CN116103502B - Method for recycling iron-aluminum slag - Google Patents
Method for recycling iron-aluminum slag Download PDFInfo
- Publication number
- CN116103502B CN116103502B CN202310074038.2A CN202310074038A CN116103502B CN 116103502 B CN116103502 B CN 116103502B CN 202310074038 A CN202310074038 A CN 202310074038A CN 116103502 B CN116103502 B CN 116103502B
- Authority
- CN
- China
- Prior art keywords
- iron
- aluminum
- ammonium fluoride
- solution
- organic phase
- 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.)
- Active
Links
- 239000002893 slag Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000000605 extraction Methods 0.000 claims abstract description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000012074 organic phase Substances 0.000 claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 41
- 229910001610 cryolite Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000002195 synergetic effect Effects 0.000 claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 21
- 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 claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 17
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 16
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 12
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 12
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- -1 carboxylic acid compound Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 235000014413 iron hydroxide Nutrition 0.000 abstract 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000003756 stirring Methods 0.000 description 27
- 239000002244 precipitate Substances 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011572 manganese Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
- 229910000398 iron phosphate Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012045 crude solution Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 108010084680 Heterogeneous-Nuclear Ribonucleoprotein K Proteins 0.000 description 1
- 241000557116 Macleaya <angiosperm> Species 0.000 description 1
- 102100023482 Mitogen-activated protein kinase 14 Human genes 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/52—Double compounds containing both fluorine and other halide groups
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling iron-aluminum slag, which comprises the steps of adding acid liquor into iron-aluminum slag for leaching and dissolving, adopting a synergistic extraction extractant to extract leaching liquid to obtain an iron-containing organic phase and an aluminum-containing raffinate, adding sodium hydroxide into the aluminum-containing raffinate for reaction to obtain a sodium metaaluminate solution, adding first ammonium fluoride for reaction to obtain cryolite, adding second ammonium fluoride into the iron-containing organic phase for back extraction, separating to obtain an organic phase and ammonium hexafluoroferrite, and adding ammonia water into the ammonium hexafluoroferrite for reaction to adjust the pH value to 8.5-9.0, thereby obtaining an iron hydroxide solution and an ammonium fluoride solution. According to the invention, a novel carboxylic acid extractant BC196 and a phosphoric acid extractant P204 are used for cooperatively separating iron and aluminum to obtain a purer iron source and an aluminum source, and the reaction conditions are controlled by removing impurities and adding auxiliary materials to prepare ferric hydroxide and cryolite products, so that the ferric hydroxide can be further prepared into battery-grade ferric phosphate products, and waste is changed into valuable.
Description
Technical Field
The invention belongs to the field of hydrometallurgy in waste battery recovery, and particularly relates to a method for recycling iron-aluminum slag.
Background
In recent years, with the rapid development of consumer electronics, electric vehicles and various energy storage markets, the demand of lithium batteries has also increased, and ternary lithium batteries have been widely used because of their high energy density, good power and the like. The ternary lithium battery contains rich nickel, cobalt, manganese and other resources, however, a large number of ternary lithium batteries become waste ternary lithium batteries after a batch of discharge, and the waste ternary lithium batteries have the risk of environmental pollution if being improperly disposed. Therefore, the recycling of the waste ternary lithium battery to prepare a new ternary lithium battery not only realizes the resource regeneration and greatly reduces the pollution of the waste battery to the environment, but also reduces the preparation cost of the ternary lithium battery.
In the process for preparing the ternary positive electrode precursor by recycling the waste ternary lithium batteries in the existing factory, the process flow is as follows: pretreatment, leaching, extraction and synthesis of ternary precursors. Iron and aluminum are very important steps in leaching and impurity removal, and iron and aluminum slag is used as the only outlet of iron and aluminum, so that the problems of high yield and high treatment cost are often caused. Patent CN105506290a describes a method for comprehensive utilization of iron-aluminum slag: selectively leaching the iron-aluminum slag, and dissolving nickel, cobalt, aluminum and iron in slag; then adding sodium sulfide into the nickel, cobalt and aluminum leaching solution, precipitating and recovering nickel and cobalt in the solution, and obtaining an aluminum sulfate crude solution; adding an oxidant and sodium hydroxide into the aluminum sulfate crude solution to remove iron, then adding sodium sulfate in the aluminum sulfate crude solution, and preparing the solution into a stock solution for producing sodium aluminum sulfate; evaporating and crystallizing the stock solution to obtain an aluminum sodium sulfate product. The method for preparing sodium aluminum sulfate from the iron-aluminum slag is simple and easy to implement and low in cost, but the selective leaching with sulfuric acid can solve the problem of incomplete iron-aluminum separation, and causes the loss and waste of main metal-Fe of the iron-aluminum slag.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a method for recycling iron-aluminum slag, which takes iron-aluminum slag generated in the iron-aluminum removing process of waste ternary batteries as a raw material, uses a novel carboxylic acid extractant BC196 and a phosphoric acid extractant P204 to cooperatively separate iron and aluminum to obtain purer iron sources and aluminum sources, prepares iron phosphate and cryolite products by controlling reaction conditions through impurity removal and auxiliary material addition, changes wastes into valuables, conforms to the environmental protection concept, and obtains economic benefits through the iron phosphate and the cryolite products.
According to one aspect of the invention, a method for recycling iron-aluminum slag is provided, which comprises the following steps:
S1: adding acid liquor into the iron-aluminum slag to carry out leaching dissolution, and carrying out solid-liquid separation to obtain leaching liquid;
s2: extracting the leaching solution by adopting a synergistic extraction agent to obtain an iron-containing organic phase and an aluminum-containing raffinate, wherein the synergistic extraction agent consists of an extraction agent BC196, an extraction agent P204 and solvent oil;
S3: adding sodium hydroxide into the aluminum-containing raffinate to react, filtering to remove impurities to obtain a sodium metaaluminate solution, and adding first ammonium fluoride to react to obtain cryolite; adding second ammonium fluoride into the iron-containing organic phase for back extraction, and separating to obtain an organic phase and ammonium hexafluoroferrite; cryolite preparation equation ：3Na++6F-+4NH4 ++AlO2 -→Na3AlF6↓+4NH3↑+2H2O;
S4: and adding ammonia water into the ammonium hexafluoroferrite to adjust the pH value to 8.5-9.0 for reaction, so as to obtain ferric hydroxide and ammonium fluoride solution.
In some embodiments of the invention, in step S1, the main metal composition of the ferro-aluminum slag comprises sodium-iron-alum slag and aluminum hydroxide.
In some embodiments of the invention, in step S1, the leaching and dissolving temperature is 85-95 ℃. Further, the leaching and dissolving reaction time is 3-4h.
In some embodiments of the present invention, in step S1, the iron-aluminum slag is further subjected to a grinding treatment before leaching, and the particle size of the iron-aluminum slag powder obtained by grinding is 200-500 mesh.
In some preferred embodiments of the present invention, in step S1, the acid solution is sulfuric acid with a mass concentration of 50% -80%. Further, the solid-to-liquid ratio of the iron aluminum slag to the acid liquor is 100-200g/L.
In some embodiments of the present invention, in step S2, the extractant BC196 is a carboxylic acid compound having the structure: wherein m and n are each independently selected from integers of 1 to 21, and 10.ltoreq.m+n.ltoreq.22. Further, the extractant BC196 is provided by scow macleaya cycle technology limited.
In some embodiments of the present invention, in step S2, the volume fraction of the extracting agent BC196 is 1% to 10% and the volume fraction of the extracting agent P204 is 25% to 40%.
In some embodiments of the invention, in step S2, the solvent oil is at least one of kerosene, glycerol, or octanol.
In some embodiments of the present invention, in step S2, the volume ratio of the leachate to the synergistic extractant is 1: (2-4), wherein the extraction temperature is 10-45 ℃. Further, the extraction time is 5-10min; further, the extraction stage number is 3-5; further, the extraction equilibrium pH is 1.0-1.8.
In some embodiments of the invention, in step S3, the molar ratio of sodium hydroxide to aluminum ions in the aluminum-containing raffinate is (6-8): 1.
In some embodiments of the invention, in step S3, the mass concentration of the sodium hydroxide is 40% -60%.
In some embodiments of the invention, in step S3, the sodium hydroxide is added to perform the reaction at a temperature of 60-80 ℃ for a time of 4-6 hours.
In some embodiments of the invention, in step S3, the molar ratio of the first ammonium fluoride to sodium metaaluminate in the sodium metaaluminate solution is (6.5-8): 1. further, the mass concentration of the first ammonium fluoride is 20% -30%.
In some embodiments of the invention, in step S3, the first ammonium fluoride is added to react at a temperature of 85-95 ℃ for a period of 1.5-3 hours.
In some embodiments of the present invention, in step S3, the mass concentration of the second ammonium fluoride is 20% -30%, and the volume ratio of the iron-containing organic phase to the second ammonium fluoride is (2-3): 1.
In some embodiments of the invention, in step S3, the temperature of the back extraction is 25-50 ℃ for 3-8min. Further, the number of stages of the back extraction is a single stage.
In some embodiments of the present invention, in step S3, the separated organic phase is washed with water and then returned to step S2 as an extractant for recycling.
In some embodiments of the invention, during step S3 to produce the cryolite, the reaction product further comprises ammonia gas, which is used to produce the aqueous ammonia of step S4.
In some embodiments of the invention, in step S4, the temperature of the reaction of adding the aqueous ammonia is 80-90 ℃. Further, the ammonia water is added for 0.5-1h.
In some embodiments of the invention, in step S4, the ammonium fluoride solution is recycled for use in step S3 as a stripping reagent for the cryolite preparation feedstock or the iron-containing organic phase.
In some embodiments of the present invention, in step S4, further includes: mixing the ferric hydroxide with phosphoric acid for reaction to obtain ferric phosphate. Specifically, mixing the ferric hydroxide with phosphoric acid, regulating the temperature to 90-95 ℃ and the pH to 1.8-2.0, continuously stirring for reaction, standing, and finally cooling, filtering, washing and drying to obtain the ferric phosphate. Further, the method for adjusting the pH value is to add ammonia water with the mass concentration of 20-50%, and continuously stir for 2-3h; further, the standing time is 3-8 hours.
In some embodiments of the present invention, in step S4, the mass concentration of the phosphoric acid is 40% -60%, and the molar ratio of the iron element in the ferric hydroxide to the phosphorus element in the phosphoric acid is 1: (1.1-1.3).
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
1. the invention uses the novel carboxylic acid extractant BC196 and the phosphoric acid extractant P204 to cooperatively extract, which not only has low cost and easy industrialization, but also improves the purity and extraction rate (> 95%) of the iron source in the organic phase, so that most of aluminum, calcium, nickel, cobalt and manganese enter the raffinate (the extraction rate is less than 1%), and simultaneously, the dual effects of iron-aluminum separation and iron source impurity removal are achieved.
2. The invention adds excessive sodium hydroxide to remove impurities, which not only can convert the impurities such as iron, nickel, cobalt, manganese and the like in the raffinate into hydroxide precipitates and then filter the hydroxide precipitates to remove impurities, but also can convert aluminum ions in the raffinate into sodium metaaluminate to become a precursor for preparing cryolite.
3. According to the invention, ammonium fluoride is added in the aluminum recycling process to prepare cryolite, the ammonia gas generated by collection can be used for preparing an ammonia water solution, the ammonia gas is used for regulating the pH value of ammonium hexafluoroferrite obtained by back extraction of ammonium fluoride in the iron recycling process, and the ammonium fluoride solution is obtained while ferric hydroxide is generated, so that the regeneration and circulation of ammonium fluoride are realized, and the resources are saved.
4. Preferably, the organic phase is washed after back extraction, so that the regeneration and circulation of the extractant can be realized, and the resource is saved.
5. According to the invention, the iron-aluminum slag is recycled, cryolite and ferric hydroxide are prepared, and the ferric hydroxide can be further prepared into a battery-grade ferric phosphate product, so that not only is the reduction of solid waste realized, and the cost outside the commission reduced, but also the process is simple, the cost is low, the industrialization is easy, and certain economic benefit can be obtained.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a process flow diagram of example 1 of the present invention;
FIG. 2 is an XRD pattern of the ferro-aluminum slag of example 1 of the present invention;
FIG. 3 is a SEM image of the ferro-aluminum slag of example 1 of the present invention at 5000 times;
FIG. 4 is a SEM image of 10000 times of the iron-aluminum slag of example 1;
FIG. 5 is a SEM image of the ferro-aluminum slag of example 1 of the present invention at 50000 times;
FIG. 6 is an SEM image of cryolite according to example 1 of the present invention;
FIG. 7 is an XRD pattern for cryolite according to example 1 of the present invention;
FIG. 8 is an SEM image of the iron phosphate of example 1 of the present invention;
Fig. 9 is an XRD pattern of iron phosphate according to example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
Referring to fig. 1, the method for recycling iron and aluminum slag comprises the following specific processes:
(1) 100g of ferro-aluminum slag is obtained, the morphology of which is shown in figures 3-5, and the components of which are measured by XRD (figure 2): sodium jarosite-aluminium hydroxide, in which the metal content is measured by ICP: 10.10wt% of Fe, 6.30wt% of Al, 0.63wt% of Ni, 0.21wt% of Co, 0.41wt% of Mn, 0.13wt% of Li, 0.18wt% of Ca and 0.01wt% of Mg;
(2) Drying and grinding the iron-aluminum slag wet material to 200 meshes, adding 100ml of pure water and 500ml of sulfuric acid with concentration of 60%, adjusting the temperature to 85 ℃, stirring and reacting for 4 hours at the speed of 300r/min, and filtering to obtain 500ml of leaching solution;
(3) The volume fraction is BC196-5% (provided by Suzhou Bo extract circulation technology Co., ltd., the structural formula is as follows: ) Extracting 3-stage extraction with P204-30% and kerosene-65% synergistic extraction agent at 25deg.C, wherein the synergistic extraction agent has a ratio of O to A=2:1, the time is 8min, the pH is stabilized at 1.55, and the extraction is carried out to obtain 500ml aqueous aluminum sulfate solution and iron-containing organic phase;
(4) ICP detects that the Al content in the water phase is 5.80g/L, sodium hydroxide with the concentration of 40% is added, the molar quantity of the added sodium hydroxide is 7 times that of aluminum ions in the solution, the temperature is regulated to 80 ℃, and the reaction is stirred for 4 hours at the speed of 300 r/min; cooling and filtering to obtain sodium metaaluminate solution, adding 140ml of ammonium fluoride with concentration of 20%, adjusting the temperature to 90 ℃, continuously stirring at the speed of 300r/min for reaction for 3 hours, standing for 1 hour, cooling, filtering and drying to obtain 20.59g cryolite;
(5) Back-extracting the ferric organic phase obtained in the step (3) by using an ammonium fluoride solution with the concentration of 30%, wherein the ratio of the ferric organic phase to the ammonium fluoride solution in back-extraction is 2:1, reacting for 5min at 45 ℃, standing and separating to obtain white precipitate and an organic phase after back extraction, washing the organic phase with pure water, and returning to the step (3) to be used as an extractant for recycling;
(6) Collecting ammonia gas generated in the reaction for preparing cryolite in the step (4), introducing the ammonia gas into pure water to prepare ammonia water solution, adjusting the temperature of a water bath where white precipitate is positioned to be 85 ℃, starting an automatic stirrer at the rotating speed of 300r/min, adding ammonia water into the ammonia water to adjust the pH to 8.74, continuing stirring for 0.5 hour, and filtering and separating to obtain red ferric hydroxide precipitate and ammonium fluoride solution; the ammonium fluoride solution can be used for cryolite preparation reaction in the step (4) or used as a stripping agent for stripping and recycling in the step (5);
(7) Adding 24ml of 40% phosphoric acid into red precipitate according to the molar ratio of iron element to phosphorus element of 1:1.1, adjusting the temperature to 95 ℃, starting stirring at the speed of 300r/min, adjusting the pH value to 1.86 by using 40% ammonia water solution, continuing stirring for 3h, standing for 8h, filtering, washing and drying to obtain 13.38g of battery grade ferric phosphate product.
Example 2
A method for recycling iron and aluminum slag comprises the following specific processes:
(1) 100g of ferro-aluminum slag is obtained, and the components thereof are as follows by XRD: sodium jarosite-aluminium hydroxide, in which the metal content is measured by ICP: 10.10wt% of Fe, 6.30wt% of Al, 0.63wt% of Ni, 0.21wt% of Co, 0.41wt% of Mn, 0.13wt% of Li, 0.18wt% of Ca and 0.01wt% of Mg;
(2) Drying and grinding the iron-aluminum slag wet material to 200 meshes, adding 100ml of pure water and 500ml of 80% sulfuric acid, adjusting the temperature to 90 ℃, stirring and reacting for 3 hours at the speed of 300r/min, and filtering to obtain 500ml of leaching solution;
(3) Performing 3-stage extraction at 25deg.C with a synergistic extraction agent with volume fraction of BC196-8% (provided by Suzhou Bo extraction circulation technology Co., ltd.), P204-35% and kerosene-57%, wherein the synergistic extraction agent has a ratio of O to leachate of A=2:1, the time is 5min, the pH is stable at 1.34, and the aqueous phase aluminum sulfate solution and the ferric organic phase are separated after extraction to obtain 500 ml;
(4) ICP detects that the Al content in the water phase is 6.08g/L, sodium hydroxide with the concentration of 40% is added, the molar quantity of the added sodium hydroxide is 7 times of that of aluminum ions, the temperature is regulated to 80 ℃, and the reaction is stirred for 5 hours at the speed of 300 r/min; cooling and filtering to obtain sodium metaaluminate solution, adding 146ml of ammonium fluoride with concentration of 20%, adjusting the temperature to 95 ℃, continuously stirring at the speed of 300r/min for reaction for 3 hours, standing for 1 hour, cooling, filtering and drying to obtain 22.12g cryolite;
(5) Back-extracting the ferric organic phase obtained in the step (3) by using an ammonium fluoride solution with the concentration of 30%, wherein the ratio of the ferric organic phase to the ammonium fluoride solution in back-extraction is 2:1, reacting for 6min at 50 ℃, standing and separating to obtain white precipitate and an organic phase after back extraction, washing the organic phase with pure water, and returning to the step (3) to be used as an extractant for recycling;
(6) Collecting ammonia gas generated in the reaction for preparing cryolite in the step (4), introducing the ammonia gas into pure water to prepare ammonia water solution, adjusting the temperature of a water bath where white precipitate is positioned to 90 ℃, starting an automatic stirrer at the rotating speed of 300r/min, adding ammonia water into the ammonia water to adjust the pH to 8.67, continuing stirring for 0.5 hour, and filtering and separating to obtain red ferric hydroxide precipitate and ammonium fluoride solution; the ammonium fluoride solution can be used for cryolite preparation reaction in the step (4) or used as a stripping agent for stripping and recycling in the step (5);
(7) Adding 18ml of phosphoric acid with the concentration of 60% into red precipitate according to the molar ratio of iron element to phosphorus element of 1:1.1, adjusting the temperature to 90 ℃, starting stirring at the speed of 300r/min, adjusting the pH value to 1.98 by using an ammonia water solution with the concentration of 40%, continuing stirring for 3h, standing for 8h, filtering, washing and drying to obtain 14.51g of battery grade ferric phosphate product.
Example 3
A method for recycling iron and aluminum slag comprises the following specific processes:
(1) 100g of ferro-aluminum slag is obtained, and the components thereof are as follows by XRD: sodium jarosite-aluminium hydroxide, in which the metal content is measured by ICP: 12.73wt% of Fe, 6.23wt% of Al, 0.98wt% of Ni, 0.52wt% of Co, 0.50wt% of Mn, 0.31wt% of Li, 0.23wt% of Ca and 0.02wt% of Mg;
(2) Drying and grinding the iron-aluminum slag wet material to 200 meshes, adding 100ml of pure water and 500ml of 80% sulfuric acid, adjusting the temperature to 90 ℃, stirring and reacting for 3 hours at the speed of 300r/min, and filtering to obtain 500ml of leaching solution;
(3) Performing 3-stage extraction at 25deg.C with a synergistic extraction agent with volume fraction of BC196-8% (provided by Suzhou Bo extraction circulation technology Co., ltd.), P204-35% and kerosene-57%, wherein the synergistic extraction agent has a ratio of O to leachate of A=2:1, the time is 5min, the pH is stable at 1.18, and the aqueous phase aluminum sulfate solution and the ferric organic phase are separated after extraction to obtain 500 ml;
(4) ICP detects that the Al content in the water phase is 5.98g/L, sodium hydroxide with the concentration of 60% is added, the molar quantity of the added sodium hydroxide is 8 times that of aluminum ions, the temperature is regulated to 80 ℃, and the reaction is stirred for 5 hours at the speed of 300 r/min; cooling and filtering to obtain sodium metaaluminate solution, adding 144ml of ammonium fluoride with concentration of 20%, adjusting the temperature to 95 ℃, continuously stirring at the speed of 300r/min for reaction for 3h, standing for 1h, cooling, filtering and drying to obtain 21.03g cryolite;
(5) Back-extracting the ferric organic phase obtained in the step (3) by using an ammonium fluoride solution with the concentration of 30%, wherein the ratio of the ferric organic phase to the ammonium fluoride solution in back-extraction is 2:1, reacting for 5min at 50 ℃, standing and separating to obtain white precipitate and an organic phase after back extraction, washing the organic phase with pure water, and returning to the step (3) to be used as an extractant for recycling;
(6) Collecting ammonia gas generated in the reaction for preparing cryolite in the step (4), introducing the ammonia gas into pure water to prepare ammonia water solution, adjusting the temperature of a water bath where white precipitate is positioned to 90 ℃, starting an automatic stirrer at the rotating speed of 300r/min, adding ammonia water into the ammonia water to adjust the pH to 8.56, continuing stirring for 0.5 hour, and filtering and separating to obtain red ferric hydroxide precipitate and ammonium fluoride solution; the ammonium fluoride solution can be used for cryolite preparation reaction in the step (4) or used as a stripping agent for stripping and recycling in the step (5);
(7) Adding 17ml of phosphoric acid with the concentration of 60% into red precipitate according to the molar ratio of iron element to phosphorus element of 1:1.1, adjusting the temperature to 95 ℃, starting stirring at the speed of 300r/min, adjusting the pH value to 1.83 by using an ammonia water solution with the concentration of 40%, continuing stirring for 3h, standing for 8h, filtering, washing and drying to obtain 13.78g of battery grade ferric phosphate product.
Comparative example 1
The method for recycling the iron-aluminum slag is different from the method in the embodiment 1 in that the extractant BC196 is not added, and the specific process is as follows:
(1) 100g of ferro-aluminum slag is obtained, and the components thereof are as follows by XRD: sodium jarosite-aluminium hydroxide, in which the metal content is measured by ICP: 10.10wt% of Fe, 6.30wt% of Al, 0.63wt% of Ni, 0.21wt% of Co, 0.41wt% of Mn, 0.13wt% of Li, 0.18wt% of Ca and 0.01wt% of Mg;
(2) Drying and grinding the iron-aluminum slag wet material to 200 meshes, adding 100ml of pure water and 500ml of sulfuric acid with concentration of 60%, adjusting the temperature to 85 ℃, stirring and reacting for 4 hours at the speed of 300r/min, and filtering to obtain 500ml of leaching solution;
(3) Extracting 3-stage with extractant with volume fraction of P204-30% and kerosene-70% at 25deg.C, wherein the ratio of extractant to leachate, O, is A=2:1, the time is 8min, the pH is stabilized at 1.55, and separating to obtain 500ml water phase and iron-containing organic phase after extraction;
(4) ICP detects that the Al content in the water phase is 4.87g/L, sodium hydroxide with the concentration of 40% is added, the molar quantity of the added sodium hydroxide is 7 times that of aluminum ions in the solution, the temperature is regulated to 80 ℃, and the reaction is stirred for 4 hours at the speed of 300 r/min; cooling and filtering to obtain sodium metaaluminate solution, adding 118ml of ammonium fluoride with concentration of 20%, adjusting the temperature to 90 ℃, continuously stirring at the speed of 300r/min for reaction for 3 hours, standing for 1 hour, cooling, filtering and drying to obtain 18.91g cryolite;
(5) Back-extracting the ferric organic phase obtained in the step (3) by using an ammonium fluoride solution with the concentration of 30%, wherein the ratio of the ferric organic phase to the ammonium fluoride solution in back-extraction is 2:1, reacting for 5min at 45 ℃, standing and separating to obtain white precipitate and an organic phase after back extraction, washing the organic phase with pure water, and returning to the step (3) to be used as an extractant for recycling;
(6) Collecting ammonia gas generated in the reaction for preparing cryolite in the step (4), introducing the ammonia gas into pure water to prepare ammonia water solution, adjusting the temperature of a water bath where white precipitate is positioned to be 85 ℃, starting an automatic stirrer at the rotating speed of 300r/min, adding ammonia water into the ammonia water to adjust the pH to 8.73, continuing stirring for 0.5 hour, and filtering and separating to obtain red ferric hydroxide precipitate and ammonium fluoride solution; the ammonium fluoride solution can be used for cryolite preparation reaction in the step (4) or used as a stripping agent for stripping and recycling in the step (5);
(7) Adding 20ml of 40% phosphoric acid into the red precipitate according to the molar ratio of iron element to phosphorus element of 1:1.1, adjusting the temperature to 95 ℃, starting stirring at the speed of 300r/min, adjusting the pH value to 1.84 by using 40% ammonia water solution, continuing stirring for 3h, standing for 8h, filtering, washing and drying to obtain 11.11g battery grade ferric phosphate product.
Comparative example 2
The difference between the method for recycling the iron-aluminum slag and the embodiment 1 is that the composition of the synergistic extraction agent is different, and the specific process is as follows:
(1) 100g of ferro-aluminum slag is obtained, and the components thereof are as follows by XRD: sodium jarosite-aluminium hydroxide, in which the metal content is measured by ICP: 10.10wt% of Fe, 6.30wt% of Al, 0.63wt% of Ni, 0.21wt% of Co, 0.41wt% of Mn, 0.13wt% of Li, 0.18wt% of Ca and 0.01wt% of Mg;
(2) Drying and grinding the iron-aluminum slag wet material to 200 meshes, adding 100ml of pure water and 500ml of sulfuric acid with concentration of 60%, adjusting the temperature to 85 ℃, stirring and reacting for 4 hours at the speed of 300r/min, and filtering to obtain 500ml of leaching solution;
(3) Performing 3-level extraction at 25deg.C with a synergistic extraction agent with volume fraction of BC196-15%, P204-15% and kerosene-70%, wherein the synergistic extraction agent has a ratio of O to A=2:1, the time is 8min, the pH is stable to 1.55, and 500ml water phase and iron-containing organic phase are obtained by separation after extraction;
(4) ICP detects that the Al content in the water phase is 5.07g/L, sodium hydroxide with the concentration of 40% is added, the molar quantity of the added sodium hydroxide is 7 times of the molar quantity of aluminum ions in the solution, the temperature is regulated to 80 ℃, and the reaction is stirred for 4 hours at the speed of 300 r/min; cooling and filtering to obtain sodium metaaluminate solution, adding 130ml of ammonium fluoride with concentration of 20%, adjusting the temperature to 90 ℃, continuously stirring at the speed of 300r/min for reaction for 3 hours, standing for 1 hour, cooling, filtering and drying to obtain 18.67g cryolite;
(5) Back-extracting the ferric organic phase obtained in the step (3) by using an ammonium fluoride solution with the concentration of 30%, wherein the ratio of the ferric organic phase to the ammonium fluoride solution in back-extraction is 2:1, reacting for 5min at 45 ℃, standing and separating to obtain white precipitate and an organic phase after back extraction, washing the organic phase with pure water, and returning to the step (3) to be used as an extractant for recycling;
(6) Collecting ammonia gas generated in the reaction for preparing cryolite in the step (4), introducing the ammonia gas into pure water to prepare ammonia water solution, adjusting the temperature of a water bath where white precipitate is positioned to be 85 ℃, starting an automatic stirrer at the rotating speed of 300r/min, adding ammonia water into the ammonia water to adjust the pH to 8.77, continuing stirring for 0.5 hour, and filtering and separating to obtain red ferric hydroxide precipitate and ammonium fluoride solution; the ammonium fluoride solution can be used for cryolite preparation reaction in the step (4) or used as a stripping agent for stripping and recycling in the step (5);
(7) Adding 22ml of 40% phosphoric acid into the red precipitate according to the molar ratio of iron element to phosphorus element of 1:1.1, adjusting the temperature to 95 ℃, starting stirring at the speed of 300r/min, adjusting the pH value to 1.89 by using 40% ammonia water solution, continuing stirring for 3h, standing for 8h, filtering, washing and drying to obtain 12.27g of battery grade ferric phosphate product.
Performance detection
TABLE 1 synergistic extraction separation effect
| Extraction yield (%) | Fe | Al | Ca | Ni | Co | Mn | Li | Mg |
| Example 1 | 98.06％ | 0.50％ | 0.63％ | 0.41％ | 0.19％ | 0.38％ | 0.07％ | 0.11％ |
| Example 2 | 95.99％ | 0.39％ | 0.49％ | 0.33％ | 0.15％ | 0.27％ | 0.05％ | 0.10％ |
| Example 3 | 97.68％ | 0.55％ | 0.65％ | 0.47％ | 0.23％ | 0.39％ | 0.18％ | 0.13％ |
| Comparative example 1 | 91.08％ | 1.06％ | 0.98％ | 0.75％ | 0.45％ | 0.73％ | 0.29％ | 0.38％ |
| Comparative example 2 | 93.86％ | 0.97％ | 1.02％ | 0.84％ | 0.62％ | 0.81％ | 0.39％ | 0.47％ |
As shown in Table 1, the BC196+P204 synergistic extraction system used in the invention can separate pure Fe with extraction rate >95%, and the extraction rate of other impurity ions is less than 1%, and the synergistic extraction mainly uses the difference of the selective complexing capacities of two kinds of extracting agents on metal ions, so that the synergistic extraction can realize better complexing curve, thereby achieving the effects of improving the extraction rate of iron and reducing the extraction rate of aluminum and other impurities. Compared with comparative example 1, the deep extraction of iron is effectively realized by only using P204 for extraction and separation, and the organic phase obtained by separation has fewer impurities, so that the purity is improved; comparative example 2 uses a synergistic extractant composition exceeding BC196 defined in the present invention: 1% -10%, P204:25-40%, the iron-aluminum separation effect is not significantly inferior to that of example 1, and the impurity components in the organic phase are more.
Table 2 cryolite performance test
As can be seen from Table 2, the cryolite product prepared by the invention has better quality than the comparative example, and meets the national standard of cryolite products: al is more than or equal to 12 percent, F is more than or equal to 52 percent, na is less than or equal to 33 percent.
Table 3 battery grade iron phosphate Performance detection
| Content (%) | Fe | P | Fe/P | Al | Ni | Co | Mn | Li | Ca | Mg |
| Example 1 | 36.58 | 20.71 | 0.98 | 0.003 | 0.002 | 0.001 | 0.002 | / | 0.003 | 0.001 |
| Example 2 | 36.55 | 20.82 | 0.97 | 0.002 | 0.002 | 0.001 | 0.002 | / | 0.002 | 0.001 |
| Example 3 | 36.51 | 20.24 | 1.00 | 0.003 | 0.003 | 0.002 | 0.002 | 0.001 | 0.003 | 0.001 |
| Comparative example 1 | 31.05 | 19.31 | 0.89 | 0.005 | 0.005 | 0.004 | 0.004 | 0.002 | 0.005 | 0.002 |
| Comparative example 2 | 32.11 | 18.85 | 0.94 | 0.004 | 0.004 | 0.003 | 0.003 | 0.002 | 0.003 | 0.001 |
As can be seen from Table 3, the quality of the battery grade ferric phosphate product prepared by the invention is superior to that of the comparative example, and meets the standard of the standard bangpu group enterprise standard Q/CSBP J061.001-2022 lithium battery waste recycling product ferric phosphate standard: fe is 35.8-36.8%, P is 20.0-21.0%, and the ratio of Fe to P is 0.96-1.02.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (8)
1. The method for recycling the iron and aluminum slag is characterized by comprising the following steps of:
S1: adding acid liquor into the iron-aluminum slag to carry out leaching dissolution, and carrying out solid-liquid separation to obtain leaching liquid;
s2: extracting the leaching solution by adopting a synergistic extraction agent to obtain an iron-containing organic phase and an aluminum-containing raffinate, wherein the synergistic extraction agent consists of an extraction agent BC196, an extraction agent P204 and solvent oil;
S3: adding sodium hydroxide into the aluminum-containing raffinate to react, filtering to remove impurities to obtain a sodium metaaluminate solution, and adding first ammonium fluoride to react to obtain cryolite; adding second ammonium fluoride into the iron-containing organic phase for back extraction, and separating to obtain an organic phase and ammonium hexafluoroferrite;
S4: adding ammonia water into the ammonium hexafluoroferrite to adjust the pH value to 8.5-9.0 for reaction to obtain ferric hydroxide and ammonium fluoride solution;
the extractant BC196 is a carboxylic acid compound, and has the structure as follows: Wherein m and n are each independently selected from integers of 1 to 21, and 10.ltoreq.m+n.ltoreq.22;
In step S2, in the synergistic extraction agent, the volume fraction of the extraction agent BC196 is 1% -10%, and the volume fraction of the extraction agent P204 is 25% -40%.
2. The method according to claim 1, wherein in step S2, the solvent oil is at least one of kerosene, glycerol or octanol.
3. The method according to claim 1, wherein in step S2, the volume ratio of the leachate to the synergistic extractant is 1: (2-4), wherein the extraction temperature is 10-45 ℃.
4. The method according to claim 1, wherein in step S3, the molar ratio of sodium hydroxide to aluminum ions in the aluminum-containing raffinate is (6-8): 1.
5. The method according to claim 1, characterized in that in step S3, the molar ratio of the first ammonium fluoride to sodium metaaluminate in the sodium metaaluminate solution is (6.5-8): 1.
6. The method of claim 1, wherein during step S3 to produce the cryolite, the reaction product further comprises ammonia gas, the ammonia gas being used to produce the aqueous ammonia of step S4.
7. The method according to claim 1, characterized in that in step S4 the ammonium fluoride solution is recycled for use in step S3 as a stripping reagent for the cryolite preparation feedstock or the iron-containing organic phase.
8. The method according to claim 1, characterized in that in step S4, further comprising: mixing the ferric hydroxide with phosphoric acid for reaction to obtain ferric phosphate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310074038.2A CN116103502B (en) | 2023-01-31 | 2023-01-31 | Method for recycling iron-aluminum slag |
| PCT/CN2023/083923 WO2024159599A1 (en) | 2023-01-31 | 2023-03-26 | Method for resource utilization of iron-aluminum slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310074038.2A CN116103502B (en) | 2023-01-31 | 2023-01-31 | Method for recycling iron-aluminum slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116103502A CN116103502A (en) | 2023-05-12 |
| CN116103502B true CN116103502B (en) | 2024-10-18 |
Family
ID=86259423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310074038.2A Active CN116103502B (en) | 2023-01-31 | 2023-01-31 | Method for recycling iron-aluminum slag |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN116103502B (en) |
| WO (1) | WO2024159599A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024179048A1 (en) * | 2023-11-17 | 2024-09-06 | 广东邦普循环科技有限公司 | Method for preparing phosphorus removal agent by mixing iron-aluminum slag recycled from waste batteries and pyrolusite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913632A (en) * | 2010-08-30 | 2010-12-15 | 昆明理工大学 | Method for extracting alumina, silicon oxide and iron oxide from coal gangue combustion ash |
| CN112501445A (en) * | 2020-11-27 | 2021-03-16 | 北京博萃循环科技有限公司 | Method for preparing battery-grade nickel-cobalt-manganese |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107109523B (en) * | 2014-08-07 | 2019-02-05 | 南澳大学 | Method for the selective separation of iron and aluminium |
| CN104480307A (en) * | 2014-12-22 | 2015-04-01 | 广西师范大学 | Mixed extraction agent for separating iron, aluminium and nickel-cobalt-magnesium from nickel oxide oresulfuric acid leaching solution as well as separation method |
| CN104946889B (en) * | 2015-06-11 | 2017-10-27 | 广州绿华环保科技有限公司 | A kind of method of extract and separate iron and aluminium from hydrochloric acid medium |
| CN105506290B (en) * | 2015-11-30 | 2018-01-09 | 湖南邦普循环科技有限公司 | A kind of method of iron aluminum slag comprehensive utilization |
| CN114134341B (en) * | 2020-09-04 | 2023-01-13 | 苏州博萃循环科技有限公司 | Method for recovering nickel, cobalt and manganese in feed liquid containing nickel, cobalt and manganese |
| CN112593080A (en) * | 2020-12-21 | 2021-04-02 | 北京博萃循环科技有限公司 | Method for treating laterite-nickel ore by combination of pyrogenic process and wet process |
| CN114085994A (en) * | 2021-11-09 | 2022-02-25 | 苏州博萃循环科技有限公司 | Method for recovering valuable metal from waste nickel-hydrogen battery |
| CN114804048A (en) * | 2022-04-06 | 2022-07-29 | 安徽南都华铂新材料科技有限公司 | Method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag |
-
2023
- 2023-01-31 CN CN202310074038.2A patent/CN116103502B/en active Active
- 2023-03-26 WO PCT/CN2023/083923 patent/WO2024159599A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913632A (en) * | 2010-08-30 | 2010-12-15 | 昆明理工大学 | Method for extracting alumina, silicon oxide and iron oxide from coal gangue combustion ash |
| CN112501445A (en) * | 2020-11-27 | 2021-03-16 | 北京博萃循环科技有限公司 | Method for preparing battery-grade nickel-cobalt-manganese |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116103502A (en) | 2023-05-12 |
| WO2024159599A1 (en) | 2024-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113277489A (en) | Method for preparing high-purity iron phosphate by using ferrophosphorus waste | |
| CN112375910B (en) | Recovery processing method of waste power battery powder | |
| CN113896211A (en) | Resource treatment method for waste lithium iron phosphate batteries | |
| CN104659438A (en) | Method for preparing ternary positive electrode material precursor by virtue of waste batteries | |
| EP4087015A1 (en) | Battery-level ni-co-mn mixed solution and preparation method for battery-level mn solution | |
| CN117144140A (en) | A method for extracting nickel from waste ternary lithium-ion batteries | |
| CN116103502B (en) | Method for recycling iron-aluminum slag | |
| CN115261605A (en) | Recovery method of lithium iron phosphate | |
| CN1295357C (en) | Recovery method of valuable element in neodymium iron boron waste material | |
| Teng et al. | Recovery of vanadium and nickel from spent-residue oil hydrotreating catalyst by direct acid leaching-solvent extraction | |
| CN117144139A (en) | A method for extracting cobalt from waste ternary lithium-ion batteries | |
| CN115072688B (en) | Method for recycling all components of waste lithium iron phosphate battery | |
| CN113122725A (en) | Method for improving metal recovery rate and purity of waste lithium battery | |
| CN113753874B (en) | Method for recovering active substances from PVDF-containing lithium iron phosphate positive electrode material | |
| CN114572949A (en) | Production process of lithium dihydrogen phosphate | |
| CN115072687B (en) | Method for preparing battery-grade ferric phosphate by using sulfuric acid cinder | |
| CN117500753A (en) | Method for removing aluminum and copper in ferrophosphorus slag and application thereof | |
| CN112342383B (en) | Separation and recovery method of nickel, cobalt, manganese and lithium in ternary waste | |
| CN116590524A (en) | Method for separating and extracting molybdenum and nickel from carbon-containing nickel-molybdenum ore | |
| CN115784188A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| CN115744851A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| CN116477591A (en) | A method for comprehensive utilization of waste lithium iron phosphate cathode material | |
| CN114645143B (en) | Method for separating nickel, cobalt, copper and manganese from laterite-nickel ore | |
| CN113735179A (en) | Method for preparing high-purity ferric sulfate by using ferro-manganese | |
| CN116462172B (en) | Method for preparing battery-grade ferric phosphate by using carbon-containing crude ferric phosphate generated by selectively extracting lithium from waste ferric phosphate |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |