Adsorbing material as well as preparation method and application thereof

Abstract

The invention provides an adsorption material and a preparation method and application thereof, the preparation method of the adsorption material comprises the following steps: S1, dispersing a metal atom cluster compound, an amino ligand and an organic acid in a first solvent, and carrying out solvothermal synthesis reaction to obtain an adsorption material precursor; and S2, taking the adsorption material precursor and the fluorine aldehyde group ligand, and carrying out reflux treatment to obtain the adsorption material. Hydrophobic groups are grafted on the surface of the prepared adsorption material, so that the hydrophobicity of the adsorption material is greatly improved, and the oil gas adsorption performance of the adsorption material in a high-humidity environment is further enhanced.

Description

Technical Field

[0001] This application relates to the field of oil and gas field environmental protection, and particularly to an adsorbent material, a preparation method thereof, and an application thereof. Background Art

[0002] Volatile organic compounds (VOCs) are an important task in air pollution control, and it is urgent to efficiently and precisely control the emissions of VOCs. The main components of VOCs in oil and gas fields are alkanes, which have high recovery value. Among the VOCs recovery technologies, the adsorption method is widely used in the oil and gas recovery field due to its economic effectiveness and other characteristics. The adsorbent is the primary factor affecting the oil and gas adsorption recovery effect. However, the adsorption performance of traditional adsorbents is insufficient in high-humidity environments, which limits their wider application. Therefore, the development of efficient oil and gas adsorbents is of great significance for the recovery of VOCs in oil and gas fields.

[0003] Currently, metal-organic framework materials (MOFs) have characteristics such as a large specific surface area, abundant functional groups (-NH2, -CHO, etc.), and easy modification, and show great application potential in the oil and gas recovery field. However, the adsorption capacity of traditional MOF materials for oil and gas in high-humidity environments drops sharply due to the competitive adsorption of water molecules, which greatly limits their practical applications. Therefore, the hydrophobic functionalization of MOF materials helps to improve the adsorption performance of oil and gas in humid environments and has important research significance.

[0004] Based on this, in the face of the technical problems that the adsorption materials in the prior art have a small adsorption amount and poor adsorption effect on volatile organic compounds in high-humidity environments, it is urgent to provide an adsorbent material and a preparation method thereof to improve the above problems. Summary of the Invention

[0005] The main purpose of the present invention is to provide an adsorbent material, a preparation method thereof, and an application thereof, so as to solve the technical problems that the adsorption materials in the prior art have a small adsorption amount and poor adsorption effect on volatile organic compounds in high-humidity environments.

[0006] To achieve the above object, according to one aspect of the present invention, a preparation method of an adsorbent material is provided. The preparation method includes the following steps: Step S1, a metal cluster compound, an amino ligand, and an organic acid are dispersed in a first solvent, and then a solvothermal synthesis reaction is carried out to obtain an adsorbent material precursor; Step S2, the adsorbent material precursor and a fluoroaldehyde ligand are subjected to reflux treatment to obtain an adsorbent material.

[0007] Further, the organic acid is selected from one or more of formic acid, acetic acid, butyric acid, n-octanoic acid or benzoic acid; preferably, the metal cluster compound is selected from one or more of ZrCl4, AlCl3·6H2O, Ti(OiPr)4, Zn(NO3)2·4H2O, FeCl3·6H2O; preferably, the organic acid is selected from one or more of formic acid, acetic acid, butyric acid, n-octanoic acid or benzoic acid.

[0008] Further, by weight percentage, the weight ratio of the metal cluster compound: amino ligand: first solvent: organic acid is 1:1:20:(0-90).

[0009] Further, the first solvent is N,N-dimethylformamide; preferably, the solvothermal synthesis reaction is carried out in a high-pressure autoclave with a Teflon liner, the temperature of the solvothermal reaction is 120-150°C, and the reaction time is 20-30 h.

[0010] Further, the fluoroaldehyde ligand is selected from one or more of 4-trifluoromethylbenzaldehyde, 4-fluoro-3-trifluoromethylbenzaldehyde, 6-trifluoromethylpyridine-3-carbaldehyde, o-trifluoromethylbenzaldehyde or pentafluorobenzaldehyde; preferably, by weight percentage, the weight ratio of the fluoroaldehyde ligand to the adsorbent material precursor is (0.1-0.3):1.

[0011] Further, the reflux treatment conditions are: the reaction temperature is 50-100°C, and the reaction time is 10-20 h.

[0012] Further, step S1 includes: dispersing the metal cluster compound and amino ligand in the first solvent, adding the organic acid for solvothermal synthesis reaction, and then successively performing centrifugation, first washing and first drying treatments to obtain the adsorbent material precursor; step S2, performing a substitution reaction on the adsorbent material precursor and the fluoroaldehyde ligand, and then successively performing second washing and second drying treatments to obtain the adsorbent material; preferably, the dispersion is carried out in an ultrasonic instrument, the ultrasonic frequency is 20-1000 kHz, and the treatment time is 10-20 min.

[0013] In order to achieve the above object, according to one aspect of the present invention, an adsorbent material is provided, and the adsorbent material is obtained by the preparation method of the above adsorbent material.

[0014] Further, the adsorbent material is a porous material, the average pore diameter is 0.4-2.3 nm, and the specific surface area is 650-1450 cm 2 / g.

[0015] According to another aspect of the present invention, an application of the adsorbent material in the adsorption field of volatile organic compounds in oil and gas fields is provided.

[0016] The adsorbent material prepared by the technical solution of the present invention has hydrophobic groups grafted on its surface, thus greatly improving the hydrophobicity of the material, and further improving the oil and gas adsorption performance of the adsorbent material in a high-humidity environment, making its comprehensive performance better. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings forming a part of this specification are used to provide a further understanding of the present invention. The schematic embodiments and descriptions thereof of the present invention are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0018] Figure 1 is the N2 adsorption-desorption isotherm diagram of the adsorbent material precursor and the adsorbent material prepared according to Example 1 of the present invention;

[0019] Figure 2 is the FTIR diagram of the adsorbent material precursor and the adsorbent material prepared according to Example 1 of the present invention;

[0020] Figure 3 is the water vapor adsorption isotherm diagram of the adsorbent material precursor and the adsorbent material prepared according to Example 1 of the present invention;

[0021] Figure 4 is the contact angle diagram of the adsorbent material precursor and the adsorbent material prepared according to Example 1 of the present invention;

[0022] Figure 5 is the dynamic water vapor adsorption diagram of the adsorbent material precursor and the adsorbent material prepared according to Example 1 of the present invention; and

[0023] Figure 6 is the high-humidity oil and gas adsorption diagram of the adsorbent material precursor and the adsorbent material prepared according to Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0024] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments. It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other.

[0025] As described in the background art section of the present invention, the prior art adsorbent materials have the technical problems of small adsorption capacity and poor adsorption effect on volatile organic compounds in a high-humidity environment. Based on this, the present invention provides an adsorbent material and a preparation method thereof, wherein the preparation method includes the following steps: Step S1, taking a metal cluster compound, an amino ligand and an organic acid, dispersing them in a first solvent, and then carrying out a solvothermal synthesis reaction to obtain an adsorbent material precursor; Step S2, taking the adsorbent material precursor and a fluoroaldehyde ligand to carry out a substitution reaction to obtain an adsorbent material.

[0026] In view of the problem that the adsorption performance of existing adsorption materials decreases under high-humidity conditions, the present invention first uses different organic acids as regulators to make the pore size of the adsorption material controllable. Further, a surface modification strategy is adopted, and a fluoroaldehyde ligand reacts with an aminated adsorption material precursor by a substitution reaction to graft the above-mentioned hydrophobic group on the material surface, thereby greatly improving the hydrophobicity of the material, and further improving its oil and gas adsorption performance in a high-humidity environment, and solving the above technical problems.

[0027] In a preferred embodiment, the organic acid is selected from one or more of formic acid, acetic acid, butyric acid, n-octanoic acid or benzoic acid; in order to further improve the adsorption performance of the material, preferably the metal cluster compound is selected from one or more of ZrCl4, AlCl3·6(H2O), Ti(OiPr)4, Zn(NO3)2·4H2O, FeCl3·6H2O; preferably the amino ligand is selected from 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid and / or 2-aminoterephthalic acid, so as to further improve the hydrophobicity of the material and its oil and gas adsorption performance in a high-humidity environment.

[0028] In a preferred embodiment, by weight percentage, the weight ratio of the metal cluster compound: amino ligand: first solvent: organic acid is 1:1:20:(0-90), so that the solvothermal reaction is more sufficient and complete, and the prepared adsorption material precursor has better stability, preparing for the preparation of the adsorption material.

[0029] In order to further disperse and dissolve the raw materials sufficiently in the solvent, improve the reaction efficiency of the solvothermal reaction and increase the reaction rate, preferably the first solvent is N,N-dimethylformamide; further preferably, the solvothermal reaction is carried out in a high-pressure autoclave with a Teflon lining, preferably the temperature of the solvothermal reaction is 120-150°C, and the reaction time is 20-30 h.

[0030] In a preferred embodiment, the fluoroaldehyde ligand is selected from one or more of 4-trifluoromethylbenzaldehyde, 4-fluoro-3-trifluoromethylbenzaldehyde, 6-trifluoromethylpyridine-3-carbaldehyde, o-trifluoromethylbenzaldehyde or pentafluorobenzaldehyde; in order to carry out a substitution reaction between the fluoroaldehyde ligand and the aminated adsorption material precursor to graft the above-mentioned hydrophobic group on the material surface, thereby greatly improving the hydrophobicity of the material, and further improving its oil and gas adsorption performance in a high-humidity environment. Further preferably, by weight percentage, the weight ratio of the fluoroaldehyde ligand to the adsorption material precursor is (0.1-0.3):1.

[0031] In order to further promote the full progress of the substitution reaction, preferably the reaction temperature of the substitution reaction is 50-100°C, and the reaction time is 10-20 h, so as to improve the hydrophobicity of the material and its oil and gas adsorption performance in a high-humidity environment.

[0032] In a preferred embodiment, step S1 includes: dispersing a metal cluster compound and an amino ligand in a first solvent, adding an organic acid to carry out a solvothermal synthesis reaction, and then successively performing centrifugation, primary washing, and primary drying treatments to obtain a precursor of the adsorbent material; in step S2, taking the precursor of the adsorbent material and a fluoroaldehyde ligand to carry out a substitution reaction, and then successively performing secondary washing and secondary drying treatments to obtain the adsorbent material; wherein the dispersion is carried out in an ultrasonic instrument, the ultrasonic frequency is 20-1000 kHz, and the treatment time is 10-20 min.

[0033] Those skilled in the art first disperse the metal cluster compound and the amino ligand in a first solvent, then add an organic acid to carry out a solvothermal synthesis reaction, and then successively perform centrifugation, primary washing, and primary drying treatments to obtain a precursor of the adsorbent material; then take the precursor of the adsorbent material and a fluoroaldehyde ligand to carry out a substitution reaction, and then successively perform secondary washing and secondary drying treatments to obtain the adsorbent material. In particular, the dispersion is carried out in an ultrasonic instrument, the ultrasonic frequency is 20-1000 kHz, the treatment temperature is room temperature, and the treatment time is 10-20 min. The adsorbent material prepared by the present invention has excellent adsorption performance in a highly humid environment, with relatively good comprehensive performance, and the preparation method is simple and easy to operate, suitable for large-scale production, and has broad industrial application prospects.

[0034] Another aspect of the present invention provides an adsorbent material, which is the adsorbent material obtained by the above-mentioned preparation method of the adsorbent material. As described above, this adsorbent material has excellent adsorption performance in a highly humid environment and relatively good comprehensive performance.

[0035] In a preferred embodiment, the adsorbent material is a porous material, with an average pore diameter of 0.4-2.3 nm and a specific surface area of 650-1450 cm 2 / g, and it has good adsorption performance and relatively good comprehensive performance.

[0036] Another aspect of the present invention also provides an application of the adsorbent material in the field of adsorption of volatile organic compounds in oil and gas fields.

[0037] The following detailed descriptions are all exemplary descriptions, aiming to provide further detailed descriptions of the present invention. Unless otherwise specified, all technical terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. The terms used in the present invention are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention.

[0038] Example 1

[0039] 1 mmol of ZrCl4 and 1 mmol of BDC-NH2 (2-aminoterephthalic acid) were separately ultrasonically dispersed in 10 mL of N,N-dimethylformamide (DMF). Then, these two dispersed solutions were mixed and ultrasonically treated for 10 min at room temperature with an ultrasonic frequency of 20 kHz. After adding 90 mmol of formic acid and shaking well, the mixture was transferred into a Teflon-lined autoclave for solvothermal synthesis (150 °C, 24 h). Subsequently, the precipitate was centrifuged, washed (with methanol), and dried, and this process was repeated three times to obtain FA-UiO-66-NH2. Then, FA-UiO-66-NH2 was ultrasonically dispersed in 50 ml of methanol, and 20 mmol of 4-trifluoromethylbenzaldehyde was added and stirred evenly. Under the protection of nitrogen, the mixture was refluxed at 80 °C for 12 h. Finally, the obtained precipitate was washed and dried, and this operation was repeated three times to obtain the adsorption material, named FA-UiO-66-CF3. P / P0

[0040] Example 2

[0041] 1 mmol of AlCl3·6(H2O) and 1 mmol of BDC-NH2 were separately ultrasonically dispersed in 10 mL of N,N-dimethylformamide (DMF). Then, these two dispersed solutions were mixed and ultrasonically treated for 10 min at room temperature with an ultrasonic frequency of 20 kHz. After adding 60 mmol of acetic acid and shaking well, the mixture was transferred into a Teflon-lined autoclave for solvothermal synthesis (130 °C, 24 h). Subsequently, the precipitate was centrifuged, washed (with methanol), and dried, and this process was repeated three times to obtain AA-CAU-NH2. Then, AA-CAU-NH2 was ultrasonically dispersed in 50 ml of methanol, and 10 mmol of 4-fluoro-3-trifluoromethylbenzaldehyde was added and stirred evenly. Under the protection of nitrogen, the mixture was refluxed at 70 °C for 15 h. Finally, the obtained precipitate was washed and dried, and this operation was repeated three times to obtain the adsorption material, named AA-CAU-F.

[0042] Example 3

[0043] 1 mmol of TiOiPr and 1 mmol of BDC-NH2 were separately ultrasonicated and dispersed in 10 mL of N,N-dimethylformamide (DMF), and then these two dispersed solutions were mixed. They were ultrasonicated for 10 min at room temperature with an ultrasonic frequency of 20 kHz. After adding 80 mmol of n-octanoic acid and shaking well, the mixture was transferred into a Teflon-lined autoclave for solvothermal synthesis (100 °C, 24 h). Subsequently, the precipitate was centrifuged, washed (with methanol), and dried, and this process was repeated three times to obtain OA-MIL-125-NH2. Then, OA-MIL-125-NH2 was ultrasonicated and dispersed in 50 ml of methanol, and 30 mmol of 2-(trifluoromethyl)benzaldehyde was added and stirred evenly. Under the protection of nitrogen, the mixture was refluxed at 80 °C for 12 h. Finally, the obtained precipitate was washed and dried, and this operation was repeated three times to obtain the adsorbent material, named OA-MIL-125-F.

[0044] Example 4

[0045] 1 mmol of ZrCl4 and 1 mmol of 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid were separately ultrasonicated and dispersed in 10 mL of N,N-dimethylformamide (DMF), and then these two dispersed solutions were mixed. They were ultrasonicated for 10 min at room temperature with an ultrasonic frequency of 20 kHz. After adding 90 mmol of benzoic acid and shaking well, the mixture was transferred into a Teflon-lined autoclave for solvothermal synthesis (150 °C, 24 h). Subsequently, the precipitate was centrifuged, washed (with methanol), and dried, and this process was repeated three times to obtain BeA-UiO-67-(NH2)2. Then, BeA-UiO-67-(NH2)2 was ultrasonicated and dispersed in 50 ml of methanol, and 25 mmol of 6-(trifluoromethyl)nicotinaldehyde was added and stirred evenly. Under the protection of nitrogen, the mixture was refluxed at 100 °C for 6 h. Finally, the obtained precipitate was washed and dried, and this operation was repeated three times to obtain the adsorbent material, named BeA-UiO-67-F.

[0046] Example 5

[0047] 1 mmol of Zn(NO3)2·4H2O and 1 mmol of BDC-NH2 were separately ultrasonically dispersed in 10 mL of N,N-dimethylformamide (DMF). Then, these two dispersed solutions were mixed and ultrasonically treated for 10 min at room temperature with an ultrasonic frequency of 20 kHz. After adding 50 mmol of butyric acid and shaking well, the mixture was transferred into a Teflon-lined autoclave for solvothermal synthesis (135 °C, 20 h). Subsequently, the precipitate was centrifuged, washed (with methanol), and dried, and this process was repeated three times to obtain BuAA-IRMOF-3. Then, BuAA-IRMOF-3 was ultrasonically dispersed in 50 mL of methanol, and 15 mmol of pentafluorobenzaldehyde was added and stirred evenly. Under the protection of nitrogen, the mixture was refluxed at 80 °C for 12 h. Finally, the obtained precipitate was washed and dried, and this operation was repeated three times to obtain the adsorbent material, named BuA-IRMOF-3-F.

[0048] Example 6

[0049] 1 mmol of FeCl3·6H2O was ultrasonically dispersed in 10 mL of N,N-dimethylformamide (DMF), and 1 mmol of BDC-NH2 was ultrasonically dispersed in 10 mL of DMF. Then, these two dispersed solutions were mixed and ultrasonically treated for 10 min at room temperature with an ultrasonic frequency of 20 kHz. After adding 40 mmol of acetic acid and shaking well, the mixture was transferred into a Teflon-lined autoclave for solvothermal synthesis (120 °C, 22 h). Subsequently, the precipitate was centrifuged, washed (with methanol), and dried, and this process was repeated three times to obtain AA-IRMOF-3. Then, AA-IRMOF-3 was ultrasonically dispersed in 50 mL of methanol, and 20 mmol of 4-fluoro-3-(trifluoromethyl)benzaldehyde was added and stirred evenly. Under the protection of nitrogen, the mixture was refluxed at 90 °C for 13 h. Finally, the obtained precipitate was washed and dried, and this operation was repeated three times to obtain the adsorbent material, named AA-MIL-101-F.

[0050] Comparative Example 1

[0051] 1 mmol of ZrCl4 and 1 mmol of BDC-NH2 were separately ultrasonically dispersed in 10 mL of DMF. Then, these two dispersed solutions were mixed and ultrasonically treated for 10 min. After adding 90 mmol of FA and shaking well, the mixture was transferred into a Teflon-lined autoclave for solvothermal synthesis (150 °C, 24 h). Subsequently, the precipitate was centrifuged, washed (with methanol), and dried, and this process was repeated three times to obtain FA-UiO-66-NH2.

[0052] Taking the characterization results of the high-performance FA-UiO-66-NH2 and FA-UiO-66-CF3 materials prepared in Example 1 as representatives to illustrate the effects of the method of the present invention, the characterization results of the materials prepared in other examples are not provided one by one;

[0053] Performance Test:

[0054] (1) N2 adsorption isotherm diagrams of FA-UiO-66-NH2 and FA-UiO-66-CF3

[0055] The adsorption-desorption isotherms of N2 (77K) were measured using an Autosorb-IQ2 from Quantachrome Corporation, USA. The specific surface area was calculated by the Brunauer-Emmett-Teller (BET) method. The micropore specific surface area was calculated by the V-t plot method. As Figure 1 shown, the adsorption isotherms of FA-UiO-66-NH2 and FA-UiO-66-CF3 both rise sharply in the low-pressure region, indicating that both have micropores. The BET surface area of FA-UiO-66-NH2 calculated in this study is about 1146 m 2 / g. However, after the inner surface modification, the BET surface area of FA-UiO-66-CF3 decreased to about 905 m 2 / g, which is due to the fact that the introduction of the hydrophobic F-functional group ligand occupies some of the pores.

[0056] (2) FTIR spectra of FA-UiO-66-NH2 and FA-UiO-66-CF3

[0057] Functional groups were recorded using Fourier transform infrared spectroscopy (FT-IR) (Thermo Fisher* / IS50). As Figure 2 shown, the peaks at 3442 cm -1 and 3370 cm -1 are the asymmetric and symmetric stretching vibrations of the free NH2 groups. The spectrum of FA-UiO-66-CF3 has peaks at 1580 cm -1 and 1678 cm -1 which are the bending vibrations of the C=N bond. At the same time, a new characteristic band was observed at 1067 cm -1 which is mainly attributed to the bending vibration of the C-F bond of the 4-trifluoromethylbenzaldehyde molecule. The FTIR spectrum further confirmed the successful synthesis of FA-UiO-66-CF3 by inner surface modification.

[0058] (3) Water vapor adsorption isotherm diagrams of FA-UiO-66-NH2 and FA-UiO-66-CF3

[0059] The hydrophobic FA-UiO-66-CF3 prepared in the present invention was subjected to water vapor measurement and analysis using an Autosorb-IQ2 specific surface area and pore size distribution analyzer from Quantachrome Corporation, USA to study its hydrophobic properties. Figure 3The water vapor adsorption isotherm curves of FA-UiO-66-NH2 and FA-UiO-66-CF3 are shown. It can be seen that the water adsorption capacity of FA-UiO-66-CF3 is reduced by about 50% compared with that of the original FA-UiO-66-NH2. This indicates that the interaction force between FA-UiO-66-CF3 and water vapor is weak.

[0060] (4) Contact angle diagrams of FA-UiO-66-NH2 and FA-UiO-66-CF3

[0061] The surface hydrophobicity was tested on a standard contact angle (WAC) measuring instrument (DSA25, Germany), as Figure 4 shown. FA-UiO-66-NH2 is a typical hydrophilic material, with the measured WAC = 18.2°. The hydrophobic modification significantly increased the water contact angle (WAC = 156°), indicating that FA-UiO-66-CF3 has superhydrophobic properties.

[0062] (5) Dynamic water vapor adsorption diagrams of FA-UiO-66-NH2 and FA-UiO-66-CF3

[0063] A dynamic adsorption experiment of water vapor was carried out using a modified TGA / DSC 3+. Before the adsorption test, about 5 mg of the sample was heated to 150 °C and placed for 30 min to remove the residual gas in the pores. After cooling to the adsorption temperature (30 °C), bubbling was carried out in the adsorption chamber to complete the adsorption of water vapor on the sample. As Figure 5 shown, the variation law of the water adsorption capacity of FA-UiO-66-NH2 and FA-UiO-66-CF3 with time was studied. It can be seen that compared with FA-UiO-66-NH2, the water adsorption capacity of FA-UiO-66-CF3 decreased significantly, indicating that the grafting of F functional groups reduces the surface energy of the material and hinders the adsorption of water.

[0064] (6) Adsorption diagrams of high-humidity oil and gas of FA-UiO-66-NH2 and FA-UiO-66-CF3

[0065] Using n-hexane as a representative of oil and gas, an oil and gas adsorption experiment was studied using an improved gravimetric adsorption device TGA / DSC 3+ analyzer under the conditions of 50% humidity and a temperature of 303 K. As Figure 6As shown, compared with FA-UiO-66-NH2, FA-UiO-66-CF3 increases the adsorption amount of oil and gas in a high-humidity environment. This is because the grafting of F functional groups enhances the pore hydrophobicity of FA-UiO-66-CF3, hinders water from entering the pore channels, and thus improves the adsorption of oil and gas in a high-humidity environment, showing good industrial application prospects. For the adsorption material prepared by the present invention, hydrophobic groups are grafted on its surface, thus greatly improving the hydrophobicity of the material, and further improving the oil and gas adsorption performance of the adsorption material in a high-humidity environment, making its comprehensive performance better.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications or equivalent substitutions can still be made to the specific embodiments of the present invention. Any modification or equivalent substitution that does not depart from the spirit and scope of the present invention shall be covered by the protection scope of the claims of the present invention.

Claims

1. A method for preparing an adsorbent material, characterized in that, The preparation method includes the following steps: Step S1: After dispersing a metal cluster compound, an amino ligand, and an organic acid in a first solvent, a solvothermal synthesis reaction is carried out to obtain a precursor of the adsorbent material; Step S2: The precursor of the adsorbent material and a fluoroaldehyde ligand are taken for reflux treatment to obtain the adsorbent material.

2. The preparation method of the adsorption material according to claim 1, characterized in that, The organic acid is selected from one or more of formic acid, acetic acid, butyric acid, n-octanoic acid, or benzoic acid; Preferably, the metal cluster compound is selected from one or more of ZrCl4, AlCl3·6(H2O), Ti(OiPr)4, Zn(NO3)2·4H2O, FeCl3·6H2O; Preferably, the amino ligand is selected from 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid and / or 2-aminoterephthalic acid.

3. The preparation method of the adsorption material according to claim 1, wherein, By weight percentage, the weight ratio of the metal cluster compound: the amino ligand: the first solvent: the organic acid is 1:1:20:(0-90).

4. The preparation method of the adsorption material according to claim 1, wherein, The first solvent is N,N-dimethylformamide; Preferably, the solvothermal synthesis reaction is carried out in an autoclave with a Teflon liner. The temperature of the solvothermal reaction is 120-150°C, and the reaction time is 20-30 h.

5. The preparation method of the adsorption material according to claim 1, characterized in that, The fluoroaldehyde ligand is selected from one or more of 4-trifluoromethylbenzaldehyde, 4-fluoro-3-trifluoromethylbenzaldehyde, 6-trifluoromethylpyridine-3-carbaldehyde, o-trifluoromethylbenzaldehyde, or pentafluorobenzaldehyde; Preferably, by weight percentage, the weight ratio of the fluoroaldehyde ligand to the precursor of the adsorbent material is (0.1-0.3):

1.

6. The preparation method of the adsorption material according to claim 1, characterized in that, The reflux treatment conditions are: the reaction temperature is 50-100°C, and the reaction time is 10-20 h.

7. The preparation method of the adsorption material according to claim 1, wherein Step S1 includes: After dispersing a metal cluster compound and an amino ligand in a first solvent, an organic acid is added for a solvothermal synthesis reaction, and then centrifugation, primary washing, and primary drying treatments are carried out in sequence to obtain a precursor of the adsorbent material; Step S2: The precursor of the adsorbent material and a fluoroaldehyde ligand are taken for a substitution reaction, and then secondary washing and secondary drying treatments are carried out in sequence to obtain the adsorbent material; Preferably, the dispersion is carried out in an ultrasonic instrument, the ultrasonic frequency is 20-1000 kHz, and the treatment time is 10-20 min.

8. An adsorbent material, characterized in that, The adsorbent material is prepared by the preparation method of the adsorbent material according to any one of claims 1 to 8.

9. The adsorbent material according to claim 8, wherein The adsorbent material is a porous material with an average pore diameter of 0.4 to 2.3 nm and a specific surface area of 650 to 1450 cm 2 / g.

10. An application of the adsorbent material according to claim 8 or 9 in the field of adsorption of volatile organic compounds in oil and gas fields.

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