CN116855761A - Method for extracting lithium element from lithium-containing solid waste - Google Patents
Method for extracting lithium element from lithium-containing solid waste Download PDFInfo
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- CN116855761A CN116855761A CN202310611386.9A CN202310611386A CN116855761A CN 116855761 A CN116855761 A CN 116855761A CN 202310611386 A CN202310611386 A CN 202310611386A CN 116855761 A CN116855761 A CN 116855761A
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- solid waste
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 163
- 239000002910 solid waste Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 76
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000000047 product Substances 0.000 claims abstract description 38
- 238000001914 filtration Methods 0.000 claims abstract description 35
- 238000000605 extraction Methods 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 229910001610 cryolite Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011819 refractory material Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 13
- 238000004064 recycling Methods 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 33
- 229910052782 aluminium Inorganic materials 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- -1 fluorine ions Chemical class 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000002386 leaching Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The application relates to the technical field of metallurgical solid waste recycling treatment, in particular to a method for extracting lithium element from lithium-containing solid waste; the method comprises the following steps: mixing the lithium-containing solid waste powder and the lithium extraction agent, stirring, and filtering to obtain a first filtrate; adding a first alkaline regulator into the first filtrate to reach a first target pH value, and filtering to obtain a second filtrate; adding a second alkaline regulator into the second filtrate to reach a second target pH value, and filtering to obtain a third filtrate; treating the third filtrate with resin to remove calcium and magnesium ions and obtain a fourth filtrate; concentrating the fourth filtrate, adding sodium carbonate to perform lithium precipitation reaction, and filtering to obtain precipitate; washing the precipitate, and drying to obtain a lithium salt product; the first target PH value is 5-7, and the second target PH value is 8-11; the neutral partial alkali reaction system is used as an extraction system, so that the corrosion damage of the acid and strong alkali system to equipment is avoided, and meanwhile, a lithium carbonate product with higher purity is obtained.
Description
Technical Field
The application relates to the technical field of metallurgical solid waste recycling treatment, in particular to a method for extracting lithium element from lithium-containing solid waste.
Background
The existing lithium extraction technology for lithium-containing solid wastes has the problems of low lithium leaching rate, corrosion of equipment due to strong acid and strong alkali contained in a leaching system and environmental protection of leached waste liquid, and meanwhile, most of the technology adopts roasting before mixing, so that the energy consumption of the equipment can be greatly increased in the lithium extraction process. At present, the field of more treatment for lithium-containing electrolyte is concentrated in the utilization field of overhaul slag, and most of the utilization field of the overhaul slag is concentrated in the recovery of sodium fluoride products, and the related technology for recovering lithium resources is almost blank.
Most of the existing technologies for extracting lithium elements from lithium-containing solid wastes utilize an acid system to extract lithium elements in lithium-containing resources, and in the process of extracting lithium by adopting the acid system, on one hand, the risk of harm of the acid system to equipment corrosion exists, and on the other hand, the problems of complex impurity types, high impurity content and the like in a solution after extracting the lithium elements exist, and the subsequent impurity removal difficulty is high, the cost is high, and the lithium recovery rate is low; therefore, how to provide a method for extracting lithium elements from solid wastes containing lithium, so as to solve the problems of difficult lithium extraction and impurity removal, high cost and low lithium recovery rate of the existing strong acid and strong alkali, and the method is a technical problem to be solved at present.
Disclosure of Invention
The application provides a method for extracting lithium elements from solid wastes containing lithium, which aims to solve the technical problems that a non-acid system cannot be adopted in the lithium extraction process and the recovery rate of extracted lithium is low in the prior art.
The application provides a method for extracting lithium elements from solid waste containing lithium, which comprises the following steps:
mixing the lithium-containing solid waste powder and the lithium extraction agent, stirring to leach lithium elements, and filtering to obtain a first filtrate;
adding a first alkaline regulator into the first filtrate to reach a first target pH value, and filtering to obtain a second filtrate;
adding a second alkaline regulator into the second filtrate until the second target pH value is reached, and filtering to obtain a third filtrate;
treating the third filtrate with resin to remove calcium and magnesium ions and obtain a fourth filtrate;
concentrating the fourth filtrate, adding sodium carbonate to perform lithium precipitation reaction, and filtering to obtain precipitate;
washing the precipitate, and drying to obtain a lithium salt product;
wherein the first target pH value is 5-7, and the second target pH value is 8-11.
Optionally, the temperature of the stirring is 30-100 ℃; and/or the number of the groups of groups,
the stirring time is 0.5-2.5 h.
Optionally, the lithium extraction agent comprises Al (NO 3 ) 3 、Al 2 (SO 4 ) 3 、Al(OH) 3 And CaSO 4 At least one of them.
Optionally, the first alkaline regulator comprises NaOH and/or KOH.
Optionally, the second alkaline modifier comprises Ca (OH) 2 And/or CaO.
Optionally, the temperature of the lithium precipitation reaction is more than or equal to 90 ℃; and/or the number of the groups of groups,
the time of the lithium precipitation reaction is 2-4 hours.
Optionally, the actual adding amount of the sodium carbonate is 1.1-2 times of the theoretical adding amount of the sodium carbonate, and the theoretical adding amount of the sodium carbonate is determined by the content of lithium in the fourth filtrate.
Optionally, the lithium-containing solid waste comprises lithium-containing electrolyte and/or overhaul slag.
Optionally, the mixing of the lithium-containing solid waste powder and the lithium extraction agent, and stirring to leach lithium element, and then filtering to obtain a first filtrate, includes the steps of:
crushing the lithium-containing solid waste, grinding, and sieving to obtain lithium-containing solid waste powder;
mixing the lithium-containing solid waste powder and the lithium extraction agent, stirring to leach lithium elements, and filtering to obtain a first filtrate and filter residues respectively;
washing the filter residues to be neutral, and drying to obtain cryolite products and/or refractory materials and/or carbon powder.
Optionally, the granularity of the screening is 50-200 meshes; and/or the number of the groups of groups,
the solid-to-liquid ratio of the washing is 1: 3-1: 5.
compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
compared with the traditional method for extracting lithium by leaching with acid and alkali, the method provided by the embodiment of the application has the advantages that the pH value of the filtrate after lithium extraction is adjusted to be neutral, then the second alkaline regulator containing calcium is adopted to adjust the pH value, meanwhile, fluoride ion, iron, copper, nickel, boron, manganese, silicon, aluminum and other ions in the solution are sufficiently removed, then the resin is used for purifying and removing calcium and magnesium ions in the solution, then sodium carbonate is added after the solution is concentrated, lithium carbonate products can be generated by the reaction of the carbonate ions in the lithium ions and the sodium carbonate, so that the neutral alkaline reaction system is used as a main extraction system, the corrosion damage of the acid and alkali system to equipment can be avoided, meanwhile, the lithium carbonate products with higher purity can be obtained by the alkaline system, the full extraction of lithium in the lithium-containing solid waste can be realized, in addition, the leaching toxicity index of the extracted lithium-containing solid waste, especially the fluoride index can be ensured to meet the standard requirement, and the different recycling products such as cryolite products, refractory materials and carbon powder can be obtained, and the full utilization of the lithium-containing solid waste can be realized.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a method for extracting lithium elements from lithium-containing solid waste according to an embodiment of the present application;
FIG. 2 is a detailed schematic flow chart of a method for extracting lithium elements from solid waste containing lithium according to an embodiment of the present application;
fig. 3 is a schematic diagram of an actual flow of a method for extracting lithium elements from solid waste containing lithium according to an embodiment of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
The inventive thinking of the application is:
existing techniques for extracting lithium elements from lithium-containing solid waste include:
1. the method for selectively leaching the lithium element in the aluminum electrolyte by using the inorganic acid can realize the separation of lithium salt and an electrolyte main body, thereby extracting the lithium element in the aluminum electrolyte and simultaneously obtaining a cryolite product; meanwhile, the technology of removing lithium and purifying the aluminum electrolyte by adopting the nitric acid solution with a low concentration range realizes recycling of part of nitric acid on the premise of not damaging the structure of the aluminum electrolyte.
2. Crushing lithium-containing waste aluminum electrolyte to be treated to obtain electrolyte powder; uniformly mixing the electrolyte powder with a reactant, roasting at 600-1400 ℃ for 0.5-5h, cooling, and grinding to obtain mixture powder; mixing the mixture powder with water, stirring for reaction, and filtering to obtain filter residues and filtrate; the filtrate is used for precipitating lithium to obtain lithium salt;
3. leaching the electrolyte with 2.5-5mol/l sodium hydroxide solution at 80-100deg.C to obtain Na 2 LiAlF 6 The conversion to LiF, liF is present in the filter residue, which is leached with 1-4mol/l acid at 50-90℃to dissolve out Li.
On the one hand, the risk of harm of an acid system or a strong alkali leaching solution to equipment corrosion exists in the process, and on the other hand, the problem of low extraction and recovery rate of lithium elements exists; therefore, how to provide a method for extracting lithium element from solid waste containing lithium, so as to solve the technical problems that the existing lithium extraction cannot adopt a non-acid system and the lithium extraction efficiency is low.
As shown in fig. 1, an embodiment of the present application provides a method for extracting lithium element from solid waste containing lithium, the method comprising:
s1, mixing lithium-containing solid waste powder and a lithium extraction agent, stirring to leach lithium elements, and filtering to obtain a first filtrate;
s2, adding a first alkaline regulator into the first filtrate to reach a first target pH value, and filtering to obtain a second filtrate;
s3, adding a second alkaline regulator into the second filtrate to reach a second target pH value, and filtering to obtain a third filtrate;
s4, treating the third filtrate by resin to remove calcium and magnesium ions to obtain a fourth filtrate;
s5, concentrating the fourth filtrate, adding sodium carbonate to perform lithium precipitation reaction, and filtering to obtain a precipitate;
s6, washing the precipitate, and drying to obtain a lithium salt product;
wherein the first target pH value is 5-7, and the second target pH value is 8-11.
In the embodiment of the application, the pH value of the first target is controlled to be biased towards neutral, and the solubility of fluorine ions, aluminum ions and calcium ions in the first filtrate can be adjusted through the pH value, so that the fluorine ions in the solution are removed, and meanwhile, the content of indissolvable substances in the neutral solution, such as aluminum ions, iron ions, silicon ions and the like, is reduced, so that the content of harmful elements in the lithium-containing solid waste is reduced.
The second target pH value is controlled to be alkaline, so that impurity ions in the solution can be guaranteed to be precipitated in an alkaline environment, and therefore iron, copper, nickel, boron, manganese, magnesium, silicon, aluminum and other ions are removed, and carbonate and lithium are guaranteed to fully react in the subsequent stage of adding sodium carbonate, and a high-purity lithium carbonate product is obtained.
In some alternative embodiments, the temperature of the agitation is from 30 ℃ to 100 ℃; and/or the number of the groups of groups,
the stirring time is 0.5-2.5 h.
In the embodiment of the application, the stirring temperature and the stirring time are controlled, so that the mixing of the lithium-containing solid waste and the lithium extracting agent is ensured to be sufficient, the leaching effect of lithium is ensured, and the lithium ions in the lithium-containing solid waste are ensured to be leached cleanly.
In some alternative embodiments, the lithium extraction agent comprises Al (NO 3 ) 3 、Al 2 (SO 4 ) 3 、Al(OH) 3 And CaSO 4 At least one of them.
In the embodiment of the application, the specific lithium extraction agent is controlled, so that the leaching effect of lithium elements in the lithium-containing solid waste can be ensured, and enough lithium elements can be obtained.
In some alternative embodiments, the first alkaline modifier comprises NaOH and/or KOH.
In some alternative embodiments, the second alkaline modifier comprises Ca (OH) 2 And/or CaO.
In the embodiment of the application, the specific first alkaline regulator and the second alkaline regulator are controlled, so that the regulating effect of the first alkaline regulator and the second alkaline regulator on the pH value of the solution can be ensured, excessive impurities are avoided being introduced, and the high purity of the subsequent lithium carbonate product is ensured.
In some alternative embodiments, the temperature of the lithium precipitation reaction is greater than or equal to 90 ℃; and/or the number of the groups of groups,
the time of the lithium precipitation reaction is 2-4 hours.
In the embodiment of the application, the specific temperature and specific time of the lithium precipitation reaction are controlled, so that the complete reaction of lithium in the fourth filtrate and carbonate in sodium carbonate can be ensured, and a high-purity lithium carbonate product is obtained.
In some alternative embodiments, the actual amount of sodium carbonate added is 1.1 to 2 times the theoretical amount of sodium carbonate added, which is determined by the lithium content of the fourth filtrate.
In the embodiment of the application, the relation between the actual adding amount and the theoretical adding amount of the sodium carbonate is controlled, so that the complete reaction of the sodium carbonate and lithium in the fourth filtrate can be ensured, and a high-purity lithium carbonate product is obtained.
In some alternative embodiments, the lithium-containing solid waste comprises lithium-containing electrolyte and/or overhaul slag.
In the embodiment of the application, the specific lithium-containing solid waste is controlled, so that the applicable treatment object range of the method can be ensured, and the subsequent high-purity lithium carbonate product can be ensured.
In some alternative embodiments, as shown in fig. 2, the mixing of the lithium-containing solid waste powder and the lithium extraction agent, and stirring to leach out lithium element, and filtering to obtain a first filtrate, includes the steps of:
s101, crushing the lithium-containing solid waste, grinding, and sieving to obtain lithium-containing solid waste powder;
s102, mixing the lithium-containing solid waste powder and the lithium extraction agent, stirring to leach lithium elements, and filtering to obtain first filtrate and filter residues respectively;
s103, washing the filter residues to be neutral, and drying to obtain cryolite products and/or refractory materials and/or carbon powder.
According to the embodiment of the application, the lithium-containing solid waste is firstly ground to obtain the lithium-containing solid waste powder with smaller particle size, and then the lithium-containing solid waste powder and the lithium extracting agent are treated, so that lithium in the lithium-containing solid waste can be effectively extracted, and filter residues are washed and dried, so that cryolite products and/or refractory materials and/or carbon powder in the lithium-containing solid waste can be effectively recovered.
In some alternative embodiments, the size of the screen is 50 mesh to 200 mesh.
In the embodiment of the application, the specific granularity of screening is controlled, so that the particle size of the lithium-containing solid waste powder is ensured to be within a reasonable size, the mixing between the lithium-containing solid waste powder and the lithium extraction agent is further ensured to be sufficient, and the lithium extraction effect is ensured.
In some alternative embodiments, the washed solids to liquid ratio is 1: 3-1: 5.
in the embodiment of the application, the specific washing conditions are controlled, so that the washing effect on filter residues can be ensured, and the washing is ensured to be neutral, thereby obtaining pure cryolite products and/or refractory materials and/or carbon powder.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
The specific practical process flow chart is shown in fig. 3:
step 1: electrolyte lithium extraction:
(1) Crushing and grinding the lithium-containing aluminum electrolyte, and sieving with a 50-200 mesh sieve;
(2) Weighing aluminum electrolyte powder, and weighing a certain amount of Al (OH) 3 A proper amount of water is measured, and lithium-containing electrolyte powder and Al (OH) are mixed 3 Mixing, stirring at 100deg.C for 0.5 hr;
(3) And (3) carrying out solid-liquid separation on the mixed solution after the reaction is finished to obtain a first filtrate and filter residues, washing the filter residues according to a solid-liquid ratio of 1:3, washing the filter residues, and drying the filter residues to obtain the cryolite product.
Step 2: and (3) recycling lithium:
(1) And (3) adding a first alkaline regulator (such as potassium hydroxide) into the lithium-containing solution obtained in the step (3) to regulate the pH value to 5-7, removing fluorine ions in the solution, removing part of aluminum ions, iron ions, silicon ions and the like, and filtering to obtain a second filtrate.
(2) And adding a second alkaline regulator (such as calcium oxide) into the obtained second filtrate to regulate the pH value to 8-11, removing ions such as iron, copper, nickel, boron, manganese, magnesium, silicon and aluminum in the solution, and filtering to obtain a third filtrate.
(3) And (3) passing the third filtrate through resin to remove calcium ions and magnesium ions in the solution, so as to obtain a fourth filtrate.
(4) Evaporating the fourth filtrate to concentrate the lithium ion concentration to more than 20g/L, adding sodium carbonate solution, heating to more than 90 ℃, precipitating lithium for 2 hours, thermally filtering, washing and drying the obtained precipitate to obtain a lithium carbonate product, wherein the purity of the obtained lithium carbonate product is 99.70%.
Example 2
Example 2 and example 1 were compared, and the difference between example 2 and example 1 is that:
step 1: electrolyte lithium extraction:
(1) Crushing and grinding the lithium-containing aluminum electrolyte, and sieving with a 50-200 mesh sieve;
(2) Weighing aluminum electrolyte powder, and weighing a certain amount of Al 2 (SO 4 ) 3 Measuring proper amount of water, mixing lithium-containing electrolyte powder with Al 2 (SO 4 ) 3 Mixing, stirring at 50deg.C for 2 hr;
(3) And (3) carrying out solid-liquid separation on the mixed solution after the reaction is finished to obtain a first filtrate and filter residues, wherein the solid-liquid ratio is 1: and 4, washing filter residues, and drying the filter residues after washing to obtain a cryolite product.
Step 2: and (3) recycling lithium:
(1) And (3) adding a first alkaline regulator (such as sodium hydroxide) into the lithium-containing solution obtained in the step (3) to regulate the pH to 5-7, removing fluorine ions in the solution, removing part of aluminum ions, iron ions, silicon ions and the like, and filtering to obtain a second filtrate.
(2) Adding a second alkaline regulator (such as calcium hydroxide) into the obtained second filtrate to regulate the pH value to 8-11, removing ions such as iron, copper, nickel, boron, manganese, magnesium, silicon and aluminum in the solution, and filtering to obtain a third filtrate.
(3) And (3) passing the third filtrate through resin to remove calcium ions and magnesium ions in the solution, so as to obtain a fourth filtrate.
(4) Evaporating the fourth filtrate to concentrate the lithium ion concentration to more than 20g/L, adding sodium carbonate solution, heating to more than 90 ℃, precipitating lithium for 3 hours, thermally filtering, washing and drying the obtained precipitate to obtain a lithium carbonate product, wherein the purity of the obtained lithium carbonate product is 99.65%.
Example 3
Example 3 was compared with example 1, and the difference between example 3 and example 1 was:
step 1: and (3) carrying out lithium extraction on overhaul slag:
(1) Crushing and grinding the lithium-containing overhaul slag, and sieving with a 50-200 mesh sieve;
(2) Weighing the overhaul slag powder, and weighing a certain amount of Al (NO) 3 ) 3 Measuring proper amount of water, mixing the lithium-containing overhaul slag powder with Al (NO) 3 ) 3 Mixing, stirring at 80deg.C for 1.0h;
(3) And (3) carrying out solid-liquid separation on the mixed solution after the reaction is finished to obtain a first filtrate and filter residues, washing the filter residues according to a solid-liquid ratio of 1:5, washing the filter residues, and drying the filter residues to obtain a carbon powder product.
Step 2: and (3) recycling lithium:
(1) And (3) adding a first alkaline regulator (such as sodium hydroxide) into the lithium-containing solution obtained in the step (3) to regulate the pH to 5-7, and filtering to obtain a second filtrate.
(2) Adding a second alkaline regulator (such as calcium oxide) into the obtained second filtrate to regulate the pH value to 8-11, removing ions such as iron, copper, nickel, boron, manganese, magnesium, silicon and aluminum in the solution, and filtering to obtain a third filtrate.
(3) And (3) passing the third filtrate through resin to remove calcium ions and magnesium ions in the solution, so as to obtain a fourth filtrate.
(4) Evaporating the fourth filtrate to concentrate the lithium ion concentration to more than 20g/L, adding sodium carbonate solution, heating to more than 90 ℃, precipitating lithium for 2.5h, hot filtering, washing and drying the obtained precipitate to obtain a lithium carbonate product, wherein the purity of the obtained lithium carbonate product is 99.75%.
Example 4
Example 4 and example 1 were compared, and example 4 and example 1 differ in that:
step 1: and (3) carrying out lithium extraction on overhaul slag:
(1) Crushing and grinding the lithium-containing overhaul slag, and sieving with a 50-200 mesh sieve;
(2) Weighing overhaul slag powder, and weighing a certain amount of CaSO 4 Measuring a proper amount of water, mixing the lithium-containing overhaul slag powder with CaSO 4 Mixing, stirring at 30deg.C for 2.5h;
(3) And (3) carrying out solid-liquid separation on the mixed solution after the reaction is finished to obtain a first filtrate and filter residues, washing the filter residues according to a solid-liquid ratio of 1:5, washing the filter residues, and drying the filter residues to obtain the refractory raw material.
Step 2: and (3) recycling lithium:
(1) And (3) adding a first alkaline regulator (such as potassium hydroxide) into the lithium-containing solution obtained in the step (3) to regulate the pH to 5-7, and filtering to obtain a second filtrate.
(2) Adding a second alkaline regulator (such as calcium hydroxide) into the obtained second filtrate to regulate the pH value to 8-11, removing ions such as iron, copper, nickel, boron, manganese, magnesium, silicon and aluminum in the solution, and filtering to obtain a third filtrate.
(3) And (3) passing the third filtrate through resin to remove calcium ions and magnesium ions in the solution, so as to obtain a fourth filtrate.
(4) Evaporating the fourth filtrate to concentrate the lithium ion concentration to more than 20g/L, adding sodium carbonate solution, heating to more than 90 ℃, precipitating lithium for 4 hours, hot filtering, washing and drying the obtained precipitate to obtain a lithium carbonate product, wherein the purity of the obtained lithium carbonate product is 99.8%.
One or more technical solutions in the embodiments of the present application at least have the following technical effects or advantages:
(1) The embodiment of the application provides a method for extracting lithium elements from solid wastes containing lithium, which has the leaching rate of more than 90 percent, short process flow and adopts a non-acid non-alkali non-roasting lithium extraction process.
(2) The embodiment of the application provides a method for extracting lithium elements from lithium-containing solid waste, and cryolite products and/or refractory materials and/or carbon powder can be obtained after the method is used for processing. The cryolite product can be returned to the electrolytic tank for recycling, the refractory raw material can be returned to be used for producing the refractory product, the carbon powder can be returned to be used for producing carbon products, and meanwhile, a lithium salt product with high added value can be prepared, so that the full resource recycling of the solid waste containing lithium is realized.
(3) The embodiment of the application provides a method for extracting lithium elements from lithium-containing solid waste, the comprehensive recovery rate of lithium is more than 90%, the purity of the product is more than 99%, the impurity content in the first filtrate is low, the impurity removal process is short, and the lithium is basically free from loss.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for extracting lithium element from solid waste containing lithium, the method comprising:
mixing the lithium-containing solid waste powder and the lithium extraction agent, stirring to leach lithium elements, and filtering to obtain a first filtrate;
adding a first alkaline regulator into the first filtrate to reach a first target pH value, and filtering to obtain a second filtrate;
adding a second alkaline regulator into the second filtrate to reach a second target pH value, and filtering to obtain a third filtrate;
treating the third filtrate with resin to remove calcium and magnesium ions and obtain a fourth filtrate;
concentrating the fourth filtrate, adding sodium carbonate to perform lithium precipitation reaction, and filtering to obtain precipitate;
washing the precipitate, and drying to obtain a lithium salt product;
wherein the first target pH value is 5-7, and the second target pH value is 8-11.
2. The method of claim 1, wherein the temperature of the agitation is from 30 ℃ to 100 ℃; and/or the number of the groups of groups,
the stirring time is 0.5-2.5 h.
3. The method of claim 1, wherein the lithium extraction agent comprises Al (NO 3 ) 3 、Al 2 (SO 4 ) 3 、Al(OH) 3 And CaSO 4 At least one of them.
4. The method of claim 1, wherein the first alkaline modifier comprises NaOH and/or KOH.
5. The method of claim 1, wherein the second alkaline modifier comprises Ca (OH) 2 And/or CaO.
6. The method according to claim 1, wherein the temperature of the lithium precipitation reaction is not less than 90 ℃; and/or the number of the groups of groups,
the time of the lithium precipitation reaction is 2-4 hours.
7. The method according to claim 1, wherein the actual addition amount of sodium carbonate is 1.1 to 2 times the theoretical addition amount of sodium carbonate, which is determined by the content of lithium in the fourth filtrate.
8. The method of claim 1, wherein the lithium-containing solid waste comprises lithium-containing electrolyte and/or overhaul slag.
9. The method according to claim 1, wherein the mixing of the lithium-containing solid waste powder and the lithium extraction agent and stirring to leach out the lithium element, and then filtering to obtain a first filtrate, comprises the steps of:
crushing the lithium-containing solid waste, grinding, and sieving to obtain lithium-containing solid waste powder;
mixing the lithium-containing solid waste powder and the lithium extraction agent, stirring to leach lithium elements, and filtering to obtain a first filtrate and filter residues respectively;
washing the filter residues to be neutral, and drying to obtain cryolite products and/or refractory materials and/or carbon powder.
10. The method of claim 9, wherein the size of the screen is 50 mesh to 200 mesh; and/or the number of the groups of groups,
the solid-to-liquid ratio of the washing is 1: 3-1: 5.
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