CN115784274B - Method for separating and recovering trace lithium in aluminum nitrate solution - Google Patents
Method for separating and recovering trace lithium in aluminum nitrate solution Download PDFInfo
- Publication number
- CN115784274B CN115784274B CN202211361583.1A CN202211361583A CN115784274B CN 115784274 B CN115784274 B CN 115784274B CN 202211361583 A CN202211361583 A CN 202211361583A CN 115784274 B CN115784274 B CN 115784274B
- Authority
- CN
- China
- Prior art keywords
- lithium
- lino
- separating
- nitrate solution
- aluminum
- 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.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 60
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 title claims abstract description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910013553 LiNO Inorganic materials 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 24
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- 238000000889 atomisation Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 15
- 238000004090 dissolution Methods 0.000 claims abstract description 14
- 238000001728 nano-filtration Methods 0.000 claims abstract description 13
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 8
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims abstract description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 24
- 230000008020 evaporation Effects 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- -1 aluminum ions Chemical class 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 230000003287 optical effect 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
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Classifications
-
- 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
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for separating and recovering trace lithium in an aluminum nitrate solution. The method comprises the following steps of S1: nitric acid leaching solution obtained by nitric acid leaching of lithium ores is separated by a nanofiltration membrane, so that monovalent ion liquid and multivalent ion liquid are obtained; s2: preheating and evaporating the multivalent ion liquid obtained in the step S1 by utilizing nitrogen oxide gas generated by atomization and calcination, and then evaporating and concentrating to obtain the Al (NO) 3 、LiNO 3 Is a mixed solution of (a) and (b); s3: atomizing and calcining the mixed solution to generate powdery Al 2 O 3 With LiNO 3 Nitrogen oxide gas containing water vapor; s4: powdered Al 2 O 3 With LiNO 3 Is subjected to water dissolution and then is filtered to realize aluminum-lithium separation, and crude Al is obtained 2 O 3 And LiNO 3 A solution. The invention realizes the high-efficiency recovery of trace lithium, improves the aluminum separation rate, reduces the energy consumption and improves the energy utilization efficiency.
Description
Technical Field
The invention belongs to the technical fields of chemical metallurgy and lithium recovery, and particularly relates to a method for separating and recovering trace lithium in an aluminum nitrate solution.
Background
Lithium is the lightest and least dense metal with unique physical and chemical properties, and is known as industrial monosodium glutamate, and has a body shadow in various traditional industrial fields. With the development of new energy industry, lithium batteries are in great demand, and lithium is also called "energy metal" in the 21 st century. The lithium resource is widely applied to industries such as glass and ceramic manufacture, alloy and raw aluminum production, lithium battery production, medicine, optical materials and the like. In addition, the method has application in the military industry and the nuclear industry. Lithium is regarded as a new economic growth point by various countries as an important supporting mineral for the development of strategically emerging industries, and is also one of mineral resources necessary for the strategically emerging industries in seven major countries of China.
The current method for recovering and extracting trace lithium elements in solution refers to a method for extracting lithium from salt lakes, mainly comprises a carbonate precipitation method, a solvent extraction method and an adsorption method, and the carbonate precipitation method greatly improves the production cost because the concentrated brine contains supersaturated magnesium chloride and a large amount of sodium carbonate is needed to consume the magnesium in the brine. Although the solvent extraction method has better selective complexation of crown ether to lithium ions, the prior art is limited to experimental stages and is not popularized, and the common organic adsorbent for the adsorption method is artificial resin, which has the defects of poor selectivity of the adsorbent to lithium ions, incomplete separation and high production cost, and all three methods have certain limitations.
Disclosure of Invention
The invention discloses a method for separating and recovering trace lithium in an aluminum nitrate solution, which aims to solve the problems of poor selectivity to lithium ions, incomplete separation and low lithium recovery rate in the prior art. The method aims at aluminum nitrate solution (namely multivalent ion solution) containing trace lithium, and uses high-temperature NO generated in the subsequent atomization and calcination process x The (x is 1 or 2) gas preheats and evaporates the aluminum nitrate solution, and then uses a water-vapor separation device to separate NO x (x is 1 or 2), separating, recycling and preparing nitric acid and recycling the nitric acid for a leaching process; will be preheated and evaporated subsequently with Al (NO) 3 Mainly contains trace LiNO 3 And evaporating and concentrating to obtain the multivalent ion liquid containing Al (NO) 3 、LiNO 3 Will contain Al (NO) 3 、LiNO 3 The mixed solution of (2) is atomized and calcined to obtain powdery Al 2 O 3 With LiNO 3 Is a mixture of (2)Dissolving with water to obtain crude Al 2 O 3 LiNO 3 Solution of LiNO 3 The solution was used to prepare battery grade lithium carbonate.
The method provided by the invention has the advantages that the generated heat energy is utilized in a gradient manner, trace lithium in the separation solution is effectively recovered, meanwhile, nitric acid in the working procedure is recycled, the production cost of the process is reduced, the recovery rate of lithium in the working procedure is improved, the maximization of resource utilization is realized, the whole working procedure is simple, and the industrial production is easy to realize.
The invention aims to provide a method for separating and recovering trace lithium in an aluminum nitrate solution, which comprises the following steps of:
s1: nitric acid leaching solution obtained by nitric acid leaching of lithium ore is separated by a nanofiltration membrane, and LiNO is obtained 3 Predominantly monovalent ionic liquids and based on Al (NO) 3 A predominantly multivalent ionic liquid;
s2: purifying and removing impurities from the monovalent ion liquid obtained in the step S1, and then preparing battery-grade lithium carbonate; preheating and evaporating the multivalent ion liquid obtained in the step S1 by utilizing nitrogen oxide gas generated by atomization and calcination, and then evaporating and concentrating to obtain the Al (NO) 3 、LiNO 3 Is a mixed solution of (a) and (b);
s3: al (NO) contained in S2 3 、LiNO 3 The mixed solution of (2) is atomized and calcined to generate powdery Al 2 O 3 With LiNO 3 Nitrogen oxide gas containing water vapor; the temperature of atomization calcination is 400-750 ℃;
s4: the powdery Al obtained in S3 2 O 3 With LiNO 3 Is subjected to water dissolution and then is filtered to realize aluminum-lithium separation, and crude Al is obtained 2 O 3 And LiNO 3 And the lithium nitrate solution is used for preparing battery-grade lithium carbonate for recycling.
Preferably, in S1, the nanofiltration membrane is multi-stage nanofiltration, the number of stages is 2-7, and the nanofiltration pressure is 2.0-8.0MPa.
Preferably, in S1, the content of lithium ions in the multivalent ion liquid after nanofiltration membrane separation is 0.01-3g/L, and the concentration of aluminum ions is 3-15g/L. It will be appreciated that it additionally contains small amounts of impurities such as calcium, magnesium, iron and the like.
Preferably, in S2, the temperature of the evaporation concentration is 70-110 ℃, and the concentration of aluminum ions after the evaporation concentration is 40-70g/L. Under the preferred scheme, the recovery rate of lithium is improved, and the separation rate of aluminum is improved.
Preferably, in S3, the temperature of the atomization calcination is 400-700 ℃, and Al (NO) is contained 3 、LiNO 3 The atomization flow of the mixed solution is 15-85L/min, and the atomization calcination time is 1-5h. Under the preferred scheme, the recovery rate of lithium is improved, and the separation rate of aluminum is improved.
Preferably, in S4, the mass ratio of liquid to solid in the water dissolution is 2-4:1, the temperature of the water dissolution is 30-90 ℃, and the time of the water dissolution is 0.5-3h.
More preferably, the temperature of water dissolution is 60-90 ℃. Under the preferred scheme, the recovery rate of lithium is improved, and the separation rate of aluminum is improved.
More preferably, the water-soluble liquid-to-solid mass ratio is 3-4:1. Under the preferred scheme, the recovery rate of lithium is improved, and the separation rate of aluminum is improved.
Preferably, S3 further includes: and (3) performing water-vapor separation on the finally obtained nitrogen oxide gas containing water vapor to obtain nitrogen oxide and water vapor, wherein the nitrogen oxide is used for preparing nitric acid through water absorption and is recycled in the nitric acid leaching process of S1.
The invention has at least the following beneficial effects:
according to the invention, by utilizing the characteristics that nitrate is easy to decompose at high temperature and different nitrate decomposition temperatures are different, nitric acid recycling is realized through high-temperature atomization calcination, impurities such as aluminum nitrate are changed into water-insoluble oxides, lithium nitrate exists in the form of nitrate due to higher decomposition temperature, the calcined mixture is dissolved by water, the physical separation of aluminum oxide and trace lithium in solution is realized through filtration, and the filtrate is purified and purified to remove impurities and then is used for preparing battery-grade lithium carbonate so as to realize efficient recovery of lithium, and meanwhile, the aluminum separation rate is improved. In addition, the invention introduces heat energy for gradient utilization, preheats and evaporates the high-temperature nitrogen oxide gas on the aluminum nitrate solution, reduces the evaporation capacity of the subsequent evaporation concentration working section, reduces the energy consumption and improves the energy utilization efficiency. Compared with the existing carbonate precipitation method, solvent extraction method, adsorption method and other methods, the method has the characteristics of low cost, simple process flow, no need of additional chemical agents and the like.
The invention provides a method for separating and recovering trace lithium in an aluminum nitrate solution for the first time, which comprises the steps of preheating and evaporating high-temperature nitrogen oxide gas generated by a subsequent atomization and calcination process for a nitrate multivalent ion solution, increasing the concentration of the multivalent ion solution, realizing heat gradient utilization, and further evaporating and concentrating the preheated and evaporated solution to obtain the aluminum Nitrate (NO) 3 、LiNO 3 For the mixed solution containing Al (NO) 3 、LiNO 3 The mixed solution of (2) is decomposed by atomization and calcination to obtain powdery Al 2 O 3 And LiNO 3 Is a mixture of (a) and (b); dissolving the mixture obtained after atomization and calcination in water, and filtering and separating to obtain crude Al 2 O 3 And LiNO 3 Solution, liNO 3 The solution is returned to the system for preparing the battery grade lithium carbonate after purification and impurity removal, and the separation of metal aluminum and lithium is realized without using other chemical auxiliary materials. The process is simple, green and environment-friendly, byproducts are comprehensively recycled, the production cost is low, and the large-scale production is easy to realize.
In the invention, preferably, after the final high-temperature nitrogen oxide gas is subjected to water-vapor separation, the obtained nitrogen oxide is recycled to prepare nitric acid for the front-end lithium ore leaching process, so that the recycling of nitric acid is realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram for separating and recovering trace lithium in an aluminum nitrate solution according to the invention.
Detailed Description
Aiming at the separation and recovery of metal lithium in the multivalent ion liquid mainly comprising aluminum nitrate, the method provided by the invention directly carries out preheating, evaporation concentration, atomization calcination and water dissolution on the multivalent ion solution after membrane separation, realizes effective separation and nitric acid recovery and utilization of aluminum and lithium metal ions in the multivalent ion liquid without using other auxiliary materials, carries out preliminary preheating evaporation and evaporation concentration on the multivalent ion liquid by utilizing high-temperature nitrogen oxide gas to realize heat echelon utilization, improves the energy utilization efficiency, reduces the loss of metal lithium, effectively improves the total recovery rate of lithium, has short process flow, is simple and applicable, has low production cost, has better economic value and environment-friendly process.
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The analysis results of the partial components of the high valence ionic liquid after multistage nanofiltration used in the examples are shown in Table 1.
TABLE 1 analysis results of partial Components of high valent ion liquid after multistage nanofiltration
Example 1
As shown in fig. 1, the process flow chart for separating and recovering trace lithium in the aluminum nitrate solution of the invention comprises the following detailed steps:
the method for separating and recovering trace lithium in the lithium nitrate solution specifically comprises the following steps:
s1: nitric acid leaching solution obtained by nitric acid leaching of lithium ore is separated by a nanofiltration membrane, and LiNO is obtained 3 Predominantly monovalent ionic liquids and based on Al (NO) 3 The main multivalent ion liquid.
S2: purifying and removing impurities from the monovalent ion liquid obtained in the step S1, and then preparing battery-grade lithium carbonate; preheating and evaporating the multivalent ion liquid obtained in the step S1 by utilizing high-temperature nitrogen oxide gas generated by atomization and calcination, and then evaporating and concentrating to obtain the Al (NO) -containing ion liquid 3 、LiNO 3 Is a mixed solution of (a) and (b); the evaporating concentration temperature is 90 ℃, and the concentration of aluminum ions after evaporating concentration is 58g/L.
S3: al (NO) contained in S2 3 、LiNO 3 Is atomized and calcined for 1h at 550 ℃, and naturally cooled to obtain Al 2 O 3 With LiNO 3 Is atomized at a flow rate of 60L/min; NO containing water vapor produced x The (x is 1 or 2) gas is used for preheating and evaporating multivalent ion liquid, and finally the nitrogen oxide gas of the obtained water-containing steam is separated into NO by using a water-vapor separation device x (x is 1 or 2) for preparing HNO 3 。
S4: the powdery Al obtained in S3 2 O 3 With LiNO 3 Adding water into the mixture according to the mass ratio of 3:1 pulping, dissolving in water at 65deg.C for 1 hr, and filtering to obtain crude Al 2 O 3 And LiNO 3 And the lithium nitrate solution is used for preparing battery-grade lithium carbonate for recycling.
The yield of lithium in this example was 97.2% by mass, and the separation rate of aluminum was 95.4%.
Example 2
The method for separating and recovering trace lithium in the lithium nitrate solution was carried out as described in example 1, except that:
in S3, the atomization calcining temperature is 600 ℃.
S4, water and Al 2 O 3 With LiNO 3 The liquid-solid mass ratio of the mixture of (2) is 4:1, the water dissolution temperature was 75 ℃.
The yield of lithium in this example was 97.4%, and the separation rate of aluminum was 96.6%.
Example 3
The method for separating and recovering trace lithium in the lithium nitrate solution was carried out as described in example 1, except that:
in S3, the atomization calcining temperature is 700 ℃.
In S4, water and crude Al 2 O 3 、LiNO 3 The liquid-solid mass ratio of the mixture of (2) is 4:1, water dissolution temperatureIs 85 ℃.
The lithium yield of this example was 97.7%, and the aluminum separation rate was 94.1%.
Example 4
The method for separating and recovering trace lithium in the lithium nitrate solution was carried out as described in example 3, except that: in S4, water and crude Al 2 O 3 、LiNO 3 The liquid-solid mass ratio of the mixture of (2) is 4:1, the water dissolution temperature was 60 ℃.
The yield of lithium in this example was 95.3%, and the separation rate of aluminum was 93.2%.
Example 5
The method for separating and recovering trace lithium in the lithium nitrate solution was carried out as described in example 3, except that: in S4, water and crude Al 2 O 3 、LiNO 3 The liquid-solid ratio of the mixture of (2) is 4:1, the water dissolution temperature was 30 ℃.
The yield of lithium in this example was 81.2%, and the separation rate of aluminum was 93.0%.
Example 6
The method for separating and recovering trace lithium in the lithium nitrate solution was carried out as described in example 3, except that: in S4, water and crude Al 2 O 3 、LiNO 3 The liquid-solid ratio of the mixture of (2): 1, the water dissolution temperature was 85 ℃.
The yield of lithium in this example was 84.1%, and the separation rate of aluminum was 90.2%.
Comparative example 1
The method for separating and recovering trace lithium in the lithium nitrate solution was carried out as described in example 3, except that: in S3, the atomization calcining temperature is 300 ℃.
The yield of lithium in this example was 90.3%, and the separation rate of aluminum was 40.2%.
Comparative example 2
The method for separating and recovering trace lithium in the lithium nitrate solution was carried out as described in example 3, except that: in S3, the atomization calcining temperature is 900 ℃.
The yield of lithium in this example was 70.8%, and the separation rate of aluminum was 96.2%.
The foregoing is only a partial embodiment of the invention, and it should be noted that it will be apparent to those skilled in the art that modifications and adaptations can be made without departing from the principles of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (9)
1. The method for separating and recovering trace lithium in the aluminum nitrate solution is characterized by comprising the following steps of:
s1: nitric acid leaching solution obtained by nitric acid leaching of lithium ore is separated by a nanofiltration membrane, and LiNO is obtained 3 Predominantly monovalent ionic liquids and based on Al (NO 3 ) 3 A predominantly multivalent ionic liquid;
s2: purifying and removing impurities from the monovalent ion liquid obtained in the step S1, and then preparing battery-grade lithium carbonate; preheating and evaporating the multivalent ion liquid obtained in the step S1 by utilizing nitrogen oxide gas generated by atomization and calcination, and then evaporating and concentrating to obtain the Al (NO) 3 ) 3 、LiNO 3 Is a mixed solution of (a) and (b);
s3: al (NO) containing S2 3 ) 3 、LiNO 3 The mixed solution of (2) is atomized and calcined to generate powdery Al 2 O 3 With LiNO 3 Nitrogen oxide gas containing water vapor; the temperature of atomization calcination is 400-750 ℃;
s4: the powdery Al obtained in S3 2 O 3 With LiNO 3 Is subjected to water dissolution and then is filtered to realize aluminum-lithium separation, and crude Al is obtained 2 O 3 And LiNO 3 And the lithium nitrate solution is used for preparing battery-grade lithium carbonate for recycling.
2. The method for separating and recovering trace lithium from an aluminum nitrate solution according to claim 1, wherein in S2, the temperature of the evaporation concentration is 70-110 ℃, and the concentration of aluminum ions after the evaporation concentration is 40-70g/L.
3. The method according to claim 1A method for separating and recovering trace lithium in aluminum nitrate solution is characterized in that in S3, the atomization calcining temperature is 400-700 ℃, and Al (NO) 3 ) 3 、LiNO 3 The atomization flow of the mixed solution is 15-85L/min, and the atomization calcination time is 1-5h.
4. The method for separating and recovering trace lithium in an aluminum nitrate solution according to claim 1, wherein in S4, the mass ratio of liquid to solid in the water solution is 2-4:1, the temperature of the water solution is 30-90 ℃, and the time of the water solution is 0.5-3h.
5. The method for separating and recovering a trace amount of lithium in an aluminum nitrate solution according to claim 4, wherein in S4, the temperature of the water dissolution is 60 to 90 ℃.
6. The method for separating and recovering a trace amount of lithium in an aluminum nitrate solution according to claim 4 or 5, wherein in S4, the mass ratio of liquid to solid in the water solution is 3-4:1.
7. The method for separating and recovering trace lithium in an aluminum nitrate solution according to claim 1, wherein in the step S1, the nanofiltration membrane is a multistage nanofiltration, the number of stages is 2-7, and the nanofiltration pressure is 2.0-8.0MPa.
8. The method for separating and recovering trace lithium in an aluminum nitrate solution according to claim 1, wherein in S1, the lithium ion content in the multivalent ion solution is 0.01-3g/L, and the aluminum ion concentration is 3-15g/L.
9. The method for separating and recovering a trace amount of lithium in an aluminum nitrate solution according to claim 1, wherein S3 further comprises: and (3) performing water-vapor separation on the finally obtained nitrogen oxide gas containing water vapor to obtain nitrogen oxide and water vapor, wherein the nitrogen oxide is used for preparing nitric acid through water absorption and is recycled in the nitric acid leaching process of S1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211361583.1A CN115784274B (en) | 2022-11-02 | 2022-11-02 | Method for separating and recovering trace lithium in aluminum nitrate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211361583.1A CN115784274B (en) | 2022-11-02 | 2022-11-02 | Method for separating and recovering trace lithium in aluminum nitrate solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115784274A CN115784274A (en) | 2023-03-14 |
| CN115784274B true CN115784274B (en) | 2024-01-09 |
Family
ID=85434957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211361583.1A Active CN115784274B (en) | 2022-11-02 | 2022-11-02 | Method for separating and recovering trace lithium in aluminum nitrate solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115784274B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509790A (en) * | 2011-10-20 | 2012-06-20 | 四川天齐锂业股份有限公司 | LiFePO4 (lithium iron phosphate) positive electrode material with specific morphology and structure and lithium secondary battery |
| CN109704412A (en) * | 2018-12-05 | 2019-05-03 | 郑州中科新兴产业技术研究院 | A kind of retired lithium-ion-power cell nickle cobalt lithium manganate tertiary cathode material recycling and reusing method |
| CN111137908A (en) * | 2019-12-27 | 2020-05-12 | 长沙市原鹏化工科技有限公司 | System method for extracting lithium-containing brine from lepidolite and manufacturing lithium salt |
| CN111394745A (en) * | 2020-03-25 | 2020-07-10 | 意定(上海)信息科技有限公司 | Method for preparing lithium hydroxide from lithium-containing low-magnesium brine |
| CN113365947A (en) * | 2018-11-29 | 2021-09-07 | 伊希普私人有限公司 | Preparation of lithium chemicals and lithium metal |
| CN113772696A (en) * | 2021-09-09 | 2021-12-10 | 四川顺应动力电池材料有限公司 | Method for producing various lithium products by processing lepidolite through nitric acid pressurization method |
| CN114105171A (en) * | 2021-11-04 | 2022-03-01 | 四川顺应动力电池材料有限公司 | Method for recycling and comprehensively utilizing lepidolite and lithium hydroxide prepared by method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10450633B2 (en) * | 2017-07-21 | 2019-10-22 | Larry Lien | Recovery of lithium from an acid solution |
-
2022
- 2022-11-02 CN CN202211361583.1A patent/CN115784274B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509790A (en) * | 2011-10-20 | 2012-06-20 | 四川天齐锂业股份有限公司 | LiFePO4 (lithium iron phosphate) positive electrode material with specific morphology and structure and lithium secondary battery |
| CN113365947A (en) * | 2018-11-29 | 2021-09-07 | 伊希普私人有限公司 | Preparation of lithium chemicals and lithium metal |
| CN109704412A (en) * | 2018-12-05 | 2019-05-03 | 郑州中科新兴产业技术研究院 | A kind of retired lithium-ion-power cell nickle cobalt lithium manganate tertiary cathode material recycling and reusing method |
| CN111137908A (en) * | 2019-12-27 | 2020-05-12 | 长沙市原鹏化工科技有限公司 | System method for extracting lithium-containing brine from lepidolite and manufacturing lithium salt |
| CN111394745A (en) * | 2020-03-25 | 2020-07-10 | 意定(上海)信息科技有限公司 | Method for preparing lithium hydroxide from lithium-containing low-magnesium brine |
| CN113772696A (en) * | 2021-09-09 | 2021-12-10 | 四川顺应动力电池材料有限公司 | Method for producing various lithium products by processing lepidolite through nitric acid pressurization method |
| CN114105171A (en) * | 2021-11-04 | 2022-03-01 | 四川顺应动力电池材料有限公司 | Method for recycling and comprehensively utilizing lepidolite and lithium hydroxide prepared by method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115784274A (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111268701B (en) | Method for preparing battery-grade lithium hydroxide by using lepidolite | |
| CN114105171B (en) | Method for comprehensively utilizing lepidolite resources and lithium hydroxide prepared by method | |
| CN104745823B (en) | Method for recycling lithium from waste lithium ion battery | |
| CN103773966B (en) | The extraction and application method of neodymium iron boron waste material | |
| CN104928475B (en) | A kind of recovery method of the aluminium scrap silicon containing rare earth | |
| CN107381604A (en) | A kind of method that lithium carbonate is reclaimed from ferric phosphate lithium cell | |
| CN111792656B (en) | Method for preparing lithium sulfate from salt lake brine | |
| CN115321562B (en) | Method for producing lithium carbonate by lithium ore nitric acid leaching solution membrane method | |
| CN115286019A (en) | Method for producing high-purity lithium carbonate from spodumene | |
| CN115893346A (en) | Method for recovering and preparing battery-grade iron phosphate after lithium extraction of waste lithium iron phosphate cathode material | |
| CN114436328B (en) | Method for preparing vanadyl sulfate electrolyte from sodium vanadate-containing solution | |
| CN110550646A (en) | preparation method of cesium sulfate and rubidium sulfate | |
| CN109987618A (en) | The preparation method of battery-level lithium carbonate | |
| CN116477858B (en) | Method for preparing battery-grade lithium carbonate by pressure leaching of clay lithium ore | |
| CN115784274B (en) | Method for separating and recovering trace lithium in aluminum nitrate solution | |
| CN116924472A (en) | Comprehensive utilization method of tungsten-containing magnesium ammonium phosphate slag | |
| CN102633292A (en) | Method for preparing copper sulphate by using copper sponge without roasting and evaporating | |
| CN106892479B (en) | Method for recovering oxalic acid and hydrochloric acid from rare earth oxalic acid precipitation wastewater | |
| CN115786715A (en) | Method for efficiently recycling nickel, cobalt, manganese and lithium metal from ternary lithium battery anode waste by membrane method | |
| CN109824068B (en) | Extraction of Rb from Low-concentration brine+And method for producing highly pure rubidium salt | |
| CN112390266A (en) | Boric acid composite extracting agent and method for recovering boric acid, magnesium and lithium from salt lake old brine | |
| CN112569736B (en) | Tail gas recycling method in uranium oxide preparation process by ammonium uranyl tricarbonate | |
| CN221656566U (en) | System for from oil gas field produced water preparation and purification lithium carbonate | |
| CN118637656B (en) | Method for promoting calcium nitrate crystallization in phosphorite decomposition process by nitric acid | |
| CN218146877U (en) | Comprehensive brine utilization system |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |