CN118047409A - Method for recycling aluminum electrolysis solid waste by using soluble calcium salt - Google Patents
Method for recycling aluminum electrolysis solid waste by using soluble calcium salt Download PDFInfo
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- CN118047409A CN118047409A CN202410074511.1A CN202410074511A CN118047409A CN 118047409 A CN118047409 A CN 118047409A CN 202410074511 A CN202410074511 A CN 202410074511A CN 118047409 A CN118047409 A CN 118047409A
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- filtrate
- solid waste
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- 238000000034 method Methods 0.000 title claims abstract description 77
- 159000000007 calcium salts Chemical class 0.000 title claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 38
- 239000002910 solid waste Substances 0.000 title claims abstract description 28
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 18
- 238000004064 recycling Methods 0.000 title abstract description 7
- 238000002386 leaching Methods 0.000 claims abstract description 74
- 239000000706 filtrate Substances 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 21
- 239000002699 waste material Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims description 7
- 238000004131 Bayer process Methods 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 3
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910020826 NaAlF6 Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000004281 calcium formate Substances 0.000 claims description 3
- 229940044172 calcium formate Drugs 0.000 claims description 3
- 235000019255 calcium formate Nutrition 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 239000004330 calcium propionate Substances 0.000 claims description 3
- 235000010331 calcium propionate Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910001610 cryolite Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 18
- 238000011084 recovery Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000009466 transformation Effects 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
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recycling aluminum electrolysis solid waste by using soluble calcium salt. A method for recovering aluminum electrolysis solid waste with a soluble calcium salt comprising: s1, screening solid waste; s2, mixing soluble calcium salt and water to prepare first slurry; s3, mixing the first powder and the first slurry, leaching and filtering to obtain a first filtrate and a first filter residue; s4, carrying out acid leaching on the first filter residue, and filtering to obtain a second filtrate and a second filter residue, wherein the second filter residue is calcium fluoride; s5, evaporating the second filtrate to obtain aluminum salt; s6, evaporating and drying the first filtrate to obtain alkali mainly containing sodium hydroxide.
Description
Technical Field
The invention relates to the technical field of extraction and recovery of aluminum electrolyte, in particular to a method for recovering aluminum electrolysis solid waste by using soluble calcium salt.
Background
The increasing development of the world industry is accompanied by a growing demand for aluminium materials. Currently, the main process for producing aluminum still relies on electrolytic processes. Thus, the production of aluminum is expanded and simultaneously the great output of waste electrolyte generated by aluminum production is accompanied. The accumulation of waste electrolytes not only causes a great amount of empty consumption of land area, but also causes great harm to the environment. Therefore, an environment-friendly method for recycling the aluminum electrolyte is urgently needed.
Different recovery methods have been developed for different elements in waste electrolytes, but most focus on wet strong acid and strong base leaching. The Chinese patent CN108569711A proposes a method for leaching elements in waste electrolyte by using high-concentration sulfuric acid at high temperature. Removing calcium from the leached filtrate, and extracting lithium by adding alkaline salt. The method can change Li element in the electrolyte into soluble lithium salt by utilizing strong acid leaching, thereby achieving the purpose of extracting lithium. However, the method only focuses on the Li element, and the Al element is partially dissolved in the strong acid leaching process, so that high-value element loss is caused. And the vast majority of Li exists in the electrolyte in China as Li 2NaAlF6 instead of free LiF. Therefore, the leaching rate is lower when the single strong acid is dissolved. Meanwhile, a large amount of F element in the electrolyte can be converted into harmful HF in the acid leaching process, so that high-value F element is lost, and the environment and the operation are greatly damaged.
The Chinese patent CN115216630A discloses a process of extracting lithium by multi-stage leaching. Firstly, mixing electrolyte with NaOH, KOH, ca (OH) 2 and the like, leaching by a wet method, then adding the same reactants as the above-mentioned NaOH, KOH and the like again for secondary leaching, and adding sodium carbonate into the leached filtrate for extracting lithium. The leached slag is a mixture of fluorite powder and calcium aluminate. And the filtrate after lithium extraction is converted into an aqueous mixture of aluminium and calcium salts after evaporation. Although this method avoids the hazards of HF gas, it is still mainly focused on the recovery of lithium element, and the remaining elements in the electrolyte are not effectively recovered. Wherein a part of Al is converted into calcium aluminate and doped into the main phase fluorite powder of calcium, so that the obtained product has extremely low taste and no high value. And the other part of the Al enters the filtrate to be converted into a mixed aqueous mixture together with the calcium salt, and the mixture cannot be further used. So that the recovery level for the electrolyte as a whole is low. And the two sections of the leaching process need to use the same reactant for leaching, all materials cannot be recycled in the whole process, the process is complex, the material utilization level is low, and the secondary hazardous waste production level is high.
Chinese patent CN115198111a discloses a method for recovering Li from waste electrolyte by phase transformation using high temperature calcination. Mixing electrolyte with MgCl 2、BaCl2、Mg(NO3)2、CaSO4 and the like, roasting at 850-1200 ℃, converting Li into soluble acidic salt, and extracting lithium by combining a water leaching process. The process has the advantages of harsh conditions, extremely high roasting temperature and high energy consumption, the acid salt roasting adopted by the process has extremely harsh corrosion resistance to equipment, and the leaching solution after leaching lithium by water is not treated, so that secondary dangerous waste is caused.
Chinese patent CN116692917A discloses a resource utilization method of lithium-containing waste aluminum electrolyte, which mainly aims at recycling of lithium-containing electrolyte in the aluminum electrolysis production process, and utilizes an alkaline leaching method to recycle lithium from waste lithium-containing raw materials. However, the used leaching solution has quite complex ion components and contains a large amount of sulfate radicals and calcium ions, so that after a plurality of production cycles are carried out, a large amount of impurity ions are enriched, the cross influence among the ions is difficult to control, and the product quality is influenced.
From the above, it is known that a large amount of F element in the electrolyte is converted into harmful HF by acid leaching, which not only causes loss of high-value F element, but also causes great harm to environment and operation; the method of adding high-temperature calcination of calcium salt can cause that Al is difficult to separate, so that the purity is low, and the industrialized popularization is seriously influenced; the recovery by high temperature calcination is energy-consuming, the process is strictly regulated, and the acid salt calcination is liable to cause corrosion to equipment, so it is very important to develop a method for recovering aluminum electrolysis solid waste by using soluble calcium salt.
Disclosure of Invention
The invention aims to solve the technical problems that: the existing electrolyte recovery method can only recover lithium elements in the electrolyte, but omits Na with higher content in the electrolyte, and can generate stimulating gases such as HF and a large amount of waste materials, so that environmental pollution is caused, and secondary waste materials are generated, so that energy consumption is increased.
To solve the above technical problems, embodiments of the present disclosure provide a method for recovering aluminum electrolysis solid waste using a soluble calcium salt, comprising:
s1, crushing the solid waste, and screening out a part with the granularity less than or equal to 200 meshes to prepare first powder;
s2, mixing soluble calcium salt with water to prepare first slurry;
S3, uniformly mixing the first powder and the first slurry for leaching, controlling the pH value of the reaction, and filtering after the reaction is finished to obtain a first filtrate and a first filter residue;
s4, carrying out acid leaching on the first filter residue, filtering to obtain second filter residue and second filtrate, drying the second filtrate to obtain aluminum salt, and drying the second filter residue to obtain calcium fluoride;
s5, evaporating and drying the first filtrate to obtain sodium hydroxide containing trace potassium hydroxide.
In some embodiments, the method for recycling waste aluminum electrolyte by using soluble calcium salt as described above, wherein the solid waste in S1 comprises one or more of waste aluminum electrolyte, furnace bottom precipitate and anode coating, and the solid waste comprises one or more of Na3AlF6、Na5Al3F14、K2NaAlF6、LiNa2AlF6 and LiF, wherein the solid waste comprises 0-5% by mass of Li, 5-30% by mass of Na, 5-30% by mass of Al, and 5-60% by mass of F.
In some embodiments, the aforementioned method for recovering spent aluminum electrolyte from soluble calcium salt, wherein the soluble calcium salt in S2 comprises: one or more of calcium oxide, calcium hydroxide, calcium formate and calcium propionate.
In some embodiments, the aforementioned method for recovering waste aluminum electrolyte from soluble calcium salt, wherein the mass ratio of soluble calcium salt to water in S2 is 1 (1-10).
In some embodiments, the specific conditions of the reaction in S3 are that the liquid-solid ratio is 5-60, the temperature is 20-200 ℃, the time is 0.5-8h, the reaction pH is 9-14, and the reaction pressure is 0.1Mpa-15Mpa.
In some embodiments, the specific conditions of the acid leaching reaction in S4 are that the liquid-solid ratio is 1-20, the temperature is 20-220 ℃, the time is 0.5-5h, the pressure is 0.1Mpa-15Mpa, wherein the acid leaching solution is any one of hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the acid leaching solution is 0.1-10mol/L.
In some embodiments, in the method for recovering waste aluminum electrolyte by using the soluble calcium salt, if the content of Ca ions in the second filtrate exceeds 0.5g/L in S4, soluble carbonate is added to the second filtrate and filtered to obtain calcium carbonate precipitate, so as to remove Ca ions in the second filtrate;
wherein the soluble carbonate comprises: one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, ammonium carbonate and ammonium bicarbonate.
In some embodiments, the method for recovering waste aluminum electrolyte from soluble calcium salt, wherein before evaporating and drying the first filtrate in S6, if the content of Ca ions in the first filtrate exceeds 0.5g/L, soluble carbonate is added and filtering is performed to remove Ca ions in the first filtrate, and if the content of Li ions in the first filtrate exceeds 0.5g/L, soluble carbonate is continuously added and filtering is performed to remove Li ions in the first filtrate.
In some embodiments, the aforementioned method for recovering spent aluminum electrolyte from soluble calcium salt, wherein the first filter residue in S3 may further be used in S3 as a solvent of the bayer process after removal of Ca ions and Li ions to prepare alumina by the bayer process.
Through the technical scheme, the method for recycling the aluminum electrolysis solid waste by using the soluble calcium salt is safe to operate and environment-friendly, and HF gas is not generated in the whole process. Compared with the materials proposed by most of the patents at present, the method has wider range in terms of the object to be treated, and is applicable to most of waste materials such as waste electrolyte (containing lithium or not) generated in the electrolysis process, anode covering material, furnace bottom sediment and the like. In terms of recovery, the method aims to prepare Na rich in solid waste into alkali with high industrial demand and Al into aluminum salt with high added value, wherein lithium is extracted if lithium is contained in electrolyte. From the aspect of process flow, the method has the advantages of simple flow, no need of high-temperature roasting, no need of leaching with strong acid and strong alkali, no generation of irritant toxic gas in the reaction process, no generation of secondary dangerous waste, and simple ion components of leaching liquid, no need of considering the cross influence of complex ions, high product purity and high utilization efficiency of the process flow on materials, and all generated filter residues and filter liquor are made into products or recycled.
Drawings
FIG. 1 is an experimental flow chart of a method for recovering aluminum electrolysis solid waste with soluble calcium salts disclosed in the examples of the present disclosure;
Figure 2 XRD of leached residue after acid leaching in example 1;
Figure 3 XRD of solid product of precipitated lithium in example 1.
Detailed Description
The drying in the embodiment of the invention is carried out for 12 hours at 90 ℃. Evaporation was at 100 ℃ until a solid precipitated.
The present invention will be described in detail with reference to examples.
Example 1
S1, taking waste furnace bottom sediment (23.48 wt% of Na, 15.40wt% of Al, 55.24wt% of F, 2.27wt% of K, 2.28wt% of Li and 2.01wt% of Ca) of an aluminum factory, crushing an aluminum electrolyte, and screening out a part with granularity less than or equal to 200 meshes to prepare first powder;
S2, weighing 40g of calcium oxide, adding 2L of water, and stirring to prepare a first slurry;
S3, weighing 20g of first powder, uniformly mixing the first powder with the first slurry according to a liquid-solid ratio of 50, leaching the mixture for 3 hours at a temperature of 90 ℃, and controlling the pH value to be 11 in the leaching process to obtain first filtrate and first filter residue, wherein 31.56g of first filter residue;
S4, carrying out acid leaching on the first filter residue for 0.5h by using 3mol/L nitric acid at 50 ℃ under the condition of a liquid-solid ratio of 4 to obtain second filter residue and second filtrate, drying the second filter residue to obtain 22.58g of calcium fluoride, detecting the F content of 49.12%, evaporating and drying the second filtrate to obtain 34.54g of solid, and detecting the Al content of 8.81%;
FIG. 2 is XRD of the filter residue after acid leaching;
S5, adding 140ml of 3mol/L sodium carbonate into the first filtrate in the step S3, reacting for 1h at 20 ℃, filtering after the reaction to obtain a third filtrate and a third filter residue, and drying the third filter residue to obtain 41.72g of calcium carbonate;
S6, evaporating the third filtrate in the step S5 until the Li content in the third filtrate is more than 10g/L, adding 65ml of 0.5mol/L sodium carbonate solution according to the Li +/CO3 2- mol ratio of 2, filtering after the reaction to obtain a fourth filtrate and a fourth filter residue, drying the fourth filter residue to obtain 2.38g of lithium carbonate, and detecting the lithium content in the fourth filter residue to be 17.98%;
wherein, figure 3 is XRD of lithium carbonate product;
S7, evaporating and drying the fourth filtrate remained in the S6 to obtain 26.77g of mixed solid of sodium hydroxide and potassium hydroxide, and detecting the Na content 94.57% and the K content to be 1.68%.
The whole procedure was 99.61% for F, 93.89% for Li, 95.85% for Na (Na introduced during S6 and S7 removal), 99.06% for K and 98.79% for Al.
Example 2
S1, crushing aluminum electrolyte (25.48 wt% of Na, 13.50wt% of Al, 57.14wt% of F, 2.23wt% of K and 2.01wt% of Ca), and screening out a part with the granularity less than or equal to 200 meshes to prepare first powder;
S2, weighing 40g of calcium oxide, adding 1.8L of water, and stirring to prepare a first slurry;
s3, weighing 20g of first powder, uniformly mixing the first powder with the first slurry according to a liquid-solid ratio of 30, leaching for 4 hours at the temperature of 80 ℃, and controlling the pH value to be 12 in the leaching process to obtain first filtrate and first filter residue, wherein 30.78g of first filter residue;
S4, leaching the first filter residue for 4 hours by using 5mol/L sodium hydroxide under the action of a liquid-solid ratio of 5 at 100 ℃ to obtain second filter residue and second filtrate, drying the second filter residue to obtain 22.37g of calcium fluoride, detecting F content 48.72% in the second filter residue, adding seed crystal into the second filtrate to obtain 5.94g of aluminum oxide, detecting that the Al content is 46.47%, and repeatedly applying the rest of the second filtrate to the next alkaline leaching process (Bayer process);
s5 53mL of the second filtrate remaining in S4 was applied to the S4 alkaline leaching process (Bayer Process)
The overall flow was 98.32% for F, 98.44% for Na, 97.82% for K and 89.62% for Al.
Example 3
The procedure was as in example 1, except that:
the material used in S1 was an anode coating material, (Na: 13.8wt%, al:26.8wt%, F:25.3wt%, K:1.50wt%, li:1.39wt%, ca:1.02 wt%)
The soluble calcium salt used in S2 is calcium chloride, and the mass ratio of the first powder to the soluble calcium salt is 1:10;
S3, the liquid-solid ratio in the leaching process is 60, the leaching temperature is 200 ℃, the leaching time is 5h, and the pH value is controlled to be 9;
S4, in the acid leaching process, the liquid-solid ratio is 1, the leaching temperature is 90 ℃, and the leaching time is 5 hours;
S5, adding 3mol/L sodium carbonate into the first filtrate in the step S3, wherein the reaction temperature is 60 ℃, and the reaction time is 2 hours;
the overall flow was 99.32% for F, 96.65% for Li, 96.63% for Na (Na introduced during S6 and S7 removal), 99.24% for K and 88.71% for Al.
Example 4
The procedure was as in example 1, except that:
The mass ratio of the first powder to the soluble calcium salt in the S2 is 1:3;
s3, the liquid-solid ratio in the leaching process is 40, the leaching temperature is 90 ℃, the leaching time is 1h, and the pH value is controlled to be 10;
s5, adding 2mol/L potassium carbonate into the first filtrate in the step S3, wherein the reaction temperature is 40 ℃ and the reaction time is 1h;
the overall flow was 98.46% for F, 92.08% for Li, 93.11% for Na, 97.94% for K (K introduced during S6 and S7 removal) and 90.16% for Al.
Example 5
The procedure was as in example 1, except that:
The soluble calcium salt used in S2 is calcium hydroxide, and the mass ratio of the first powder to the soluble calcium salt is 1:7;
S3, the liquid-solid ratio in the leaching process is 5, the leaching temperature is 110 ℃, the leaching time is 2h, and the pH value is controlled to be 10.5;
in the S4 acid leaching process, the liquid-solid ratio is 10, the leaching temperature is 55 ℃, and the leaching time is 2.5 hours;
S5, adding 4mol/L ammonium carbonate into the first filtrate in the step S3, wherein the reaction temperature is 50 ℃, and the reaction time is 1h;
The overall flow was 99.51% for F, 94.09% for Li, 95.88% for Na, 98.98% for K and 88.81% for Al.
Example 6
The procedure was as in example 1, except that:
the mass ratio of the first powder to the soluble calcium salt in the S2 is 1:6;
s3, the liquid-solid ratio in the leaching process is 60, the leaching temperature is 60 ℃, the leaching time is 2h, and the pH value is controlled to be 9;
in the S4 acid leaching process, the liquid-solid ratio is 14, the leaching temperature is 55 ℃, and the leaching time is 2.5 hours;
s5, adding 8mol/L ammonium bicarbonate into the first filtrate in the step S3, wherein the reaction temperature is 40 ℃ and the reaction time is 2 hours;
the overall flow was 99.02% for F, 94.08% for Li, 94.98% for Na, 98.63% for K and 89.06% for Al.
Example 7
The procedure was as in example 1, except that:
The soluble calcium salt used in S2 is calcium formate, and the mass ratio of the first powder to the soluble calcium salt is 1:2;
s3, the liquid-solid ratio in the leaching process is 50, the leaching temperature is 20 ℃, the leaching time is 3h, and the pH value is controlled at 12;
in the S4 acid leaching process, the liquid-solid ratio is 5:1, the leaching temperature is 20 ℃, and the leaching time is 4 hours;
s5, adding 4mol/L sodium carbonate into the first filtrate in the step S3, wherein the reaction temperature is 20 ℃ and the reaction time is 1h;
The overall flow was 97.32% for F, 90.79% for Li, 91.03% for Na (Na introduced during decalcification and lithium extraction), 93.56% for K, and 91.70% for Al.
Example 8
The soluble calcium salt used in S2 is calcium propionate, and the mass ratio of the first powder to the soluble calcium salt is 1:1;
s3, the liquid-solid ratio in the leaching process is 50, the leaching temperature is 90 ℃, the leaching time is 8 hours, and the pH value is controlled at 12;
In the S4 acid leaching process, the liquid-solid ratio is 1:10, the leaching temperature is 30 ℃, and the leaching time is 5 hours;
s5, adding 2mol/L ammonium carbonate into the first filtrate in the step S3, wherein the reaction temperature is 30 ℃, and the reaction time is 3 hours;
The overall flow was 95.02% for F, 93.28% for Li, 93.22% for Na, 96.63% for K and 90.09% for Al.
The foregoing examples are set forth in order to provide a more thorough description of the present application, and are not intended to limit the scope of the application, as those skilled in the art will readily appreciate that modifications of the various equivalent forms of the application are within the scope of the application as defined in the appended claims.
Claims (9)
1. A method for recovering aluminum electrolysis solid waste using a soluble calcium salt, characterized by: the method comprises the following steps:
s1, crushing the solid waste, and screening out a part with the granularity less than or equal to 200 meshes to prepare first powder;
s2, mixing soluble calcium salt with water to prepare first slurry;
S3, uniformly mixing the first powder with the first slurry for leaching, controlling the pH value of the reaction, and filtering after the reaction is finished to obtain a first filtrate and a first filter residue;
s4, carrying out acid leaching on the first filter residue and filtering to obtain a second filter residue and a second filtrate, drying the second filtrate to obtain aluminum salt, and drying the second filter residue to obtain calcium fluoride;
S5, evaporating and drying the first filtrate to obtain sodium hydroxide containing trace potassium hydroxide.
2. The method for recovering solid waste from aluminum electrolysis according to claim 1, wherein the solid waste in S1 comprises one or more of a waste aluminum electrolyte, a hearth deposit and an anode covering material, and the solid waste has a mass ratio of Li of 0 to 5%, a mass ratio of Na of 5 to 30%, a mass ratio of Al of 5 to 30%, a mass ratio of F of 5 to 60%, and a phase of the solid waste comprises one or more of Na3AlF6、Na5Al3F14、K2NaAlF6、LiNa2AlF6、Al2O3 and LiF.
3. A method for recovering aluminum electrolysis solid waste with soluble calcium salt according to claim 1, wherein the soluble calcium salt in S2 comprises: one or more of calcium oxide, calcium hydroxide, calcium formate and calcium propionate.
4. A method for recovering aluminum electrolysis solid waste using a soluble calcium salt according to claim 1, wherein the mass ratio of the soluble calcium salt to water in S2 is 1 (1-10).
5. The method for recovering solid waste from aluminum electrolysis according to claim 1, wherein the specific conditions of the reaction in S3 are that the liquid-solid ratio is 5-60, the temperature is 20-200 ℃, the time is 0.5-8h, the pH of the reaction is 9-14, and the pressure of the reaction is 0.1Mpa-15Mpa.
6. The method for recovering aluminum electrolytic solid waste using soluble calcium salt as claimed in claim 1, wherein the specific conditions of the acid leaching reaction in S4 are that the liquid-solid ratio is 1-20, the temperature is 20-220 ℃, the time is 0.5-5h, the pressure is 0.1Mpa-15Mpa, wherein the acid leaching solution is any one of hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the acid leaching solution is 0.1-10mol/L.
7. The method for recovering solid waste from aluminum electrolysis using soluble calcium salt according to claim 1, wherein if the content of Ca ions in the second filtrate exceeds 0.5g/L in S4, soluble carbonate is added to the second filtrate and filtered to obtain calcium carbonate precipitate, so as to remove Ca ions in the second filtrate;
wherein the soluble carbonate comprises: one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and potassium carbonate.
8. The method for recovering aluminum electrolytic solid waste using a soluble calcium salt according to claim 1, wherein in S5, before the first filtrate is evaporated and dried, if the content of Ca ions in the first filtrate exceeds 0.5g/L, soluble carbonate is added and filtered to remove Ca ions in the first filtrate, and if the content of Li ions in the first filtrate exceeds 0.5g/L, soluble carbonate is continuously added and filtered to remove Li ions in the first filtrate.
9. A method for recovering aluminum electrolysis solid waste using soluble calcium salt according to claim 1, wherein the first filter residue in S3 is further used in S3 as a solvent of bayer process after removal of Ca ion and Li ion to prepare alumina by bayer process.
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