Metal organic framework Ni-BTC adsorbent and preparation method thereof

Abstract

The invention discloses a metal organic framework Ni-BTC adsorbent and a preparation method thereof, and belongs to the technical field of carbon dioxide adsorbents. The preparation method comprises the following steps: preparing nickel chloride hexahydrate, 1, 3, 5-benzenetricarboxylic acid, 2-methylimidazole and N, N-dimethylformamide into a mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and heating for reaction; and after the reaction is finished, cooling to room temperature, taking out the reaction kettle, centrifuging, washing and drying to obtain the adsorbent. The invention provides a preparation method of a metal organic framework Ni-BTC adsorbent, and the metal organic framework Ni-BTC adsorbent can adsorb CO2 and is used for capturing and utilizing CO2 in flue gas. The method has the characteristics of low raw material cost, simple process and easiness in operation.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon dioxide adsorbents, and specifically relates to a low-cost and high-efficiency CO 2 Capture material and method for preparing the same. Background Art

[0002] With the rapid development of industry, the consumption of fossil fuels has increased sharply and environmental pollution has intensified. Global warming has posed a threat to both the economic development of society and the ecological environment. 2 It accounts for a major share of global warming. For some time to come, fossil fuels will remain the main energy source that is difficult to replace, especially in industrial fields such as coal-fired power plants, cement and steel. 2 Capture is the key to controlling atmospheric CO 2 Carbon capture and storage is the key to the concentration of carbon dioxide, which is of great significance to controlling the greenhouse effect and global warming. 2 One of the effective methods.

[0003] Various technologies that have been developed include solid adsorbent adsorption, chemical solvent absorption, membrane separation, low-temperature separation, etc. Chemical solvent absorption is the most widely used method, but it is gradually being replaced due to its easy corrosion of equipment, huge energy consumption and easy pollution to the environment. In recent years, the method of physical or chemical adsorption of solid adsorbents and gas molecules has attracted attention due to its low cost, low energy consumption, simple process flow, high adsorption capacity and selectivity.

[0004] Metal-organic framework (MOFs) is a type of porous material with a periodic network structure formed by self-assembly of metal ions or clusters and organic ligands through coordination bonds. The metal center ions are equivalent to the nodes of the network structure, and the ligands are equivalent to bridges connecting them. The ultra-high porosity and specific surface area, adjustable three-dimensional structure and unsaturated metal sites make it show great potential in adsorption separation, catalysis and other aspects. In theory, by changing the metal ions or cluster centers, organic ligands and functionalizing the MOFs material, an unlimited variety of MOFs structures can be obtained. Therefore, various types of MOFs materials can be obtained through corresponding adjustments and applied to various fields.

[0005] Adding suitable reaction additives to the reaction is a very effective strategy to improve material performance. Additives can change material properties by regulating electronic structure, chemical properties, etc. The addition of a small amount of additives can produce unexpected changes in material properties. Summary of the invention

[0006] The purpose of the present invention is to provide a novel method for preparing a novel nanostructured carbon nanotube with low-cost raw materials and simple preparation. 2 The metal organic framework material with high adsorption capacity has good recycling performance, and the solvent required in the preparation process can also be recycled and reused, so it can be used in CO 2 Industrial application in the field of adsorption separation.

[0007] In order to solve the above technical problems, the present invention adopts the following technical solutions: a cheap and efficient CO 2 Capture material, the CO 2 Ni-BTC is selected as the capture material.

[0008] Furthermore, Ni-BTC uses nickel chloride hexahydrate and 1,3,5-benzenetricarboxylic acid as the metal center source and organic ligand source, respectively.

[0009] Furthermore, 2-methylimidazole is selected as an auxiliary agent for the Ni-BTC material.

[0010] Furthermore, N,N-dimethylformamide is selected as the reaction solvent.

[0011] A method for preparing a cheap and efficient carbon dioxide capture material comprises the following steps:

[0012] S1: dissolving a certain amount of nickel chloride hexahydrate in DMF and stirring to form solution A;

[0013] S2: dissolving a certain amount of 1,3,5-benzenetricarboxylic acid in DMF to form solution B;

[0014] S3: dissolving a certain amount of 2-methylimidazole to form solution C;

[0015] S4: slowly adding solution A and solution B into solution C at room temperature, stirring and ultrasonically mixing for a period of time to form solution D;

[0016] S5: transferring solution D to a high pressure reactor and preparing the desired material by a one-step solvothermal synthesis method;

[0017] S6: After the reaction in the high-pressure reactor is completed, the obtained product is subjected to centrifugation, washing and drying steps in sequence to obtain a new type of Ni-BTC material.

[0018] Furthermore, the molar ratio of nickel chloride hexahydrate in step S1 to 1,3,5-benzenetricarboxylic acid in step S2 is 0.67-2:1, and the molar ratio of nickel chloride hexahydrate in step S1 to 2-methylimidazole in step S3 is 1-6:1.

[0019] Further, in step S4, the ultrasonic mixing time is 0.2-1h;

[0020] Furthermore, in step S5, the washing conditions are 5 times of washing with 10 mL of DMF and 5 times of washing with 10 mL of anhydrous ethanol; the drying conditions are a vacuum environment at 60-80° C., and the drying time is 12-24 h. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The XRD pattern of the Ni-BTC adsorbent material in Example 1 and the XRD pattern of the theoretical Ni-BTC;

[0022] Figure 2 This is the TEM image of the Ni-BTC adsorption material in Example 1;

[0023] Figure 3 is the N of the Ni-BTC adsorbent material in Example 1 2 Adsorption-desorption curves;

[0024] Figure 4 is the pore size distribution curve of the Ni-BTC adsorbent material in Example 1;

[0025] Figure 5 CO is the Ni-BTC adsorbent material in Example 1 at 273K and 298K. 2 Adsorption isotherms. DETAILED DESCRIPTION

[0026] The present invention is further described in detail below in conjunction with embodiments and drawings, but the embodiments of the present invention are not limited thereto.

[0027] Unless otherwise specified, the chemical reagents involved in the following embodiments can be purchased from chemical reagent companies.

[0028] The adsorption method of a cheap and efficient carbon dioxide capture material of the present invention is experimentally operated using the following 6 embodiments.

[0029] Example 1

[0030] 0.3564g nickel chloride hexahydrate was dissolved in 1mL DMF and stirred to form solution A; 0.21g 1,3,5-benzenetricarboxylic acid was dissolved in 4mL DMF and stirred and ultrasonically treated to form solution B; 0.027g 2-methylimidazole was dissolved in 1mL DMF and stirred and ultrasonically treated to form solution C; at room temperature, solution A and solution B were slowly added to solution C to form solution D, and after ultrasonic treatment for 30 minutes, it was transferred into a high-pressure reactor lined with polytetrafluoroethylene and heated at 170°C for 48 hours. After the reaction was completed, the obtained product was centrifuged, washed and dried to obtain a new Ni-BTC material.

[0031] Example 2

[0032] 0.3564g nickel chloride hexahydrate was dissolved in 1mL DMF and stirred to form solution A; 0.21g 1,3,5-benzenetricarboxylic acid was dissolved in 4mL DMF and stirred and ultrasonically treated to form solution B; 0.055g 2-methylimidazole was dissolved in 1mL DMF and stirred and ultrasonically treated to form solution C; at room temperature, solution A and solution B were slowly added to solution C to form solution D, and after ultrasonic treatment for 30 minutes, it was transferred into a high-pressure reactor lined with polytetrafluoroethylene and heated at 170°C for 48 hours. After the reaction was completed, the obtained product was centrifuged, washed and dried to obtain a new Ni-BTC material.

[0033] Example 3

[0034] 0.3564g nickel chloride hexahydrate was dissolved in 1mL DMF and stirred to form solution A; 0.21g 1,3,5-benzenetricarboxylic acid was dissolved in 4mL DMF and stirred and ultrasonically treated to form solution B; 0.082g 2-methylimidazole was dissolved in 1mL DMF and stirred and ultrasonically treated to form solution C; at room temperature, solution A and solution B were slowly added to solution C to form solution D, and after ultrasonic treatment for 30 minutes, it was transferred into a high-pressure reactor lined with polytetrafluoroethylene and heated at 170°C for 48 hours. After the reaction was completed, the obtained product was centrifuged, washed and dried to obtain a new Ni-BTC material.

[0035] Example 4

[0036] 0.2376g nickel chloride hexahydrate was dissolved in 1mL DMF and stirred to form solution A; 0.21g 1,3,5-benzenetricarboxylic acid was dissolved in 4mL DMF and stirred and ultrasonically treated to form solution B; 0.055g 2-methylimidazole was dissolved in 1mL DMF and stirred and ultrasonically treated to form solution C; at room temperature, solution A and solution B were slowly added to solution C to form solution D, and after ultrasonic treatment for 30 minutes, it was transferred into a high-pressure reactor lined with polytetrafluoroethylene and heated at 170°C for 48 hours. After the reaction was completed, the obtained product was centrifuged, washed and dried to obtain a new Ni-BTC material.

[0037] Example 5

[0038] 0.4752g nickel chloride hexahydrate was dissolved in 1mL DMF and stirred to form solution A; 0.21g 1,3,5-benzenetricarboxylic acid was dissolved in 4mL DMF and stirred and ultrasonically treated to form solution B; 0.055g 2-methylimidazole was dissolved in 1mL DMF and stirred and ultrasonically treated to form solution C; at room temperature, solution A and solution B were slowly added to solution C to form solution D, and after ultrasonic treatment for 30 minutes, it was transferred into a high-pressure reactor lined with polytetrafluoroethylene and heated at 170°C for 48 hours. After the reaction was completed, the obtained product was centrifuged, washed and dried to obtain a new Ni-BTC material.

[0039] Example 6

[0040] 0.3564g nickel chloride hexahydrate was dissolved in 1mL DMF and stirred to form solution A; 0.315g 1,3,5-benzenetricarboxylic acid was dissolved in 4mL DMF and stirred and ultrasonically treated to form solution B; 0.055g 2-methylimidazole was dissolved in 1mL DMF and stirred and ultrasonically treated to form solution C; at room temperature, solution A and solution B were slowly added to solution C to form solution D, and after ultrasonic treatment for 30 minutes, it was transferred into a high-pressure reactor lined with polytetrafluoroethylene and heated at 170°C for 48 hours. After the reaction was completed, the obtained product was centrifuged, washed and dried to obtain a new Ni-BTC material.

[0041] The Ni-BTC material obtained in Example 1 was analyzed, and the pore structure and specific surface area are shown in the table.

[0042]

[0043] In summary, the novel material prepared by the present invention is simple to prepare, the raw materials are cheap, and the introduced reaction aid can adjust the material structure, which can further enhance its ability to efficiently adsorb gas. The material in the present invention can reduce environmental pollution and reduce energy consumption. The material of the present invention has low requirements for equipment, is easy to operate, stable, and has strong repeatability. It has a good regulating effect on the multifunctionality of the material, and is not easy to produce a large amplification effect. It is easy to produce engineering production and is also suitable for large-scale industrial use.

Claims

1. A method for preparing a cheap and efficient carbon dioxide capture material, characterized in that: The following steps are involved: S1: dissolving a certain amount of nickel chloride hexahydrate in DMF and stirring to form solution A; S2: dissolving a certain amount of 1,3,5-benzenetricarboxylic acid in DMF to form solution B; S3: dissolving a certain amount of 2-methylimidazole to form solution C; S4: slowly adding solution A and solution B into solution C at room temperature, stirring and ultrasonically mixing for a period of time to form solution D; S5: transferring solution D to a high pressure reactor and preparing the desired material by a one-step solvothermal synthesis method; S6: After the reaction in the high-pressure reactor is completed, the obtained product is subjected to centrifugation, washing and drying steps in sequence to obtain a new type of Ni-BTC material.

2. The method according to claim 1, characterized in that The molar ratio of nickel chloride hexahydrate in step S1 to 1,3,5-benzenetricarboxylic acid in step S2 is 0.67-2:1, and the molar ratio of nickel chloride hexahydrate in step S1 to 2-methylimidazole in step S3 is 1-6:

1.

3. The method according to claim 1, characterized in that In step S4, the ultrasonic mixing time is 0.2-1h.

4. The method according to claim 1, characterized in that In step S5, the washing conditions are 5 times of washing with 10 mL of DMF and 5 times of washing with 10 mL of anhydrous ethanol; the drying conditions are a vacuum environment at 60-80° C. and the drying time is 12-24 h.

5. A carbon dioxide capture material prepared according to the method according to any one of claims 1 to 4.

6. Use of the carbon dioxide capture material prepared by the method according to any one of claims 1 to 4 for capturing carbon dioxide.

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