Lithium ion adsorbent and preparation method thereof, and lithium ion adsorption and desorption method

Abstract

The invention discloses a preparation method of a lithium ion adsorbent, which comprises the following steps: dissolving a metal ion substrate and an organic ligand material in a solvent according to a molar ratio of (1-10): (1-10) to obtain a mixed solution; heating the mixed solution; and cooling the heated mixed solution to room temperature, and then carrying out centrifugal separation, washing and vacuum drying treatment to obtain the lithium ion adsorbent, wherein the metal ion substrate is selected from one or more of Al (NO3) 3, Fe (NO3) 3, Ni (NO3) 3, ZrCl4, AlCl3, FeCl3 and CuCl2, and the organic ligand material is selected from one or more of 1, 4-phthalic acid, 1, 3, 5-benzene tricarboxylic acid, 1, 2, 4, 5-benzene tetracarboxylic acid, 2, 6-naphthalic acid, 4, 4 '-biphenyl dicarboxylic acid, 1, 4, 5, 8-naphthalene tetracarboxylic acid and 3, 3', 4, 4 '-biphenyl tetracarboxylic acid.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium adsorption, and in particular to a lithium ion adsorbent and a preparation method thereof, and a lithium ion adsorption and desorption method. Background Art

[0002] Lithium and its compounds have important applications in lithium batteries, ceramics and glass, lubricants, atomic energy thermonuclear fusion (reaction) and other fields. As a key strategic mineral resource, lithium is mainly distributed in lithium ores and brines. Among the many lithium extraction technologies, the adsorption method has become the preferred technology for liquid phase lithium extraction due to its strong applicability, simple operation, environmental friendliness and low cost. This method uses specific adsorbents to selectively capture lithium ions, and then uses eluents to elute and enrich lithium ions to achieve effective separation from impurity ions. The core of the adsorption method is to develop high-performance adsorbents. These adsorbents need to have excellent lithium ion selectivity, stable adsorption-desorption performance, and be simple to prepare, cost-effective and environmentally friendly.

[0003] However, current lithium-ion adsorption materials still face many challenges, such as complex preparation processes and some organic substances used in the preparation process that are harmful to the environment and human health. Therefore, the development of new adsorbents is particularly urgent. Summary of the invention

[0004] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a lithium ion adsorbent and a preparation method thereof, and a lithium ion adsorption and desorption method, so as to solve the problem that in the existing lithium resource extraction process using the adsorption method, the preparation process of the adsorption material is complicated and there is a high environmental impact during the preparation process.

[0005] The present invention first provides a method for preparing a lithium ion adsorbent, the preparation method comprising the following steps:

[0006] S1, dissolving the metal ion substrate and the organic ligand material in a solvent at a molar ratio of 1-10:1-10 to obtain a mixed solution;

[0007] S2, heating the mixed solution in step S1;

[0008] S3, cooling the heated mixed solution to room temperature, and then centrifuging, washing and vacuum drying to obtain a lithium ion adsorbent;

[0009] In which, the metal ion substrate in step S1 is selected from one or more of Al(NO3)3, Fe(NO3)3, Ni(NO3)3, ZrCl4, AlCl3, FeCl3 and CuCl2, and the organic ligand material is selected from one or more of 1,4-benzenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and 3,3',4,4'-biphenyltetracarboxylic acid.

[0010] Preferably, in step S2, the mixed solution is heated into a reaction kettle and heated at 100° C. to 300° C. for 1 h to 72 h.

[0011] Preferably, the solvent in step S1 is selected from one or more of deionized water, methanol, ethanol, acetonitrile, acetone, N,N-dimethylformamide, N,N-diethylformamide and dimethyl sulfoxide.

[0012] Preferably, the volume of the solvent in step S1 is 20 mL to 150 mL.

[0013] The present invention also provides a lithium ion adsorbent prepared by the above preparation method.

[0014] The present invention also provides a method for adsorbing and desorbing lithium ions, which uses the above-mentioned lithium ion adsorbent. The adsorption and desorption method comprises:

[0015] S10, dispersing a lithium ion adsorbent in a lithium salt solution, so that the lithium ion adsorbent adsorbs lithium ions in the lithium salt solution;

[0016] S20, adding a magneton to the lithium salt solution containing the lithium ion adsorbent, and centrifuging in a magnetic stirrer to separate the lithium ion adsorbent;

[0017] S30, using an acidic solution to perform a desorption treatment on the lithium ion adsorbent after centrifugal separation, so that the lithium ions on the lithium ion adsorbent are removed from the lithium ion adsorbent.

[0018] Preferably, the centrifugal separation time in step S20 is 0.1h to 0.5h.

[0019] Preferably, the concentration of the acidic solution is 0.1 mol / L to 5 mol / L.

[0020] Preferably, in step S30, the lithium ion adsorbent is desorbed using an acidic solution for 1 to 5 times, with each desorption lasting 1 hour to 24 hours.

[0021] Beneficial effects: The present invention adopts metal ion substrate and organic ligand material to prepare lithium ion adsorbent, wherein the materials used all meet the green chemistry standards, are non-toxic and harmless, and ensure the long-term feasibility in environmental protection and resource conservation. Furthermore, the process of synthesizing lithium ion adsorbent using the selected metal ion substrate and organic ligand material is simple, which simplifies the synthesis process, reduces the technical difficulty of operation, greatly reduces the preparation cost of materials, and improves the economy of the entire adsorption process. Furthermore, the prepared lithium ion adsorbent meets the efficient lithium ion adsorption effect, which is of great significance for the effective extraction and utilization of lithium resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The present invention provides a flow chart of a method for preparing a lithium ion adsorbent. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical scheme and advantages of this application clearer, the present invention is further described below in conjunction with the accompanying drawings and embodiments, and the embodiments of the present invention include but are not limited to the following embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0024] In this embodiment, the term "and / or" is merely a term used to describe the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may represent three situations: A exists alone, A and B exist at the same time, and B exists alone.

[0025] The terms "first" and "second" in the description and claims of this embodiment are used to distinguish different objects rather than to describe a specific order of objects. For example, a first target object and a second target object are used to distinguish different target objects rather than to describe a specific order of target objects.

[0026] In the embodiments of the present application, words such as "exemplary" or "for example" are used to indicate examples, illustrations or descriptions. Any embodiment or design described as "exemplary" or "for example" in the embodiments of the present application should not be interpreted as being more preferred or more advantageous than other embodiments or designs. Specifically, the use of words such as "exemplary" or "for example" is intended to present related concepts in a specific way.

[0027] In the description of the embodiments of the present application, unless otherwise specified, the meaning of "multiple" refers to two or more than two. For example, multiple processing units refer to two or more processing units; multiple systems refer to two or more systems.

[0028] Figure 1The flowchart of the preparation method of the lithium ion adsorbent provided by the present invention is shown in FIG. Figure 1 The preparation method of the lithium ion adsorbent comprises the following steps:

[0029] S1. Dissolve the metal ion substrate and the organic ligand material in a solvent at a molar ratio of 1-10:1-10 to obtain a mixed solution.

[0030] Wherein, the metal ion substrate in step S1 is selected from one or more of Al(NO3)3, Fe(NO3)3, Ni(NO3)3, ZrCl4, AlCl3, FeCl3 and CuCl2.

[0031] The organic ligand material is selected from one or more of 1,4-benzenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and 3,3',4,4'-biphenyltetracarboxylic acid.

[0032] Wherein, the structural formula of the 1,4-phthalic acid is:

[0033] The structural formula of the 1,3,5-benzenetricarboxylic acid is:

[0034] The structural formula of the 1,2,4,5-benzenetetracarboxylic acid is:

[0035] The structural formula of the 2,6-naphthalene dicarboxylic acid is:

[0036] The structural formula of the 4,4'-biphenyldicarboxylic acid is:

[0037] The structural formula of the 1,4,5,8-naphthalenetetracarboxylic acid is:

[0038] The structural formula of the 3,3',4,4'-biphenyltetracarboxylic acid is:

[0039]

[0040] Wherein, the solvent is selected from one or more of deionized water, methanol, ethanol, acetonitrile, acetone, N,N-dimethylformamide, N,N-diethylformamide and dimethyl sulfoxide.

[0041] The volume of the solvent in step S1 is 20 mL to 150 mL.

[0042] S2, heating the mixed solution in step S1.

[0043] Wherein, in step S2, the mixed solution is heated into a reaction kettle and heated at 100° C. to 300° C. for 1 h to 72 h, and then cooled to room temperature after the reaction is completed.

[0044] S3, centrifuging, washing and vacuum drying the cooled mixed solution in step S1 to obtain a lithium ion adsorbent.

[0045] The embodiment of the present invention further provides a method for adsorbing and desorbing lithium ions, using the lithium ion adsorbent described above, and the adsorption and desorption method comprises:

[0046] S10, dispersing a lithium ion adsorbent in a lithium salt solution, so that the lithium ion adsorbent adsorbs lithium ions in the lithium salt solution.

[0047] S20, adding magnetons to the lithium salt solution containing the lithium ion adsorbent, and centrifuging in a magnetic stirrer to separate the lithium ion adsorbent.

[0048] Wherein, the centrifugal separation time in step S20 is 0.1h to 0.5h.

[0049] In a specific implementation scheme, the prepared lithium ion adsorbent is dispersed into a centrifuge tube containing a lithium salt solution, and a magnet is added, and the mixture is stirred on a magnetic stirrer for 1 h to 24 h.

[0050] S30, using an acidic solution to perform a desorption treatment on the lithium ion adsorbent after centrifugal separation, so that the lithium ions on the lithium ion adsorbent are removed from the lithium ion adsorbent.

[0051] The concentration of the acidic solution is 0.1 mol / L to 5 mol / L. In the step S30, the lithium ion adsorbent is desorbed using the acidic solution for 1 to 5 times, each desorption lasting 1 hour to 24 hours.

[0052] The preparation of the lithium ion adsorbent in the present invention and the extraction of lithium resources using the prepared lithium ion adsorbent have the following advantages:

[0053] 1. The present invention adopts a metal ion substrate and an organic ligand material to form a metal-organic framework lithium ion adsorbent, and uses the lithium ion adsorbent to extract lithium resources. This method can achieve efficient lithium ion adsorption effect, which is of great significance for the effective extraction and utilization of lithium resources.

[0054] 2. The metal ion substrate and organic ligand materials used in the present invention, due to their low price and wide sources, combined with a simplified synthesis process, greatly reduce the material preparation cost and improve the economy of the entire adsorption process.

[0055] 3. The lithium ion preparation system and adsorption system of the present invention are designed with emphasis on simplicity, making the configuration process simple and intuitive, and very convenient to operate, thereby significantly improving work efficiency and reducing the technical difficulty of operation.

[0056] 4. The materials used in the present invention all meet the green chemistry standards, are non-toxic and harmless, are environmentally friendly and safe, and help promote the development of lithium adsorption technology in a more efficient and environmentally friendly direction.

[0057] Example 1

[0058] Example 1 provides a method for preparing a lithium ion adsorbent and a method for adsorbing and desorbing lithium ions, as follows:

[0059] Preparation of lithium ion adsorbent: Al(NO3)3 and organic ligand material 1,2,4,5-benzenetetracarboxylic acid are dissolved in 20mL of deionized water at a molar ratio of 4:1 and stirred until completely dissolved. Then the mixed solution is transferred to a reactor and heated at 210°C for 24 hours to react. After the reaction is completed, the mixed solution is cooled to room temperature, centrifuged, washed with solvent, and vacuum dried to prepare a lithium ion adsorbent.

[0060] Adsorption and desorption of lithium ions: The prepared lithium ion adsorbent was dispersed into a solution containing lithium salts and a magnet was added. After stirring on a magnetic stirrer for 24 hours, the lithium ion adsorbent was separated by centrifugation, and then the lithium ions were desorbed three times using a 0.5 mol / L HCl solution, each time for 12 hours. The amount of lithium ions adsorbed under this condition was measured by inductively coupled plasma emission spectrometry to be 49.49 mg / g.

[0061] Example 2

[0062] Example 2 provides a method for preparing a lithium ion adsorbent and a method for adsorbing and desorbing lithium ions, as follows:

[0063] Preparation of lithium ion adsorbent: Al(NO3)3 and organic ligand material 1,4,5,8-naphthalenetetracarboxylic acid are dissolved in 20mL deionized water at a molar ratio of 1:1 and stirred until completely dissolved. Then the mixed solution is transferred to a reactor and heated at 210°C for 24 hours to react. After the reaction is completed, the mixed solution is cooled to room temperature, and after centrifugation, solvent washing, and vacuum drying, a lithium ion adsorbent is prepared.

[0064] Adsorption and desorption of lithium ions: The prepared lithium ion adsorbent was dispersed into a solution containing lithium salts and a magnet was added. After stirring on a magnetic stirrer for 12 hours, the lithium ion adsorbent was separated by centrifugation, and then the lithium ions were desorbed three times using a 0.5 mol / L HCl solution, each time for 12 hours. The amount of lithium ions adsorbed under this condition was measured by inductively coupled plasma emission spectrometry to be 42.56 mg / g.

[0065] Example 3

[0066] Example 3 provides a method for preparing a lithium ion adsorbent and a method for adsorbing and desorbing lithium ions, as follows:

[0067] Preparation of lithium ion adsorbent: Al(NO3)3 and organic ligand material 1,4-phthalic acid are dissolved in 20mL acetonitrile at a molar ratio of 1:1 and stirred until completely dissolved. Then the mixed solution is transferred to a reactor and heated at 130°C for 22 hours to react. After the reaction is completed, the mixed solution is cooled to room temperature, centrifuged, washed with solvent, and vacuum dried to prepare a lithium ion adsorbent.

[0068] Adsorption and desorption of lithium ions: The prepared lithium ion adsorbent was dispersed into a solution containing lithium salts and a magnet was added. After stirring on a magnetic stirrer for 24 hours, the lithium ion adsorbent was separated by centrifugation, and then the lithium ions were desorbed three times using a 0.5 mol / L HCl solution, each time for 12 hours. The amount of lithium ions adsorbed under this condition was measured by inductively coupled plasma emission spectrometry to be 49.24 mg / g.

[0069] Example 4

[0070] Example 4 provides a method for preparing a lithium ion adsorbent and a method for adsorbing and desorbing lithium ions, as follows:

[0071] Preparation of lithium ion adsorbent: Al(NO3)3 and organic ligand material 2,6-naphthalene dicarboxylic acid are dissolved in 30mL N,N-dimethylformamide at a molar ratio of 1:1 and stirred until completely dissolved. Then the mixed solution is transferred to a reactor and heated at 120°C for 24 hours to react. After the reaction is completed, the mixed solution is cooled to room temperature and centrifuged, washed with solvent, and vacuum dried to prepare a lithium ion adsorbent.

[0072] Adsorption and desorption of lithium ions: The prepared lithium ion adsorbent was dispersed into a solution containing lithium salts and a magnet was added. After stirring on a magnetic stirrer for 24 hours, the lithium ion adsorbent was separated by centrifugation, and then the lithium ions were desorbed twice using a 0.5 mol / L HCl solution, each desorption lasting 24 hours. The amount of lithium ions adsorbed under this condition was measured by inductively coupled plasma emission spectrometry to be 39.19 mg / g.

[0073] Example 5

[0074] Example 5 provides a method for preparing a lithium ion adsorbent and a method for adsorbing and desorbing lithium ions, as follows:

[0075] Preparation of lithium ion adsorbent: Al(NO3)3 and organic ligand material 4,4'-biphenyldicarboxylic acid are dissolved in 30mL N,N-dimethylformamide at a molar ratio of 1:1 and stirred until completely dissolved. Then the mixed solution is transferred to a reactor and heated at 120°C for 24 hours to react. After the reaction is completed, the mixed solution is cooled to room temperature, centrifuged, washed with solvent, and vacuum dried to prepare a lithium ion adsorbent.

[0076] Adsorption and desorption of lithium ions: The prepared lithium ion adsorbent was dispersed into a solution containing lithium salts and a magnet was added. After stirring on a magnetic stirrer for 24 hours, the lithium ion adsorbent was separated by centrifugation, and then the lithium ions were desorbed twice using a 0.5 mol / L HCl solution, each time for 24 hours. The amount of lithium ions adsorbed under this condition was measured by inductively coupled plasma emission spectrometry to be 40.02 mg / g.

[0077] Example 6

[0078] Example 6 provides a method for preparing a lithium ion adsorbent and a method for adsorbing and desorbing lithium ions, as follows:

[0079] Preparation of lithium ion adsorbent: AlCl3 and organic ligand material 3,3',4,4'-biphenyltetracarboxylic acid are dissolved in 120mL methanol at a molar ratio of 2:1 and stirred until completely dissolved. Then the mixed solution is transferred to a reactor and heated at 125°C for 5 hours to react. After the reaction is completed, the mixed solution is cooled to room temperature, centrifuged, washed with solvent, and vacuum dried to prepare a lithium ion adsorbent.

[0080] Adsorption and desorption of lithium ions: The prepared lithium ion adsorbent was dispersed into a solution containing lithium salts and a magnet was added. After stirring on a magnetic stirrer for 12 hours, the lithium ion adsorbent was separated by centrifugation, and then the lithium ions were desorbed three times using a 0.3 mol / L HCl solution, each time for 12 hours. The amount of lithium ions adsorbed under this condition was measured by inductively coupled plasma emission spectrometry to be 39.49 mg / g.

[0081] Through Examples 1-6, it can be seen that the lithium ion adsorbent prepared by the present invention has high adsorption efficiency and selectivity, and the preparation process of the entire lithium ion adsorbent is simple.

[0082] In summary, the present invention provides a lithium ion adsorbent, which is a new lithium adsorbent that utilizes metal ions and organic ligands to form a metal organic framework (MOFs). The new lithium adsorbent of the metal organic framework is a crystalline porous material. Based on the prepared new lithium adsorbent, an efficient liquid-phase lithium ion adsorption system is provided to achieve more environmentally friendly and safe lithium extraction.

[0083] The above is only a specific implementation of the present application. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present application. These improvements and modifications should also be regarded as the scope of protection of the present application.

Claims

1. A method for preparing a lithium ion adsorbent, characterized in that: The preparation method comprises the following steps: S1, dissolving the metal ion substrate and the organic ligand material in a solvent at a molar ratio of 1-10:1-10 to obtain a mixed solution; S2, heating the mixed solution in step S1; S3, cooling the heated mixed solution to room temperature, and then centrifuging, washing and vacuum drying to obtain a lithium ion adsorbent; In which, the metal ion substrate in step S1 is selected from one or more of Al(NO3)3, Fe(NO3)3, Ni(NO3)3, ZrCl4, AlCl3, FeCl3 and CuCl2, and the organic ligand material is selected from one or more of 1,4-benzenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and 3,3',4,4'-biphenyltetracarboxylic acid.

2. The method for preparing a lithium ion adsorbent according to claim 1, characterized in that: In the step S2, the mixed solution is heated into a reaction kettle and heated at 100° C. to 300° C. for 1 h to 72 h.

3. The method for preparing a lithium ion adsorbent according to claim 1, characterized in that: The solvent in step S1 is selected from one or more of deionized water, methanol, ethanol, acetonitrile, acetone, N,N-dimethylformamide, N,N-diethylformamide and dimethyl sulfoxide.

4. The method for preparing a lithium ion adsorbent according to claim 1, characterized in that: The volume of the solvent in step S1 is 20 mL to 150 mL.

5. A lithium ion adsorbent prepared by the preparation method according to any one of claims 1 to 4.

6. A method for adsorption and desorption of lithium ions, characterized in that: Using the lithium ion adsorbent according to claim 5, the adsorption and desorption method comprises: S10, dispersing a lithium ion adsorbent in a lithium salt solution, so that the lithium ion adsorbent adsorbs lithium ions in the lithium salt solution; S20, adding a magneton to the lithium salt solution containing the lithium ion adsorbent, and centrifuging in a magnetic stirrer to separate the lithium ion adsorbent; S30, using an acidic solution to perform a desorption treatment on the lithium ion adsorbent after centrifugal separation, so that the lithium ions on the lithium ion adsorbent are removed from the lithium ion adsorbent.

7. A lithium ion adsorption and desorption method according to claim 6, characterized in that: The centrifugal separation time in step S20 is 0.1h to 0.5h.

8. The method for adsorption and desorption of lithium ions according to claim 6, characterized in that: The concentration of the acidic solution is 0.1 mol / L to 5 mol / L.

9. The method for adsorption and desorption of lithium ions according to claim 6, characterized in that: In the step S30, the lithium ion adsorbent is desorbed using an acidic solution for 1 to 5 times, each desorption lasting 1 hour to 24 hours.

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