrated water, feeding the concentrated water into a triple-effect evaporator, concentrating and crystallizing by taking redundant steam of a thermal power plant as a heat source to generate a high-purity ammonium sulfate product, and recycling condensed water;
step e: d, mixing the iron phosphate crude product obtained in the step d with 1.0mol/l phosphoric acid solution, and carrying out heat preservation reaction at the temperature of 100 ℃ for 2 hours to convert the iron phosphate crude product into iron phosphate slurry;
step f: the ferric phosphate slurry enters a filter pressing washing system through a pressing pump to separate ferric phosphate and conversion mother liquor; washing, drying and calcining the filter cake iron phosphate to obtain battery-grade iron phosphate, wherein the drying temperature is 120 ℃, and the calcining temperature is 750 ℃;
step g: blending and mixing the iron phosphate conversion mother liquor with rough phosphoric acid with the phosphoric acid concentration being more than 35 percent prepared from phosphorite pickle liquor, purifying and purifying to obtain refined phosphoric acid, providing raw materials for the production of iron phosphate, and producing the refined phosphoric acid in linkage with the iron phosphate; adding sulfuric acid into a mixed solution of iron phosphate conversion mother liquor and crude phosphoric acid to prepare a solution with the phosphoric acid content of 30%, wherein the adding amount of the sulfuric acid is 8%; (2) purifying phosphoric acid by a fractional extraction process, wherein kerosene is used as solvent oil, an extracting agent is TBP, the volume concentration of the extracting agent is 85%, and the balance is solvent oil; the extraction stage number is 10 stages, the O/A ratio is 5, the extraction temperature is 40 ℃, and the mixing time of the two phases is 7 minutes; (3) performing back extraction, wherein the back extraction agent is deionized water, the O/A ratio is 5, the back extraction temperature is 40 ℃, the two phases are mixed for 5 minutes, the water phase is a phosphoric acid solution, and the phosphoric acid content is 45 percent; (4) and (4) extracting and purifying again, repeating the steps (1) to (3) by using the phosphoric acid obtained in the step (3), and further purifying the phosphoric acid to obtain the refined phosphoric acid, wherein the content of the phosphoric acid is 50%, and the total amount of impurity components such as sulfate, arsenate, fluoride, chloride and the like is less than 0.05 g/L.
Example 2
Step a: preparing a ferrous sulfate solution, a sodium carbonate solution, oxygen and a phosphoric acid solution, wherein the concentrations are all 1.5 mol/l;
step b: injecting a ferrous sulfate solution, oxygen and a phosphoric acid solution into a reaction kettle A in a continuous parallel flow and bottom feeding mode, and controlling the reaction temperature to be 60 ℃; the molar ratio of the ferrous sulfate to the oxidant to the phosphoric acid is 1: 1: 0.8;
step c: when the feed liquid in the reaction kettle A rises to an overflow port positioned at the upper part of the reaction kettle, the material naturally flows into the reaction kettle B from the overflow port, and the material is injected from a feed port at the middle part of the reaction kettle B; injecting a sodium carbonate solution into the reaction kettle B, injecting a material from a feed inlet at the middle part of the reaction kettle B, controlling the pH value of the reaction process to be 3.0, and controlling the reaction temperature to be 40 ℃;
step d: overflowing the reaction material into an aging kettle from a discharge hole of the reaction kettle B, aging the material for 1 hour under heat preservation, and then entering a filter pressing washing system through a pressing pump to generate synthetic reaction wastewater and a crude iron phosphate product; the synthetic reaction wastewater enters a reverse osmosis membrane concentration-triple effect evaporation crystallization system for treatment; the total salt content of purified water produced by concentration of the reverse osmosis membrane is 0.05 percent, and the purified water is reused for production; adding 110% of ferric sulfate contained in phosphorus into the concentrated water, removing phosphate radicals, adjusting the pH value of the filtered clear solution to 4.5, precipitating to remove iron ions, removing phosphorus and iron from the concentrated water, feeding the concentrated water into a triple-effect evaporator, concentrating and crystallizing by taking redundant steam of a thermal power plant as a heat source to generate a high-purity ammonium sulfate product, and recycling condensed water;
step e: d, mixing the iron phosphate crude product obtained in the step d with 1.5mol/l phosphoric acid solution, and carrying out heat preservation reaction at the temperature of 95 ℃ for 3 hours to convert the iron phosphate crude product into iron phosphate slurry;
step f: the ferric phosphate slurry enters a filter pressing washing system through a pressing pump to separate ferric phosphate and conversion mother liquor; washing, drying and calcining the filter cake iron phosphate to obtain battery-grade iron phosphate, wherein the drying temperature is 100 ℃, and the calcining temperature is 650 ℃;
step g: blending and mixing the iron phosphate conversion mother liquor with rough phosphoric acid with the phosphoric acid concentration being more than 35 percent prepared from phosphorite pickle liquor, purifying and purifying to obtain refined phosphoric acid, providing raw materials for the production of iron phosphate, and producing the refined phosphoric acid in linkage with the iron phosphate; adding sulfuric acid into a mixed solution of iron phosphate conversion mother liquor and crude phosphoric acid to prepare a solution with the phosphoric acid content of 20%, wherein the adding amount of the sulfuric acid is 5%; (2) purifying phosphoric acid by a fractional extraction process, wherein kerosene is used as solvent oil, an extracting agent is a mixed extracting agent of TBP and MIBK, the volume concentration of the extracting agent is 70%, and the balance is solvent oil; the extraction stage number is 12, the O/A ratio is 3, the extraction temperature is 30 ℃, and the mixing time of the two phases is 10 minutes; (3) performing back extraction, wherein the back extraction agent is deionized water, the O/A ratio is 5, the back extraction temperature is 30 ℃, the two phases are mixed for 8 minutes, the water phase is a phosphoric acid solution, and the phosphoric acid content is 60 percent; (4) and (4) extracting and purifying again, repeating the steps (1) to (3) by using the phosphoric acid obtained in the step (3), and further purifying the phosphoric acid to obtain the refined phosphoric acid, wherein the content of the phosphoric acid is 80%, and the total amount of impurity components such as sulfate, arsenate, fluoride, chloride and the like is less than 0.05 g/L.
Example 3
Step a: preparing ferrous sulfate solution, ammonium bicarbonate solution, hydrogen peroxide and phosphoric acid solution, wherein the concentration is 0.5 mol/l;
step b: injecting a ferrous sulfate solution, hydrogen peroxide and a phosphoric acid solution into a reaction kettle A in a continuous parallel flow and bottom feeding mode, and controlling the reaction temperature to be 60 ℃; the molar ratio of the ferrous sulfate to the oxidant to the phosphoric acid is 1: 1: 0.9;
step c: when the feed liquid in the reaction kettle A rises to an overflow port positioned at the upper part of the reaction kettle, the material naturally flows into the reaction kettle B from the overflow port, and the material is injected from a feed port at the middle part of the reaction kettle B; injecting an ammonium bicarbonate solution into the reaction kettle B, injecting a material from a feed inlet in the middle of the reaction kettle B, controlling the pH value of the reaction process to be 2.0, and controlling the reaction temperature to be 50 ℃;
step d: overflowing the reaction material into an aging kettle from a discharge hole of the reaction kettle B, aging the material for 1 hour under heat preservation, and then entering a filter pressing washing system through a pressing pump to generate synthetic reaction wastewater and a crude iron phosphate product; the synthetic reaction wastewater enters a reverse osmosis membrane concentration-triple effect evaporation crystallization system for treatment; the total salt content of purified water produced by concentration of the reverse osmosis membrane is 0.1 percent, and the purified water is reused for production; adding 108% of polymeric ferric sulfate contained in phosphorus into the concentrated water, removing phosphate radicals, adjusting the pH value of the filtered clear solution to 4.5, precipitating to remove iron ions, removing phosphorus and iron from the concentrated water, feeding the concentrated water into a triple-effect evaporator, concentrating and crystallizing by taking redundant steam of a thermal power plant as a heat source to generate a high-purity ammonium sulfate product, and recycling condensed water;
step e: d, mixing the iron phosphate crude product obtained in the step d with 1.0mol/l phosphoric acid solution, and carrying out heat preservation reaction at the temperature of 100 ℃ for 2 hours to convert the iron phosphate crude product into iron phosphate slurry;
step f: the ferric phosphate slurry enters a filter pressing washing system through a pressing pump to separate ferric phosphate and conversion mother liquor; washing, drying and calcining the filter cake iron phosphate to obtain battery-grade iron phosphate, wherein the drying temperature is 120 ℃, and the calcining temperature is 750 ℃;
step g: blending and mixing the iron phosphate conversion mother liquor with rough phosphoric acid with the phosphoric acid concentration being more than 35 percent prepared from phosphorite pickle liquor, purifying and purifying to obtain refined phosphoric acid, providing raw materials for the production of iron phosphate, and producing the refined phosphoric acid in linkage with the iron phosphate; adding sulfuric acid into a mixed solution of iron phosphate conversion mother liquor and crude phosphoric acid to prepare a solution with the phosphoric acid content of 30%, wherein the adding amount of the sulfuric acid is 8%; (2) purifying phosphoric acid by a fractional extraction process, wherein kerosene is used as solvent oil, an extracting agent is TBP, the volume concentration of the extracting agent is 85%, and the balance is solvent oil; the extraction stage number is 10 stages, the O/A ratio is 5, the extraction temperature is 40 ℃, and the mixing time of the two phases is 7 minutes; (3) performing back extraction, wherein the back extraction agent is deionized water, the O/A ratio is 5, the back extraction temperature is 40 ℃, the two phases are mixed for 5 minutes, the water phase is a phosphoric acid solution, and the phosphoric acid content is 45 percent; (4) and (4) extracting and purifying again, repeating the steps (1) to (3) by using the phosphoric acid obtained in the step (3), and further purifying the phosphoric acid to obtain the refined phosphoric acid, wherein the content of the phosphoric acid is 50%, and the total amount of impurity components such as sulfate, arsenate, fluoride, chloride and the like is less than 0.05 g/L.
Example 4
Step a: preparing a ferrous sulfate solution, a sodium acetate solution, oxygen and a phosphoric acid solution, wherein the concentrations are all 1.5 mol/l;
step b: injecting a ferrous sulfate solution, oxygen and a phosphoric acid solution into a reaction kettle A in a continuous parallel flow and bottom feeding mode, and controlling the reaction temperature to be 60 ℃; the molar ratio of the ferrous sulfate to the oxidant to the phosphoric acid is 1: 1: 0.8;
step c: when the feed liquid in the reaction kettle A rises to an overflow port positioned at the upper part of the reaction kettle, the material naturally flows into the reaction kettle B from the overflow port, and the material is injected from a feed port at the middle part of the reaction kettle B; injecting a sodium acetate solution into the reaction kettle B, injecting a material from a feed inlet at the middle part of the reaction kettle B, controlling the pH value of the reaction process to be 3.0, and controlling the reaction temperature to be 40 ℃;
step d: overflowing the reaction material into an aging kettle from a discharge hole of the reaction kettle B, aging the material for 1 hour under heat preservation, and then entering a filter pressing washing system through a pressing pump to generate synthetic reaction wastewater and a crude iron phosphate product; the synthetic reaction wastewater enters a reverse osmosis membrane concentration-triple effect evaporation crystallization system for treatment; the total salt content of purified water produced by concentration of the reverse osmosis membrane is 0.05 percent, and the purified water is reused for production; adding 110% of ferric sulfate contained in phosphorus into the concentrated water, removing phosphate radicals, adjusting the pH value of the filtered clear solution to 4.5, precipitating to remove iron ions, removing phosphorus and iron from the concentrated water, feeding the concentrated water into a triple-effect evaporator, concentrating and crystallizing by taking redundant steam of a thermal power plant as a heat source to generate a high-purity ammonium sulfate product, and recycling condensed water;
step e: d, mixing the iron phosphate crude product obtained in the step d with 1.5mol/l phosphoric acid solution, and carrying out heat preservation reaction at the temperature of 95 ℃ for 3 hours to convert the iron phosphate crude product into iron phosphate slurry;
step f: the ferric phosphate slurry enters a filter pressing washing system through a pressing pump to separate ferric phosphate and conversion mother liquor; washing, drying and calcining the filter cake iron phosphate to obtain battery-grade iron phosphate, wherein the drying temperature is 100 ℃, and the calcining temperature is 650 ℃;
step g: blending and mixing the iron phosphate conversion mother liquor with rough phosphoric acid with the phosphoric acid concentration being more than 35 percent prepared from phosphorite pickle liquor, purifying and purifying to obtain refined phosphoric acid, providing raw materials for the production of iron phosphate, and producing the refined phosphoric acid in linkage with the iron phosphate; adding sulfuric acid into a mixed solution of iron phosphate conversion mother liquor and crude phosphoric acid to prepare a solution with the phosphoric acid content of 20%, wherein the adding amount of the sulfuric acid is 5%; (2) purifying phosphoric acid by a fractional extraction process, wherein kerosene is used as solvent oil, an extracting agent is a mixed extracting agent of TBP and MIBK, the volume concentration of the extracting agent is 70%, and the balance is solvent oil; the extraction stage number is 12, the O/A ratio is 3, the extraction temperature is 30 ℃, and the mixing time of the two phases is 10 minutes; (3) performing back extraction, wherein the back extraction agent is deionized water, the O/A ratio is 5, the back extraction temperature is 30 ℃, the two phases are mixed for 8 minutes, the water phase is a phosphoric acid solution, and the phosphoric acid content is 60 percent; (4) and (4) extracting and purifying again, repeating the steps (1) to (3) by using the phosphoric acid obtained in the step (3), and further purifying the phosphoric acid to obtain the refined phosphoric acid, wherein the content of the phosphoric acid is 80%, and the total amount of impurity components such as sulfate, arsenate, fluoride, chloride and the like is less than 0.05 g/L.
The performance test data for the battery grade iron phosphate prepared in examples 1-4 are as follows:
| example 1 | Example 2 | Example 3 | Example 4 | |
| Particle size D50(μm) | 4.09 | 4.13 | 4.20 | 4.16 |
| Sulfur content (ppm) | 30 | 32 | 31 | 35 |
| Specific surface area (m)2/g) | 10.315 | 9.578 | 11.125 | 10.525 |
| Iron (%) | 36.43 | 36.45 | 36.52 | 36.47 |
| Phosphorus (%) | 20.75 | 20.76 | 20.71 | 20.74 |
| Iron to phosphorus ratio | 0.973 | 0.974 | 0.978 | 0.975 |
| Tap density (g/m)3) | 0.852 | 0.864 | 0.882 | 0.876 |
| Copper (ppm) | 5 | 4 | 3 | 2 |
| Manganese (ppm) | 4 | 3 | 2 | 5 |
| Chromium (ppm) | 3 | 5 | 2 | 1 |
| Cobalt (ppm) | 6 | 7 | 6 | 8 |
| Nickel (ppm) | 7 | 8 | 6 | 9 |
| Magnesium (ppm) | Not detected out | Not detected out | Not detected out | Not detected out |
| Lead (ppm) | 15 | 18 | 20 | 19 |
| Zinc (ppm) | 18 | 17 | 15 | 16 |
| Potassium (ppm) | Not detected out | Not detected out | Not detected out | Not detected out |
| Calcium (ppm) | Not detected out | Not detected out | Not detected out | Not detected out |
| Sodium (ppm) | Not detected out | Not detected out | Not detected out | Not detected out |
From the data in the table, the content of each impurity of the battery-grade iron phosphate prepared by the invention is very low, below 50PPm, and partially below 10PPm, and the content of impurities such as iron phosphate S, Mg, Mn and the like produced by the conventional process is generally about 150 PPm. The tap density is 0.85g/cm3In the above, the tap density of the iron phosphate produced by the conventional process is generally between 0.6 and 0.7. The iron phosphate produced by the process has stable quality, good product consistency, high iron phosphate crystal purity, low impurity content, good product purity and uniform crystal size, can be directly used for manufacturing lithium iron phosphate, is an efficient raw material for manufacturing lithium iron phosphate of a battery, and has high economic efficiency.
Claims (9)
1. A linkage production process of battery-grade iron phosphate and refined phosphoric acid is characterized by comprising the following steps: the method comprises the following steps:
step a: preparing a ferrous solution, a weak acid salt solution, an oxidant and a phosphoric acid solution;
step b: injecting a ferrous solution, an oxidant and a phosphoric acid solution into a reaction kettle A in a continuous parallel flow and bottom feeding mode, and controlling the reaction temperature to be 30-70 ℃;
step c: when the feed liquid in the reaction kettle A rises to an overflow port positioned at the upper part of the reaction kettle, the material naturally flows into the reaction kettle B from the overflow port, and the material is injected from a feed port at the middle part of the reaction kettle B; injecting weak acid salt solution into the reaction kettle B, injecting materials from a feed inlet at the middle part of the reaction kettle B, controlling the pH value of the reaction process to be 2.0-3.5, and controlling the reaction temperature to be 40-70 ℃;
step d: when the feed liquid in the reaction kettle B rises to an overflow port positioned at the upper part of the reaction kettle, the material naturally flows into the aging kettle from the overflow port, and the material is subjected to heat preservation and aging for 0.5-1 hour, then filtered and washed to obtain a crude iron phosphate product;
step e: mixing the iron phosphate crude product obtained in the step d with a phosphoric acid solution, and carrying out heat preservation reaction at the temperature of 80-100 ℃ for 1-3 hours to convert the iron phosphate crude product into iron phosphate slurry;
step f: filtering the iron phosphate slurry to obtain an iron phosphate conversion mother solution; washing, drying and calcining the filter cake iron phosphate to obtain battery-grade iron phosphate;
step g: blending and mixing the ferric phosphate conversion mother liquor with rough phosphoric acid produced by a phosphoric acid production system, purifying and purifying to obtain refined phosphoric acid, providing raw materials for the production of the ferric phosphate, and producing the refined phosphoric acid in linkage with the ferric phosphate; wherein (1) adding sulfuric acid into the mixed solution of the ferric phosphate conversion mother liquor and the rough phosphoric acid to prepare a solution with the phosphoric acid content of 10-35%, wherein the adding amount of the sulfuric acid is 0.5-10%; (2) purifying phosphoric acid by a fractional extraction process, adding solvent oil and an extracting agent, wherein the volume concentration of the extracting agent is 10-95%, and the balance is the solvent oil; the extraction stage number is 6-15, the O/A phase ratio is 0.5-5.0, the extraction temperature is 20-60 ℃, and the mixing time of the two phases is 5-20 minutes; (3) performing back extraction, wherein the back extraction agent is deionized water, the O/A ratio is 0.1-10, the back extraction temperature is 20-60 ℃, the two phases are mixed for 1-10 minutes, the water phase is a phosphoric acid solution, and the content of phosphoric acid is 15-85%; (4) and (3) extracting and purifying again, repeating the steps (1) to (3) by using the phosphoric acid obtained in the step (3), and further purifying the phosphoric acid to obtain refined phosphoric acid, wherein the content of the phosphoric acid is 50-85 percent, and the total salt content of impurities is less than 0.1 percent.
2. The linkage production process of battery-grade iron phosphate and refined phosphoric acid according to claim 1, characterized in that: the concentrations of the ferrous solution, the weak acid salt solution, the oxidant and the phosphoric acid solution in the step a are 0.5-2.5 mol/l; the weak acid salt is one or more of soluble bicarbonate, carbonate and acetate; the oxidant is one or more of sodium hypochlorite, sodium chlorate, hydrogen peroxide, peroxysulfuric acid, oxygen and air; the ferrous iron is ferrous sulfate or ferrous chloride.
3. The linkage production process of battery-grade iron phosphate and refined phosphoric acid according to claim 1, characterized in that: the molar ratio of the ferrous iron, the oxidant and the phosphoric acid injected into the reaction kettle A in the step b is 1: (0.5-1.5): (0.5 to 1).
4. The linkage production process of battery-grade iron phosphate and refined phosphoric acid according to claim 1, characterized in that: the concentration of the phosphoric acid solution in the step e is 1.5-2.5 mol/l.
5. The linkage production process of battery-grade iron phosphate and refined phosphoric acid according to claim 1, characterized in that: in the step f, the drying temperature is 80-120 ℃, and the calcining temperature is 500-750 ℃.
6. The linkage production process of battery-grade iron phosphate and refined phosphoric acid according to claim 1, characterized in that: and g, the crude phosphoric acid refers to leachate obtained after phosphate ore reacts with sulfuric acid in a phosphoric acid production system, wherein the concentration of phosphoric acid is more than 35 percent.
7. The linkage production process of battery-grade iron phosphate and refined phosphoric acid according to claim 1, characterized in that: in the step g, kerosene is used as solvent oil, and the extracting agent is one or more of TBP, N235, N-octanol, P204, P507 and MIBK (methyl isobutyl ketone).
8. The linkage production process of battery-grade iron phosphate and refined phosphoric acid according to claim 1, characterized in that: d, the wastewater generated by filtering and washing in the step d enters a reverse osmosis membrane concentration-triple effect evaporation crystallization system for treatment; purified water produced by reverse osmosis membrane concentration is reused for production; adding a proper amount of ferric salt into the concentrated water to remove phosphate radical, adjusting the pH value to remove iron, feeding the purified residual liquid into a triple-effect evaporator, concentrating and crystallizing by taking steam as a heat source to obtain a high-purity related salt product, and recycling condensed water.
9. The linkage production process of battery-grade iron phosphate and refined phosphoric acid according to claim 8, characterized in that: the ferric salt is ferric sulfate, ferric chloride or polymeric ferric sulfate, and the adding amount of the ferric salt is as follows: p molar ratio (1.05-1.1): 1; and the pH value is 3.0-4.5 in the process of adjusting the pH value to remove iron.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115108673A (en) * | 2022-08-31 | 2022-09-27 | 深圳永清水务有限责任公司北京分公司 | Recycling process for ferric phosphate mother liquor produced by oxidation method |
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| CN115490219A (en) * | 2022-09-02 | 2022-12-20 | 广东邦普循环科技有限公司 | Ferric phosphate and synthesis process, system and application thereof |
| CN116409763A (en) * | 2021-12-30 | 2023-07-11 | 中国科学院过程工程研究所 | Method for preparing high-purity ferric phosphate from wet-process crude phosphoric acid |
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| CN116409763A (en) * | 2021-12-30 | 2023-07-11 | 中国科学院过程工程研究所 | Method for preparing high-purity ferric phosphate from wet-process crude phosphoric acid |
| CN116409763B (en) * | 2021-12-30 | 2024-09-10 | 中国科学院过程工程研究所 | Method for preparing high-purity ferric phosphate from wet-process crude phosphoric acid |
| CN114572950A (en) * | 2022-01-28 | 2022-06-03 | 宜昌邦普宜化新材料有限公司 | Preparation method and application of high-purity iron phosphate |
| CN115367722A (en) * | 2022-08-03 | 2022-11-22 | 宜都兴发化工有限公司 | Method for preparing iron phosphate from phosphosiderite |
| CN115367722B (en) * | 2022-08-03 | 2023-10-27 | 宜都兴发化工有限公司 | Method for preparing ferric phosphate from ferrophosphorus ore |
| CN115108673A (en) * | 2022-08-31 | 2022-09-27 | 深圳永清水务有限责任公司北京分公司 | Recycling process for ferric phosphate mother liquor produced by oxidation method |
| CN115108673B (en) * | 2022-08-31 | 2022-12-06 | 深圳永清水务有限责任公司 | Recycling process for ferric phosphate mother liquor produced by oxidation method |
| CN115490219A (en) * | 2022-09-02 | 2022-12-20 | 广东邦普循环科技有限公司 | Ferric phosphate and synthesis process, system and application thereof |
| WO2024045516A1 (en) * | 2022-09-02 | 2024-03-07 | 广东邦普循环科技有限公司 | Iron phosphate, and synthesis process and system therefor and use thereof |
| CN115490219B (en) * | 2022-09-02 | 2024-03-12 | 广东邦普循环科技有限公司 | Ferric phosphate and synthesis process, system and application thereof |
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