Method for extracting lithium from brine based on novel lithium ion sieve adsorbent material

Abstract

A method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material comprises the following steps: firstly, adsorbing the brine by using the novel lithium ion adsorbent material M1y (LixM21-x) O2; wherein M1 is selected from non-lithium alkali metal elements Na and / or K; 0 lt; y is less than or equal to 1, M2 is selected from at least one of transition metal elements Fe, Co, Ni and Mn, and Li and the transition metal element M2 occupy a lattice position, 0 lt; xlt; 0.5 part; after adsorption is completed, clear water is used for flushing, and residual brine on the surface of the material is washed away; then carrying out acid liquid elution on the M1y (LixM21-x) O2 after adsorbing the lithium; after fully eluting, washing with clear water; then carrying out alkali liquor treatment on the material to recover the adsorption performance of the material; then washing with clear water to wash away residual alkali liquor on the surface of the material, and obtaining the regenerated adsorption material which can enter the next adsorption lithium extraction cycle; the scheme provided by the invention has the advantages that the industrial process is simple, the cost is low, and the long-term circulation capability of the novel adsorption material can be realized, so that the application prospect is very good.

Description

Technical Field

[0001] The present application relates to the technical field of lithium extraction from brine, and in particular to a method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material. Background Art

[0002] Lithium, widely used in energy, electronics, chemicals, aerospace, and other fields, has been hailed as the "industrial MSG," "the energy metal driving global progress," and "white oil." Currently, approximately three-quarters of the world's lithium resources are used in the manufacture of lithium-ion batteries. Salt lake brines contain vast quantities of lithium, accounting for approximately 60% of the world's lithium resources. Lithium extraction from brine has become the primary method for extracting lithium from salt lake brines. Adsorbent extraction, solvent extraction, and membrane extraction are the most prominent methods for extracting lithium from salt lake brines. Adsorption, due to its excellent ion selectivity, environmental friendliness, and high recycling rate, is considered one of the most promising methods for extracting lithium from brine.

[0003] The applicant's earlier application is a patent document with the publication number CN 117101599 B, which provides a new lithium adsorption material M1 y (Li x M2 1-x )O2, because this material is different from traditional adsorbent materials such as HMn2O4, H 1.33 Mn 1.67 O4、H 1.6 Mn 1.6 O4, H2TiO3, etc., innovatively uses the M1-Li exchange principle, so the traditional adsorption process of directly recycling after pickling is no longer applicable to this adsorption material. This is because the traditional pickling only washes away the adsorbed lithium without replenishing new M1, and the initial state cannot be restored after pickling; Therefore, it is necessary to target the new lithium adsorption material M1 disclosed in the patent document CN 117101599 B. y (Li x M2 1-x )O2 characteristics for the development of lithium extraction technology. Summary of the Invention

[0004] In response to the above-mentioned deficiencies in the prior art, the present application provides a method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material, which has a simple industrial process, low cost, the ability to enable long-term circulation of the novel adsorption material, and good application prospects.

[0005] In order to solve the above technical problems, the technical solution adopted in this application is: a method for extracting lithium from brine based on a new lithium ion sieve adsorbent material, the steps of the method comprising:

[0006] (1) First, use the new lithium ion adsorbent material M1 y (Li xM2 1-x )O2 (CN117101599 B) adsorbs brine; wherein M1 is selected from the alkali metal elements Na and / or K other than lithium; 0 < y ≤ 1, M2 is selected from at least one of the transition metal elements Fe, Co, Ni, and Mn, and Li and the transition metal element M2 together occupy one lattice position, 0 < x < 0.5;

[0007] (2) After the adsorption is completed, rinse with clear water to wash away the residual brine on the surface of the material;

[0008] (3) Then, for the novel lithium ion adsorbent material M1 y (Li x M2 1-x )O2 is eluted with acid solution;

[0009] (4) After sufficient elution, rinse with clear water to wash away the residual acid solution on the surface of the material;

[0010] (5) Treat the material with an alkali solution to restore its adsorption performance;

[0011] (6) Then rinse with clear water to wash away the residual alkali solution on the surface of the material, and the regenerated adsorbent material can enter the next lithium extraction by adsorption cycle.

[0012] Furthermore, the brine described in step (1) includes, but is not limited to, at least one of salt lake raw brine, old brine, qualified liquid, lithium precipitation mother liquor, etc.; the lithium concentration in the brine is not less than 0.05 g / L, and the adsorption capacity of the adsorbent material can be fully exerted.

[0013] Furthermore, the adsorption methods described in step (1) include, but are not limited to, static adsorption, column dynamic adsorption, and stirring adsorption.

[0014] Furthermore, for the static adsorption described in step (1), the time is in the range of 10 min - 72 h, and the temperature is in the range of 0°C - 100°C.

[0015] Furthermore, for the dynamic adsorption described in step (1), control the brine flow rate at 1 - 24 bv / h (bv / h is the representation of space velocity, that is, the average liquid volume flowing through the unit volume of resin per unit time (h) in the column, sometimes called specific volume (sv) or resin bed volume (bv) for short), the time is in the range of 10 min - 72 h, and the ambient temperature is in the range of 0°C - 100°C.

[0016] Furthermore, the methods of rinsing with clear water described in step (2) or step (4) or step (6) include, but are not limited to, column cleaning and stirring cleaning.

[0017] Furthermore, the flow rate of the column cleaning is 1-24 bv / h, the time is 10 min-72 h, and the ambient temperature is in the range of 0°C-100°C.

[0018] Furthermore, the stirring and cleaning stirring speed is 50-3000 rpm, the ambient temperature is in the range of 0°C-100°C, and the time is 10 minutes-72 hours.

[0019] Furthermore, the acid solution used for the acid elution in step (2) includes but is not limited to at least one of hydrochloric acid, sulfuric acid, oxalic acid, etc., and the concentration of the acid is between 0.05M-5M (mol / L).

[0020] Furthermore, the acid elution in step (2) includes but is not limited to column elution, stirring elution, and static elution to fully precipitate the lithium adsorbed by the brine.

[0021] Furthermore, the column cleaning flow rate is 1-24 bv / h, the time is 10 min-72 h, and the ambient temperature is in the range of 0°C-100°C.

[0022] Furthermore, the stirring and cleaning has a stirring speed of 50-3000 rpm, a time of 10 min-72 h, and an ambient temperature in the range of 0°C-100°C.

[0023] Furthermore, the static soaking time is between 10 minutes and 72 hours, and the temperature is between 0°C and 100°C.

[0024] Furthermore, the alkali solution used in the alkali solution treatment described in step (5) includes but is not limited to alkaline solutions of sodium, potassium, rubidium, cesium, ammonium, etc., the pH range of the solution is between 7-14, and the concentration of cations (sodium, potassium, rubidium, cesium, ammonium, etc. ions) is between 0.01M-10M.

[0025] Furthermore, the cations of the alkaline solution in step (5) and the new lithium ion adsorbent material M1 y (Li x M2 1-x )The type of M1 in O2 (CN117101599 B) is consistent.

[0026] Furthermore, the alkali solution treatment method described in step (5) includes but is not limited to column passing, stirring, and static soaking.

[0027] Furthermore, the column cleaning flow rate is 1-24 bv / h, the time is 10 min-72 h, and the ambient temperature is in the range of 0°C-100°C.

[0028] Furthermore, the stirring and cleaning has a stirring speed of 50-3000 rpm, a time of 10 min-72 h, and an ambient temperature in the range of 0°C-100°C.

[0029] Furthermore, the static soaking time is in the range of 10 min - 72 h, and the temperature is in the range of 0°C - 100°C.

[0030] Advantages and beneficial effects of the present invention:

[0031] 1. For the first time, this application targets the specific new lithium-ion adsorbent material M1 in the publication number CN 117101599 B y (Li x M2 1-x )O2, where M1 is selected from non-lithium alkali metal elements Na and / or K; 0 < y ≤ 1, M2 is selected from at least one of the transition metal elements Fe, Co, Ni, and Mn, Li and the transition metal element M2 jointly occupy one lattice position, 0 < x < 0.5; M1 and M2 in the above structural formula are taken as a whole respectively, and each represents the corresponding element type; a lithium extraction process is developed for this specific-structured new lithium-ion adsorbent material. The setting of this process enables this new lithium-ion adsorbent material to extract lithium cyclically, thus effectively saving the loss of the adsorbent material, enabling it to be recycled, and reducing costs; moreover, the regeneration process of this application has a simple operation process and is suitable for industrial operation, enabling the new adsorbent material to have the ability of long-term cyclic use and having good application prospects.

[0032] 2. This application targets the specific new lithium-ion adsorbent material M1 in the publication number CN 117101599 B y (Li x M2 1-x )O2. Based on the adsorption principle of this adsorbent material being the M1-Li exchange principle, a regeneration process for this adsorbent material is developed. This regeneration process can replenish the lost M1 through alkali solution treatment, making the adsorbent material return to its original composition and structure, and realizing the regeneration and recycling of its adsorption function; moreover, the adsorption performance after regeneration is made more stable by effectively controlling the concentration of the alkali solution. This is because if the concentration is too small, the water consumption is large and the recovery speed is slow, while if the concentration is too large, it will cause the dissolution of M2 and damage the material structure.

[0033] 3. The specific new lithium-ion adsorbent material M1 mentioned in the publication number CN 117101599 B y (Li x M2 1-x )O2 does not de-lithiate after adsorbing lithium, but instead uses the M1 y (Li x M2 1-x) O2 as a whole is directly used as a raw material to prepare lithium battery positive electrode materials. Although the lithium removal process is saved, this adsorption material with excellent performance cannot be regenerated and recycled, which reduces its utilization efficiency. Therefore, this application is the first to target this specific new lithium ion adsorbent material M1 in the publication number CN117101599 B. y (Li x M2 1-x )O2, a regeneration process and a method for cyclically adsorbing lithium are set up. The regeneration method is based on the principle of adsorption of the adsorption material, which is the M1-Li exchange principle. The M1 lost through the exchange is replenished again through the corresponding alkali solution, so that the adsorption material can be regenerated through this specific process and replenishment process after adsorbing lithium, thereby realizing its recycling function; this solution of the present application can make M1 y (Li x M2 1-x ) The adsorption performance of O2 will drop below 50% only after it is recycled about 2,000 times. Therefore, the cycle period is long and the utilization efficiency is high. In addition, the regeneration process does not require high-temperature sintering and other operations. The reaction conditions are mild, and energy consumption can be effectively reduced while achieving regeneration. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Schematic diagram of the brine lithium extraction process of this application.

[0035] Figure 2 Comparison of XRD spectra of the original adsorbent material and the adsorbent material after alkali treatment. DETAILED DESCRIPTION

[0036] The following will clearly and completely describe the technical solutions in the embodiments of this application in conjunction with the embodiments and drawings. Obviously, the embodiments described are only preferred embodiments, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of this invention.

[0037] Example 1

[0038] Prepare sufficient qualified lithium-containing solution with Li concentration of 0.8 g / L, Na concentration of 0.3 g / L, K concentration of 0.8 g / L, and Mg concentration of 1.6 g / L. Add 160 ml of new adsorption material to a 200 ml single column. At room temperature of 25 ° C, the qualified solution is passed at a flow rate of 8 bv / h for 6 hours to fully adsorb it. After that, clean water is passed at 15 bv / h for 1 hour, and then 0.1 M hydrochloric acid is passed at 12 bv / h for 12 hours to fully analyze and remove lithium. Then, clean water is passed at 15 bv / h for 1 hour, and sodium hydroxide solution is passed. The cations (Na +) The total concentration is 10M, the flow rate is set to 12bv / L, the introduction time is 8h, and then clean water is introduced at 15bv / h for 1h, and then qualified liquid is introduced with the same parameters, and the cycle is repeated.

[0039] Figure 2 This is a comparison of the XRD spectra of the original adsorbent and the adsorbent material after alkali solution treatment. It can be seen that the main peak of the XRD after alkali solution treatment is consistent with the main peak of the XRD of the original material, indicating that the material structure has been well repaired and can be put into recycling again.

[0040] The adsorption material obtained by the regeneration method of the present application can be continuously recycled. As the number of regenerations increases, the adsorption performance will tend to gradually decay, and it is estimated that the decay each time is <0.05%. The number of recycling times is estimated to be around 2000 times, and the adsorption performance will drop below 50%. At this time, regeneration is no longer required and it can be treated as waste adsorption material.

[0041] Example 2

[0042] Prepare sufficient lithium-containing brine with a Li concentration of 0.4 g / L, a Na concentration of 0.8 g / L, a K concentration of 0.2 g / L, and a Mg concentration of 50 g / L. Add 160 ml of new adsorption material to a 200 ml single column. In a 30 °C environment, pass the qualified liquid at a flow rate of 4 bv / h for 6 hours to ensure sufficient adsorption. Then, pass clean water at 8 bv / h for 2 hours, and then pass 0.1 M hydrochloric acid at 8 bv / h for 6 hours to fully resolve and remove lithium. Then, pass clean water at 8 bv / h for 1 hour, set the temperature to 50 °C, pass potassium hydroxide alkali solution, the total cation concentration is 2 M, the flow rate is set to 8 bv / L, the passage time is 12 hours, and then pass clean water at 8 bv / h for 1 hour. Then, pass the qualified liquid with the same parameters and repeat the cycle.

[0043] Example 3

[0044] Prepare sufficient lithium-containing brine with a Li concentration of 0.4 g / L, a Na concentration of 0.6 g / L, a K concentration of 0.4 g / L, and a Mg concentration of 30 g / L. Add 160 ml of new adsorption material to a 200 ml single column. In a 30 °C environment, pass the qualified liquid at a flow rate of 4 bv / h for 6 hours to ensure sufficient adsorption. Then, pass clean water at 8 bv / h for 2 hours, and then pass 0.1 M hydrochloric acid at 8 bv / h for 6 hours to fully resolve and remove lithium. Then, pass clean water at 8 bv / h for 1 hour, set the temperature to 80 °C, pass sodium hydroxide solution, the total cation concentration is 2 M, the flow rate is set to 8 bv / L, the passage time is 12 hours, and then pass clean water at 8 bv / h for 1 hour. Then, pass the qualified liquid with the same parameters and repeat the cycle.

[0045] Example 4

[0046] Prepare sufficient lithium-containing brine with a Li concentration of 0.4 g / L, a Na concentration of 0.6 g / L, a K concentration of 0.4 g / L, a Mg concentration of 30 g / L, and a Ca concentration of 2 g / L. Add 160 ml of the new adsorption material to a 200 ml single column. In a 25 °C environment, pass the qualified liquid at a flow rate of 4 bv / h for 6 hours to ensure sufficient adsorption. Then, pass clean water at 8 bv / h for 2 hours, and then pass 1 M hydrochloric acid at 8 bv / h for 6 hours to fully resolve and remove lithium. Then, pass clean water at 8 bv / h for 1 hour, set the temperature to 80 °C, pass sodium hydroxide solution, the total cation concentration is 0.2 M, the flow rate is set to 8 bv / L, the passage time is 12 hours, and then pass clean water at 8 bv / h for 1 hour. Then, pass the qualified liquid with the same parameters and repeat the cycle.

[0047] Comparative Example 1

[0048] Prepare a sufficient amount of qualified lithium-containing liquid with a Li concentration of 0.8 g / L, a Na concentration of 0.3 g / L, a K concentration of 0.8 g / L, and a Mg concentration of 1.6 g / L. Add 160 ml of the new adsorption material to a 200 ml single column. At room temperature of 25°C, the qualified liquid is passed at a flow rate of 8 bv / h for 6 hours to ensure sufficient adsorption. After that, clean water is passed at 15 bv / h for 1 hour, and then 0.1 M hydrochloric acid is passed at 12 bv / h for 12 hours to fully resolve and remove lithium. After clean water is passed at 15 bv / h for 1 hour, the eluted adsorption material is obtained, and then the lithium in the qualified lithium-containing liquid is adsorbed. That is, the adsorption material directly after acid elution is subjected to lithium adsorption in this comparative example. The results show that there is no adsorption capacity for lithium at all.

[0049] Through the above examples and test results, it can be seen that this application is directed to the specific new lithium ion adsorbent material M1 in the publication number CN 117101599 B. y (Li x M2 1-x )O2, wherein M1 is selected from non-lithium alkali metal elements Na and / or K; 0

Claims

1. A method for extracting lithium from brine based on a new type of lithium ion sieve adsorbent material, characterized in that: The steps of the method include: (1) First, use the new lithium ion adsorbent material M1 y (Li x M2 1-x )O2 is used to adsorb the brine; where M1 is selected from non-lithium alkali metal elements Na and / or K; 0 < y ≤ 1, M2 is selected from at least one of the transition metal elements Fe, Co, Ni, and Mn, Li and the transition metal element M2 together occupy one lattice position, 0 < x < 0.5; (2) After adsorption, rinse with clean water to remove the brine remaining on the surface of the material; (3) Then the new lithium ion adsorbent material M1 y (Li x M2 1-x )O2 for acid elution; (4) After sufficient elution, rinse with clean water to remove the residual acid on the surface of the material; (5) treating the material with alkali solution to restore its adsorption performance; (6) Then rinse with clean water to wash away the residual alkali solution on the surface of the material, and the regenerated adsorption material can enter the next adsorption and lithium extraction cycle.

2. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 1, characterized in that: The brine described in step (1) includes but is not limited to at least one of salt lake raw brine, old brine, qualified liquid, and lithium precipitation mother liquor; the lithium concentration in the brine is not less than 0.05g / L.

3. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 1, characterized in that: The adsorption method described in step (1) includes but is not limited to static adsorption, column dynamic adsorption, and stirring adsorption.

4. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 3, characterized in that: The static adsorption time of step (1) is 10min-72h, and the temperature is in the range of 0°C-100°C; the dynamic adsorption of step (1) controls the brine flow rate to 1-24bv / h, the time is 10min-72h, and the ambient temperature is in the range of 0°C-100°C.

5. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 1, characterized in that: The method of washing with clean water in step (2) or step (4) or step (6) includes but is not limited to column washing and stirring washing.

6. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 5, characterized in that: The flow rate of the column cleaning is 1-24bv / h, the time is 10min-72h, and the ambient temperature is in the range of 0℃-100℃; the stirring speed of the stirring cleaning is 50-3000rpm, the ambient temperature is in the range of 0℃-100℃, and the time is 10min-72h.

7. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 1, characterized in that: The acid used for the acid elution in step (2) includes but is not limited to at least one of hydrochloric acid, sulfuric acid, and oxalic acid, and the acid concentration is between 0.05M and 5M; the acid elution in step (2) includes but is not limited to column elution, stirring elution, and static elution, so as to fully precipitate the lithium adsorbed by the brine.

8. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 7, characterized in that: The column cleaning flow rate is 1-24bv / h, the time is 10min-72h, and the ambient temperature is in the range of 0℃-100℃; the stirring cleaning stirring speed is 50-3000rpm, the time is 10min-72h, and the ambient temperature is in the range of 0℃-100℃; the static immersion time is 10min-72h, and the temperature is in the range of 0℃-100℃.

9. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 1, characterized in that: The alkali solution used in the alkali solution treatment in step (5) includes but is not limited to an alkaline solution of sodium, potassium, rubidium, cesium, or ammonium, the pH range of the solution is between 7 and 14, and the cation concentration is between 0.01 M and 10 M; the cations of the alkali solution in step (5) react with the novel lithium ion adsorbent material M1 y (Li x M2 1-x )The type of M1 in O2 is consistent; the alkali solution treatment method described in step (5) includes but is not limited to column passing, stirring, and static immersion.

10. The method for extracting lithium from brine based on a novel lithium ion sieve adsorbent material according to claim 9, characterized in that: The column cleaning flow rate is 1-24bv / h, the time is 10min-72h, and the ambient temperature is in the range of 0℃-100℃; the stirring cleaning stirring speed is 50-3000rpm, the time is 10min-72h, and the ambient temperature is in the range of 0℃-100℃; the static immersion time is 10min-72h, and the temperature is in the range of 0℃-100℃.

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