CN114590829A - Aluminum-lithium-containing solid waste resource recycling method - Google Patents
Aluminum-lithium-containing solid waste resource recycling method Download PDFInfo
- Publication number
- CN114590829A CN114590829A CN202210300451.1A CN202210300451A CN114590829A CN 114590829 A CN114590829 A CN 114590829A CN 202210300451 A CN202210300451 A CN 202210300451A CN 114590829 A CN114590829 A CN 114590829A
- Authority
- CN
- China
- Prior art keywords
- aluminum
- lithium
- solid waste
- recycling
- containing solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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
- 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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- 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
Abstract
The invention discloses a method for recycling aluminum-lithium-containing solid waste, belonging to the technical field of solid waste recycling. The method comprises the following steps: adding the aluminum-lithium-containing solid waste, aluminum salt, inorganic acid and water into a reaction kettle according to a ratio, stirring for reaction for 3-5h, filtering in a filter press, washing a filter cake for 2-3 times to obtain cryolite, and recycling; adding alkali into the filtrate to adjust the pH value, precipitating and separating out aluminum hydroxide colloid, filtering and removing impurities, primarily concentrating the filtrate, removing salt in the solution to obtain a lithium-enriched solution, adding a complexing agent into the lithium-enriched solution for further concentration, centrifugally removing impurities, cooling, crystallizing, and filtering to obtain the lithium hydroxide. The method has simple process and low cost, can recover the cryolite and co-produce the lithium hydroxide, improves the utilization rate of valuable elements, and provides a new method for recycling the aluminum-lithium-containing solid waste.
Description
Technical Field
The invention belongs to the technical field of solid waste recovery, and particularly relates to a method for recycling aluminum-lithium-containing solid waste.
Background
In the modern electrolytic aluminum production process, a cryolite-alumina molten salt electrolysis method is generally adopted, but medium-low-grade bauxite contains a large amount of potassium and lithium, the content of lithium salt in electrolyte is increased along with the continuous production, so that the electrolyte components are continuously changed, and the electrolyte cannot be used and becomes waste electrolyte which is main solid waste in the electrolytic aluminum industry along with the gradual increase of the content of lithium in the electrolyte. Along with the rapid development of economy and industry in China, the waste electrolyte generated by electrolytic aluminum is also increased sharply, and due to the huge discharge amount and insufficient effective utilization, the accumulated stockpiling amount is huge, the stockpiling occupies a large amount of land resources, pollutes underground water, influences the ecological environment, causes the waste of aluminum and lithium resources, and the effective and comprehensive utilization of the waste electrolyte becomes a problem to be solved urgently. In recent years, a high-value utilization technology of waste electrolyte is developed successively by a plurality of domestic units, but most of the waste electrolyte only recycles the cryolite in solid waste, so that the waste of lithium resources is caused. With the development of industrial technology, the industrial application field of lithium salt is continuously expanded. Therefore, the lithium element in the solid waste of the aluminum lithium is extracted and recovered by adopting a proper process, so that the sustainable development of the electrolytic aluminum industry is facilitated, and the extracted lithium salt can be used in the fields of lithium batteries and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for recycling aluminum-lithium-containing solid waste, which improves the utilization rate of valuable elements and provides a new method for recycling the aluminum-lithium-containing solid waste.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for recycling aluminum-containing lithium solid waste comprises the following steps:
(1) adding aluminum-lithium-containing solid waste, aluminum salt, inorganic acid and water into a reaction kettle according to the proportion, heating to 70-95 ℃, and stirring for reaction for 3-5 hours to obtain slurry;
(2) filtering the slurry obtained in the step (1) by a filter press to obtain a filter cake and filtrate, wherein the filter cake is cryolite, washing for 2-3 times, and recycling;
(3) adding alkali into the filtrate obtained in the step (2) to adjust the pH value, precipitating and separating out aluminum hydroxide colloid, filtering to remove the aluminum hydroxide colloid, then entering a concentration kettle, and evaporating and concentrating to separate out salt in the solution;
(4) the concentrated solution obtained in the step (3) enters a centrifugal machine, and is subjected to centrifugation to remove impurities, so that a lithium enrichment solution is obtained;
(5) and adding a complexing agent into the lithium enrichment solution, further concentrating, centrifugally removing impurities, cooling, crystallizing, and filtering to obtain the lithium hydroxide.
Further, the solid waste of the aluminum lithium in the step (1) is waste cryolite generated by electrolytic aluminum.
Further, the aluminum salt in the step (1) is one or more of aluminum chloride, aluminum nitrate and aluminum sulfate.
Further, the inorganic acid in the step (1) is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Further, in the step (1), the ratio of the aluminum lithium solid waste to the aluminum salt and the inorganic acid is mSolid waste of aluminum lithium:mAluminium salts:mInorganic acid:mWater (W)=（1~2）:1:0.1:1.2。
Further, the alkali in the step (3) is one or more of sodium hydroxide and potassium hydroxide.
Further, the pH range in the step (3) is 7-9.
Further, the complexing agent in the step (5) is one or more of ethylenediamine tetraacetate, diethylenetriamine pentacarboxylate and cyclohexanediamine tetraacetate.
Further, the adding amount of the complexing agent in the step (5) is 1-3% of the mass of the solid waste of the aluminum lithium.
Adding water into lithium-aluminum-containing solid waste for size mixing, acidifying with inorganic acid, adding soluble aluminum salt for replacement and purification to prepare cryolite and a soluble lithium compound, filtering and separating the cryolite and the soluble lithium compound, washing and drying the cryolite, and recycling the cryolite; adding alkali into the filtrate to adjust the pH, precipitating and separating out aluminum hydroxide colloid, filtering, entering a concentration kettle, evaporating part of water, and separating out salt in the solution; and adding a complexing agent into the lithium enrichment solution, removing iron in the solution, further concentrating, centrifugally removing impurities, cooling, crystallizing and filtering to obtain the lithium hydroxide.
The main reaction equation is as follows:
3LiF + Al3+→AlF3↓+ 3Li+
nNaF + AlF3→nNaF·AlF3↓
Al3++ 3OH-→Al(OH)3↓
Fe3++EDTA4-→[Fe(EDTA)]-。
compared with the prior art, the invention has the following beneficial effects:
(1) provides a method for recycling aluminum-containing lithium solid waste.
(2) The method has simple process and low cost, can recover the cryolite and co-produce the lithium hydroxide, improves the utilization rate of valuable elements, and provides a new method for recycling the aluminum-lithium-containing solid waste.
Drawings
FIG. 1 is a process flow diagram of the recycling process of solid waste containing aluminum and lithium.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all insubstantial modifications and variations thereof which can be made by one skilled in the art based on the teachings of the invention as described above.
Example 1
A method for recycling aluminum-containing lithium solid waste comprises the following steps:
1) 1000g of aluminum-lithium-containing solid waste and 1000g of AlCl3Adding 1200g of pure water into a reaction kettle, mixing, adding 100g of hydrochloric acid (30% by weight), adjusting the pH value of the system, and stirring at 90 ℃ for reaction for 3 hours to obtain slurry;
2) filtering the slurry obtained in the step 1) to obtain a filter cake and filtrate, washing the filter cake for 3 times, and drying to obtain 900g of cryolite product;
3) adding NaOH into the filtrate obtained in the step 2) to adjust the pH to be =9, precipitating and separating out aluminum hydroxide colloid, filtering and removing impurities, then feeding the aluminum hydroxide colloid into a concentration kettle, evaporating and concentrating to separate out salt in the solution, feeding the concentrated solution into a centrifugal machine, removing the salt in the solution, and obtaining a lithium enrichment solution;
4) adding 15g of EDTA into the lithium enrichment solution, further concentrating, carrying out centrifugal impurity removal, cooling, crystallizing and filtering to obtain 21g of lithium hydroxide.
Example 2
A method for recycling aluminum-lithium-containing solid waste comprises the following steps:
1) 2000g of aluminum-lithium-containing solid waste and 2000g of AlCl3Adding 2400g of pure water into a reaction kettle, mixing, adding 200g of hydrochloric acid (30 wt%), adjusting the pH value of the system, and stirring at 85 ℃ for reaction for 4 hours to obtain slurry;
2) filtering the slurry obtained in the step 1) to obtain a filter cake and filtrate, washing the filter cake for 3 times, and drying to obtain 1700g of cryolite product;
3) adding NaOH into the filtrate obtained in the step 2) to adjust the pH value to be =7.5, precipitating and separating out aluminum hydroxide colloid, filtering and removing impurities, then feeding the filtrate into a concentration kettle, evaporating and concentrating to separate out salt in the solution, feeding the concentrated solution into a centrifugal machine, removing NaCl in the solution, and obtaining a lithium enrichment solution;
4) and adding 40g of EDTA into the lithium enrichment solution, further concentrating, centrifugally removing impurities, cooling, crystallizing and filtering to obtain 44g of lithium hydroxide.
Example 3
A method for recycling aluminum-containing lithium solid waste comprises the following steps:
1) 1500g of aluminum-containing lithium solid waste and 1200g of AlCl3Adding 1400g of pure water into a reaction kettle, mixing, adding 150g of hydrochloric acid (30 wt%), adjusting the pH value of the system, and stirring at 90 ℃ for reaction for 3 hours to obtain slurry;
2) filtering the slurry obtained in the step 1) to obtain a filter cake and filtrate, washing the filter cake for 3 times, and drying to obtain 1300g of cryolite product;
3) adding NaOH into the filtrate obtained in the step 2) to adjust the pH to be =7, precipitating and separating out aluminum hydroxide colloid, filtering and removing impurities, then feeding the aluminum hydroxide colloid into a concentration kettle, evaporating and concentrating to separate out salt in the solution, feeding the concentrated solution into a centrifugal machine, removing NaCl in the solution, and obtaining a lithium enrichment solution;
4) and adding 30g of EDTA into the lithium enrichment solution, further concentrating, centrifugally removing impurities, cooling, crystallizing, and filtering to obtain 30g of lithium hydroxide.
In this test example, cryolite and lithium hydroxide obtained in examples 1 to 3 were examined, and the results are shown in tables 1 and 2.
TABLE 1 cryolite test results obtained in examples 1 to 3
TABLE 2 detection results of lithium hydroxide obtained in examples 1 to 3
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A method for recycling aluminum-containing lithium solid waste is characterized by comprising the following steps:
(1) adding aluminum-lithium-containing solid waste, aluminum salt, inorganic acid and water into a reaction kettle according to the proportion, heating to 70-95 ℃, and stirring for reaction for 3-5 hours to obtain slurry;
(2) filtering the slurry obtained in the step (1) by a filter press to obtain a filter cake and filtrate, wherein the filter cake is cryolite, washing for 2-3 times, and recycling;
(3) adding alkali into the filtrate obtained in the step (2) to adjust the pH value, precipitating and separating out aluminum hydroxide colloid, filtering to remove the aluminum hydroxide colloid, then entering a concentration kettle, and evaporating and concentrating to separate out salt in the solution to obtain a concentrated solution;
(4) the concentrated solution obtained in the step (3) enters a centrifugal machine, and is subjected to centrifugation to remove impurities, so that a lithium enrichment solution is obtained;
(5) and adding a complexing agent into the lithium enrichment solution, further concentrating, centrifugally removing impurities, cooling, crystallizing, and filtering to obtain the lithium hydroxide.
2. The method for recycling the aluminum-lithium-containing solid waste as claimed in claim 1, wherein the aluminum-lithium solid waste in the step (1) is waste cryolite generated by electrolytic aluminum.
3. The method for recycling the aluminum-containing lithium solid waste according to claim 1, wherein the aluminum salt in the step (1) is one or more of aluminum chloride, aluminum nitrate and aluminum sulfate.
4. The method for recycling the aluminum-lithium-containing solid waste according to claim 1, wherein the inorganic acid in the step (1) is one or more of hydrochloric acid, sulfuric acid and nitric acid.
5. The method for recycling aluminum-lithium-containing solid waste as resources according to claim 1, wherein the ratio of aluminum-lithium-containing solid waste to aluminum salt, inorganic acid and water in the step (1) is mSolid waste of aluminum lithium:mAluminium salt:mInorganic acid:mWater (W)=（1~2）:1:0.1:1.2。
6. The method for recycling the aluminum-containing lithium solid waste according to claim 1, wherein the alkali in the step (3) is one or two of sodium hydroxide and potassium hydroxide.
7. The method for recycling the aluminum-lithium-containing solid waste according to claim 1, wherein the pH value in the step (3) is adjusted to 7-9 by adding alkali.
8. The method for recycling the solid waste containing aluminum and lithium as claimed in claim 1, wherein the complexing agent in the step (5) is one or more of ethylenediamine tetraacetate, diethylenetriamine pentacarboxylate and cyclohexanediamine tetraacetate.
9. The method for recycling the aluminum-lithium-containing solid waste as claimed in claim 1, wherein the amount of the complexing agent added in the step (5) is 1-3% of the mass of the aluminum-lithium solid waste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210300451.1A CN114590829A (en) | 2022-03-25 | 2022-03-25 | Aluminum-lithium-containing solid waste resource recycling method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210300451.1A CN114590829A (en) | 2022-03-25 | 2022-03-25 | Aluminum-lithium-containing solid waste resource recycling method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114590829A true CN114590829A (en) | 2022-06-07 |
Family
ID=81810836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210300451.1A Pending CN114590829A (en) | 2022-03-25 | 2022-03-25 | Aluminum-lithium-containing solid waste resource recycling method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114590829A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304086A (en) * | 2022-07-20 | 2022-11-08 | 山西大学 | Method for producing lithium carbonate by mineralizing aluminum-lithium slag with flue gas |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1345625A (en) * | 1962-10-04 | 1963-12-13 | Kaiser Aluminium Chem Corp | Lithium recovery with or without cryolite recovery |
| CN101214978A (en) * | 2007-12-28 | 2008-07-09 | 四川天齐锂业股份有限公司 | Method for preparing battery-stage monohydrate lithium hydroxide |
| CN105349786A (en) * | 2015-11-16 | 2016-02-24 | 多氟多化工股份有限公司 | Lithium-aluminum-contained electrolyte comprehensive recycling method |
| US20190248667A1 (en) * | 2017-06-15 | 2019-08-15 | Energysource Minerals Llc | System and process for recovery of lithium from a geothermal brine |
| CN110442946A (en) * | 2019-07-30 | 2019-11-12 | 郑州中科新兴产业技术研究院 | A kind of aluminum-extracted pulverized fuel ash process system integrated optimization method |
| KR102132120B1 (en) * | 2019-03-27 | 2020-07-09 | 박태형 | A recycling method for the spent lithium ion secondary battery using carbon dioxide |
| CN111519042A (en) * | 2012-08-13 | 2020-08-11 | 瑞德高级材料有限公司 | Process for treating lithium-containing materials |
| CN112919507A (en) * | 2021-01-21 | 2021-06-08 | 郑州大学 | Method for extracting lithium salt from aluminum electrolyte |
| CN113957254A (en) * | 2021-09-28 | 2022-01-21 | 广东邦普循环科技有限公司 | Method for efficiently removing fluorine from waste lithium battery |
| US20220041460A1 (en) * | 2019-04-12 | 2022-02-10 | Qinghai Institute Of Salt Lakes, Chinese Academy Of Sciences | Preparation method of lithium hydroxide |
| CN114195175A (en) * | 2021-12-30 | 2022-03-18 | 江西赣锋循环科技有限公司 | Method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder |
-
2022
- 2022-03-25 CN CN202210300451.1A patent/CN114590829A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1345625A (en) * | 1962-10-04 | 1963-12-13 | Kaiser Aluminium Chem Corp | Lithium recovery with or without cryolite recovery |
| CN101214978A (en) * | 2007-12-28 | 2008-07-09 | 四川天齐锂业股份有限公司 | Method for preparing battery-stage monohydrate lithium hydroxide |
| CN111519042A (en) * | 2012-08-13 | 2020-08-11 | 瑞德高级材料有限公司 | Process for treating lithium-containing materials |
| CN105349786A (en) * | 2015-11-16 | 2016-02-24 | 多氟多化工股份有限公司 | Lithium-aluminum-contained electrolyte comprehensive recycling method |
| US20190248667A1 (en) * | 2017-06-15 | 2019-08-15 | Energysource Minerals Llc | System and process for recovery of lithium from a geothermal brine |
| KR102132120B1 (en) * | 2019-03-27 | 2020-07-09 | 박태형 | A recycling method for the spent lithium ion secondary battery using carbon dioxide |
| US20220041460A1 (en) * | 2019-04-12 | 2022-02-10 | Qinghai Institute Of Salt Lakes, Chinese Academy Of Sciences | Preparation method of lithium hydroxide |
| CN110442946A (en) * | 2019-07-30 | 2019-11-12 | 郑州中科新兴产业技术研究院 | A kind of aluminum-extracted pulverized fuel ash process system integrated optimization method |
| CN112919507A (en) * | 2021-01-21 | 2021-06-08 | 郑州大学 | Method for extracting lithium salt from aluminum electrolyte |
| CN113957254A (en) * | 2021-09-28 | 2022-01-21 | 广东邦普循环科技有限公司 | Method for efficiently removing fluorine from waste lithium battery |
| CN114195175A (en) * | 2021-12-30 | 2022-03-18 | 江西赣锋循环科技有限公司 | Method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304086A (en) * | 2022-07-20 | 2022-11-08 | 山西大学 | Method for producing lithium carbonate by mineralizing aluminum-lithium slag with flue gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110040748B (en) | Method for producing potassium salt and sodium salt by utilizing waste incineration fly ash | |
| CN102851693B (en) | Technology for recovering production of electrolytic copper and zinc from smelting ash | |
| CN109110788B (en) | Method for comprehensively utilizing lithium and magnesium resources in salt lake brine | |
| CN103966446A (en) | Method for separating and recovering copper, nickel and iron from electroplating sludge | |
| CN109439908A (en) | Preparation method for preparing high-purity copper powder and recycling crystalline aluminum chloride by using waste etching solution containing copper chloride | |
| WO2018072499A1 (en) | Method for recovering basic copper chloride from copper-containing waste liquid in sulfuric acid system | |
| CN107190140A (en) | A kind of method of the recovering rare earth from ion adsorption type rare earth ore and aluminium | |
| CN114590829A (en) | Aluminum-lithium-containing solid waste resource recycling method | |
| CN103539164B (en) | A kind of by the method containing the refining glauber salt of chromium saltcake | |
| CN116334410A (en) | Method for separating lithium from lithium-containing electrolyte waste residues in aluminum electrolysis | |
| CN112359224B (en) | Method for purifying cadmium-containing nickel-cobalt solution to remove cadmium | |
| CN103787396A (en) | Method for preparing high-purity potassium alum and aluminum sulfate from alunite ore | |
| CN109609978B (en) | Method for electrodepositing flaky zinc in alkaline medium | |
| CN106811609A (en) | A kind of method that bastnasite produces rare earth fluoride | |
| CN110735048A (en) | Method for removing magnesium and fluorine from zinc-containing solution of wet-method zinc smelting | |
| CN103911513B (en) | Move back the treatment process of tin waste liquid | |
| CN109970102A (en) | A kind of method that aluminium ash prepares aluminium polychloride coproduction vanadic anhydride | |
| CN111020187A (en) | Method for preparing nickel hydroxide | |
| CN110184459A (en) | A method of basic copper chloride is produced using copper-contained sludge | |
| CN211896069U (en) | System for continuously producing electroplating-grade copper oxide by using circuit board etching waste liquid as raw material | |
| CN114436335B (en) | Method for removing magnesium from manganese sulfate solution | |
| CN103253696A (en) | Method for recovering cuprous chloride from alkaline waste etching solution | |
| CN113336252B (en) | Method for removing calcium from pickle liquor of coal-based solid waste | |
| CN103255435A (en) | Recycling method for electrolyte solution produced during cathode copper production | |
| CN107475524A (en) | A kind of cadmium alkaline residue processing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |