CN110240182B - Resourceful treatment method of lithium-rich aluminum electrolyte - Google Patents
Resourceful treatment method of lithium-rich aluminum electrolyte Download PDFInfo
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- CN110240182B CN110240182B CN201910609881.XA CN201910609881A CN110240182B CN 110240182 B CN110240182 B CN 110240182B CN 201910609881 A CN201910609881 A CN 201910609881A CN 110240182 B CN110240182 B CN 110240182B
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003792 electrolyte Substances 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 43
- 238000002386 leaching Methods 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 20
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 aluminum ions Chemical class 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 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 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 229910001610 cryolite Inorganic materials 0.000 description 17
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
-
- 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
- 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
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- 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
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Agronomy & Crop Science (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a resource treatment method of lithium-rich aluminum electrolyte, which comprises the steps of firstly, carrying out heat treatment on the lithium-rich aluminum electrolyte to be treated to obtain a product A; leaching the roasted product A in water by using water-soluble inorganic salt as a leaching agent, and filtering to obtain filter residue B and filtrate B; adding alkali or its water solution into the filtrate B, and removing aluminum ions in the filtrate B to obtain filtrate C; and adding water-soluble carbonate or a water solution thereof into the filtrate C to convert lithium ions in the filtrate C into lithium carbonate precipitate, and filtering to obtain lithium carbonate and filtrate D. The invention solves the technical problems that the content of rich lithium in surplus aluminum electrolyte is high and valuable metals cannot be effectively utilized in the aluminum electrolysis industry, improves the economic benefit and promotes the stable production of the aluminum electrolysis enterprise.
Description
Technical Field
The invention relates to a recycling treatment method of lithium-rich aluminum electrolyte, in particular to a recycling treatment method of acidic lithium-rich aluminum electrolyte, belonging to the technical field of metallurgical waste treatment.
Background
In recent years, some electrolytic aluminum enterprises in China face that lithium impurities contained in aluminum oxide raw materials are high and are continuously accumulated in aluminum electrolytes, so that the lithium content in the aluminum electrolytes is correspondingly and greatly improved. Generally, the enrichment amount of lithium salt is 1-3 wt% which is beneficial to reducing the primary crystal temperature of the aluminum electrolyte, the enrichment amount of lithium salt is more than 5wt% which affects the condition of the aluminum electrolytic cell to a certain extent, and the enrichment amount of lithium salt of some aluminum electrolysis enterprises even reaches 8-10 wt%, which causes low temperature of the aluminum electrolytic cell, reduced solubility of aluminum oxide, increased precipitation at the furnace bottom and great disadvantages to energy consumption and stable production. Generally, the lithium salt enrichment amount in the aluminum electrolyte is more than 3wt%, and the aluminum electrolyte can be regarded as a lithium-rich aluminum electrolyte.
Most aluminum electrolysis enterprises generally scoop out lithium-rich aluminum electrolyte, supplement low-lithium aluminum electrolyte and generate a large amount of surplus lithium-rich aluminum electrolyte, and at present, the resource is not paid attention to in China or is utilized due to immature technology. Most of them are still stored and piled up, and can not be effectively utilized.
In the prior art, the patent CN105293536A selects inorganic acid leaching in the treatment process, the patent CN105293536A selects a concentrated acid leaching mode at high temperature, and the patent CN105543504B selects a mode of firstly roasting pretreatment and then leaching at normal temperature. Overall, direct leaching of mineral acids is not efficient and typically requires pretreatment. In the leaching process, energy consumption is increased due to leaching at high temperature with inorganic acid, hydrogen fluoride gas is generated to corrode equipment, hydrofluoric acid generated by acid leaching at normal temperature also corrodes the equipment, a large amount of alkali is consumed to neutralize the inorganic acid before subsequent addition of carbonate to precipitate lithium, and economic benefit is low.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a method for recycling lithium-rich aluminum electrolyte, which can effectively recover useful elements or useful substances such as lithium element and reduce the processing cost.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the resource treatment method of the lithium-rich aluminum electrolyte comprises the following steps:
s1, carrying out heat treatment on the lithium-rich aluminum electrolyte to obtain a product A;
s2, leaching the product A obtained in the step S1 in water by using water-soluble inorganic salt as a leaching agent, and filtering to obtain filter residue B and filtrate B;
s3, adding alkali or an aqueous solution thereof into the filtrate B obtained in the step S2, and removing aluminum ions in the filtrate B to obtain a filtrate C;
s4, adding water-soluble carbonate or a water solution thereof into the filtrate C obtained in the step S3 to convert lithium ions in the filtrate C into lithium carbonate precipitate, and filtering to obtain lithium carbonate and a filtrate D; generally, the water-soluble carbonate can be slowly added until no precipitate is generated; preferably, wherein the carbonate is present in an amount sufficient to CO3 2-With Li in filtrate C+The molar ratio of (A) to (B) is 1-3: 1.
Further, before S1, the lithium-rich aluminum electrolyte to be treated is crushed and ground into lithium-rich aluminum electrolyte powder.
Further, the lithium-rich aluminum electrolyte is an acidic lithium-rich aluminum electrolyte.
Further, in S1, heat treatment is carried out for 1.5-3.5h under the conditions of 750-1100 ℃. Alternatively, the heat treatment method can also be performed by referring to the method in patent CN 105543504B.
Further, in S1, the heat treatment adjusts the molecular ratio of the lithium-rich aluminum electrolyte to 2.8 to 3.8.
In general, the ratio of the number of molecules of sodium fluoride to the number of molecules of aluminum fluoride is understood as the molecular ratio.
Further, in S2, crushing the product A obtained in S1, adding water for size mixing to obtain slurry; and then, adding water-soluble inorganic salt into the slurry, stirring for 1-3h, and filtering to obtain filter residue B and filtrate B. Preferably, after the crushing treatment, sieving the crushed materials by a sieve of 80 to 300 meshes, and taking undersize materials to prepare slurry; further, the oversize can be further crushed.
Further, the solid-to-liquid ratio of the slurry is 1: 5-25.
Further, in S2, the water-soluble inorganic salt is used in an amount satisfying: the molar amount of the cation in the water-soluble inorganic salt is equal to the amount of Li in the product A+、Ca2+、Na+In a ratio of 4 to 8:9, generally 5 to 7:9, preferably 5.5 to 6.5: 9.
preferably, in the leaching treatment in S2, the temperature of the reaction system is 20 to 120 ℃.
Further, in S2, the water-soluble inorganic salt includes one or more of sodium sulfate, sodium nitrate, sodium chloride, aluminum sulfate, aluminum nitrate, aluminum chloride, potassium sulfate, potassium nitrate, and potassium chloride.
Further, in S3, the alkali includes sodium hydroxide and/or potassium hydroxide.
Further, in S3, a base or an aqueous solution thereof is added to the filtrate B obtained in S2, the pH of the solution is controlled to 5 to 8, preferably 6 to 7, and aluminum ions in the filtrate B are removed to obtain a filtrate C. Controlling the appropriate pH to form stable Al (OH)3Precipitating and further removing aluminum ions in the filtrate B.
Further, in S4, the water-soluble carbonate includes sodium carbonate and/or potassium carbonate.
Further, the method also comprises the steps of evaporating and crystallizing the filtrate D.
S1, the main component of the lithium-rich aluminum electrolyte to be treated comprises cryolite (Na)3AlF6) Lithium sodium cryolite (LiNa)2AlF6) Sodium lithium cryolite (Na)2LiAlF6) Cryolite (NaF. AlF)3) Calcium fluoride (CaF)2). The main component of the heat-treated product A comprises cryolite (Na)3AlF6) Lithium fluoride (LiF), cryolite (NaF. AlF)3) Calcium fluoride (CaF)2)。
In S2, the product A may be slurried with water and then a water-soluble inorganic salt or a saturated solution thereof may be added. The filter residue B mainly comprises cryolite (Na)3AlF6) Cryolite (NaF. AlF)3) Calcium fluoride (CaF)2) The product can be returned to the aluminum electrolytic cell for service after adjusting the molecular ratio according to the condition
In S3, the main reaction formula of the impurity removal process is as follows:
Al3++OH-=Al(OH)3↓
in S4, the reaction formula of the lithium deposition process is:
Li++CO3 2-=Li2CO3↓
FIG. 1 is a schematic flow diagram of the present invention. The method can recover lithium element from the aluminum electrolyte and realize the recycling of cryolite and other substances, has wide application range, and is particularly suitable for domestic acid aluminum electrolyte. Wherein, the existing form of lithium in the acid aluminum electrolyte takes lithium sodium cryolite and sodium lithium cryolite as main components. By adopting the working procedures of heat treatment, inorganic salt leaching, impurity removal, precipitation and the like, the lithium element is recovered, and substances such as cryolite, calcium fluoride and the like are recovered, so that resource utilization is realized.
Compared with the prior art, the invention has the following beneficial effects:
(1) aiming at the main existing phase of lithium salt in the acidic aluminum electrolyte, which is a stable and extremely insoluble substance such as lithium sodium cryolite and sodium lithium cryolite, the method carries out heat treatment, the lithium-containing product is lithium fluoride which is easier to leach than the lithium sodium cryolite and the sodium lithium cryolite, the preparation is made for subsequent leaching, other impurities are not introduced in the process, only the molecular ratio is changed, toxic gases such as hydrogen fluoride and the like are not generated, and the operation is simple.
(2) After heat treatment, water-soluble inorganic salt is directly used for leaching treatment, compared with the prior art such as patent CN105293536 and the like, the leaching condition is milder, the energy consumption increased by the leaching of inorganic acid at high temperature can be avoided, hydrogen fluoride gas is generated, and a large amount of alkali is added before the subsequent lithium precipitation to neutralize the inorganic acid, so that the treatment process of the treatment method is safer and more environment-friendly, the F element is not lost, the acid and alkali consumption is less, the alkali consumption can be reduced by more than 3 times, and the treatment cost is lower. The cryolite is filtered and then properly adjusted in proportion and can be returned to the aluminum electrolysis cell for use.
(3) The whole process of the subsequent wet-method lithium extraction can be completed at normal temperature and normal pressure, and the method has low cost and high benefit.
(4) The invention breaks through the traditional acidic leaching means, provides a new idea for the resource treatment of the waste aluminum electrolyte, solves the technical problem that valuable metals cannot be effectively utilized, improves the economic benefit and promotes the stable production of electrolytic aluminum enterprises.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
FIG. 2 is an XRD spectrum of acid lithium-rich aluminum electrolyte heat treatment slag of a certain electrolytic aluminum plant.
FIG. 3 is an XRD pattern of acid lithium-rich aluminum electrolyte leaching residue of a certain electrolytic aluminum plant.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The method for recovering lithium from the acid lithium-rich potassium electrolyte specifically comprises the following steps:
step 1: crushing 100g of acid lithium-rich aluminum electrolyte, carrying out heat treatment for 2h at 960 ℃ to ensure that the material molecular ratio is 3.6, cooling the obtained product A to room temperature, and crushing the product A.
Step 2: adding the crushed product A into water to prepare slurry, wherein the solid-to-liquid ratio is 1:15, adding 40g of aluminum nitrate into the mixture in a constant-temperature magnetic stirrer at the temperature of 50 ℃ to leach for 2 hours, and filtering to obtain filtrate B and filtrate B.
And step 3: and adding sodium hydroxide into the filtrate B to adjust the pH value to 7, reacting for 10min, and filtering aluminum hydroxide to obtain filtrate C.
And 4, step 4: to the filtrate C was added 15g of sodium carbonate, reacted for 20min, and then filtered to obtain 12.37g of lithium carbonate and filtrate D.
And 5: concentrating and enriching the filtrate D to obtain sodium nitrate.
Example 2
The method for recovering lithium from the acid lithium-rich aluminum electrolyte specifically comprises the following steps:
step 1: crushing 100g of acid lithium-rich aluminum electrolyte, carrying out heat treatment for 2h at 960 ℃ to ensure that the material molecular ratio is 3.6, obtaining a product A, cooling to room temperature, and crushing the product A.
Step 2: adding water into the crushed roasted product A to prepare slurry, wherein the solid-to-liquid ratio is 1:10, adding 20g of sodium sulfate and 25g of aluminum sulfate octadecahydrate into a constant-temperature magnetic stirrer at the temperature of 50 ℃, leaching for 2 hours, and filtering to obtain filtrate B and filter residue B.
And step 3: and adding sodium hydroxide into the filtrate B to adjust the pH value to 7, reacting for 10min, and filtering aluminum hydroxide to obtain filtrate C.
And 4, step 4: 17g of sodium carbonate was added to the filtrate C, and after reacting for 20min, filtration was carried out to obtain filtrate D and 10.25g of lithium carbonate.
And 5: concentrating and enriching the filtrate D to obtain sodium sulfate.
The above description is only an embodiment of the present invention, and not all embodiments, and those skilled in the art will read the present invention and take any equivalent changes to the technical solution of the present invention, and all embodiments are within the scope of the claims of the present invention.
Claims (6)
1. The resource treatment method of the lithium-rich aluminum electrolyte is characterized by comprising the following steps:
s1, carrying out heat treatment on the acid lithium-rich aluminum electrolyte to obtain a product A;
wherein the molecular ratio of the product A is 3.6-3.8;
s2, leaching the product A obtained in the step S1 in water by using water-soluble inorganic salt as a leaching agent, and filtering to obtain filter residue B and filtrate B;
wherein the water-soluble inorganic salt is one or more of sodium sulfate, sodium nitrate, sodium chloride, aluminum sulfate, aluminum nitrate, aluminum chloride, potassium sulfate, potassium nitrate and potassium chloride;
s3, adding alkali or an aqueous solution thereof into the filtrate B obtained in the step S2, and removing aluminum ions in the filtrate B to obtain a filtrate C;
s4, adding water-soluble carbonate or a water solution thereof into the filtrate C obtained in the step S3 to convert lithium ions in the filtrate C into lithium carbonate, precipitating the lithium carbonate, and filtering to obtain lithium carbonate and filtrate D.
2. The resource processing method according to claim 1, wherein in S2, the product A obtained in S1 is crushed, and water is added to prepare slurry; and then, adding water-soluble inorganic salt into the slurry, stirring for 1-3h, and filtering to obtain filter residue B and filtrate B.
3. The method according to claim 1, wherein the water-soluble inorganic salt is used in an amount satisfying, in S2: the molar amount of the cation in the water-soluble inorganic salt and the heat-treated productLi in A+、Ca2+、Na+The ratio of the sum of the molar amounts of (a) to (b) is 4-8: 9.
4. The resource treatment method according to claim 1, wherein in S3, the alkali comprises sodium hydroxide and/or potassium hydroxide.
5. The recycling method according to claim 1, wherein in S4, the water-soluble carbonate includes sodium carbonate and/or potassium carbonate.
6. A resource processing method according to any one of claims 1 to 5, characterized by further comprising the step of evaporating and crystallizing the filtrate D.
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| CN112342386B (en) * | 2020-10-19 | 2021-07-20 | 东北大学 | Resource treatment method for complex aluminum electrolyte |
| CN112919507B (en) * | 2021-01-21 | 2023-04-07 | 郑州大学 | Method for extracting lithium salt from aluminum electrolyte |
| CN113684369B (en) * | 2021-09-16 | 2022-06-14 | 中南大学 | Method for treating waste industrial lithium-containing aluminum electrolyte |
| CN114457237B (en) * | 2022-01-27 | 2023-05-26 | 东北大学 | Method for recovering lithium from acidic leaching solution of aluminum electrolyte |
| CN114804171A (en) * | 2022-04-29 | 2022-07-29 | 郑州大学 | Method for preparing aluminum fluoride and lithium carbonate by lithium-containing aluminum electrolyte |
| CN115216630B (en) * | 2022-07-19 | 2023-11-14 | 中南大学 | Recycling treatment method of waste lithium-containing aluminum electrolyte |
| CN115198111B (en) * | 2022-07-19 | 2023-06-13 | 中南大学 | Lithium extraction method of lithium-containing waste aluminum electrolyte |
| CN115558801A (en) * | 2022-10-25 | 2023-01-03 | 白东华 | Processing device and processing technology for lithium removal, purification and lithium recovery of aluminum electrolyte |
| CN115818675B (en) * | 2022-12-07 | 2024-01-23 | 湖南国重智能科技有限公司 | Comprehensive utilization method of lithium-aluminum-containing waste electrolyte |
| CN116334410A (en) * | 2023-03-29 | 2023-06-27 | 江苏大学 | Method for separating lithium from lithium-containing electrolyte waste residues in aluminum electrolysis |
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