CN116835626A - Method for comprehensively utilizing fluorogypsum and aluminum electrolyte - Google Patents
Method for comprehensively utilizing fluorogypsum and aluminum electrolyte Download PDFInfo
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- CN116835626A CN116835626A CN202310867268.4A CN202310867268A CN116835626A CN 116835626 A CN116835626 A CN 116835626A CN 202310867268 A CN202310867268 A CN 202310867268A CN 116835626 A CN116835626 A CN 116835626A
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- fluorogypsum
- aluminum electrolyte
- aluminum
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- roasting
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 78
- 239000003792 electrolyte Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000003513 alkali Substances 0.000 claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002699 waste material Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- -1 hetero ions Chemical class 0.000 claims abstract description 10
- 150000004645 aluminates Chemical class 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 238000001179 sorption measurement Methods 0.000 claims description 26
- 238000002386 leaching Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003463 adsorbent Substances 0.000 claims description 16
- 229910001437 manganese ion Inorganic materials 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical group [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- 150000002500 ions Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 abstract description 20
- 239000010440 gypsum Substances 0.000 abstract description 19
- 229910052602 gypsum Inorganic materials 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 229910004261 CaF 2 Inorganic materials 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 4
- 159000000002 lithium salts Chemical class 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 43
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 229910001388 sodium aluminate Inorganic materials 0.000 description 17
- 239000000292 calcium oxide Substances 0.000 description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000012535 impurity Substances 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 9
- 235000011130 ammonium sulphate Nutrition 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000010436 fluorite Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910001610 cryolite Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004131 Bayer process Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 108010063123 alfare Proteins 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- 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
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0693—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for comprehensively utilizing fluorogypsum and aluminum electrolyte, belonging to the technical field of metallurgical solid waste treatment. The method for comprehensively utilizing the fluorine gypsum and the aluminum electrolyte of the invention comprises the steps of roasting fluorine element in aluminum electrolyte waste slag powder and Ca in gypsum 2+ Reaction to form CaF 2 Can be used again for preparing HF, while other nonmetallic elements escape in the form of tail gas. The aluminum element and the lithium element in the aluminum electrolyte waste slag powder are dissolved in alkali liquor after roasting and phase inversion, so that separation from other hetero ions is realized, and pure lithium ion solution and aluminate solution are respectively obtained through a subsequent alkali liquor lithium extraction process and a hetero ion purification process, and can be used for preparing high-purity lithium salt and aluminum hydroxide. The method for comprehensively utilizing the fluorine gypsum and the aluminum electrolyte does not generate corrosive HF in the roasting process, and has the requirements on reaction equipmentNot high, safe and reliable, is favorable to cost control.
Description
Technical Field
The invention relates to a method for comprehensively utilizing fluorogypsum and aluminum electrolyte, belonging to the technical field of metallurgical solid waste treatment.
Background
The fluorogypsum is industrial waste generated by preparing HF by fluorite method, and contains more than 90% of CaSO 4 And a small amount of CaF 2 Impurities such as CaO, and the like, and the newly discharged fluorine gypsum contains residual H 2 SO 4 HF has a certain acidity. In theory, 1t of hydrogen fluoride can be produced as a byproduct of 3.6t of fluorine gypsum, so that the discharge amount of fluorine gypsum per year in China is more than million tons. The main component of the fluorogypsum is insoluble or insoluble II type anhydrous gypsum, which is difficult to hydrate and has low early strength, and can not be directly used in the building industry. At present, when the fluorogypsum is treated, the fluorogypsum is simply neutralized and then piled up or buried, so that not only is great resource waste caused, but also serious negative influence is caused on environmental protection.
In addition to using the modified fluorogypsum as a building material, researchers have made some studies on using recovered fluorogypsum as an industrial material. Chinese patent document CN106365476A discloses a method for preparing sulphoaluminate cement and co-producing sulfuric acid by using desulfurized gypsum, bauxite, silica and anthracite, preparing sulphoaluminate cement after calcining, and preparing tail gas SO 2 Is used for the acid making process. The method takes the desulfurized gypsum as the main material, a great amount of natural materials such as lime, bauxite, silica and the like are required to be consumed, the calcining temperature reaches 1250-1300 ℃, and the energy consumption is higher. Chinese patent document CN101486481A discloses a method for preparing superfine light calcium carbonate and co-producing ammonium sulfate by reacting fluorogypsum, ammonia water, a surfactant and ammonium bicarbonate in a solution, wherein the fluorogypsum is converted into superfine light calcium carbonate and ammonium sulfate with certain economic value, but the method has low economic benefit and limited conversion and utilization of the fluorogypsum.
Aluminium electrolysisThe material is a reaction medium for melting aluminum oxide and electrolyzing the aluminum oxide into metallic aluminum in the aluminum electrolysis process, and is prepared from cryolite (Na 3 AlF 6 ) And other fluoride salt additives such as AlF 3 、CaF 2 、MgF 2 Material composition such as LiF and CaO. However, as production continues, lithium salt enrichment can lead to reduced solubility of the alumina, affecting the efficiency of aluminum electrolysis. In order to keep the electrolyte balance in the aluminum electrolysis cell, the excessive aluminum electrolyte needs to be taken out periodically for piling up, so that great resource waste is caused. The recovery of valuable elements in the aluminum electrolyte waste residue, especially lithium resources in the aluminum electrolyte waste residue, has important significance.
The roasting-leaching method is a common method for recycling the aluminum electrolyte at present, and a phase inversion agent is added in the roasting process, so that insoluble salts in the aluminum electrolyte, such as lithium sodium cryolite and the like, can be converted into soluble or easily leachable salts, and the gradient recovery of valuable elements in the aluminum electrolyte is facilitated. The phase inversion agent used in the current roasting process includes aluminum salt (CN 114853042A), fluoride (CN 105543504A), alkali or alkaline oxide (CN 115216630A, CN113684369A, CN110284157A, CN 115216645A), acid salt (CN 105925819A), etc. Chinese patent document CN110284157a discloses a recycling method, comprising the steps of: mixing and roasting the aluminum electrolysis anode waste residue, calcium-containing substances (lime, limestone and calcium hydroxide) and alkali-containing substances (sodium carbonate, sodium bicarbonate and sodium hydroxide) at a high temperature of 700-1400 ℃, performing alkaline leaching treatment on a roasting product to obtain calcium fluoride, sodium aluminate and caustic alkali solution, and returning the calcium fluoride, the sodium aluminate and the caustic alkali solution to the Bayer process alumina production process. However, the method is to bake in a strong alkali environment, and the recovery rate of lithium element is not higher than 75%.
In view of the foregoing, from the standpoint of reducing the cost of raw materials and environmental protection, there is a need to develop a method capable of comprehensively utilizing fluorogypsum and aluminum electrolyte, so as to achieve the purpose of simultaneously treating fluorogypsum and extracting valuable elements (lithium elements) in the aluminum electrolyte, thereby solving the problems of limited conversion and utilization of fluorogypsum and lower recovery rate in extracting lithium elements in the aluminum electrolyte when the fluorogypsum is treated at present.
Disclosure of Invention
The invention aims to provide a method for comprehensively utilizing fluorogypsum and aluminum electrolyte, which can solve the problems of limited conversion and utilization of fluorogypsum and lower recovery rate in extracting lithium element in the aluminum electrolyte in the prior art.
In order to achieve the above purpose, the method for comprehensively utilizing fluorogypsum and aluminum electrolyte of the invention adopts the following technical scheme:
a method for comprehensively utilizing fluorogypsum and aluminum electrolyte comprises the following steps:
(1) Roasting a mixture mainly composed of aluminum electrolyte waste slag powder, fluorogypsum and a roasting agent, wherein the roasting agent is ammonium carbonate and/or ammonium bicarbonate;
(2) And (3) alkaline leaching is carried out on the solid roasting product obtained in the step (1) by adopting alkali liquor, solid-liquid separation is carried out, then, an adsorbent is adopted to carry out adsorption treatment on lithium ions in liquid obtained by the solid-liquid separation, then, the adsorbent after adsorption treatment is eluted to obtain a lithium ion solution, and meanwhile, the liquid after adsorption treatment and hydrogen peroxide are mixed to react to prepare an aluminate solution.
The method for comprehensively utilizing the fluorogypsum and the aluminum electrolyte comprises the steps of firstly roasting a mixture mainly comprising aluminum electrolyte waste slag powder, fluorogypsum and a roasting agent, wherein fluorine element in the aluminum electrolyte waste slag powder and Ca in the gypsum 2+ Reaction to form CaF 2 Can be used again for preparing HF, while other nonmetallic elements escape in the form of tail gas. The aluminum element and the lithium element in the aluminum electrolyte waste slag powder are dissolved in alkali liquor after roasting and phase inversion, so that separation from other hetero ions is realized, and pure lithium ion solution and aluminate solution are respectively obtained through a subsequent alkali liquor lithium extraction process and a hetero ion purification process, and can be used for preparing high-purity lithium salt and aluminum hydroxide. In addition, the method for comprehensively utilizing the fluorine gypsum and the aluminum electrolyte does not generate corrosive HF in the roasting process, has low requirements on reaction equipment, and is safe and reliable; in addition, the main materials used in the method for comprehensively utilizing the fluorogypsum and the aluminum electrolyte are solid waste fluorogypsum and waste aluminum slag, which is beneficial to cost control.
According to the method for comprehensively utilizing the fluorogypsum and the aluminum electrolyte, disclosed by the invention, from the viewpoints of reducing the cost of raw materials and protecting the environment, the roasting agent is used as a modifier of the fluorogypsum-aluminum electrolyte mixed roasting recovery process, and valuable elements in the fluorogypsum and the aluminum electrolyte are extracted through the leaching process, the lithium extraction process and the purification process, so that the synergistic recycling of two solid wastes is realized.
It will be appreciated that the lithium ion solution produced in step (2) may be concentrated for use in the production of battery grade lithium salts.
It is understood that the aluminum electrolyte slag powder contains lithium element.
In order to ensure that the mixture is sufficiently subjected to mixed roasting, it is preferable that the particle size of the aluminum electrolyte slag powder is not less than 50 mesh. Further, the granularity of the aluminum electrolyte slag powder is not less than 200 meshes.
In order to enhance the firing effect, it is preferable that the average particle size of the mixture is less than 30 μm.
Preferably, the molar ratio of the fluoride ion, the calcium ion and the carbonate ion in the mixture is (1.5-2): 1-1.2): 1.2-1.5. The fluoride ion is F - The calcium ion is Ca 2+ The carbonate ion is CO 3 2- 。
In the roasting process, calcium sulfate in the fluorogypsum reacts with a roasting agent to obtain calcium carbonate and ammonium sulfate, the ammonium sulfate is further heated and decomposed to obtain ammonia gas, nitrogen gas, sulfur dioxide and steam, meanwhile, the calcium carbonate is heated and decomposed to generate calcium oxide and carbon dioxide, and the calcium oxide in the fluorogypsum, the calcium oxide generated by the heating and decomposition of the calcium carbonate, the calcium oxide in the aluminum electrolyte, cryolite in the aluminum electrolyte waste slag powder and AlF are heated and decomposed to generate calcium oxide and calcium oxide in the aluminum electrolyte waste slag powder 3 The LiF reacts to generate corresponding oxide and calcium fluoride, and when the roasting agent is ammonium carbonate, the specific chemical reaction is as follows:
CaSO 4 +(NH 4 ) 2 CO 3 ﹦(NH 4 ) 2 SO 4 +CaCO 3
3(NH 4 ) 2 SO 4 ＝4NH 3 ↑+N 2 ↑+3SO 2 ↑+6H 2 O↑
CaCO 3 ＝CaO+CO 2 ↑
3CaO+2AlF 3 ﹦Al 2 O 3 +3CaF 2
CaO+2LiF﹦Li 2 O+CaF 2
3CaO+Na 3 AlF 6 ﹦NaAlO 2 +Na 2 O+3CaF 2 。
calcination is to react calcium sulfate in the fluorogypsum with a calcination agent, and further decompose the calcium carbonate and ammonium sulfate obtained by heating, and it is necessary to decompose calcium oxide, cryolite, alF 3 The LiF reacts to form the corresponding oxides and calcium fluoride, and thus the firing temperature and firing time can be determined according to the temperature required for the above reaction. Preferably, the temperature of the calcination is 750 ℃ to 900 ℃. For example, the firing temperature is 800 ℃. The conversion of the waste residue at a higher firing temperature is also possible, but is not preferable because of high requirements for high temperature resistance of the equipment and high energy consumption.
Preferably, the roasting time is 1-2 hours. For example, the calcination time is 2 hours.
In order to avoid environmental pollution and to fully utilize resources, it is preferable to use dilute ammonia to absorb the exhaust gas generated by calcination. The waste gas generated by roasting is absorbed by dilute ammonia water, and then air is introduced to obtain an ammonium sulfate solution which can be used as a fertilizer raw material.
It can be understood that in the step (2), when the solid roasting product obtained in the step (1) is subjected to alkaline leaching by adopting alkaline liquor, the chemical reaction is as follows: al (Al) 2 O 3 +2OH - ＝2AlO 2 - +H 2 O；Li 2 O+H 2 O＝2LiOH；Na 2 O+H 2 O=2 NaOH. When the alkaline compound in the alkaline solution is sodium hydroxide, the alkaline immersed system contains CaF 2 Solids and solutions containing sodium ions, lithium ions and metaaluminate ions.
Preferably, in the step (2), the mass ratio of the solid roasting product to the alkali liquor is 1 (5-10).
Preferably, in the step (2), the alkaline leaching is performed at a temperature of 20-90 ℃. For example, in step (2), the alkaline leaching is carried out at a temperature of 60 ℃.
The purpose of the alkaline leaching is to react the aluminium oxide with the alkaline liquor to form an aluminate, whereby the pH and amount of alkaline liquor can be determined depending on whether the aluminium oxide is fully reactive or not, preferably in step (2) the pH of the alkaline liquor is between 10 and 12.
Preferably, in step (2), the lye consists essentially of water and an alkaline compound. In order to avoid introducing other impurities, preferably, the basic compound is sodium hydroxide and/or sodium carbonate.
It will be appreciated that in step (2), the solid obtained by solid-liquid separation has a CaF as the main component 2 And drying to obtain the regenerated fluorite. In the step (2), the main component of the liquid obtained by the solid-liquid separation is a solution containing sodium ions, lithium ions and metaaluminate ions.
It can be understood that when the adsorbent is used to perform adsorption treatment on lithium ions in the liquid obtained by solid-liquid separation, the adsorbent and the liquid obtained by solid-liquid separation can be mixed, then the solid-liquid separation is performed, the liquid obtained by solid-liquid separation is the liquid after adsorption treatment, and the solid obtained by solid-liquid separation is the adsorbent after adsorption treatment; or the liquid obtained by solid-liquid separation passes through an adsorption column containing an adsorbent, the adsorbent is the adsorbent after adsorption treatment after adsorbing lithium ions, and the liquid obtained by solid-liquid separation passes through the adsorption column and is the liquid after adsorption treatment.
Preferably, in step (2), the adsorbent is an ion sieve adsorbent. Further, in the step (2), the ion sieve type adsorbent is a manganese ion sieve.
Preferably, in step (2), the eluent used for the elution is water or an inorganic acid. Preferably, the mineral acid is dilute sulfuric acid. Preferably, the mass fraction of the dilute sulfuric acid is 5-30%. For example, the mass fraction of the dilute sulfuric acid is 10%.
Preferably, in the step (2), after the liquid after the adsorption treatment is mixed with hydrogen peroxide for reaction, solid-liquid separation is carried out, and the liquid obtained by the solid-liquid separation is the sodium aluminate solution.
It will be appreciated that in step (2), the main component of the liquid after the adsorption treatment isMixing the solution containing sodium ion, manganese ion and metaaluminate ion with hydrogen peroxide to obtain solid precipitate and sodium aluminate solution, wherein the main components of the solid precipitate are MnO (OH) and MnO 2 . The chemical reactions that occur are: mn (Mn) 2+ +H 2 O 2 +OH - ＝MnO(OH)↓+H 2 O，Mn 2+ +H 2 O 2 +2OH - ＝MnO 2 ↓+2H 2 O。
Preferably, in the step (2), the mass fraction of the hydrogen peroxide is 30-90%. The amount of hydrogen peroxide can be determined according to the amount of manganese ions in the liquid after the adsorption treatment. In the step (2), the ratio of the molar quantity of the hydrogen peroxide in the hydrogen peroxide to the molar quantity of the manganese ions in the liquid after the adsorption treatment is (1.05-1.2): 1. The manganese ions can be completely precipitated by adopting a little excessive hydrogen peroxide, and the excessive hydrogen peroxide can be decomposed into water and oxygen in alkali liquor without introducing impurities.
After the sodium aluminate solution is prepared, in order to further recycle the aluminum resource and the sodium resource, preferably, the method for comprehensively utilizing the fluorogypsum and the aluminum electrolyte further comprises the following steps: and (3) carrying out a mixing reaction on the sodium aluminate solution and carbon dioxide, carrying out solid-liquid separation, wherein the solid obtained by the solid-liquid separation is aluminum hydroxide, and concentrating and crystallizing the liquid obtained by the solid-liquid separation to obtain sodium carbonate. After the sodium carbonate is prepared, the sodium carbonate can be used for preparing alkali liquor for alkaline leaching or mixing the sodium carbonate with lithium ion solution to prepare lithium carbonate.
Drawings
FIG. 1 is a schematic process flow diagram of a method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
The method for comprehensively utilizing the fluorogypsum and the aluminum electrolyte in the embodiment, as shown in fig. 1, specifically comprises the following steps:
(1) Obtaining the CaSO in the fluorine gypsum waste residue of a certain HF production plant 4 94% by mass of CaF 2 The mass fraction of CaO is 2-3%, and the mass fraction of CaO is 1-2%;
obtaining waste aluminum electrolyte of an electrolytic aluminum plant, crushing and screening the waste aluminum electrolyte to obtain 50-mesh aluminum electrolyte waste slag powder, wherein Al in the aluminum electrolyte waste slag powder 3+ Is 14-20% of Na by mass + The mass fraction of F is 20-30 percent - The mass fraction of the catalyst is 40-50%, li + The mass fraction of CaO is 1-3%, and the mass fraction of CaO is 4-6%;
(2) Uniformly mixing 100g of aluminum electrolyte waste slag powder, 200g of fluorogypsum and 175g of ammonium carbonate, and grinding for 2 hours by a micro powder mill to obtain a mixture with the average granularity smaller than 30 mu m, wherein the molar ratio of fluorine ions, calcium ions and carbonate ions in the mixture is (1.5-2): (1.1-1.2): 1.3;
(3) Mixing and roasting the mixture obtained in the step (2) for 2 hours at 800 ℃ to obtain 173g of solid roasting product; simultaneously, absorbing tail gas generated by roasting by adopting dilute ammonia water, and simultaneously introducing air into liquid obtained by absorption to obtain an ammonium sulfate solution;
(4) Mixing the solid roasting product obtained in the step (3) with 1L of alkali liquor (the alkali liquor is prepared by mixing water and sodium hydroxide, and the pH value is 11), carrying out alkaline leaching at 60 ℃ for 2 hours, wherein the pH value of the alkali liquor is increased after the alkali liquor is added due to the fact that the solid roasting product contains lithium oxide and sodium oxide, but the pH value of the alkali liquor is reduced along with the reaction of hydroxide radicals in the alkali liquor and aluminum oxide, and in order to ensure that the aluminum oxide is completely converted into metaaluminate, when the pH value of a system is less than 12, adding the alkali liquor into the system to control the pH value of the system to be 12-13; after the alkaline leaching is finished, an alkaline leaching system with the pH value of 12-13 is obtained, and the alkaline leaching system is filtered to obtain filter residue A and filtrate A; calcining the filter residue A to obtain 110g of regenerated fluorite, and determining CaF in the regenerated fluorite 2 The content is 94%, and the regenerated fluorite also contains a small amount of MgF 2 And CaO.SiO 2 Impurities;
(5) Dynamically adsorbing lithium in the filtrate A by an adsorption column filled with excessive manganese ion sieves at room temperature, washing the manganese ion sieves after adsorbing the lithium by pure water, and eluting by dilute sulfuric acid with the mass fraction of 10%, wherein the eluent is lithium ion solution;
meanwhile, adding 10mL of hydrogen peroxide with the mass fraction of 90% (the ratio of the molar quantity of hydrogen peroxide in the hydrogen peroxide to the molar quantity of manganese ions in the liquid after the adsorption treatment is 1.2:1) into the filtrate A (lithium extraction mother liquor) after the adsorption treatment, stirring for 30min, then filtering to obtain solid which is insoluble impurities, and filtering to obtain liquid which is sodium aluminate solution (the content of other impurities except water and sodium aluminate in the sodium aluminate solution is lower than 1%, and the recovery rate of aluminum element is 92%); in order to further recycle aluminum resources and sodium resources, introducing carbon dioxide into a sodium aluminate solution to enable the sodium aluminate and the carbon dioxide to react to generate aluminum hydroxide and sodium carbonate, filtering after the reaction is finished to obtain 50.7g of aluminum hydroxide solid, and concentrating and crystallizing the liquid obtained by filtering to obtain sodium carbonate; after preparing sodium carbonate, the sodium carbonate can be used for preparing alkali liquor used for alkaline leaching or mixing the sodium carbonate with lithium ion solution to prepare lithium carbonate;
(6) And (3) heating and concentrating the lithium ion solution prepared in the step (5), cooling to obtain a concentrated solution (the mass fraction of lithium element in the concentrated solution is 20%), adding 20g of sodium carbonate into the concentrated solution, stirring at 20 ℃ until no precipitate is generated, filtering, and drying the solid obtained by filtering to obtain 13.7g of lithium carbonate product (the purity is 99.68%), namely, the total mass of the recovered lithium element is 2.6g.
Example 2
The method for comprehensively utilizing the fluorogypsum and the aluminum electrolyte in the embodiment specifically comprises the following steps:
(1) Uniformly mixing 560g of aluminum electrolyte waste slag powder, 1000g of fluorogypsum and 890g of ammonium carbonate, and grinding for 2 hours by a micro powder mill to obtain a mixture with the average granularity smaller than 30 mu m, wherein the molar ratio of fluorine ions, calcium ions and carbonate ions in the mixture is (1.6-2) 1:1.2; the aluminum electrolyte waste slag powder and the fluorine gypsum used in the method for comprehensively utilizing fluorine gypsum and aluminum electrolyte of the present embodiment are respectively the same as the aluminum electrolyte waste slag powder and the fluorine gypsum used in the method for comprehensively utilizing fluorine gypsum and aluminum electrolyte of the embodiment 1;
(2) Mixing and roasting the mixture obtained in the step (2) for 2 hours at 750 ℃ to obtain 945g of solid roasting product; simultaneously, absorbing tail gas generated by roasting by adopting dilute ammonia water, and simultaneously introducing air into liquid obtained by absorption to obtain an ammonium sulfate solution;
(3) Mixing the solid roasting product obtained in the step (3) with 6L of alkali liquor (the alkali liquor is prepared by mixing water and sodium hydroxide, and the pH value is 10), carrying out alkaline leaching at 20 ℃ for 2 hours, wherein the pH value of the alkali liquor is increased after the alkali liquor is added due to the fact that the solid roasting product contains lithium oxide and sodium oxide, but the pH value of the alkali liquor is reduced along with the reaction of hydroxide radicals in the alkali liquor and aluminum oxide, and in order to ensure that the aluminum oxide is completely converted into metaaluminate, when the pH value of a system is less than 12, adding the alkali liquor into the system to control the pH value of the system to be 12-13; after the alkaline leaching is finished, an alkaline leaching system with the pH value of 12-13 is obtained, and the alkaline leaching system is filtered to obtain filter residue A and filtrate A; calcining the filter residue A to obtain 576g of regenerated fluorite, and determining CaF in the regenerated fluorite 2 The content is 96%;
(4) Dynamically adsorbing lithium in the filtrate A by an adsorption column filled with excessive manganese ion sieves at room temperature, washing the manganese ion sieves after adsorbing the lithium by pure water, and eluting by dilute sulfuric acid with the mass fraction of 10%, wherein the eluent is lithium ion solution;
meanwhile, 150mL of hydrogen peroxide with the mass fraction of 30% (the ratio of the molar quantity of hydrogen peroxide in the hydrogen peroxide to the molar quantity of manganese ions in the liquid after the adsorption treatment is 1.05:1) is added into the filtrate A (lithium extraction mother liquor) after the adsorption treatment, stirring is carried out for 30min, then filtration is carried out, the obtained solid is insoluble impurities, and the obtained liquid is sodium aluminate solution (the content of other impurities except water and sodium aluminate in the sodium aluminate solution is lower than 1%, and the recovery rate of aluminum element is 85%);
(5) And (3) heating and concentrating the lithium ion solution prepared in the step (4), cooling to obtain a concentrated solution (the mass fraction of lithium element in the concentrated solution is 20%), adding 20g of sodium carbonate into the concentrated solution, stirring at 20 ℃ until no precipitate is generated, filtering, and drying the solid obtained by filtering to obtain 82.3g of lithium carbonate product (the purity is 99.73%), namely, the total mass of the recovered lithium element is 15.5g.
Example 3
The method for comprehensively utilizing the fluorogypsum and the aluminum electrolyte in the embodiment specifically comprises the following steps:
(1) Uniformly mixing 1000g of aluminum electrolyte waste slag powder, 2200g of fluorogypsum and 2000g of ammonium carbonate, and grinding for 2 hours by a micro powder mill to obtain a mixture with the average granularity smaller than 30 mu m, wherein the molar ratio of fluorine ions, calcium ions and carbonate ions in the mixture is (1.55-2) 1.2:1.5; the aluminum electrolyte waste slag powder and the fluorine gypsum used in the method for comprehensively utilizing fluorine gypsum and aluminum electrolyte of the present embodiment are respectively the same as the aluminum electrolyte waste slag powder and the fluorine gypsum used in the method for comprehensively utilizing fluorine gypsum and aluminum electrolyte of the embodiment 1;
(2) Mixing and roasting the mixture obtained in the step (2) for 1h at 900 ℃ to obtain 1870g of solid roasting product; meanwhile, absorbing tail gas generated by roasting by adopting dilute ammonia water to obtain an ammonium sulfate solution;
(3) Mixing the solid roasting product obtained in the step (3) with 10L of alkali liquor (the alkali liquor is prepared by mixing water and sodium hydroxide, and the pH value is 12), carrying out alkaline leaching at 20 ℃ for 2 hours, wherein the pH value of the alkali liquor is increased after the alkali liquor is added due to the fact that the solid roasting product contains lithium oxide and sodium oxide, but the pH value of the alkali liquor is reduced along with the reaction of hydroxide radicals in the alkali liquor and aluminum oxide, and in order to ensure that the aluminum oxide is completely converted into metaaluminate, when the pH value of a system is less than 12, adding the alkali liquor into the system to control the pH value of the system to be 12-13; filtering the alkaline leaching system after the alkaline leaching is finished to obtain filter residue A and filtrate A; calcining the filter residue A to obtain 1200g of regenerated fluorite, and determining CaF in the regenerated fluorite 2 The content is 90 percent;
(4) Dynamically adsorbing lithium in the filtrate A by an adsorption column filled with excessive manganese ion sieves at room temperature, washing the manganese ion sieves after adsorbing the lithium by pure water, and eluting by dilute sulfuric acid with the mass fraction of 10%, wherein the eluent is lithium ion solution;
meanwhile, adding 100mL of hydrogen peroxide with the mass fraction of 90% (the ratio of the molar quantity of hydrogen peroxide in the hydrogen peroxide to the molar quantity of manganese ions in the liquid after the adsorption treatment is 1.1:1) into the filtrate A (lithium extraction mother liquor) after the adsorption treatment, stirring for 30min, then filtering to obtain solid which is insoluble impurities, and filtering to obtain liquid which is sodium aluminate solution (the content of other impurities except water and sodium aluminate in the sodium aluminate solution is lower than 1%, and the recovery rate of aluminum element is 94%);
(5) And (3) heating and concentrating the lithium ion solution prepared in the step (4), cooling to obtain a concentrated solution (the mass fraction of lithium element in the concentrated solution is 20%), adding 20g of sodium carbonate into the concentrated solution, stirring at 20 ℃ until no precipitate is generated, filtering, and drying the solid obtained by filtering to obtain 153.3g of lithium carbonate product (the purity is 99.59%), namely, the total mass of recovered lithium element is 28.8g.
Experimental example
The lithium carbonate products prepared in examples 1-3 were tested using battery grade lithium carbonate industry standard YS/T582-2013, and the composition and impurity content of the lithium carbonate are shown in Table 1;
TABLE 1 composition and impurity content of lithium carbonate
As can be seen from table 1, the lithium carbonate prepared by the method for comprehensively utilizing the fluorogypsum and the aluminum electrolyte of the invention meets the industry standard of battery grade lithium carbonate.
Claims (10)
1. A method for comprehensively utilizing fluorogypsum and aluminum electrolyte is characterized by comprising the following steps:
(1) Roasting a mixture mainly composed of aluminum electrolyte waste slag powder, fluorogypsum and a roasting agent, wherein the roasting agent is ammonium carbonate;
(2) And (3) alkaline leaching is carried out on the solid roasting product obtained in the step (1) by adopting alkali liquor, solid-liquid separation is carried out, then, an adsorbent is adopted to carry out adsorption treatment on lithium ions in liquid obtained by the solid-liquid separation, then, the adsorbent after adsorption treatment is eluted to obtain a lithium ion solution, and meanwhile, the liquid after adsorption treatment and hydrogen peroxide are mixed to react to prepare an aluminate solution.
2. The method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to claim 1, wherein the molar ratio of fluoride ions, calcium ions and carbonate ions in the mixture is (1.5-2): (1-1.2): (1.2-1.5).
3. The method for the comprehensive utilization of fluorogypsum and aluminum electrolyte according to claim 1, wherein the average particle size of the mixture is less than 30 μm.
4. The method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to any one of claims 1-3, wherein the baking temperature is 750 ℃ to 900 ℃.
5. A method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to any one of claims 1 to 3, wherein the baking time is 1 to 2 hours.
6. The method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to claim 1, wherein in the step (2), the mass ratio of the solid calcined product to the alkali solution is 1 (5-10); the alkali liquor mainly comprises water and an alkaline compound; the alkaline compound is sodium hydroxide and/or sodium carbonate.
7. The method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to any one of claims 1-3 and 6, wherein in the step (2), the pH of the alkali solution is 10 to 12.
8. The method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to any one of claims 1-3 and 6, wherein in the step (2), the alkaline leaching is performed at a temperature of 20-90 ℃.
9. The method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to any one of claims 1-3 and 6, wherein in the step (2), the adsorbent is an ion sieve type adsorbent; the eluent adopted in the elution is water or inorganic acid.
10. The method for comprehensively utilizing fluorogypsum and aluminum electrolyte according to claim 9, wherein in the step (2), the ion sieve type adsorbent is a manganese ion sieve.
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