CN117303333A - Method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite - Google Patents
Method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite Download PDFInfo
- Publication number
- CN117303333A CN117303333A CN202311141154.8A CN202311141154A CN117303333A CN 117303333 A CN117303333 A CN 117303333A CN 202311141154 A CN202311141154 A CN 202311141154A CN 117303333 A CN117303333 A CN 117303333A
- Authority
- CN
- China
- Prior art keywords
- ilmenite
- titanium
- ferric phosphate
- battery
- rich
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 91
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims abstract description 74
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000010936 titanium Substances 0.000 title claims abstract description 70
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 70
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 61
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 61
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002893 slag Substances 0.000 claims abstract description 47
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008188 pellet Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005453 pelletization Methods 0.000 claims abstract description 11
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 60
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 238000007605 air drying Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 13
- 238000000926 separation method Methods 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 239000012535 impurity Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001465 metallisation Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000009172 bursting Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229940116007 ferrous phosphate Drugs 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
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing titanium-rich material and battery-grade ferric phosphate by ilmenite, which comprises the following steps: (1) Adding a binder and proper water into ilmenite powder, uniformly mixing, pelletizing the mixed material to obtain ilmenite pellets, and drying and oxidizing the ilmenite pellets; (2) placing the oxidized pellets in hydrogen for reduction treatment; (3) Crushing and screening the reduced ilmenite pellets to obtain reduced ilmenite powder, adding the reduced ilmenite powder and a rust agent into water, and introducing oxygen to obtain rust ilmenite; (4) Separating rusted ferrotitanium to obtain a titanium-rich material and titanium-iron slag; (5) Adding a mixed acid solution of sulfuric acid and phosphoric acid into the ferrotitanium slag, heating, stirring, reacting, and filtering to obtain leaching filtrate and titanium-rich filter residues; (6) Adjusting the pH value of the filtrate, heating and stirring the filtrate at a set temperature for reaction, and aging and filtering the filtrate to obtain crude ferric phosphate; (7) And calcining the crude ferric phosphate, and cooling to obtain the battery grade ferric phosphate.
Description
Technical Field
The invention belongs to the field of comprehensive recycling of solid wastes, and relates to a method for preparing titanium-rich materials and battery-grade ferric phosphate by using ilmenite.
Background
Titanium element is widely distributed in crust, the abundance in crust is 0.61%, the activity of simple substance titanium is very high, and various titanium-containing oxygen compounds are formed by combining with oxygen element, often TiO 2 Or in the form of titanates in minerals. It is counted that the titanium-containing minerals with titanium content higher than 1% are more than 140, and the titanium-containing minerals with industrial development and utilization values are mainly rutile and ilmenite. Natural rutile is very scarce, accounts for about 10% of the worldwide titanium resource reserves, cannot meet the development demands of the titanium industry, and more depends on ilmenite to provide stable high-quality raw materials for the titanium industry, and the basic reserves on earth are close to 14 hundred million tons (TiO 2 Content meter). At present, the raw materials used for industrially producing the titanium-rich material are mainly ilmenite, and the method mainly comprises three steps: the electric furnace melting separation method, the reduction rust generation method and the acid leaching method, wherein the reduction rust method has become the mainstream production process for preparing the artificial rutile by using ilmenite at present due to the advantages of low electricity consumption and chemical reagent amount, low production cost, nearly neutral wastewater discharged in the rust process and the like in the process of producing the artificial rutile. The reducing agent used for reducing ilmenite mainly at present is a solid carbon source, and has the advantages of high reduction technical difficulty, long corrosion time and ferrotitanium separation effectPoor effect, high emission of carbon dioxide, smoke dust and waste gas pollutants in the reduction process, and the like.
The ferric phosphate is mainly used as a precursor of a lithium iron phosphate positive electrode material and used in the field of catalysts, and is mainly classified according to the types of raw materials: reacting ferric trichloride or ferric nitrate solution with phosphoric acid, decomposing and volatilizing hydrogen chloride or nitric acid at high temperature, and neutralizing excessive acid by ammonia water to obtain ferric phosphate; acidifying ferrous sulfate with phosphoric acid, then reacting with sodium chlorate or hydrogen peroxide to generate ferric phosphate, and regulating the pH value to about 2 by using sodium hydroxide or ammonia water to generate ferric phosphate; in addition, phosphate is directly reacted with ferric sulfate to produce ferric phosphate under the condition that the pH value is less than 2. The classification according to the synthesis mode mainly comprises: precipitation, hydrothermal, sol-gel, air oxidation, controlled crystallization, and the like.
At present, raw materials for preparing ferric phosphate are usually iron sources or phosphorus sources with high purity, for example, chinese patent literature with the publication number of CN116022757A discloses a preparation method of battery-grade hydrated ferric phosphate, wherein the pH value of ferrous sulfate solution is regulated to be less than 2, calcium dihydrogen phosphate is added, the total phosphorus concentration in the ferrous sulfate solution is maintained to be less than 1mol/L, precipitation reaction is carried out for 1.0-3.0 h at the temperature of 50-90 ℃, and liquid-solid separation is carried out to obtain calcium sulfate slag and ferrous phosphate solution; and (3) adjusting the pH value and the iron/phosphorus ratio of the ferrous phosphate solution, adding hydrogen peroxide to perform oxidation reaction, and performing solid-liquid separation and washing to obtain the battery-grade hydrated ferric phosphate.
The authority number CN106450547A discloses a preparation method of ferric phosphate, which comprises mixing a phosphorus source and an oxidant with a mixture containing Fe 2+ And (3) carrying out parallel flow mixing, and adopting a pH regulator to regulate the pH value of the precipitation slurry to 1.7-1.8, thereby synthesizing the ferric phosphate with a flower-like cluster structure. The invention uses the pure iron as iron material, with high limit, multiple process flow, and the product index is general. In the method for preparing the ferric phosphate, the high-value recycling of the ferric titanium-rich slag is not well realized, the process steps are complicated, the flow steps are more, the consumption of reagents is large, the method is not environment-friendly, and the product index of the ferric phosphate is general.
Based on the above, it is necessary to provide a full-process high-value utilization method of ilmenite, which realizes high-efficiency separation and clean production of ilmenite and high-added-value utilization of iron-rich titanium slag.
Disclosure of Invention
Aiming at the problems that the separation of ferrotitanium is not thorough in the traditional process of obtaining the titanium-rich product, and the pollution of carbon dioxide, smoke dust and waste gas in the production process is high, and the high-value utilization of the iron-rich titanium slag can not be realized, the invention aims to provide a method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention discloses a method for preparing titanium-rich materials and battery-grade ferric phosphate by using ilmenite, which comprises the following steps:
(1) Adding a binder and proper water into ilmenite powder, uniformly mixing to obtain a mixed material, pelletizing the mixed material to obtain ilmenite pellets, and drying and oxidizing the ilmenite pellets to obtain oxidized pellets;
(2) Placing the oxidized pellets obtained in the step (1) in hydrogen for reduction treatment to obtain reduced ilmenite pellets;
(3) Crushing and screening the reduced ilmenite pellets obtained in the step (2) to obtain reduced ilmenite powder, adding the reduced ilmenite powder and a rust agent into water, and introducing oxygen to obtain rust ilmenite;
(4) Separating the rusted ferrotitanium obtained in the step (3) to obtain the titanium-rich material and titanium-iron slag;
(5) Adding a mixed acid solution of sulfuric acid and phosphoric acid into the ferrotitanium slag obtained in the step (4), heating, stirring, reacting, and filtering to obtain leaching filtrate and titanium-rich filter residues;
(6) Adjusting the pH value of the filtrate obtained in the step (5), heating and stirring the filtrate at a set temperature for reaction, and aging and filtering the mixture to obtain crude ferric phosphate;
(7) And (3) calcining the crude ferric phosphate obtained in the step (6), and cooling to obtain the battery grade ferric phosphate.
Further, in step (1), the ilmenite powder D 90 The addition amount of the binder is 0.1-2% and the water content is 3-10% less than 74 mu m.
In the step (1), the ilmenite pellets are dried and oxidized in a chain grate, the drying treatment is combined with forced air drying and induced draft drying, the forced air drying time is 3-4 min, the air speed is 0.5-1.5 m/s, and the temperature is 200-250 ℃;
the air draft drying time is 3-6 min, the air speed is 0.5-1.5 m/s, and the temperature is 250-350 ℃;
the temperature of the oxidation treatment is 850-950 ℃, the oxidation time is 10-120 min, the wind speed is 2.0-2.4 m/s, and the oxidation gas is air, oxygen or the mixture of the air and the oxygen.
In the step (2), the reduction temperature is 800-900 ℃, the reduction time is 30-90 min, and the hydrogen ventilation flow is 5-20L/min.
Further, in the step (3), the reduced ilmenite powder D 90 The liquid-solid ratio of ilmenite powder to water is 5-50:1, the rust temperature is 30-80 ℃, the rust agent is ammonium chloride, the solution concentration is 0.5-3.0 wt.%, and the oxygen bubbling rate is 5-30×10 3 L/(m 3 Min), and introducing oxygen for 6-12 h.
In the step (4), the rusted ferrotitanium is separated through a shaking table to obtain the titanium-rich material and the titanium-iron slag.
Further, in the step (5), the ferrotitanium slag is crushed to control the ferrotitanium slag powder D 90 The mass fraction of iron in the ferrotitanium slag is more than or equal to 40wt percent and less than 37 mu m.
Further, in the step (5), the liquid-solid ratio of the mixed acid solution to the titanium iron slag powder is 2:1-5:1, the sulfuric acid concentration is 2-4 mol/L, and the ratio of the amount of phosphoric acid substances to the amount of iron substances in the titanium iron slag is 0.9-1.3.
In the step (5), the heating temperature is 30-80 ℃, and the heating and stirring time is more than or equal to 0.5h.
In the step (5), the titanium dioxide in the titanium-rich filter residue is high in grade and is integrated into the titanium-rich material for recycling.
In the step (6), ammonia water is added to adjust the pH of the solution to 1.5-2.8, the heating temperature is 30-80 ℃, the heating time is more than or equal to 0.5h, and the aging time is 0.5-2 h.
In the step (7), the calcination temperature is 500-800 ℃ and the calcination time is 1-5 h.
The method has the obvious advantages of low acid consumption, high iron leaching rate, high purity of ferric phosphate, easy control of precipitated products, few impurity components, simple flow, wider raw material sources and the like, and the prepared ferric phosphate with high added value can reach the corresponding battery grade ferric phosphate standard.
The invention discloses a method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite, which solves the problems of complex process, large medicament consumption, more product impurities, poor quality of ferric phosphate, large flushing amount and the like in the process of preparing ferric phosphate by using the traditional acid leaching (+ oxidation) -phosphonium salt-ammonia water process of an iron raw material. Realizes a short-flow preparation process of the high-added-value ferric phosphate, and has the characteristics of simple operation, low medicament consumption, environmental protection and wide application range. The recovered ferric phosphate has high grade and reasonable phosphorus-iron ratio, can reach the application standard of battery grade, and meanwhile, the rich slag obtained by the mixed acid leaching system can reach the grade standard of titanium-rich products by a rust method, so that the full flow, high value and comprehensive utilization of closed loop materials of ilmenite can be realized.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the method for preparing the titanium-rich material and the battery-grade ferric phosphate by utilizing ilmenite, disclosed by the invention, the hydrogen reduction is used for replacing a solid carbon reduction process, so that the separation efficiency of ferrotitanium is improved, the grade of the titanium-rich material is improved, and the emission of carbon dioxide, smoke dust and waste gas pollutants in the reduction corrosion process can be reduced.
(2) According to the method for preparing the titanium-rich material and the battery-grade ferric phosphate by using the ilmenite, the iron-rich ilmenite slag is used as the raw material for preparing the battery-grade ferric phosphate, so that the source of the raw material for preparing the ferric phosphate is greatly expanded.
(3) The invention relates to a method for preparing titanium-rich material and battery-grade ferric phosphate by ilmenite, which adopts a sulfuric acid-phosphoric acid mixed acid leaching system, wherein phosphoric acid can form a complex Fe (HPO) with ferric ions 4 ) 2- Not only greatly promoteThe iron oxide is fully dissolved and converted, so that the leaching rate of the titanium iron slag is improved, the sulfuric acid consumption is reduced, the ammonia water consumption during the subsequent precipitation of ferric phosphate is reduced, and the generation of ammonium sulfate impurities is reduced; meanwhile, the titanium dioxide in the residual titanium-rich filter residue is high in grade and can be recycled in the titanium-rich material. In addition, the formation of the ferrophosphorus complex can control the concentration of iron ions in the leaching solution and reduce the generation of ferric hydroxide impurity ions in the ferric phosphate product. In addition, the phosphoric acid is used as a ternary medium-strong acid and can be used as a buffer of a leaching system, so that pH change in the leaching process can be effectively buffered, and the rate of the leaching process can be controlled.
(4) The process has high iron recovery rate, less consumption of sulfuric acid and ammonia water, and high purity of the obtained ferric phosphate product, and is environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings and the accompanying tables which are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Fig. 2 is an XRD characterization of the iron phosphate obtained in example 1.
Detailed Description
The following are specific examples given by the inventors, which should be construed as merely illustrative, and not limiting the scope of the invention. All the parameter selections within the technical scheme of the invention belong to the protection scope of the invention.
TABLE 1 ilmenite chemistry employed in the present application
Further description will be made by way of specific examples and accompanying drawings.
Example 1
A method for preparing titanium-rich material and battery grade ferric phosphate by using ilmenite comprises the following steps:
1) Uniformly mixing ilmenite and 2.0% of binder polyvinyl alcohol; pelletizing under the conditions of 8.0% of water and 12min of pelletizing time, wherein the falling strength of the obtained green pellets is 4.5 times/piece, the compressive strength is 10.2N/piece, and the bursting temperature is 420 ℃;
2) Drying and oxidizing the obtained raw gas in a chain grate, wherein the drying is combined with forced air drying and induced air drying, and the forced air drying time is 3min, the air speed is 1.2m/s, and the temperature is 200 ℃; the air draft drying time is 3min, the air speed is 1.2m/s, and the temperature is 350 ℃; the oxidation temperature is 850 ℃, the oxidation time is 30min, the wind speed is 2.4m/s, and the compression strength of the oxidized pellet is 1050N/s;
3) Directly reducing the obtained oxidized pellet with hydrogen radical at 800 ℃ for 90min and H 2 Reducing under the condition of 15L/min flow, wherein the obtained metallization rate is 87.87%;
4) Reducing the calcined ore, stirring at a temperature of 75deg.C and a stirring rate of 600r/min at a liquid-solid ratio of 10:1 at an ammonium chloride solution concentration of 2.0% and a bubbling oxygen rate of 15X10% 3 L/(m3.min), rust time of 8h, then separating rust product by gravity separation, and obtaining TiO of titanium-rich material 2 Grade 79.44% and recovery rate 88.32%; the grade of iron in the iron-containing titanium slag is 66.36 percent, and the grade of TiO is as high as 66.36 percent 2 The content is 3.25%;
5) Crushing ferrotitanium slag, and controlling the ferrotitanium slag powder D 90 Adding 3mol/L mixed acid solution of sulfuric acid and concentrated phosphoric acid into ferrotitanium slag powder, wherein the liquid-solid ratio of the mixed acid solution to the ferrotitanium slag is 4:1, the mol ratio of phosphoric acid substances to ferrotitanium substances in the ferrotitanium slag is 1.0, heating and stirring at 70 ℃ for 2 hours, and filtering to obtain filtrate and titanium-rich filter residues, wherein the titanium-rich filter residues are TiO 2 Grade is 75.06%;
6) Adding ammonia water into the filtrate to adjust the pH of the solution to 2.0, heating and stirring for 20min at 60 ℃, aging for 30min, and filtering to obtain crude ferric phosphate;
7) The crude iron phosphate was calcined at 650 ℃ for 2 hours and cooled to battery grade iron phosphate, the process flow diagram is shown in fig. 1.
Table 2 shows the chemical composition of the titanium slag, and it is clear from the table that the impurity ion element content is large.
Table 3 shows the quality of the battery grade iron phosphate prepared in this example, and example 1 shows an improvement in the metallization rate of the reduced roasting ore after reduction with hydrogen, and a titanium-rich material, tiO 2 The grade and recovery rate are improved, and the grade of iron in the iron-titanium-containing slag is improved, which indicates that the iron-titanium separation effect is improved.
Fig. 2 is an XRD characterization of the iron phosphate obtained in example 1, the battery grade iron phosphate obtained by the present invention meets the standard requirements of the iron phosphate for HG/T4701-2014 battery, and the purity of the obtained lithium phosphate is 99.91%. The characteristic peak of the calcined ferric phosphate sample is obvious, the crystallization degree is high, the number of impurity peaks is small, and compared with a standard ferric phosphate card, the characteristic peak of the material is matched with the characteristic peak of the material, so that the obtained ferric phosphate product can be fully described.
TABLE 2 chemical composition of ilmenite
Table 3 Standard requirement of iron phosphate for HG/T4701-2014 Battery and content of iron phosphate product element
Example 2
A method for preparing titanium-rich material and battery grade ferric phosphate by using ilmenite comprises the following steps:
1) Uniformly mixing ilmenite and 2.0% of binder polyvinyl alcohol; pelletizing under the conditions of 8.0% of water and 12min of pelletizing time, wherein the falling strength of the obtained green pellets is 4.5 times/piece, the compressive strength is 10.2N/piece, and the bursting temperature is 420 ℃;
2) Drying and oxidizing the obtained raw gas in a chain grate, wherein the drying is combined with forced air drying and induced air drying, and the forced air drying time is 3min, the air speed is 1.2m/s, and the temperature is 200 ℃; the air draft drying time is 3min, the air speed is 1.2m/s, and the temperature is 350 ℃; the oxidation temperature is 850 ℃, the oxidation time is 60min, the wind speed is 2.4m/s, and the compression strength of the oxidized pellet is 1050N/s;
3) Directly reducing the obtained oxidized pellet with hydrogen radical at 850 ℃ for 60min and H 2 Reducing under the condition of 15L/min flow, wherein the obtained metallization rate is 90.24%;
4) Reducing the calcined ore, stirring at a temperature of 75deg.C and a stirring rate of 600r/min at a liquid-solid ratio of 10:1 at an ammonium chloride solution concentration of 2.0% and a bubbling oxygen rate of 15X10% 3 L/(m 3 Min), the rust time is 8h, then the rust product is separated by adopting gravity separation, and the TiO of the titanium-rich material is obtained 2 Grade 84.56% and recovery rate 92.34%; the grade of iron in the iron-containing titanium slag is 60.67 percent, and the grade of TiO is 2 The content is 4.68%;
5) Crushing ferrotitanium slag, and controlling the ferrotitanium slag powder D 90 Adding 3mol/L mixed acid solution of sulfuric acid and concentrated phosphoric acid into ferrotitanium slag powder, wherein the liquid-solid ratio of the mixed acid solution to the ferrotitanium slag is 4:1, the mol ratio of phosphoric acid substances to the ferrotitanium slag is 1.0, heating and stirring at 70 ℃ for 2 hours, and filtering to obtain leaching filtrate and titanium-rich filter residues, wherein the titanium-rich filter residues are TiO 2 Grade is 55.37%;
6) Adding ammonia water into the filtrate to adjust the pH of the solution to 2.0, heating and stirring for 20min at 60 ℃, aging for 30min, and filtering to obtain crude ferric phosphate;
7) The crude iron phosphate was calcined at 700 ℃ for 2 hours and cooled to battery grade iron phosphate, and table 4 shows the product quality of the battery grade iron phosphate prepared in this example.
Table 4 Standard requirement of iron phosphate for HG/T4701-2014 Battery and content of iron phosphate product element
Example 3
A method for preparing titanium-rich material and battery grade ferric phosphate by using ilmenite comprises the following steps:
1) Uniformly mixing ilmenite and 2.0% of binder polyvinyl alcohol; pelletizing under the conditions of 8.0% of water and 12min of pelletizing time, wherein the falling strength of the obtained green pellets is 4.5 times/piece, the compressive strength is 10.2N/piece, and the bursting temperature is 420 ℃;
2) Drying and oxidizing the obtained raw gas in a chain grate, wherein the drying is combined with forced air drying and induced air drying, and the forced air drying time is 3min, the air speed is 1.2m/s, and the temperature is 200 ℃; the air draft drying time is 3min, the air speed is 1.2m/s, and the temperature is 350 ℃; the oxidation temperature is 850 ℃, the oxidation time is 50min, the wind speed is 2.4m/s, and the compression strength of the oxidized pellet is 1050N/s;
3) Directly reducing the obtained oxidized pellet with hydrogen radical at 900 deg.C for 60min and H 2 Reducing under the condition of 15L/min flow, wherein the obtained metallization rate is 93.55%;
4) Reducing the calcined ore, stirring at a temperature of 75deg.C and a stirring rate of 600r/min at a liquid-solid ratio of 10:1 at an ammonium chloride solution concentration of 2.0% and a bubbling oxygen rate of 15X10% 3 L/(m 3 Min), the rust time is 8h, then the rust product is separated by adopting gravity separation, and the TiO of the titanium-rich material is obtained 2 The grade is 87.32 percent, and the recovery rate is 94.45 percent; the grade of iron in the iron-containing titanium slag is 60.78 percent, and the grade of TiO is TiO 2 The content is 4.56%;
5) Crushing ferrotitanium slag, and controlling the ferrotitanium slag powder D 90 Adding 3mol/L mixed acid solution of sulfuric acid and concentrated phosphoric acid into ferrotitanium slag powder, wherein the liquid-solid ratio of the mixed acid solution to the ferrotitanium slag is 4:1, the mol ratio of phosphoric acid substances to the ferrotitanium slag is 1.0, heating and stirring at 75 ℃ for 2.5h, and filtering to obtain leaching filtrate and titanium-rich filter residues, and TiO of the titanium-rich filter residues 2 Grade is 72.44%;
6) Adding ammonia water into the filtrate to adjust the pH of the solution to 2.0, heating and stirring for 20min at 60 ℃, aging for 30min, and filtering to obtain crude ferric phosphate;
7) The crude iron phosphate was calcined at 700 ℃ for 2 hours and after cooling, the battery grade iron phosphate, table 5 is the elemental content of the battery grade iron phosphate prepared in this example.
Table 5 Standard requirement of iron phosphate for HG/T4701-2014 Battery and content of iron phosphate product element
Comparative example 1
A method for the utilization of ilmenite, comprising the steps of:
1) Uniformly mixing ilmenite and 2.0% of binder polyvinyl alcohol; pelletizing under the conditions of 8.0% of water and 12min of pelletizing time, wherein the falling strength of the obtained green pellets is 4.5 times/piece, the compressive strength is 10.2N/piece, and the bursting temperature is 420 ℃;
2) Drying and oxidizing the obtained raw gas in a chain grate, wherein the drying is combined with forced air drying and induced air drying, and the forced air drying time is 3min, the air speed is 1.2m/s, and the temperature is 200 ℃; the air draft drying time is 3min, the air speed is 1.2m/s, and the temperature is 350 ℃; the oxidation temperature is 850 ℃, the oxidation time is 40min, the wind speed is 2.4m/s, and the compression strength of the oxidized pellet is 1050N/s;
3) Reducing the obtained oxidized pellets in a coal-based reduction furnace at 1150 ℃ for 120min under the conditions of a C/Fe mass ratio of 0.6, wherein the metallization rate is 84.67%;
4) Reducing the calcined ore, stirring at a temperature of 75deg.C and a stirring rate of 600r/min at a liquid-solid ratio of 10:1 at an ammonium chloride solution concentration of 2.0% and a bubbling oxygen rate of 15X10% 3 L/(m 3 Min), the rust time is 8h, then the rust product is separated by adopting gravity separation, and the TiO of the titanium-rich material is obtained 2 Grade is 75.67%, recovery rate is 85.66%; the grade of iron in the iron-containing titanium slag is 59.22 percent, and the grade of TiO is 2 The content is 6.67%;
5) Adding 4mol/L sulfuric acid solution into ferrotitanium slag powder, heating and stirring for 2 hours at 70 ℃ to obtain filtrate and titanium-rich filter residues, and filtering the filtrate and the titanium-rich filter residues to obtain TiO (titanium oxide) with the titanium-rich filter residues, wherein the liquid-solid ratio of the acid solution to the ferrotitanium slag is 5:1 2 Grade is 55.37%;
6) Adding trisodium phosphate into the filtrate, wherein the mol ratio of trisodium phosphate to iron in the ferrotitanium slag raw material is 1.0, adjusting the pH of the solution to 2.0 by ammonia water, heating and stirring for 20min at 60 ℃, aging for 30min, and filtering to obtain crude ferric phosphate;
7) The crude iron phosphate was calcined at 600 ℃ for 4 hours and cooled to obtain iron phosphate.
Table 6 shows the chemical composition of the ilmenite residue in comparative example 1. Table 7 shows that the iron phosphate prepared in comparative example 1 has high content of impurity ion elements, the quality of the iron phosphate prepared in comparative example 1 cannot meet the standard requirement of iron phosphate for HG/T4701-2014 battery, the ratio of phosphorus to iron is far beyond the normal ratio of phosphorus to iron, and the product contains a large amount of iron hydroxide and ammonium sulfate impurities, because a large amount of ammonia water is required to be added to adjust the pH when precipitating the iron phosphate due to the too low pH value of the pickling solution, and the iron in the leaching solution exists in a single form and is only Fe 3+ In a form that makes Fe (OH) generation easier 3 With FePO 4 The PH ranges of the precipitates overlap, so that the crude iron phosphate product contains significant amounts of impurities and cannot be improved even if the flush level during filtration is increased.
TABLE 6 chemical composition of ilmenite in comparative example 1
Table 7 Standard requirement of iron phosphate for HG/T4701-2014 Battery and content of iron phosphate product element
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A method for preparing titanium-rich material and battery grade ferric phosphate by using ilmenite, which is characterized by comprising the following steps:
(1) Adding a binder and proper water into ilmenite powder, uniformly mixing to obtain a mixed material, pelletizing the mixed material to obtain ilmenite pellets, and drying and oxidizing the ilmenite pellets to obtain oxidized pellets;
(2) Placing the oxidized pellets obtained in the step (1) in hydrogen for reduction treatment to obtain reduced ilmenite pellets;
(3) Crushing and screening the reduced ilmenite pellets obtained in the step (2) to obtain reduced ilmenite powder, adding the reduced ilmenite powder and a rust agent into water, and introducing oxygen to obtain rust ilmenite;
(4) Separating the rusted ferrotitanium obtained in the step (3) to obtain the titanium-rich material and titanium-iron slag;
(5) Adding a mixed acid solution of sulfuric acid and phosphoric acid into the ferrotitanium slag obtained in the step (4), heating, stirring, reacting, and filtering to obtain leaching filtrate and titanium-rich filter residues;
(6) Adjusting the pH value of the filtrate obtained in the step (5), heating and stirring the filtrate at a set temperature for reaction, and aging and filtering the mixture to obtain crude ferric phosphate;
(7) And (3) calcining the crude ferric phosphate obtained in the step (6), and cooling to obtain the battery grade ferric phosphate.
2. The method for producing a titanium-rich material, battery grade iron phosphate from ilmenite according to claim 1, wherein in step (1), the ilmenite powder D 90 The addition amount of the binder is 0.1-2% and the water content is 3-10% less than 74 mu m.
3. The method for preparing titanium-rich materials and battery-grade ferric phosphate by using ilmenite according to claim 1, wherein in the step (1), ilmenite pellets are dried and oxidized in a chain grate, the drying treatment is a combination of forced air drying and induced draft drying, the forced air drying time is 3-4 min, the wind speed is 0.5-1.5 m/s, and the temperature is 200-250 ℃;
the air draft drying time is 3-6 min, the air speed is 0.5-1.5 m/s, and the temperature is 250-350 ℃;
the temperature of the oxidation treatment is 850-950 ℃, the oxidation time is 10-120 min, the wind speed is 2.0-2.4 m/s, and the oxidation gas is air, oxygen or the mixture of the air and the oxygen.
4. The method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite according to claim 1, wherein in the step (2), the reduction temperature is 800-900 ℃, the reduction time is 30-90 min, and the hydrogen ventilation flow is 5-20L/min.
5. The method for producing a titanium-rich material, battery grade iron phosphate from ilmenite according to claim 1, wherein in step (3), the ilmenite powder D is reduced 90 The liquid-solid ratio of ilmenite powder to water is 5-50:1, the rust temperature is 30-80 ℃, the rust agent is ammonium chloride, the solution concentration is 0.5-3.0 wt.%, and the oxygen bubbling rate is 5-30×10 3 L/(m 3 Min), and introducing oxygen for 6-12 h.
6. The method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite as claimed in claim 1, wherein in the step (5), the ilmenite slag is crushed to control the titaniferous slag powder D 90 The mass fraction of iron in the ferrotitanium slag is more than or equal to 40wt percent and less than 37 mu m.
7. The method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite according to claim 6, wherein in the step (5), the liquid-solid ratio of the mixed acid solution to the titanium-iron slag powder is 2:1-5:1, the sulfuric acid concentration is 2-4 mol/L, and the mol ratio of the phosphoric acid substance to the iron substance in the ilmenite is 0.9-1.3; the heating temperature is 30-80 ℃, and the heating and stirring time is more than or equal to 0.5h.
8. The method for preparing titanium-rich materials and battery-grade ferric phosphate by using ilmenite as claimed in claim 6, wherein in the step (5), the titanium dioxide in the titanium-rich filter residue is high in grade and is recycled in the titanium-rich materials.
9. The method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite according to claim 1, wherein in the step (6), ammonia water is added to adjust the pH of the solution to 1.5-2.8, the heating temperature is 30-80 ℃, the heating time is more than or equal to 0.5h, and the aging time is 0.5-2 h.
10. The method for preparing titanium-rich material and battery grade ferric phosphate by using ilmenite according to claim 1, wherein in the step (7), the calcining temperature is 500-800 ℃ and the calcining time is 1-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311141154.8A CN117303333A (en) | 2023-09-06 | 2023-09-06 | Method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311141154.8A CN117303333A (en) | 2023-09-06 | 2023-09-06 | Method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117303333A true CN117303333A (en) | 2023-12-29 |
Family
ID=89241624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311141154.8A Pending CN117303333A (en) | 2023-09-06 | 2023-09-06 | Method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117303333A (en) |
-
2023
- 2023-09-06 CN CN202311141154.8A patent/CN117303333A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101967563B (en) | Method for wet-process vanadium extraction by using vanadium- and titanium-containing converter slag | |
| CN108265178B (en) | A kind of processing method of cobalt metallurgy of nickel waste water slag | |
| CN103276218B (en) | Method for recycling vanadium from vanadium-containing electrolysis aluminum slag ash | |
| CN104261473B (en) | A kind of preparation method of Vanadium Pentoxide in FLAKES | |
| CN112159897A (en) | Method for purifying nickel-cobalt-manganese leaching solution | |
| CN113651342A (en) | Method for producing lithium product by processing lepidolite through nitric acid atmospheric pressure method | |
| CN112662896A (en) | Method for preparing titanium-rich material from titanium ore | |
| CN114684801A (en) | Method for preparing high-purity iron phosphate by using pyrite cinder | |
| CN103074496B (en) | Method for separating and purifying magnesium dioxide from anode mud | |
| CN110735032B (en) | Vanadium-titanium-iron paragenetic ore treatment process | |
| CN1674331A (en) | Method for preparing manganese-zinc ferrite granules and mixed carbonate by using waste dry batteries | |
| CN102569863B (en) | Preparation method of electrolyte used in all-vanadium redox flow battery | |
| CN112645387A (en) | Method for preparing battery-grade manganese dioxide by using anode slag | |
| CN115196609B (en) | Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof | |
| CN116477591A (en) | Comprehensive utilization method of waste lithium iron phosphate anode material | |
| CN112777642B (en) | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag | |
| CN115784188A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| CN117303333A (en) | Method for preparing titanium-rich material and battery-grade ferric phosphate by using ilmenite | |
| CN112662866B (en) | Method for reducing sulfate radical content in rare earth oxide by carbonization roasting | |
| CN113716539B (en) | Method for preparing ferric phosphate precursor by using zinc hydrometallurgy high-speed rail solution | |
| CN114976337A (en) | Comprehensive recovery method of scrapped lithium iron phosphate | |
| CN115072688A (en) | Method for recycling all components of waste lithium iron phosphate battery | |
| CN113976129A (en) | Method for preparing manganese carbonate and iron-based SCR catalyst by using manganese tailings and copperas | |
| CN109868366B (en) | Method for preparing high-purity red lead by wet-method recovery of waste lead paste through filtrate circulation | |
| CN117208874A (en) | Method for preparing battery-grade ferric phosphate from ferrotitanium slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |