CN113620268A - Method for preparing battery-grade iron phosphate by using iron source in red mud - Google Patents
Method for preparing battery-grade iron phosphate by using iron source in red mud Download PDFInfo
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- CN113620268A CN113620268A CN202110990306.6A CN202110990306A CN113620268A CN 113620268 A CN113620268 A CN 113620268A CN 202110990306 A CN202110990306 A CN 202110990306A CN 113620268 A CN113620268 A CN 113620268A
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- iron
- organic phase
- phosphate
- phosphorus
- red mud
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 102
- 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
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 33
- 238000000605 extraction Methods 0.000 claims abstract description 72
- 239000012074 organic phase Substances 0.000 claims abstract description 65
- 238000002386 leaching Methods 0.000 claims abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011574 phosphorus Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 150000001450 anions Chemical class 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 12
- 239000012071 phase Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 7
- 230000008929 regeneration Effects 0.000 claims abstract description 4
- 238000011069 regeneration method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 51
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 238000000926 separation method Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 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
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 and theoretically Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HYGWNUKOUCZBND-UHFFFAOYSA-N azanide Chemical compound [NH2-] HYGWNUKOUCZBND-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing battery-grade iron phosphate by using iron sources in red mud, which comprises the following steps: (1) adding high-concentration hydrochloric acid into the red mud for leaching to obtain iron-containing hydrochloric acid leachate; (2) adding an organic phase containing an anion extracting agent into the iron-containing hydrochloric acid leaching solution for extraction to obtain an iron-carrying organic phase; (3) adding a phosphorus-containing solution into the iron-carrying organic phase for back extraction to obtain a phosphorus/iron-rich back extraction solution and an organic phase; (4) by adjusting the pH value of the back extraction solution rich in phosphorus/iron and carrying out homogeneous precipitation at a certain temperature and under the condition of setting the iron-phosphorus ratio, FePO is generated4·2H2O; (5) for FePO4·2H2Calcining O to obtain FePO4. The invention is through H2PO4 2‑With Fe3+Coordination of (2) to FeH iron in the organic phase2PO4 2+Or Fe (H)2PO4)2 +The form of the iron-carrying organic phase enters the water phase again, and the high-efficiency back extraction of iron in the iron-carrying organic phase and the regeneration circulation of the organic phase are realized. At the same time high in concentrationThe iron phosphorus can stably exist in the water solution, the coordination balance of the iron phosphorus is destroyed and the FePO is obtained by precipitation through heating and adjusting the pH value4·2H2And (4) O crystals.
Description
Technical Field
The invention belongs to the technical field of metallurgical waste recovery and comprehensive utilization and the technical field of hydrometallurgy, and particularly relates to a method for preparing battery-grade iron phosphate by using an iron source in red mud.
Background
The red mud is solid waste generated after alumina is produced by bauxite strong alkali leaching, and has the characteristics of fine granularity and high alkalinity. At present, 1.0-1.8t of red mud is produced when 1t of alumina is produced, and with the continuous improvement of the global alumina capacity, the stock of the red mud is also continuously improved, so that a large amount of land is occupied, underground water pollution is easily caused, and in addition, the phenomena of dam break, landslide and the like of a red mud dam are also generated at times, thus threatening the surrounding environment. On the other hand, the red mud is rich in valuable metals such as iron, aluminum and the like, wherein the iron content is 10-60%, if a large amount of iron in the red mud can be recycled, on one hand, the resource utilization of the red mud can be realized, on the other hand, the economic benefit of an alumina plant can be effectively improved, and the method has obvious practical significance.
The iron in red mud is mainly hematite (Fe)2O3) The method has the form that high-efficiency separation is difficult to realize, and the conventional method for recovering iron from red mud mostly adopts a reduction roasting-magnetic separation process to recover iron-making raw materials. The method consumes a large amount of reducing agent and has low recovery rate. The wet recovery of iron from red mud has the advantages of high recovery rate, small equipment investment and the like, but a large amount of elements such as aluminum, sodium, calcium, titanium and the like are simultaneously dissolved out and enter the leachate while the iron in the red mud is leached by acid, which increases the difficulty of subsequent iron recovery operation, so that the recycling path of selectively separating the iron in the leachate and the iron is the key of the comprehensive recovery of the iron in the red mud.
LiFePO4Because of the advantages of environmental protection, excellent safety performance, long cycle life and the like, the lithium iron phosphate anode material is widely used as the anode material of lithium ion energy storage and power batteries and is required to obtain LiFePO4FePO with excellent synthesis performance and good product purity4·2H2The O precursor is critical. The homogeneous precipitation method is the large-scale industrial synthesis of FePO by the enterprises at present4·2H2The method of O has simple process and uniform product grain diameter, but most of the iron sources adopted for synthesis are high-purity iron sheets, ferric chloride or ferrous sulfate and the like, so that the synthesis cost of the ferric phosphate is higher. Therefore, if the iron in the red mud can be recycled for preparing the battery-grade iron phosphate, the red mud resource utilization value can be obviously improved, the synthesis cost of the iron phosphate can be effectively reduced, and a new way for recycling the iron in the red mud is developed.
The iron in the red mud is used for preparing the iron phosphate, and the key problems to be solved are as follows: separating iron from other components in the red mud; the separated iron is combined with phosphorus to form high purity iron phosphate. Solvent extraction, chemical precipitation and ion exchange are commonly adopted for iron separation in hydrometallurgy, and conventional chemical precipitation methods have a series of problems of low precipitation utilization rate, poor filtration performance of formed iron slag, large slag amount, easy generation of metal impurities and the like. The ion exchange method has better selectivity, but the resin has lower adsorption capacity, and is generally used for recovering low-concentration metals. The solvent extraction method has the advantages of high selectivity, good recovery effect and favorable utilization, and is also commonly used for separating and recovering iron in hydrometallurgy at present. Chinese patent (publication No. CN 111333049A) discloses a method for preparing lithium iron manganese phosphate, wherein the part related to iron resource recovery is that waste lithium iron phosphate and lithium manganese oxide materials are mixed and leached by hydrochloric acid, the acid leaching solution is precipitated by a heavy metal catching agent to obtain a second filtrate, and the separation of iron and the synthesis of iron phosphate are realized by adopting a mode of P204 extraction, sulfuric acid washing and phosphoric acid back extraction. Chinese patent publication No. CN 108384970A discloses an extraction method of iron (Fe) containing polymetallic chloride from acidic solutionThe extraction system of the method is prepared by quaternary ammonium salt R4The method is characterized in that an NX extracting agent and a oleyl alcohol extracting agent are used, the efficiency of extracting iron and titanium is high, back extraction is easy, but iron cannot be separated from a chloride acid system during extraction, hydrochloric acid solutions (4-6 mol/L and 0.1-1 mol/L) with high and different concentrations are required to be selected to separate titanium from iron in a back extraction operation part, and the operation cost and difficulty are increased. Neutral extractants such as TBP (tributyl phosphate) are often used to extract FeCl3The Chinese patent publication No. CN 107245582A discloses a method for recovering iron from waste hydrochloric acid, which uses an extraction system of 40% TBP and sulfonated kerosene to carry out three-stage countercurrent extraction of iron, and 1.0mol/L NaCl solution is used for back extraction to recover iron, and a neutral extractant has the problems of low extraction efficiency and selectivity, so the neutral extractant is often mixed with other types of extractants for synergic extraction.
FePO4In the aspect of synthesis, the FePO is obtained by taking iron or ferrous sulfate as an iron source and phosphoric acid/phosphate as a phosphorus source through homogeneous precipitation4An industrialized method for synthesis, namely Chinese patent (CN 111333047A), discloses a method for synthesizing iron phosphate by using ferrous sulfate as a titanium white byproduct as an iron source, wherein before the synthesis reaction, an adsorbent and a flocculating agent are required to be added into a solution containing ferrous sulfate for impurity removal, and a large amount of hydrogen peroxide is used for oxidation of ferrous ions, so that the problems of complex process and high cost are caused. Chinese patent (CN 111377426A) discloses a preparation method of anhydrous iron phosphate nanoparticles, wherein iron powder is used as an iron source, so that impurity removal cost is eliminated, but an oxidant is required to be added to convert Fe (II) into Fe (III), and the cost of the iron source is high.
Disclosure of Invention
The invention provides a method for preparing battery-grade iron phosphate by utilizing an iron source in red mud, aiming at the problems of the defects of the existing iron resource technology in the red mud and the high cost of iron phosphate synthesis raw materials.
The method for preparing battery-grade iron phosphate by using iron sources in red mud comprises the following steps:
(1) adding high-concentration hydrochloric acid into the red mud for leaching to obtain iron-containing hydrochloric acid leachate;
(2) adding an organic phase containing an anion extractant into the iron-containing hydrochloric acid leaching solution in the step (1) for extraction to obtain an iron-loaded organic phase;
(3) adding a phosphorus-containing solution into the iron-loaded organic phase in the step (2) for back extraction to obtain a phosphorus/iron-rich back extraction solution and an organic phase;
(4) adjusting the pH value of the phosphorus/iron-rich strip liquor obtained in the step (3), and performing homogeneous precipitation under the conditions of a certain temperature and a set iron-phosphorus ratio to generate FePO4·2H2O；
(5) For FePO in the step (5)4·2H2Calcining O to obtain FePO4。
Preferably, in the step (1), the concentration of the high-concentration hydrochloric acid is 6-10 mol/L, the leaching time is 2-3 h, the leaching temperature is 50-100 ℃, and the solid-to-liquid ratio of the leaching solution is 3-7: 1mL/g
Preferably, in the step (2), the organic phase containing the anionic extractant consists of the anionic extractant, the polarity improver and the diluent; wherein: the anion extracting agent is one or more of tertiary amine alkalescent anion extracting agent and quaternary ammonium strongly-alkaline anion extracting agent, and the anion extracting agent accounts for 10-50% of the total volume of the organic phase; the polarity improver is high-carbon alcohol or TBP, and the polarity improver accounts for 5-30% of the total volume of the organic phase; the diluent is kerosene, and the diluent is 20-85% of the total volume of the organic phase.
Further preferably, the anion extractant is N235 or Aliquat 336, and the polarity improver is one of cyclohexanol, TBP and sec-octanol.
In the preferable scheme, in the step (2), the extraction temperature is room temperature to 50 ℃, the extraction phase ratio O/A is 0.5-3, and the extraction time is 2-30 min.
Preferably, in the step (3), the phosphorus-containing solution is an aqueous solution containing at least one of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, and potassium phosphate, and theoretically, substances capable of ionizing phosphate radicals can be used as the stripping agent.
In the preferable scheme, in the step (3), the concentration of total phosphorus in the phosphorus-containing solution is 1-3 times of the concentration of iron in the organic phase; preferably, in order to prevent iron phosphate precipitation, the phosphorus-containing solution is a phosphorus-containing acid solution, and the acid concentration of the phosphorus-containing acid solution is 0-0.5 mol/L; the back extraction temperature is between room temperature and 50 ℃, the back extraction phase ratio O/A is 0.5-2, and the back extraction time is 2-30 min.
Preferably, in the step (3), the organic phase after the back extraction can be returned to the step (2) as an extracting agent, so as to realize the regeneration cycle of the organic phase.
In the preferable scheme, in the step (4), the certain temperature is 70-110 ℃, the pH value of the precipitation reaction is 0.6-1.0, ammonia water and dilute hydrochloric acid are used as pH regulators, the precipitation time is 24-48 h, and the set iron-phosphorus ratio is 0.9-1.1.
In a preferable scheme, the calcining temperature in the step (5) is 550-850 ℃, and the calcining time is 3-6 h.
The principle of the invention is as follows: the key point of the invention is to utilize Fe (III) to be easy to react with Cl in a high-concentration hydrochloric acid system-Coordination to generate FeCl4 -And FeCl3The method comprises the steps of extracting iron in leachate by using an anion extracting agent to realize the separation of Fe and other impurity metal ions, performing back extraction by using an ammonium phosphate aqueous solution to dissociate iron in an organic phase into a water phase to form a phosphorus-rich iron-rich solution, and realizing the direct precipitation of iron phosphate in the solution by the coupling action between temperature and acidity, thereby avoiding the complex impurity removal process in the traditional iron phosphate preparation process.
The invention has the beneficial effects that:
(1) the invention uses high-concentration hydrochloric acid as a leaching agent to leach the red mud, and the red mud is leached by Fe3+And Cl-Strong coordination effect to make iron in red mud use FeCl3Or FeCl4 -The form is stable in solution and thenExtracting iron by an amine anion extraction system, separating iron from other metal cations, and having the advantages of high selectivity, high extraction rate and uniform extraction organic phase, wherein over 99% of iron in the red mud leachate is extracted into the organic phase, and other metals such as Al, Ca, Na and the like are not extracted basically;
(2) the invention is through H2PO4 2-With Fe3+Coordination of (2) to FeH iron in the organic phase2PO4 2+Or Fe (H)2PO4)2 +The form of the iron-carrying organic phase enters the water phase again, and the high-efficiency back extraction of iron in the iron-carrying organic phase and the regeneration circulation of the organic phase are realized. Meanwhile, high-concentration iron phosphorus can stably exist in an aqueous solution, and FePO is obtained by heating and regulating pH to destroy the coordination balance of iron phosphorus and precipitate4·2H2And (4) O crystals.
(3) The invention uses the reextraction system of ammonium phosphate and phosphoric acid to reextract the iron-loaded organic phase, the reextraction efficiency is high, the phase separation is fast, and the regenerated organic phase can still reach very high extraction rate and reextraction efficiency after more than 7 times of cycle experiments, and the organic phase loss is little.
(4) The invention not only realizes the high-value utilization of iron in the red mud, but also reduces the synthesis cost of the iron phosphate and changes waste into valuable; the invention has the advantages of good separation effect, high economical and practical performance, simple process and easy operation.
Drawings
FIG. 1 is a flow chart of a specific process of the present invention.
FIG. 2 XRD analysis pattern of iron phosphate dihydrate obtained in example 1
FIG. 3 XRD analysis of iron phosphate dihydrate obtained in example 2
FIG. 4 XRD analysis pattern of iron phosphate dihydrate obtained in example 3
FIG. 5 XRD analysis of iron phosphate dihydrate obtained in example 4
Detailed Description
The process flow diagram of the invention is shown in figure 1, and the specific steps can be seen in the examples.
Example 1
Taking 100g of red mud, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 8mol/L, the solid ratio L/S of the leaching solution is 4:1, the leaching time is 4 hours, the leaching temperature is 90 ℃, after the leaching is finished, the leaching residue is filtered, pure water is adopted to wash the leaching residue, and the washing water and the supernatant are mixed to obtain the final leaching solution, wherein the concentration of Fe is 33.95 g/L.
Taking the leachate, taking 33% of N235, 17% of TBP and 50% of kerosene as an extraction system, extracting for 20min at 25 ℃, and obtaining an iron-loaded organic phase when the extraction ratio O/A is 1.5, wherein: the single stage extraction of iron was 99.46% with essentially no other elements extracted (see table 1).
Taking the iron-carrying organic phase, adding 0.3mol/L (NH)4)2HPO4+0.2mol/L H3PO4Is used as a stripping agent, the stripping time is 20min, the stripping temperature is 35 ℃, the stripping phase ratio O/A is 1, and a stripping solution and an organic phase are obtained after separation, wherein: the single-stage back extraction rate of the iron is 95.46 percent, and the contents of Fe and P in the back extraction solution are 21.49g/L and 15.67g/L respectively. And washing the stripped organic phase with 5% dilute hydrochloric acid for 10min to obtain a regenerated organic phase, and performing extraction-stripping-washing on the regenerated organic phase for 7 times, wherein the single-stage extraction rate and the stripping rate can still reach 98.92% and 95.13% under the extraction-stripping conditions.
TABLE 1 indices of the main elements in the solution
Remarking: TP represents total phosphorus
Taking 200mL of the stripping solution, heating with constant temperature water bath under magnetic stirring, at 90 deg.C and pH of 0.9, precipitating for 24h, and determining the crystalline product to be FePO by XRD analysis4·2H2O (see fig. 2). The contents of iron and phosphorus are 29.3% and 16.3%, respectively, Fe/P is 0.997, and tap density is 0.783g/cm3And the other indexes (shown in table 2) all meet the standard iron phosphate for HT/T4701-2014 batteries. Calcining the product at 550 ℃ for 3h to obtain FePO4And (5) producing the product.
TABLE 2 indexes of the home-made iron phosphate dihydrate product
Example 2
Taking 100g of red mud, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 8mol/L, the solid ratio L/S of the leaching solution is 4:1, the leaching time is 4 hours, the leaching temperature is 90 ℃, after the leaching is finished, the leaching residue is filtered, pure water is adopted to wash the leaching residue, washing water and supernatant are mixed to obtain the final leaching solution, and the concentration of Fe in the leaching solution is 20.15 g/L.
Taking the leachate, taking 35% of Aliquat 336, 15% of octanol and 50% of kerosene as an extraction system, extracting for 20min at the extraction temperature of 25.8 ℃, and obtaining an iron-carrying organic phase after separation, wherein the extraction ratio is 1.0, and the iron-carrying organic phase comprises the following components: the single-stage extraction of iron was 99.79% with little other elements extracted (see table 3).
Taking the iron-carrying organic phase, adding 0.4mol/L NaH2PO4The stripping agent is used as stripping agent, the stripping time is 20min, the stripping temperature is 35.3 ℃, the stripping phase ratio O/A is 1.0, and stripping solution and an organic phase are obtained after separation, wherein: the single-stage back extraction rate of the iron is 97.35 percent, the contents of the iron and the phosphorus in the back extraction solution are respectively 19.58g/L and 12.41g/L, the organic phase after the back extraction is washed for 10min by using 5 percent dilute hydrochloric acid to obtain a regenerated organic phase, and the regenerated organic phase can be used as an extracting agent to return to the extraction step.
TABLE 3 indices of main elements in the solution
Taking 200mL of the stripping solution, heating by magnetic stirring in a constant-temperature water bath at 90 ℃, pH of 0.8 and precipitating for 36h, and determining that a crystallization product is FePO by XRD analysis4·2H2O (see FIG. 3), iron and phosphorus contents of 29.5% and 16.4%, Fe/P of 0.997, tap density of 0.804g/cm3And the other indexes (shown in table 4) all meet the standard 'iron phosphate for HT/T4701-2014 batteries'. Calcining the product at 550 ℃ for 3h to obtain FePO4And (5) producing the product.
TABLE 4 indexes of the home-made iron phosphate dihydrate product
Example 3
Taking 100g of red mud, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 8mol/L, the solid ratio L/S of the leaching solution is 4:1, the leaching time is 4h, the leaching temperature is 90 ℃, after the leaching is finished, the leaching is carried out, the supernatant is the final leaching solution, and the concentration of Fe in the leaching solution is 43.25 g/L.
Taking the leachate, taking 40% of N235, 10% of cyclohexanol and 50% of kerosene as an extraction system, extracting for 20min at the extraction temperature of 35.8 ℃ and the extraction phase ratio O/A of 2.0, and separating to obtain an iron-loaded organic phase, wherein: the single-stage extraction of iron was 99.29%, and other elements were hardly extracted (see table 5).
Taking the iron-carrying organic phase, adding 0.5mol/L (NH)4)2H2PO4The method is characterized in that the method is a stripping agent, the stripping time is 20min, the stripping temperature is 35.3 ℃, the stripping phase ratio O/A is 1.0, and a stripping solution and an organic phase are obtained after separation, wherein: the single-stage back extraction rate of the iron is 99.35 percent, and the contents of the iron and the phosphorus in the back extraction solution are respectively 21.33g/L and 15.68 g/L. Washing the organic phase after back extraction with 5% dilute hydrochloric acid for 10min to obtain regenerated organic phase, and returning the regenerated organic phase to the extraction step as extractant.
TABLE 5 indices of main elements in the solution
Taking 200mL of the stripping solution, heating with constant temperature water bath under magnetic stirring, at 100 deg.C, pH of 1.0, precipitating for 36h, and determining the crystallization product to be FePO by XRD analysis4·2H2O (see FIG. 4) has contents of iron and phosphorus respectively29.7% and 16.5%, Fe/P0.988, tap density 0.813g/cm3And the other indexes (shown in table 6) all meet the standard 'iron phosphate for HT/T4701-2014 batteries'. Calcining the product at 550 ℃ for 3h to obtain FePO4And (5) producing the product.
TABLE 6 indexes of the home-made iron phosphate dihydrate product
Example 4
Taking 100g of red mud, wherein the leaching conditions are as follows: the concentration of hydrochloric acid is 8mol/L, the solid ratio L/S of the leaching solution is 4:1, the leaching time is 4 hours, the leaching temperature is 90 ℃, after the leaching is finished, the leaching residue is filtered, pure water is adopted to wash the leaching residue, and the washing water and the supernatant are mixed to obtain the final leaching solution, wherein the concentration of Fe is 33.95 g/L.
Taking the leachate, taking 35% Aliquat 336+ 15% TBP + 50% kerosene as an extraction system, extracting for 5min at the extraction temperature of 25.8 ℃, and obtaining an iron-carrying organic phase after separation, wherein: the single-stage extraction rate of iron was 99.59%, and other elements were hardly extracted (see table 7).
Taking the iron-loaded organic phase, and mixing at a ratio of 0.6mol/L H3PO4The stripping agent is used, the stripping time is 5min, the stripping temperature is 25.3 ℃, the stripping phase ratio O/A is 1.0, and a stripping solution and an organic phase are obtained after separation, wherein: the single-stage back extraction rate of the iron is 95.21%, and the contents of iron and phosphorus in the back extraction solution are 21.46g/L and 15.61g/L respectively. Washing the organic phase after back extraction with 5% dilute hydrochloric acid for 10min to obtain regenerated organic phase, and returning the regenerated organic phase to the extraction step as extractant.
TABLE 7 indices of main elements in the solution
Taking 200mL of the stripping solution, magnetically stirring and heating in a constant-temperature water bath at 100 ℃, the pH value of the solution is 0.8, and precipitating for 48 hours to obtain a crystalline product FeP determined by XRD analysisO4·2H2O (see FIG. 5), with iron and phosphorus contents of 29.5% and 16.3%, respectively, Fe/P of 1.004, and tap density of 0.825g/cm3And the other indexes (shown in table 8) meet the standard of iron phosphate for HT/T4701-2014 batteries. Calcining the product at 550 ℃ for 3h to obtain FePO4And (5) producing the product.
TABLE 8 respective indexes of the self-made iron phosphate dihydrate product
Claims (10)
1. A method for preparing battery-grade iron phosphate by using iron sources in red mud comprises the following steps:
(1) adding high-concentration hydrochloric acid into the red mud for leaching to obtain iron-containing hydrochloric acid leachate;
(2) adding an organic phase containing an anion extractant into the iron-containing hydrochloric acid leaching solution in the step (1) for extraction to obtain an iron-loaded organic phase;
(3) adding a phosphorus-containing solution into the iron-loaded organic phase in the step (2) for back extraction to obtain a phosphorus/iron-rich back extraction solution and an organic phase;
(4) adjusting the pH value of the phosphorus/iron-rich strip liquor obtained in the step (3), and performing homogeneous precipitation under the conditions of a certain temperature and a set iron-phosphorus ratio to generate FePO4·2H2O；
(5) For FePO in the step (5)4·2H2Calcining O to obtain FePO4。
2. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 1, wherein in the step (1), the concentration of high-concentration hydrochloric acid is 6-10 mol/L, the leaching time is 2-3 h, the leaching temperature is 50-100 ℃, and the solid-to-liquid ratio of leaching solution is 3-7: 1 mg/L.
3. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 1, wherein in the step (2), the organic phase containing the anionic extractant consists of the anionic extractant, the polarity improver and the diluent; wherein: the anion extracting agent is one or more of tertiary amine alkalescent anion extracting agent and quaternary ammonium strongly-alkaline anion extracting agent, and the anion extracting agent accounts for 10-50% of the total volume of the organic phase; the polarity improver is high-carbon alcohol or TBP, and the polarity improver accounts for 5-30% of the total volume of the organic phase; the diluent is kerosene, and the diluent is 20-85% of the total volume of the organic phase.
4. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 3, wherein the anion extractant is N235 or Aliquat 336, and the polarity improver is one of cyclohexanol, TBP and sec-octanol.
5. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 1, wherein in the step (2), the extraction temperature is between room temperature and 50 ℃, the extraction phase ratio O/A is 0.5-3, and the extraction time is 2-30 min.
6. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 1, wherein in the step (3), the phosphorus-containing solution is an aqueous solution containing at least one of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate and potassium phosphate.
7. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 1, wherein in the step (3), the concentration of total phosphorus in the phosphorus-containing solution is 1-3 times of the concentration of iron in the organic phase; further preferably, the back extraction temperature is room temperature to 50 ℃, the back extraction phase ratio O/A is 0.5-2, and the back extraction time is 2-30 min; the organic phase after the back extraction can be returned to the step (2) to be used as an extracting agent, so that the regeneration cycle of the organic phase is realized.
8. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 6 or 7, wherein the phosphorus-containing solution is a phosphorus-containing acid solution with an acid concentration of 0-0.5 mol/L for preventing iron phosphate precipitation.
9. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 1, wherein the certain temperature in the step (4) is 70-110 ℃, the precipitation reaction pH is 0.6-1.0, ammonia water and dilute hydrochloric acid are used as pH regulators, the precipitation time is 24-48 h, and the set iron-phosphorus ratio is 0.9-1.1.
10. The method for preparing battery-grade iron phosphate by using iron sources in red mud according to claim 1, wherein the calcination temperature in the step (5) is 550-850 ℃ and the calcination time is 3-6 h.
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