CN113955734A - Method for preparing battery-grade iron phosphate by treating solid waste with acid mine wastewater - Google Patents
Method for preparing battery-grade iron phosphate by treating solid waste with acid mine wastewater Download PDFInfo
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- CN113955734A CN113955734A CN202111477177.7A CN202111477177A CN113955734A CN 113955734 A CN113955734 A CN 113955734A CN 202111477177 A CN202111477177 A CN 202111477177A CN 113955734 A CN113955734 A CN 113955734A
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- sodium
- solid waste
- acid
- iron phosphate
- phosphate
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- 239000002910 solid waste Substances 0.000 title claims abstract description 50
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 40
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002253 acid Substances 0.000 title claims description 28
- 239000002351 wastewater Substances 0.000 title description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000002378 acidificating effect Effects 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052785 arsenic Inorganic materials 0.000 abstract description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000002893 slag Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 10
- 235000010215 titanium dioxide Nutrition 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical group O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
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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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- 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
- C01P2006/82—Compositional purity water content
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for preparing battery-grade iron phosphate by utilizing mine acidic wastewater treatment solid waste, which comprises the steps of leaching most of iron in slag through reduction reaction by taking the mine acidic wastewater treatment solid waste as an iron source, then precipitating and purifying most of impurity metal ions such as aluminum, titanium, cobalt, nickel, copper, zinc, arsenic and the like, and finally preparing the battery-grade iron phosphate (the iron phosphate for HG/T4701-. The method not only solves the problem of solid waste reduction, but also realizes high-value utilization of industrial solid waste, and has good economic benefit and environmental benefit.
Description
Technical Field
The invention relates to the technical field of material synthesis, in particular to a method for preparing battery-grade iron phosphate by treating solid waste with mine acidic wastewater.
Background
At the beginning of the development of new energy automobiles, because the theoretical energy density of the lithium iron phosphate battery is lower than that of a ternary positive electrode battery, the application of the lithium iron phosphate battery in the aspect of power batteries is limited to a certain extent. With the development of blade and PCT battery technologies in BYD and Ningde times, the energy density of a lithium iron phosphate system is increased to 160Wh/kg, the situation is improved greatly, and the lithium iron phosphate battery with high safety coefficient and low cost is paid great attention. According to the latest statistical data (month 5) of the power alliance, the domestic power battery yield is 13.8GWh in total, and the yield is increased by 165.8% on the same scale, wherein the lithium iron phosphate battery yield is 8.8GWh and accounts for 63.8%, and the monthly yield of the ternary lithium battery is exceeded for the first time in the year. From the loading amount, the loading amount of the domestic power battery in 5 months is 9.8GWH, which is improved by 178.2 percent on the same scale, wherein the loading amount of the lithium iron phosphate battery is 4.5GWH, which accounts for 45.9 percent; the proportion of the ternary lithium battery is reduced to 53 percent, and the loading amount is 5.2 GWH. According to the prediction of the skilled person, the loading amount of lithium iron phosphate is predicted to exceed that of the ternary lithium battery in 6 months, and the lithium iron phosphate returns to the first position of the power battery again.
In the industry of lithium iron phosphate cathode materials in China, the high-temperature solid-phase method is the mainstream process adopted by more than 90% of enterprises at present due to the advantages of relatively simple process, high maturity and the like, and is generally prepared by sintering an iron source, a phosphorus source and a lithium source serving as raw materials at high temperature. The iron source mainly comprises ferrous oxalate, ferric oxide and ferric phosphate, wherein the ferric phosphate process is favored by a plurality of material manufacturers due to the advantages of less raw materials, no need of solvent, water system mixing, no ammonia emission, low process cost and the like. The defects that the cost of an iron phosphate line is high, the cost of raw materials is over 30 percent only by one item of iron phosphate, and the great reduction of the cost of the iron phosphate is one of the key factors for reducing the production cost of the lithium iron phosphate. There are many production process routes for battery grade ferric phosphate in industry, and the related iron sources include high purity iron powder, ferrous sulfate, ferric nitrate, etc. Patent CN 111017900a discloses a method for synthesizing battery-grade iron phosphate by using high-purity iron powder, and patent CN 111333047a discloses a method for synthesizing high-purity iron phosphate by using ferrous sulfate as a titanium dioxide byproduct. At present, the market mainly produces battery-grade iron phosphate by taking ferrous sulfate as a byproduct of titanium dioxide as a raw material, but because titanium dioxide enterprises mainly concentrate on coastal areas, China and southwest areas in east China, the sales radius of the titanium dioxide enterprises is limited by the transportation cost; and a lot of large titanium dioxide enterprises invest in self-built iron phosphate production items (such as python, mesonuclear titanium white and the like), so that the market of the ferrous sulfate on the market is pretty and the price is raised. In comparison, the solid waste is used as an iron source to produce the battery-grade iron phosphate, so that the source is wide, the price is low, the solid waste discharge is reduced, and the environment is protected.
Acidic wastewater generated in the mining process of mines can cause serious harm to water environment, fishery, agriculture and human health due to the fact that the acidic wastewater contains a large amount of heavy metal ions. The treatment method of acid mine wastewater is various, but the most common method is lime neutralization precipitation. According to statistics, the acid mine wastewater generated in the world every year is up to 0.64-1.02 hundred million m3According to treatment 1m3The acid wastewater generates about 30kg of neutralized solid waste, and the solid waste is generated by 306 ten thousand t in each year. Normally, the solid waste contains 1.5-46.5% of Fe, 0.1-11.2% of Al, 0.001-1.48% of Cu and 0.003-22.0% of Zn, and if the metals can be recycled, 2.8-142.29 million t of Fe, 0.19-34.27 million t of Al, 0.002-4.53 million t of Cu and 0.006-67.32 million t of Zn can be recovered each year, so that the problem of regional resource shortage can be relieved, the solid waste discharge can be reduced, and the pressure of a mine tailing pond can be relieved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing battery-grade iron phosphate by treating solid waste by using acid mine wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing battery-grade iron phosphate by utilizing mine acidic wastewater treatment solid waste comprises the following steps:
s1, reduction leaching: acidifying the mine acidic wastewater treatment solid waste with dilute acid, heating, and adding a reducing agent for reduction leaching;
s2, precipitation and purification: adding an alkali solution into the slurry obtained by the reduction leaching in the step S1 to adjust the pH value to 4.5-5.5, and then removing metal impurity ions through solid-liquid separation;
s3, oxidation synthesis: adding a phosphorus source and an oxidant into the filtrate obtained in the step S2, mixing to perform an oxidation reaction, controlling the pH of the reaction end point to be 1.4-2.0 by using an alkali or acid solution, performing solid-liquid separation on the slurry after the reaction is finished, and washing for multiple sections to obtain light yellow filter residue;
s4, aging and transformation: and (5) adding diluted phosphoric acid into the light yellow filter residue obtained in the step (S3), stirring and aging to obtain light pink slurry, and performing solid-liquid separation, washing and drying to obtain the product, namely the battery-grade iron phosphate.
Further, in step S1, the dilute acid is one of sulfuric acid and hydrochloric acid, the acidity is 6-10g/L, and the dosage is 3-5 times of the dry weight of the mine acidic wastewater treatment solid waste.
Further, in step S1, the heating temperature is 60-80 ℃.
Further, in step S1, the reducing agent is one of sodium metabisulfite, sulfur dioxide, sodium sulfite, sodium thiosulfate, sodium sulfide, ascorbic acid, and glucose.
Further, in step S1, the molar weight of the reducing agent is 0.4-1.0 times of the molar weight of the iron in the solid waste from the treatment of the acid mine wastewater, and the reduction leaching time is 1-2 h.
Further, in step S2, the alkali solution is a solution of one of calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.
Further, in step S3, the phosphorus source is one of phosphoric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, potassium phosphate, and ammonium phosphate; the oxidant is one of ammonium persulfate, sodium persulfate, hydrogen peroxide, ozone and hypochlorous acid.
Further, in step S3, the alkali is one of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; the acid is one of sulfuric acid and hydrochloric acid.
Further, the molar ratio of Fe to P to the oxidant is 0.9-1.0:1-1.1: 0.55-0.8.
Furthermore, the concentration of the dilute phosphoric acid is 0.1-0.3mol/L, the stirring and aging temperature is 75-95 ℃, and the time is 0.5-2.0 h.
The invention has the beneficial effects that: the method takes the mine acidic wastewater treatment solid waste as an iron source, leaches most of iron in slag through reduction reaction, then precipitates and purifies most of impurity metal ions such as aluminum, titanium, cobalt, nickel, copper, zinc, arsenic and the like, and finally prepares battery-grade iron phosphate (the iron phosphate for HG/T4701-2014 batteries) meeting the chemical industry standard through oxidation, precipitation and aging transformation. The method not only solves the problem of solid waste reduction, but also realizes high-value utilization of industrial solid waste, and has good economic benefit and environmental benefit.
Drawings
FIG. 1 is a flow chart of a method of the present invention;
fig. 2 is an XRD pattern of the battery grade iron phosphate prepared in accordance with the present invention;
fig. 3 is a graph of the particle size distribution of battery grade iron phosphate prepared in accordance with the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
The chemical composition analysis of the mine acid wastewater treatment solid waste used in the following examples is as follows: 15.81% of Fe, 0.015% of Na, 16.76% of Ca, 0.21% of Al, 0.013% of Cu and 0.018% of Zn, and the contents of the rest of Mg, Si, Mn, Co, Ni, Cd, Ti and other elements are less than 0.01%.
Example 1
The method for preparing battery-grade iron phosphate by using the mine acidic wastewater to treat solid waste, as shown in fig. 1, specifically comprises the following steps:
(1) taking 400g of mine acid wastewater treatment solid waste (containing 50% of water), adding a dilute sulfuric acid solution with the acid concentration of 6g/L according to 3 times of the dry weight of the solid waste, and uniformly stirring; heating to 60 ℃, adding sodium pyrosulfite with the molar weight 0.4 times of that of iron in the solid waste for treating the acidic wastewater, and reacting for 2 hours;
(2) adding a calcium hydroxide solution into the slurry obtained in the step (1), adjusting the pH value of the slurry to be 4.5, and then carrying out solid-liquid separation to remove metal impurity ions;
(3) adding phosphoric acid and ammonium persulfate into the filtrate obtained in the step (2) at the same time, mixing to perform an oxidation reaction, wherein the molar ratio of Fe to P to ammonium persulfate is 0.9:1:0.55, controlling the pH value of the slurry to be 1.4 by using ammonia water, performing solid-liquid separation on the slurry after the reaction is finished, and washing in multiple stages to obtain light yellow filter residue;
(4) and (4) adding the filter residue obtained in the step (3) into 0.1mol/L diluted phosphoric acid solution, stirring and aging in a water bath at 95 ℃ for 0.5h, wherein the slurry becomes light pink, and obtaining the product of the battery-grade iron phosphate after solid-liquid separation, washing and drying.
Example 2
The method for preparing battery-grade iron phosphate by using the mine acidic wastewater to treat solid waste, as shown in fig. 1, specifically comprises the following steps:
(1) taking 400g of mine acid wastewater treatment solid waste (containing 50% of water), adding a dilute hydrochloric acid solution with the acid concentration of 8g/L according to 4 times of the dry weight of the solid waste, and uniformly stirring; heating to 70 ℃, adding sulfur dioxide gas with the molar weight 0.8 times of that of iron in the solid waste for treating the acidic wastewater, and reacting for 1.5 h;
(2) adding a sodium hydroxide solution into the slurry obtained in the step (1), adjusting the pH value of the slurry to be 5.0, and then carrying out solid-liquid separation to remove metal impurity ions;
(3) adding sodium dihydrogen phosphate and hydrogen peroxide into the filtrate obtained in the step (2) at the same time, mixing to perform oxidation reaction, wherein the molar ratio of Fe to P to hydrogen peroxide is 0.95:1.05:0.70, controlling the pH value of the slurry to be 1.7 by using sodium carbonate, performing solid-liquid separation on the slurry after the reaction is finished, and washing in multiple stages to obtain light yellow filter residue;
(4) and (4) adding the filter residue obtained in the step (3) into 0.2mol/L diluted phosphoric acid solution, stirring and aging in a water bath at 90 ℃ for 1.0h, wherein the slurry becomes light pink, and obtaining the product of the battery-grade iron phosphate after solid-liquid separation, washing and drying.
Example 3
The method for preparing battery-grade iron phosphate by using the mine acidic wastewater to treat solid waste comprises the following specific steps as shown in fig. 1:
(1) taking 400g of mine acid wastewater treatment solid waste (containing 50% of water), adding a dilute sulfuric acid solution with the acid concentration of 10g/L according to 5 times of the dry weight of the solid waste, and uniformly stirring; heating to 80 ℃, adding sodium thiosulfate with the molar weight 1.0 time of that of iron in the solid waste for treating the acidic wastewater, and reacting for 1.0 h;
(2) adding a potassium carbonate solution into the slurry obtained in the step (1), adjusting the pH value of the slurry to be 5.5, and then carrying out solid-liquid separation to remove metal impurity ions;
(3) adding potassium phosphate and hypochlorous acid into the filtrate obtained in the step (2) at the same time, mixing to perform an oxidation reaction, wherein the molar ratio of Fe to P to hypochlorous acid is 1.0:1.1:0.8, controlling the pH value of the slurry to be 2.0 by using sulfuric acid, performing solid-liquid separation on the slurry after the reaction is finished, and washing in multiple stages to obtain light yellow filter residue;
(4) and (4) adding the filter residue obtained in the step (3) into 0.3mol/L diluted phosphoric acid solution, stirring and aging in a water bath at 75 ℃ for 2.0h, wherein the slurry becomes light pink, and obtaining the product of the battery-grade iron phosphate after solid-liquid separation, washing and drying.
Example 4
The method for preparing battery-grade iron phosphate by using the mine acidic wastewater to treat solid waste, as shown in fig. 1, specifically comprises the following steps:
(1) taking 400g of mine acid wastewater treatment solid waste (containing 50% of water), adding a dilute hydrochloric acid solution with the acid concentration of 8g/L according to 3 times of the dry weight of the solid waste, and uniformly stirring; heating to 80 ℃, adding glucose, wherein the molar weight of the glucose is 0.4 times of that of iron in the solid waste for treating the acidic wastewater, and the reaction time is 1.5 h;
(2) adding a sodium bicarbonate solution into the slurry obtained in the step (1), adjusting the pH value of the slurry to be 5.5, and then carrying out solid-liquid separation to remove metal impurity ions;
(3) adding potassium dihydrogen phosphate and ozone into the filtrate obtained in the step (2) at the same time, mixing to perform oxidation reaction, wherein the molar ratio of Fe to P to ozone is 0.9:1.05:0.8, controlling the pH value of the slurry to be 1.6 by using potassium bicarbonate, performing solid-liquid separation on the slurry after the reaction is finished, and washing in multiple stages to obtain light yellow filter residue;
(4) and (4) adding the filter residue obtained in the step (3) into 0.2mol/L diluted phosphoric acid solution, stirring and aging in a water bath at 85 ℃ for 0.5h, wherein the slurry becomes light pink, and obtaining the product of the battery-grade iron phosphate after solid-liquid separation, washing and drying.
Example 5
The method for preparing battery-grade iron phosphate by using the mine acidic wastewater to treat solid waste, as shown in fig. 1, specifically comprises the following steps:
(1) taking 400g of mine acid wastewater treatment solid waste (containing 50% of water), adding a dilute hydrochloric acid solution with the acid concentration of 10g/L according to 4 times of the dry weight of the solid waste, and uniformly stirring; heating to 60 ℃, adding ascorbic acid, wherein the molar weight of the ascorbic acid is 0.8 times of that of iron in the solid waste for treating the acidic wastewater, and the reaction time is 1.0 h;
(2) adding a potassium hydroxide solution into the slurry obtained in the step (1), adjusting the pH value of the slurry to be 4.5, and then carrying out solid-liquid separation to remove metal impurity ions;
(3) adding ammonium phosphate and sodium persulfate into the filtrate obtained in the step (2) at the same time, mixing to perform an oxidation reaction, wherein the molar ratio of Fe to P to ozone is 0.95:1.1:0.55, controlling the pH value of the slurry to be 1.8 by using hydrochloric acid, performing solid-liquid separation on the slurry after the reaction is finished, and washing in multiple stages to obtain light yellow filter residue;
(4) and (4) adding the filter residue obtained in the step (3) into 0.3mol/L diluted phosphoric acid solution, stirring and aging in a water bath at 95 ℃ for 1.0h, wherein the slurry becomes light pink, and obtaining the product of the battery-grade iron phosphate after solid-liquid separation, washing and drying.
Example 6
The method for preparing battery-grade iron phosphate by using the mine acidic wastewater to treat solid waste, as shown in fig. 1, specifically comprises the following steps:
(1) taking 400g of mine acid wastewater treatment solid waste (containing 50% of water), adding a dilute sulfuric acid solution with the acid concentration of 6g/L according to 5 times of the dry weight of the solid waste, and uniformly stirring; heating to 70 ℃, adding sodium sulfide with the molar weight 1.0 time of that of iron in the solid waste for treating the acidic wastewater, and reacting for 2 hours;
(2) adding a sodium carbonate solution into the slurry obtained in the step (1), adjusting the pH value of the slurry to be 5.0, and then carrying out solid-liquid separation to remove metal impurity ions;
(3) adding ammonium dihydrogen phosphate and ammonium persulfate into the filtrate obtained in the step (2) at the same time, mixing to perform an oxidation reaction, wherein the molar ratio of Fe to P to ammonium persulfate is 1.0:1.0:0.70, controlling the pH value of the slurry to be 1.5 by using sodium hydroxide, and after the reaction is finished, performing solid-liquid separation on the slurry, and washing in multiple stages to obtain light yellow filter residue;
(4) and (4) adding the filter residue obtained in the step (3) into 0.1mol/L diluted phosphoric acid solution, stirring and aging in a water bath at 90 ℃ for 2.0h, wherein the slurry becomes light pink, and obtaining the product of the battery-grade iron phosphate after solid-liquid separation, washing and drying.
Fig. 2 is an XRD pattern of the synthesized battery grade iron phosphate, and fig. 3 is a particle size distribution of the obtained product, and the statistical results of the particle size distribution are shown in table 1.
TABLE 1
As can be seen from fig. 2, the resultant product is iron phosphate dihydrate. The chemical composition test results of the product are shown in Table 2, the Fe, P, impurity elements, moisture content, and particle size (D) of the product50) All meet the industry standard of iron phosphate for batteries (HG/T4701-.
TABLE 1 analysis of the elemental content of the product/ppm
Remarking: fe. P, unit of moisture content.
Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing battery-grade iron phosphate by utilizing mine acidic wastewater treatment solid waste is characterized by comprising the following steps:
s1, reduction leaching: acidifying the mine acidic wastewater treatment solid waste with dilute acid, heating, and adding a reducing agent for reduction leaching;
s2, precipitation and purification: adding an alkali solution into the slurry obtained by the reduction leaching in the step S1 to adjust the pH value to 4.5-5.5, and then removing metal impurity ions through solid-liquid separation;
s3, oxidation synthesis: adding a phosphorus source and an oxidant into the filtrate obtained in the step S2, mixing to perform an oxidation reaction, controlling the pH of the reaction end point to be 1.4-2.0 by using an alkali or acid solution, performing solid-liquid separation on the slurry after the reaction is finished, and washing for multiple sections to obtain light yellow filter residue;
s4, aging and transformation: and (5) adding diluted phosphoric acid into the light yellow filter residue obtained in the step (S3), stirring and aging to obtain light pink slurry, and performing solid-liquid separation, washing and drying to obtain the product, namely the battery-grade iron phosphate.
2. The method as claimed in claim 1, wherein in step S1, the dilute acid is one of sulfuric acid and hydrochloric acid, the acidity is 6-10g/L, and the dosage is 3-5 times of the dry weight of the solid waste from mine acidic wastewater treatment.
3. The method according to claim 1, wherein the heating temperature in step S1 is 60-80 ℃.
4. The method of claim 1, wherein in step S1, the reducing agent is one of sodium metabisulfite, sulfur dioxide, sodium sulfite, sodium thiosulfate, sodium sulfide, ascorbic acid and glucose.
5. The method as claimed in claim 1, wherein in step S1, the molar quantity of the reducing agent is 0.4-1.0 times of the molar quantity of the iron in the solid waste from the acidic mine wastewater treatment, and the reduction leaching time is 1-2 h.
6. The method of claim 1, wherein in step S2, the alkali solution is one of calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
7. The method of claim 1, wherein in step S3, the phosphorus source is one of phosphoric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, potassium phosphate, and ammonium phosphate; the oxidant is one of ammonium persulfate, sodium persulfate, hydrogen peroxide, ozone and hypochlorous acid.
8. The method of claim 1, wherein in step S3, the alkali is one of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; the acid is one of sulfuric acid and hydrochloric acid.
9. The process according to claim 1 or 7, wherein the molar ratio of Fe: P: oxidant is 0.9-1.0:1-1.1: 0.55-0.8.
10. The method as claimed in claim 1, wherein the concentration of dilute phosphoric acid is 0.1-0.3mol/L, the temperature for stirring and aging is 75-95 ℃, and the time is 0.5-2.0 h.
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