CN113667136B - Ultrahigh-stability and low-cost metal-organic framework material for efficiently separating acetylene/carbon dioxide and preparation method thereof - Google Patents
Ultrahigh-stability and low-cost metal-organic framework material for efficiently separating acetylene/carbon dioxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of an aluminum-based metal-organic frameworks (MOFs) material with high stability and application thereof in the field of gas adsorption and separation; the MOFs material can be used as an adsorbent to realize the high-efficiency separation of acetylene/carbon dioxide. The preparation method improves the integral reaction yield and enables the product to have good crystallinity and uniform appearance by regulating and controlling the proportion, reaction time and reaction temperature between reactants and a solvent in the synthesis process. The microporous Al-MOFs material has excellent chemical stability and structural versatility, and the characteristics of low cost and easy large-scale synthesis of aluminum greatly promote the industrial application process of the series of materials in the field of gas adsorption and separation.
Description
Technical Field
The invention relates to the technical field of metal-organic framework nano materials and gas adsorption and separation, in particular to a large-scale preparation method of aluminum-based MOFs materials (Al-MOFs) and application thereof in gas adsorption and separation. The material can be used for high-efficiency separation of acetylene/carbon dioxide, and acetylene is selectively adsorbed from mixed gas so as to achieve the aim of purifying acetylene.
Background
Acetylene, one of the very important industrial gases, can be used as a fuel and for producing other chemicals (such as vinyl chloride, acrylic acid, etc.), and is widely used in the fields of petrochemical industry, electronic industry, etc. At present, acetylene is mainly generated through processes of petroleum fractionation, cracking and the like, and is often accompanied with impurity gases such as carbon dioxide, methane and the like, so that the subsequent use benefit is greatly influenced. Thus, the purification of acetylene is a problem to be solved urgently in industry. The acetylene molecules and the carbon dioxide molecules have very similar boiling points (189.3K and 194.7K) and the same kinetic dimensions
Making acetylene/carbon dioxide separation very challenging. The traditional separation method comprises solvent extraction, cryogenic rectification and the like, but has the defects of high cost and large energy consumption. In contrast, groupThe adsorption separation technology of the porous material can realize low-energy consumption separation of acetylene/carbon dioxide, and is more energy-saving and environment-friendly.
Metal-organic frameworks (MOFs) are solid crystalline porous materials formed by connecting inorganic clusters (or secondary building units, SBUs) and organic molecules through coordination bonds. Compared with traditional porous materials such as molecular sieves and activated carbon, the porous metal-organic framework material has the advantages of high specific surface area and pore volume, precisely adjustable pore channel structure, easy functionalization and the like, and becomes one of ideal adsorbent materials for realizing the efficient separation of mixed gas.
In recent years, research on the separation of acetylene/carbon dioxide by using metal-organic framework materials as adsorbents has been advanced by using strategies such as introduction of functional sites (e.g., open metal sites), but the methods still have the disadvantages of low adsorption quantity, poor chemical stability, difficult regeneration, high cost and the like. For example, in an actual industrial process, acetylene feed gas often contains water vapor and other acidic corrosive gases. Therefore, in addition to excellent acetylene/carbon dioxide adsorption and separation performance, the chemical stability of MOFs materials is also very important for their practical industrial applications. In addition, most of the reports for C are now made 2 H 2 /CO 2 The separated MOFs material has high raw material cost, cannot be produced in a large scale and cannot meet the actual industrial application requirement. In conclusion, how to prepare the MOFs material with high separation performance, high stability, low regeneration energy consumption and low cost and realize the high-efficiency separation of acetylene/carbon dioxide has important significance on the industrial acetylene purification process and is a challenging problem.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an Al-MOFs material with ultrahigh stability and low synthesis cost and a preparation method thereof, and the preparation method controls the crystal growth process of a product by regulating and controlling the ratio, reaction time and reaction temperature between a reactant and a solvent, so that the product has uniform appearance, and the material with good crystallinity and stability is prepared. The material is used in the field of gas adsorption and separation, and can realize the high-efficiency separation of acetylene/carbon dioxide. The microporous Al-MOFs material synthesized by the method has excellent chemical stability and structural versatility, and the material has great industrial application value of acetylene/carbon dioxide separation due to the low cost of aluminum and organic ligands and the characteristic that Al-MOF is easy to synthesize in a large scale.
The invention adopts the following technical scheme:
an Al-MOFs material, which is a solid crystalline porous material with a one-dimensional network structure, and has a general structural formula of Al (OH) X (wherein X represents a dicarboxylic acid organic ligand); the Al-MOFs material can be used as an adsorbent for high-efficiency separation of acetylene/carbon dioxide.
The organic dicarboxylic acid ligand comprises isophthalic acid (1, 3-H) 2 BDC), 5-aminoisophthalic acid (5-amoIPA), 5-hydroxyisophthalic acid (5-hidPA), pyridine-3, 5-dicarboxylic acid (pyd-3,5-BDC), pyridine-2, 4-dicarboxylic acid (pyd-2,4-BDC), pyrazine-2, 6-dicarboxylic acid (pyz-2,6-BDC), pyrimidine-4, 6-dicarboxylic acid (pym-4,6-BDC), 1,3, 5-triazine-2, 4-dicarboxylic acid (1,3,5-trz-2,4-BDC), 2, 5-furandicarboxylic acid (2,5-FDC), 2, 5-thiophenedicarboxylic acid (2,5-TDC), 3, 5-pyrazoledicarboxylic acid (3,5-PyzDC), 2, 4-Furanedicarboxylic acid (2,4-FDC), 2, 4-thiophenedicarboxylic acid (2,4-TDC), 2, 4-pyrroledicarboxylic acid (2,4-PylDC), 3, 5-isoxazoledicarboxylic acid (3,5-IsxDC), 3, 5-isothiazoledicarboxylic acid (3,5-IstDC) and 2, 5-pyrroledicarboxylic acid (2, 5-PylDC).
The preparation method comprises the following steps:
1) mixing organic ligands of the dicarboxylic acid, a regulator and a solvent in proportion, carrying out ultrasonic treatment until a clear solution is obtained, adding a certain amount of soluble metal salt or metal salt solution into the solution, carrying out ultrasonic treatment until a uniform turbid solution is obtained, and then carrying out reaction by using an oven or a magnetic stirrer.
2) And after the reaction is finished, performing suction filtration, washing the mixture for three times by using one of deionized water, N-dimethylformamide and acetonitrile during suction filtration, then washing the mixture for three times by using one of anhydrous methanol, acetone, anhydrous ethanol and dichloromethane, and drying to obtain the Al-MOFs material.
In the above technical scheme, the organic ligand is isophthalic acid (1, 3-H) 2 BDC)、5-Aminoisophthalic acid (5-amoIPA), 5-hydroxyisophthalic acid (5-hidPA), pyridine-3, 5-dicarboxylic acid (pyd-3,5-BDC), pyridine-2, 4-dicarboxylic acid (pyd-2,4-BDC), pyrazine-2, 6-dicarboxylic acid (pyz-2,6-BDC), pyrimidine-4, 6-dicarboxylic acid (pym-4,6-BDC), 1,3, 5-triazine-2, 4-dicarboxylic acid (1,3,5-trz-2,4-BDC), 2, 5-furandicarboxylic acid (2,5-FDC), 2, 5-thiophenedicarboxylic acid (2,5-TDC), 3, 5-pyrazoledicarboxylic acid (3,5-PyzDC), 2, 4-Furanedicarboxylic acid (2,4-FDC), 2, 4-thiophenedicarboxylic acid (2,4-TDC), 2, 4-pyrroledicarboxylic acid (2,4-PylDC), 3, 5-isoxazoledicarboxylic acid (3,5-IsxDC), 3, 5-isothiazoledicarboxylic acid (3,5-IstDC) and 2, 5-pyrroledicarboxylic acid (2, 5-PylDC).
The soluble metal salt is a soluble aluminum salt;
the regulator comprises one or more of formic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, hydrofluoric acid, sodium hydroxide and potassium hydroxide, the regulator is reasonably selected according to the properties of the dicarboxylic acid ligand, the integral structure of the dicarboxylic acid ligand is not broken while the dicarboxylic acid ligand is deprotonated, the acid is used for regulating the meta-aromatic dicarboxylic acid organic ligand under the common condition, and the alkali is used for regulating the five-membered heterocyclic dicarboxylic acid organic ligand under the common condition;
the solvent comprises one or more of deionized water, ethanol, methanol, acetonitrile, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
the ultrasonic temperature is 25-50 ℃, and the ultrasonic time is 5-120 min;
the reaction temperature of the oven is 85-150 ℃; the reaction time of the oven is 12-96 h;
the stirring temperature of the magnetic stirrer is 85-150 ℃; the stirring speed of the stirrer is 200-500 rpm; the reaction time of the stirrer is 4-96 h;
the soluble aluminum salt comprises one or more of aluminum chloride, aluminum sulfate, basic aluminum acetate, aluminum nitrate and sodium metaaluminate;
during the suction filtration, washing with one of deionized water, N-dimethylformamide and acetonitrile for three times, and then washing with one of anhydrous methanol, acetone, anhydrous ethanol and dichloromethane for three times;
the drying treatment needs to adopt a solvent exchange method to exchange the homogeneous phase crystal material obtained after the suction filtration with one of high-purity methanol, high-purity ethanol and high-purity acetone (the high-purity concentration is more than or equal to 99.8%) for multiple times, wherein the interval is at least 3h each time, and then the homogeneous phase crystal material is sequentially subjected to vacuum drying for 12h at room temperature and 50-120 ℃ respectively to obtain the Al-MOFs material capable of being used for acetylene/carbon dioxide separation.
The molar ratio of the meta-aromatic dicarboxylic acid organic ligand to the metal salt is 1 (1-3); the ratio of the organic ligand to the regulator to the solvent is 1mmol (0-25 mL) to 3-30 mL), and the related reagents are all commercial analytical pure reagents and are not further purified before use.
The MOFs material prepared by the simple and rapid method comprises the following steps: the microporous Al-MOFs has the characteristics of good chemical stability, structural function adjustability, low synthesis cost and easiness in large-scale synthesis, so that the industrial application potential of the series of materials is far better than that of similar MOFs materials. The constructed Al-MOFs material has a proper pore structure, so that the acetylene/carbon dioxide is efficiently separated.
The invention principle of the invention is as follows:
the invention designs and synthesizes a series of Al-MOFs materials according to the current difficulty of the acetylene purification problem which is very important industrially, and the selected organic ligand is a meta-aromatic ring dicarboxylic acid organic ligand. Such as CAU-10-H synthesized using 1, 3-phthalic acid and aluminum sulfate octadecahydrate, has a size slightly larger than the kinetics of acetylene and carbon dioxide
Is
The structure can ensure that acetylene molecules are effectively accumulated in the pore channel to form an acetylene molecule cluster, thereby increasing the total adsorption amount of materials to acetylene and achieving the purpose of efficiently separating acetylene/carbon dioxide, and a CAU-10-H packed column bed is used for realizing the total pressure of 298K and 1bar and the total pressure of 2mL min -1 C at Total flow 2 H 2 /CO 2 50/50 mixed gas experiment shows that the acetylene adsorption amount of CAU-10-H is up to 3.3mmol g -1 The acetylene/carbon dioxide separation ratio is 3.4, which is one of the most excellent materials known at present. Based on the success of the CAU-10-H material in the acetylene/carbon dioxide separation field, the range is expanded to the other organic ligands of meta-aromatic ring dicarboxylic acid and five-membered heterocyclic dicarboxylic acid. Compared with the rest high-performance acetylene/carbon dioxide separation MOFs materials, the Al-MOFs materials show ultrahigh chemical stability, and can still maintain the structural stability after being soaked in water, acidic and alkaline solutions. Excellent C 2 H 2 /CO 2 The combination of the separation performance, the ultrahigh chemical stability and the low synthesis cost means that the series of Al-MOFs materials are C which has the most industrial utilization value so far 2 H 2 /CO 2 One of the materials is separated.
The invention has the beneficial effects that:
(1) an Al-MOFs material, which is a solid crystalline porous material with a one-dimensional network structure, and has a general structural formula of Al (OH) X (wherein X represents a dicarboxylic acid organic ligand); the series of materials have proper one-dimensional pore channels and functional surfaces, and can ensure that acetylene molecules form acetylene molecule clusters in the pore channels, thereby increasing the total adsorption amount of the materials on acetylene and achieving C 2 H 2 /CO 2 The purpose of high-efficiency separation is achieved; the preparation method can improve the integral reaction yield and ensure that the product has good crystallinity and uniform appearance by regulating and controlling the proportion, reaction time and reaction temperature between reactants and a solvent in the synthesis process.
(2) The series of Al-MOFs materials can be used as an adsorbent for high-efficiency separation of acetylene/carbon dioxide. At 298K, 1bar total pressure and 2mL min -1 C at total flow 2 H 2 /CO 2 50/50 experiment of mixed gas, the acetylene adsorption quantity of the Al-MOFs material>3.0mmol g -1 Acetylene/carbon dioxide separation ratio>3.0, the comprehensive performance is in front of the commercial porous materials and the reported similar materials.
(3) The series of materials have good chemical stability, can still maintain the structural stability after being soaked in water for 72 hours and soaked in a solution with the pH value of 1, 2,4, 10 and 12, and provides a powerful and reliable guarantee for the practical application of the materials in industrial environment.
(4) The material has good thermal stability. The structure remained unchanged over the 300 ℃ temperature range tested.
The series of Al-MOFs materials combine a plurality of advantages of ultrahigh stability, low synthesis cost, easiness in large-scale production and the like, greatly meet various requirements on acetylene purification and adsorption materials under the industrial background, and greatly promote the industrial application process of the MOFs materials in the field of gas adsorption and separation. The invention provides a new idea for improving the acetylene/carbon dioxide separation performance of the porous material, also provides different visual angles for developing new MOFs material with high separation performance, high stability and low cost, and is beneficial to promoting the industrial application of the MOFs material in the separation of other important gases in the long run.
Drawings
FIG. 1 is a schematic diagram of the organic ligands involved in the present invention (FIG. 1a) and used in the materials of example 1 (FIG. 1b), example 2 (FIG. 1c) and example 3 (FIG. 1 d).
FIG. 2 is a schematic representation of the microcrystalline structure of the material of example 1.
FIG. 3 is a PXRD pattern of the material of example 1.
FIG. 4 is the 77K nitrogen isothermal total adsorption curve (FIG. 4a) and pore size distribution plot (FIG. 4b) for the material of example 1.
Fig. 5 shows PXRD patterns and acetylene isothermal adsorption curves (296K) before and after testing for water stability and chemical stability of the material of example 1.
FIG. 6 is a PXRD pattern after thermal stability testing of the material of example 1.
FIG. 7 is a single component isothermal adsorption curve (296K) for acetylene and carbon dioxide for the material of example 1.
FIG. 8 is 296K equimolar C predicted by IAST theory in example 1 2 H 2 /CO 2 Two-component mixed gas competes for the adsorption curve.
FIG. 9 shows a material pair C in example 1 2 H 2 /CO 2 (50/50, v/v) and C 2 H 2 /CO 2 (2/1, v/v) IAST separation Selectivity of two ratios of mixed gases (296K).
FIG. 10 shows the results of the column packed with the material of example 1 at 298K, 1bar total pressure and 2mL min -1 C at Total flow 2 H 2 /CO 2 50/50 dynamic breakthrough experiment test curves.
FIG. 11 is a PXRD pattern for the synthesis and product of the material scale-up in example 1.
FIG. 12 is a schematic representation of the microcrystalline structure of the material of example 2.
FIG. 13 is a PXRD pattern of the material in example 2.
FIG. 14 is a 77K nitrogen isothermal total adsorption curve and pore size distribution plot for the material of example 2.
FIG. 15 is a single component isothermal adsorption curve (296K) for acetylene and carbon dioxide for the material of example 2.
FIG. 16 shows the material pair C in example 2 2 H 2 /CO 2 (50/50, v/v) IAST separation Selectivity of the mixed gas (296K).
Fig. 17 is a PXRD pattern for the material of example 3.
FIG. 18 is a 77K nitrogen isothermal total adsorption curve for the material of example 3.
FIG. 19 is a single component isothermal adsorption curve (296K) for acetylene and carbon dioxide for the material of example 3.
FIG. 20 shows the material pair C in example 3 2 H 2 /CO 2 (50/50, v/v) IAST separation Selectivity of the mixed gas (296K).
Detailed Description
The contents of the present invention will be further clarified by the following examples, which are not intended to limit the scope of the present invention, and various modifications or variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Example 1
1.2mmol (200mg) of the organic ligand isophthalic acid was dissolved in 1mL DMF solvent and sonicated to give a clear solution, 1.2mmol (800mg) of the metal salt Al 2 (SO 4 ) 3 ·18H 2 O was dissolved in 4mL of deionized water. Then the aqueous solution of metal salt is dropped into the DMF solution of isophthalic acid under stirring, the clear solution quickly becomes white paste, after a period of ultrasonic treatment, it is transferred to a hydrothermal kettle to react for 24h under the condition of 135 ℃. Subsequently, it was slowly cooled to room temperature in air. And respectively washing with DMF and deionized water for 3 times during suction filtration to obtain pure CAU-10-H.
The microscopic crystal structure of the material is schematically shown in fig. 2, and the PXRD characterization data is shown in fig. 3. And (3) exchanging the obtained homogeneous phase crystal material in absolute methanol for multiple times by adopting a solvent exchange method, wherein the interval is at least 3 hours each time, and then sequentially drying in vacuum for 12 hours at room temperature and 50 ℃ respectively to obtain the purified CAU-10-H.
To test the specific surface area of CAU-10-H, a 77K nitrogen isothermal adsorption test and a low pressure gas injection were performed, the test results are shown in FIG. 4, and the BET specific surface area is 627m 2 Per g, pore diameter of
In order to test the water stability and chemical stability of CAU-10-H, after immersing the synthesized fresh sample in water for 72H and in acid-base solution with pH 1 and 12 for 72H, PXRD data and acetylene adsorption curve of the sample are measured (fig. 5), and it can be seen from the figure that the material still maintains good structural integrity, indicating that it has excellent water stability and acid-base stability.
To characterize the thermal stability of CAU-10-H in air environment, the samples were heated to 50 deg.C, 100 deg.C, 150 deg.C, 200 deg.C, 250 deg.C, 300 deg.C and held for 12H, respectively, before PXRD characterization. As can be seen from the PXRD pattern, the sample can still keep good crystal structure integrity under the environment of 300 ℃ (FIG. 6).
In order to characterize the single-component adsorption performance of CAU-10-H to acetylene and carbon dioxide at normal temperature, C at the temperature of 296K is tested 2 H 2 And CO 2 The single-component adsorption curve of (FIG. 7) shows that CAU-10-H shows good C 2 H 2 /CO 2 And 4, selective separation prospect.
To further CAU-10-H pair C 2 H 2 /CO 2 The selective adsorption separation effect of the mixed gas is evaluated, and the equimolar C is predicted by Ideal Adsorption Solution Theory (IAST) 2 H 2 /CO 2 Two-component mixed gas competitive adsorption curves (fig. 8), from which it can be seen that CAU-10-H exhibits preferential adsorption of acetylene.
To evaluate CAU-10-H to C more intuitively 2 H 2 /CO 2 The adsorption separation effect of the mixed gas is calculated, and the adsorption separation effect is calculated for C at 296K 2 H 2 /CO 2 (50/50, v/v) IAST separation selectivity of gas mixture (FIG. 9), it can be seen that CAU-10-H has good acetylene/carbon dioxide separation performance, and is one of the most excellent materials known at present.
To simulate a practical industrial separation process, dynamic breakthrough experiments were used to evaluate CAU-10-H versus C 2 H 2 /CO 2 The actual separation effect of the mixed gas. 0.8563g of the activated sample was packed into a packed column as a fixed bed of an adsorption column, followed by 2mL min -1 Flow rate introduction 50/50C 2 H 2 /CO 2 The gas mixture was subjected to breakthrough testing (FIG. 10). As can be seen from the figure, CAU-10-H can realize pair 50/50C 2 H 2 /CO 2 And (3) high-efficiency separation of the mixed gas.
To demonstrate the feasibility of scale-up synthesis of this series of materials, the scale-up of CAU-10-H was expanded and PXRD characterization was performed on the product (FIG. 11). As can be seen from the figure, the product synthesized on a scale has good crystallinity.
Example 2
Dissolving 1.2mmol 2, 5-thiophenedicarboxylic acid in 5mL 0.4mmol/mL NaOH aqueous solution, sonicating to obtain a clear solution, and adding 0.9mmol of the metal salt AlCl 3 ·6H 2 O and 0.3mmol of NaAlO 2 After a period of ultrasonic treatment, the solution is transferred to a hydrothermal kettle at 100 DEG CAnd reacting for 24 hours. Subsequently, it was slowly cooled to room temperature in air. And respectively washing with DMF and absolute ethyl alcohol for 3 times during suction filtration to obtain Al (OH) (TDC).
The microscopic crystal structure of the material is schematically shown in fig. 12, and the PXRD characterization data is shown in fig. 13. The obtained homogeneous phase crystal material is exchanged in absolute methanol for a plurality of times by a solvent exchange method, each time at least 3 hours, and then is dried in vacuum for 12 hours at room temperature and 50 ℃ in sequence to obtain purified Al (OH) (TDC).
To test the specific surface area and pore size distribution of Al (OH) (TDC), a 77K nitrogen isothermal adsorption test was performed, the test results are shown in FIG. 14, and the BET specific surface area is 1221m 2 Per g, pore diameter of
In order to characterize the single-component adsorption performance of Al (OH) (TDC) on acetylene and carbon dioxide at normal temperature, C at the temperature of 296K is tested 2 H 2 And CO 2 The single-component adsorption curve of (FIG. 15) shows that Al (OH) (TDC) has good C 2 H 2 /CO 2 The separability was selected.
In order to more intuitively show Al (OH) (TDC) vs C 2 H 2 /CO 2 The adsorption separation effect of the mixed gas is calculated, and the adsorption separation effect is calculated for C at 296K 2 H 2 /CO 2 (50/50, v/v) IAST separation selectivity of gas mixture (FIG. 16), it can be seen that Al (OH) (TDC) has a promising application for efficient acetylene/carbon dioxide separation.
Example 3
Dissolving 1.0mmol of organic ligand 3, 5-pyrazole dicarboxylic acid in 5mL of 0.4mmol/mL NaOH aqueous solution, performing ultrasonic treatment to obtain clear solution, and adding 1.2mmol of metal salt AlCl 3 ·6H 2 O was dissolved in 4mL of deionized water. Then, the aqueous solution of the metal salt is dripped into the NaOH aqueous solution of the 3, 5-pyrazole dicarboxylic acid under stirring, after ultrasonic treatment for a period of time, the solution is transferred into a hydrothermal kettle to react for 24 hours at the temperature of 100 ℃. Subsequently, it was slowly cooled to room temperature in air. The filtration is carried out by washing with DMF and absolute methanol for 3 times respectively to obtain pure Al (OH) (PyzDC).
PXRD characterization data for the material are shown in figure 17. The obtained homogeneous phase crystal material is exchanged in absolute methanol for a plurality of times by a solvent exchange method, each time at least 3 hours, and then is dried in vacuum for 12 hours at room temperature and 50 ℃ in sequence to obtain purified Al (OH) (PyzDC).
To test the specific surface area of Al (OH) (PyzDC), a 77K nitrogen isothermal adsorption test was performed, and the test results are shown in FIG. 18, where the BET specific surface area is comparable to that of Al (OH) (TDC).
To characterize the single-component adsorption properties of Al (OH) (PyzDC) to acetylene and carbon dioxide at room temperature, C at a temperature of 296K was tested 2 H 2 And CO 2 As can be seen from the single-component adsorption curve (FIG. 19), Al (OH) (PyzDC) adsorbs acetylene first, and has a promising application prospect in acetylene/carbon dioxide separation.
For clarity of presentation of Al (OH) (PyzDC) vs. C 2 H 2 /CO 2 The adsorption separation effect of the mixed gas is calculated, and the adsorption separation effect is calculated for C at 296K 2 H 2 /CO 2 (50/50, v/v) IAST separation selectivity of the gas mixture (FIG. 20), it is clear that Al (OH) (PyzDC) has excellent acetylene/carbon dioxide separation performance.
Claims (6)
1. An Al-MOFs material is characterized in that the material is a framework material with a one-dimensional network structure, and the structural general formula is Al (OH) X, wherein X represents a dicarboxylic acid organic ligand; the Al-MOFs material can be used as an adsorbent for efficient separation of acetylene/carbon dioxide;
the dicarboxylic acid organic ligand is an organic ligand of meta-aromatic ring dicarboxylic acid or an organic ligand of five-membered heterocyclic dicarboxylic acid;
the dimension of the one-dimensional channel is between 4.0 and 6.0A.
2. The Al-MOFs material according to claim 1, wherein the total pressure is at 298K, 1bar and 2mL min -1 C at Total flow 2 H 2 /CO 2 50/50 volume ratio, the acetylene adsorption quantity of the Al-MOFs material> 3.0 mmol g -1 Acetylene/carbon dioxide separation ratio> 3.0。
3. A method for preparing the Al-MOFs material according to claim 1, characterized by the following steps: 1) mixing organic ligands of dicarboxylic acid, a regulator and a solvent in proportion, carrying out ultrasonic treatment to obtain a clear solution, adding soluble metal salt or metal salt solution into the solution, carrying out ultrasonic treatment to obtain a uniform turbid solution, then carrying out reaction by using an oven or a magnetic stirrer, carrying out suction filtration after the reaction is finished, and carrying out drying treatment to obtain the Al-MOFs material; the regulator comprises one or more of formic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, hydrofluoric acid, sodium hydroxide and potassium hydroxide; the ratio of the organic ligand of the dicarboxylic acid, the regulator and the solvent is 1mmol (0-25 mL) to (3-30 mL), and the regulator and the solvent are all commercially available analytical reagents; when the regulator is used, the regulator is reasonably selected according to the property of the dicarboxylic acid ligand, the integral structure of the dicarboxylic acid ligand is not broken while the dicarboxylic acid ligand is deprotonated, the meta-aromatic ring dicarboxylic acid organic ligand is regulated by acid, and the five-membered heterocyclic dicarboxylic acid organic ligand is regulated by alkali.
4. The method for preparing Al-MOFs materials according to claim 3, wherein said dicarboxylic acid organic ligand comprises isophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2, 5-furandicarboxylic acid, 2, 5-thiophenedicarboxylic acid, 3, 5-pyrazoledicarboxylic acid, 2, 4-furandicarboxylic acid, 2, 4-thiophenedicarboxylic acid, 2, 4-pyrroledicarboxylic acid, 3, 5-isoxazoledicarboxylic acid, 3, 5-isothiazoledicarboxylic acid and 2, 5-pyrroledicarboxylic acid;
the soluble metal salt is a soluble aluminum salt;
the solvent comprises one or more of deionized water, ethanol, methanol, acetonitrile, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
5. The method for preparing the Al-MOFs materials according to claim 3, wherein the ultrasonic temperature is 25-50 ℃ and the ultrasonic time is 5-120 min;
the reaction temperature of the oven is 85-150 ℃; the reaction time of the oven is 12-96 hours;
the stirring temperature of the magnetic stirrer is 85-150 ℃; the stirring speed of the stirrer is 200-500 rpm; the reaction time of the stirrer is 4-96 h;
the soluble aluminum salt comprises one or more of aluminum chloride, aluminum sulfate, basic aluminum acetate, aluminum nitrate and sodium metaaluminate;
during the suction filtration, washing with one of deionized water, N-dimethylformamide and acetonitrile for three times, and then washing with one of anhydrous methanol, acetone, anhydrous ethanol and dichloromethane for three times;
and the drying treatment needs to adopt a solvent exchange method to exchange the homogeneous phase crystal material obtained after the suction filtration with one of high-purity methanol, high-purity ethanol and high-purity acetone for multiple times, wherein the interval is at least 3 hours each time, and then the homogeneous phase crystal material is sequentially dried in vacuum for 12 hours at room temperature and 50-120 ℃ respectively to obtain the dried MOFs material.
6. The preparation method of the Al-MOFs materials according to claim 3, wherein the molar ratio of the organic dicarboxylic acid ligand to the metal salt is 1 (1-3).
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