Benzene adsorption separation method

Abstract

The invention relates to the field of benzene adsorption, and discloses an adsorption separation method of benzene. The method comprises the following steps: in the presence of a double-ligand metal organic framework material, enabling a mixture containing benzene to be in contact with the double-ligand metal organic framework material, ligands in the metal organic framework material comprise a first ligand and a second ligand, the first ligand is selected from at least one of ternary aromatic carboxylic acids, and the second ligand is selected from at least one of monocarboxylic acids. The method provided by the invention has the advantages of high selectivity and capability of deeply removing trace benzene in the mixture.

Description

Technical Field

[0001] This invention relates to the field of benzene adsorption, and more specifically to a method for the adsorption and separation of benzene. Background Technology

[0002] Benzene is the simplest aromatic hydrocarbon and a crucial raw material in the petrochemical industry. Its production volume and technological level are considered important indicators of a country's petrochemical development. Benzene's chemical structure gives it relatively stable chemical properties. This unique structure makes the conversion of trace amounts of benzene through chemical reactions or the separation of trace amounts from various solvents extremely challenging.

[0003] In 2017, the World Health Organization classified benzene as a Group 1 carcinogen. Studies have shown that workers with long-term exposure to benzene have a significantly increased risk of leukemia and may experience health problems such as central nervous system dysfunction, liver and kidney damage, and immune system suppression. Therefore, controlling the benzene content in everyday chemicals to extremely low levels is crucial for protecting human health.

[0004] Patent application CN117680110A discloses a method for preparing a hydrophobic MOF / HCP (hypercrosslinked polymer) composite material for adsorbing benzene pollutants. When the initial concentration of benzene gas is 3 g / L, the adsorption rate is the highest at 79.87%, which is a relatively low efficiency in adsorbing benzene.

[0005] The literature "Preparation and Performance Study of a Novel Benzene Adsorption Material" (New Chemical Materials, 2022, Vol. 50, No. 1, pp. 257-261) reports the cyclic adsorption performance of hydrophobic silica gel for benzene vapor. The results show that the modified hydrophobic silica gel has a good desorption rate for benzene, reaching over 95%, but the adsorption efficiency is low for low concentrations of benzene.

[0006] Existing technologies have low efficiency for benzene adsorption, especially for trace amounts of benzene. Therefore, there is an urgent need to develop a high-efficiency method for the adsorption of trace amounts of benzene. Summary of the Invention

[0007] The purpose of this invention is to overcome the problem of low deep removal rate of trace benzene in mixtures in the prior art, and to provide an adsorption separation method for benzene with the advantages of high selectivity and deep removal of trace benzene in mixtures.

[0008] To achieve the above objectives, the present invention provides an adsorption and separation method for benzene, wherein the method comprises: contacting a mixture containing benzene with a dual-ligand metal-organic framework material in the presence of the dual-ligand metal-organic framework material;

[0009] The ligands in the metal-organic framework material include a first ligand and a second ligand, wherein the first ligand is selected from at least one of the trivalent aromatic carboxylic acids, and the second ligand is selected from at least one of the monovalent carboxylic acids.

[0010] Preferably, the benzene content in the mixture does not exceed 500 ppm, and more preferably does not exceed 100 ppm.

[0011] Preferably, the benzene-containing mixture also contains at least one of vinyl acetate, cyclohexane, water, ethanol, and n-hexane, preferably vinyl acetate.

[0012] Preferably, the metal in the dual-ligand metal-organic framework material is Cu; more preferably, the metal in the dual-ligand metal-organic framework material is Cu. + The molar content of Cu metal is 0.5-8%, preferably 2-5%.

[0013] Through the above technical solution, this invention provides an adsorption separation method for benzene, particularly suitable for separating trace amounts of benzene from mixtures. This method can effectively remove trace benzene impurities from mixtures with benzene content as low as 100 ppm, overcoming the shortcomings of low adsorption efficiency for low-concentration benzene in existing technologies, and is especially suitable for applications requiring strict control of benzene content. By adjusting the adsorption separation conditions and the characteristics of the adsorption material, the benzene adsorption and removal effect of the material in different solvent systems can be effectively improved, exhibiting high benzene selectivity and deep removal capability, effectively solving the problem of difficult deep removal of trace benzene in various solvents. Furthermore, this method can also efficiently separate benzene in systems containing solvents such as vinyl acetate, cyclohexane, water, ethanol, and n-hexane. Attached Figure Description

[0014] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof.

[0015] Figure 1 These are SEM images of the dual-ligand metal-organic framework material in Example 3;

[0016] Figure 2 This is a SEM image of the single-ligand metal-organic framework material in Comparative Example 1. Detailed Implementation

[0017] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0018] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this invention are based on weight, unless being based on weight would not be in accordance with the common understanding of those skilled in the art.

[0019] In this invention, unless otherwise specified, "first" and "second" do not indicate a sequence or limit the specific materials or steps; they are merely used to distinguish between different materials or steps. For example, in "first solvent" and "second solvent," "first" and "second" simply indicate that they are not the same solvent; similarly, in "first contact" and "second contact," "first" and "second" simply indicate that they are not the same contact.

[0020] The present invention provides an adsorption and separation method for benzene, wherein the method comprises: contacting a mixture containing benzene with a dual-ligand metal-organic framework material in the presence of the dual-ligand metal-organic framework material;

[0021] The ligands in the metal-organic framework material include a first ligand and a second ligand, wherein the first ligand is selected from at least one of the trivalent aromatic carboxylic acids, and the second ligand is selected from at least one of the monovalent carboxylic acids.

[0022] This invention provides an adsorption separation method for benzene, which can deeply remove trace amounts of benzene from a mixture. The method separates the benzene-containing mixture by contacting it with a metal-organic framework material containing a first ligand and a second ligand. The adsorption selectivity of the material is improved through the dual-ligand design, and it exhibits excellent removal ability for mixtures with low benzene content.

[0023] The present invention does not particularly limit the content of benzene in the mixture containing benzene. Preferably, the content of benzene does not exceed 500 ppm, more preferably not exceeding 100 ppm.

[0024] The method provided by this invention has a good adsorption and separation effect on trace amounts of benzene. When the above-mentioned preferred range is used, the selectivity for benzene is better and the adsorption and removal rate is higher.

[0025] The present invention does not particularly limit the types of mixtures in the benzene-containing mixture. Preferably, the benzene-containing mixture also contains at least one of vinyl acetate, cyclohexane, water, ethanol and n-hexane, more preferably vinyl acetate.

[0026] The benzene adsorption separation method provided by this invention is particularly suitable for systems containing at least one of vinyl acetate, cyclohexane, water, ethanol, and n-hexane. Employing a dual-ligand metal-organic framework, this method exhibits better selectivity and higher removal rate for benzene when processing mixtures containing benzene and vinyl acetate. Furthermore, this method demonstrates excellent benzene adsorption performance in various complex solvent environments, exhibiting strong adaptability and significant effectiveness.

[0027] In this invention, the contact conditions are not particularly limited, and the temperature conventionally used in benzene adsorption separation in the art can be adopted. According to a preferred embodiment of the invention, the contact conditions include a temperature of 10-70°C. For example, the temperature can be 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, or any range of two values, with a more preferred temperature being 20-40°C.

[0028] It should be noted that the present invention does not particularly limit the adsorption method of the mixture containing benzene. Static adsorption or dynamic adsorption can be used, with static adsorption being preferred.

[0029] During static adsorption, there are no particular limitations on the contact conditions; the benzene adsorption separation time conventionally used in the art can be adopted. According to a preferred embodiment of the present invention, the contact time is preferably 1-24 hours. For example, the contact time of the metal can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or any range of two values, with a more preferred time being 2-8 hours.

[0030] During static adsorption, preferably, the mass ratio of the benzene-containing mixture to the dual-ligand metal-organic framework material is (5-20):1, more preferably (5-15):1.

[0031] In this invention, controlling the mass ratio of the benzene-containing mixture to the dual-ligand metal-organic framework material within the aforementioned range is beneficial for improving the selectivity and adsorption effect of the adsorbent for benzene. When the above-mentioned preferred range is adopted, the selectivity for benzene is better and the removal rate is higher.

[0032] When the dual-ligand metal-organic framework material undergoes dynamic adsorption, the contact conditions include: a volume hourly space velocity (HHSV) of 50-500 h⁻¹ for the benzene-containing mixture. -1 Further preferred is 100-250h -1 For example, it could be 100h. -1 110h -1120h -1 130h -1 140h -1 150h -1 160h -1 170h -1 180h -1 190h -1 200h -1 210h -1 220h -1 230h -1 240h -1 250h -1 Isovolute air velocity or the range between the two.

[0033] In this invention, the metal-organic framework material used for the adsorption and separation of benzene allows the process to be carried out at a lower temperature, in a shorter time, and with high adsorption and removal efficiency. When using the parameters within the above-mentioned preferred range, the metal-organic framework material exhibits higher selectivity, further improving the benzene removal rate.

[0034] In this invention, there is no particular limitation on the metal in the dual-ligand metal-organic framework material. Preferably, the metal in the dual-ligand metal-organic framework material is Cu.

[0035] In this invention, Cu is used as the metal center in the dual-ligand metal-organic framework material. Metallic Cu provides a large number of open metal active sites, enabling the metal-organic framework material to more accurately identify and capture target molecules, improve its adsorption and selectivity for benzene, and better achieve the purpose of adsorbing and removing benzene.

[0036] According to the present invention, preferably, the dual-ligand metal-organic framework material includes Cu. + and Cu 2+ .

[0037] In one embodiment of the present invention, preferably, Cu + The molar content of Cu in the metal is 0.5-8%, for example, the Cu... + The molar content of Cu can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, or any value within any range of two values, preferably 2-5%, more preferably 3-5%.

[0038] In this invention, Cu + Cu 2+The presence and content of Cu can be determined by X-ray photoelectron spectroscopy (XPS). The instrument used for testing is a Thermo Fisher ESCALAB 250Xi X-ray photoelectron spectrometer.

[0039] In the adsorption separation method of benzene, this Cu + and Cu 2+ The specific ratio significantly improves the adsorption performance of the material. Cu + The appropriate amount of [a specific ingredient] enhances the selectivity for benzene, resulting in a higher benzene removal rate and enabling separation at lower temperatures and in shorter times. Through this optimized design, the material achieves higher adsorption efficiency, making it suitable for the efficient removal of trace amounts of benzene, particularly showing better performance in mixed systems. Using the aforementioned preferred range further facilitates the adsorption and removal of benzene.

[0040] When the ratio of the total amount of metal and the total amount of the first and second ligands in the dual-ligand metal-organic framework material is within the range mentioned above, the purpose of adsorbing benzene can be better achieved. When the above preferred range is adopted, the efficiency of benzene removal can be further improved.

[0041] The present invention has a wide range of choices for the first ligand, as long as it contains an aromatic ring with three carboxyl substituents. Preferably, the first ligand is selected from at least one of pyromellitic acid, 1,2,3-phenyltricarboxylic acid, 1,2,4-phenyltricarboxylic acid, 1,2,5-phenyltricarboxylic acid, 1,3,7-naphthalenetricarboxylic acid and 1,4,7-naphthalenetricarboxylic acid, and more preferably pyromellitic acid.

[0042] The present invention has a wide range of choices for the second ligand, as long as it contains a carboxyl substituent. Preferably, the second ligand is selected from at least one of formic acid, acetic acid, propionic acid, alanine and benzoic acid, and more preferably formic acid and / or benzoic acid.

[0043] In this invention, the first ligand is selected as pyromellitic acid and the second ligand is selected as formic acid and / or benzoic acid as dual ligands of the metal-organic framework material, which helps to more effectively remove trace amounts of benzene from the mixture and achieve higher selectivity, thereby achieving a more efficient and thorough deep removal effect.

[0044] According to the present invention, preferably, the molar ratio of the first ligand and the second ligand is (0.1-5):1, more preferably (0.2-2):1.

[0045] In this invention, the first ligand and the second ligand are used in a specific ratio, which can significantly improve the selective adsorption capacity of the dual-ligand metal-organic framework material for benzene. When the molar ratio of the first ligand and the second ligand is within the above-mentioned preferred range, the metal-organic framework material has higher selectivity and better benzene removal effect.

[0046] The dual-ligand metal-organic framework material of this invention can achieve the purpose of this invention as long as it has the above-described composition. There are no particular limitations on the preparation method of the dual-ligand metal-organic framework material. Preferably, the preparation method of the dual-ligand metal-organic framework material includes the following steps:

[0047] (1) In the presence of a first solvent, the Cu precursor, the first ligand and the second ligand are subjected to a first contact reaction, followed by a first drying process;

[0048] In this invention, preferably, the method further includes step (2), which includes: in the presence of a second solvent, the solid product obtained in step (1) is subjected to a second contact reaction with a reducing agent, and then subjected to a second drying to obtain a dual-ligand metal-organic framework material.

[0049] It should be noted that, in this invention, the preparation method of the dual-ligand metal-organic framework material can be obtained by step (1), or by steps (1) and (2).

[0050] The solid product obtained in step (1) of this invention can be determined by XRD, and those skilled in the art can confirm it by comparing the XRD pattern of the material with the standard spectrum.

[0051] The first drying in step (1) and the second drying in step (2) of the present invention can be carried out under vacuum, under low pressure, or under normal pressure. Preferably, the first drying in step (1) and the second drying in step (2) are carried out under vacuum conditions.

[0052] In this invention, the selection range of the first and second ligands in the preparation method can be independently the same as the range described in the above-mentioned benzene adsorption and separation method, and will not be repeated here.

[0053] According to the present invention, preferably, the molar ratio of Cu precursor to the total amount of the first ligand and the second ligand is (0.2-5):1, more preferably (0.5-2):1.

[0054] This invention allows for a wide range of selection for the types of Cu precursors, as long as they contain Cu. 2+ Furthermore, it should be soluble in the first solvent of this invention. According to a preferred embodiment of this invention, the Cu precursor is at least one of copper nitrate, copper sulfate, and copper chloride, preferably copper nitrate.

[0055] Cu precursors may also contain water of crystallization.

[0056] According to the present invention, preferably, the molar ratio of the solid product obtained in step (1) to the reducing agent is 1:(1-10), more preferably 1:(1-5).

[0057] The reducing agent described in step (2) uses this ratio, which can effectively control Cu + When the above-mentioned preferred method is adopted, the metal-organic framework material can better play its role in the deep removal of trace amounts of benzene from the mixture, and further improve its selectivity.

[0058] The present invention has a wide range of choices for the reducing agent in step (2), which can be any reducing agent in the art that can reduce Cu, preferably at least one of transition metal ions, formic acid, formate, glucose, sulfide, thiosulfate, formalin and hydroquinone.

[0059] This invention does not particularly limit the type of transition metal ion, but Fe is preferred. 3+ Co 2+ and Ni 2+ At least one of the following.

[0060] The present invention does not particularly limit the type of formate, but preferably includes at least one of sodium formate, potassium formate, calcium formate and magnesium formate.

[0061] The present invention does not particularly limit the type of sulfide, but preferably at least one of sodium sulfide, potassium sulfide and ammonium sulfide.

[0062] The present invention does not particularly limit the type of thiosulfate, but preferably includes at least one of sodium thiosulfate, magnesium thiosulfate, potassium thiosulfate and calcium thiosulfate.

[0063] According to a preferred embodiment of the present invention, the reducing agent in step (2) is glucose and / or thiosulfate, more preferably glucose and / or sodium thiosulfate.

[0064] This invention does not particularly limit the type and amount of the first solvent, as long as it can provide the environment for the first contact. It can be added alone or mixed with other raw materials before addition. According to a specific embodiment of this invention, preferably, the first solvent in step (1) is at least one of water, a C1-C4 alcohol, N,N-dimethylformamide, N,N-dimethylacetamide, and tetrahydrofuran; more preferably, at least one of water, ethanol, and N,N-dimethylformamide; and most preferably, water and ethanol. This invention allows for a wide range of choices regarding the amount of water and ethanol used, with a preferred mass ratio of 1:(0.5-2).

[0065] The present invention does not specifically limit the mixing method, for example, it can be stirring and / or ultrasound.

[0066] The present invention does not have a particular limitation on the amount of the first solvent. For example, the mass ratio of the total amount of Cu precursor and ligand to the amount of the first solvent is 1:(5-25), preferably 1:(5-15).

[0067] This invention does not particularly limit the type and amount of the second solvent, as long as it can provide the environment for the second contact. It can be added alone or mixed with other raw materials before addition. According to a specific embodiment of this invention, preferably, the second solvent in step (2) is selected from at least one of water, C1-C4 alcohols, N,N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, and isopropanol; more preferably, it is at least one of water, ethanol, and N,N-dimethylformamide; and most preferably, it is water and ethanol. This invention allows for a wide range of choices regarding the amount of water and ethanol used, with a preferred mass ratio of 1:(0.5-2).

[0068] The present invention does not specifically limit the mixing method, for example, it can be stirring and / or ultrasound.

[0069] The present invention does not have a particular limitation on the amount of the second solvent. For example, the mass ratio of the reducing agent to the second solvent is 1:(1-200), preferably 1:(5-150), and more preferably 1:(15-120).

[0070] In this invention, the C1-C4 alcohols refer to alcohol compounds with a carbon chain length of 1-4 carbon atoms, including but not limited to methanol, ethanol, propanol and butanol.

[0071] The present invention does not have any special requirements for the first contact described in step (1), as long as it is conducive to sufficient contact of the substances described in step (1) for reaction. Those skilled in the art can make the selection according to actual needs. Preferably, the first contact reaction in step (1) includes: a reaction temperature of 60-120°C and a reaction time of 12-24h.

[0072] The present invention also includes washing and drying the solid product obtained after the first contact reaction. The washing reagent and amount are not particularly limited and can be carried out using conventional methods in the art, such as ethanol, as long as washing can remove other impurities to meet the requirements. The drying method and conditions are also not particularly limited and can also be carried out using conventional methods in the art, such as at least one of forced-air drying, vacuum drying, and freeze drying.

[0073] The present invention does not have any special requirements for the second contact described in step (2), as long as it is conducive to sufficient contact of the substances described in step (2) for reaction. Those skilled in the art can make selections according to actual needs. Preferably, the second contact reaction in step (2) includes: a reaction temperature of 25-200℃ and a reaction time of 1-72h; more preferably, a reaction temperature of 25-150℃ and a reaction time of 1-48h; and even more preferably, a reaction temperature of 50-100℃ and a reaction time of 12-24h.

[0074] The present invention also includes dispersing the solid product obtained in step (1) in a reducing agent and a second solvent. The present invention does not particularly limit the dispersion method; it can be carried out using conventional methods in the art, such as stirring and / or ultrasound.

[0075] The present invention also includes washing and drying the solid product obtained after the second contact reaction. The washing reagent and amount are not particularly limited and can be carried out using conventional methods in the art, such as methanol, as long as washing can remove other impurities to meet the requirements. The drying method and conditions are also not particularly limited and can also be carried out using conventional methods in the art, such as at least one of forced-air drying, vacuum drying, and freeze drying.

[0076] In this invention, the presence of the dual-ligand metal-organic framework material can be determined by XRD using a Bruker D8 Advance X-ray powder diffractometer. Those skilled in the art can confirm this by comparing the XRD pattern of the material with standard spectra.

[0077] The benzene adsorption separation method provided by this invention, by employing a dual-ligand metal-organic framework material and controlling the composition and ratio of the first and second ligands in the dual-ligand metal-organic framework material, successfully achieves the deep removal of trace amounts of benzene. When Cu is used as the metal, and the Cu is further optimized... + and Cu 2+ The ratio of [specific parameters] is more conducive to the highly selective adsorption and deep removal of benzene, and the removal effect is further improved when treating mixtures of low concentrations of benzene. This technology provides an effective solution to the benzene pollution problem.

[0078] The present invention will be described in detail below through embodiments, but the present invention is not limited to the following embodiments.

[0079] In this invention, the presence of the dual-ligand metal-organic framework material can be determined by XRD using a Bruker D8 Advance X-ray powder diffractometer. Those skilled in the art can confirm this by comparing the XRD pattern of the material with standard spectra.

[0080] In the following examples and comparative examples, the metal composition of the samples was determined by X-ray photoelectron spectroscopy (XPS) using a Thermo Fisher ESCALAB 250Xi X-ray photoelectron spectrometer.

[0081] Unless otherwise specified, the raw materials used in the following examples and comparative examples are all commercially available and / or prepared using methods known in the art.

[0082] Example 1

[0083] Weigh 16 parts copper nitrate trihydrate, 7 parts trimesic acid, and 1 part formic acid into a beaker, add 60 parts deionized water and 60 parts ethanol, and sonicate until fully dissolved. Transfer the completely dissolved mixture to a polytetrafluoroethylene stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the obtained solid product by XRD.

[0084] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and ultrasonically dispersed. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain metal framework material A. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0085] Weigh 1 part of metal framework material A and add it to 10 parts of benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0086] Example 2

[0087] Weigh 16 parts copper nitrate trihydrate, 4 parts trimesic acid, and 4 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD.

[0088] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and ultrasonically dispersed. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain metal framework material B. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0089] Weigh 1 part of metal framework material B and add it to 10 parts of benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0090] Example 3

[0091] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD.

[0092] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material C. The Cu content in the sample was analyzed by XPS. + Composition: The composition of the samples is shown in Table 1, and the corresponding SEM images of the MOF materials are shown below. Figure 1 As shown.

[0093] One part of the metal framework material C was weighed and added to 10 parts of a benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, the mixture was placed in an environment of 25°C for 6 hours. The benzene content in the vinyl acetate solution after adsorption was analyzed by gas chromatography, and the benzene adsorption and removal rate was calculated accordingly. See Appendix Table 2 for details.

[0094] Comparative Example 1

[0095] Weigh 16 parts copper nitrate trihydrate and 8 parts trimesic acid into a beaker, add 60 parts deionized water and 60 parts ethanol, and sonicate until fully dissolved. Transfer the completely dissolved mixture to a polytetrafluoroethylene stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD and analyze the Cu content in the sample by XPS. + Composition: The composition of the sample is shown in Table 1. SEM images of the metal framework material D are shown below. Figure 2 As shown.

[0096] Weigh 1 part of metal framework material D and add it to 10 parts of benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0097] Example 4

[0098] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, add 60 parts deionized water and 60 parts ethanol, and sonicate until fully dissolved. Transfer the completely dissolved mixture to a polytetrafluoroethylene stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the metal framework material E. Characterize the obtained solid product by XRD and analyze the Cu content in the sample by XPS. + The composition of the sample is shown in Table 1.

[0099] Weigh 1 part of metal framework material E and add it to 10 parts of benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate. See Appendix Table 2 for details.

[0100] Example 5

[0101] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD.

[0102] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 50°C for 12 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material F. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0103] Weigh 1 part of the metal framework material F and add it to 10 parts of a benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0104] Example 6

[0105] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD.

[0106] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 100°C for 24 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material G. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0107] One part of the metal framework material G was weighed and added to 10 parts of a benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, the mixture was placed in an environment of 25°C for 6 hours. The benzene content in the vinyl acetate solution after adsorption was analyzed by gas chromatography, and the benzene adsorption and removal rate was calculated accordingly. See Appendix Table 2 for details.

[0108] Example 7

[0109] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD.

[0110] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of N,N-dimethylformamide were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material H. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0111] Weigh 1 part of the metal framework material H and add it to 10 parts of a benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0112] Example 8

[0113] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts N,N-dimethylformamide. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD.

[0114] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain metal framework material I. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0115] Weigh 1 part of metal framework material I and add it to 10 parts of benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0116] Example 9

[0117] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts benzoic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD.

[0118] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material J. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0119] One part of the metal framework material J was weighed and added to 10 parts of a benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, the mixture was placed in an environment of 25°C for 6 hours. The benzene content in the vinyl acetate solution after adsorption was analyzed by gas chromatography, and the benzene adsorption and removal rate was calculated accordingly. See Appendix Table 2 for details.

[0120] Example 10

[0121] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the solid product by XRD.

[0122] One part of Na₂S₂O₃ was weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and ultrasonically dispersed. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material K. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0123] Weigh 1 part of the metal framework material K and add it to 10 parts of a benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0124] Example 11

[0125] Weigh 16 parts copper nitrate trihydrate, 6 parts 1,2,4-benzenetricarboxylic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material.

[0126] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and ultrasonically dispersed. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material L. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0127] Weigh 1 part of the metal framework material L and add it to 10 parts of benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0128] Example 12

[0129] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material.

[0130] Weigh 14 parts of glucose into a beaker, add 60 parts of deionized water and 60 parts of ethanol, and stir to dissolve. Then weigh 10 parts of the synthesized MOF material into a beaker and sonicate to disperse it thoroughly. Transfer this mixture to a polytetrafluoroethylene stainless steel reactor and react at 75°C for 18 hours. After the reaction, wash the product several times with methanol by centrifugation, recover the solid, and dry it at 80°C for 6 hours to obtain the metal framework material M. Analyze the Cu content in the sample using XPS. + The composition of the sample is shown in Table 1.

[0131] Weigh 1 part of the metal framework material M and add it to 10 parts of a benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0132] Example 13

[0133] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material.

[0134] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material N. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0135] One part of the metal framework material N was weighed and added to 10 parts of a benzene / cyclohexane mixture (benzene content: 100 ppm). After sealing, the mixture was placed in an environment of 25°C for 6 hours. The benzene content in the cyclohexane solution after adsorption was analyzed by gas chromatography, and the benzene adsorption and removal rate was calculated accordingly. See Appendix Table 2 for details.

[0136] Example 14

[0137] Weigh 16 parts copper nitrate trihydrate, 6 parts trimesic acid, and 2 parts formic acid into a beaker, and add 60 parts deionized water and 60 parts ethanol. Sonicate the mixture until fully dissolved. Transfer the completely dissolved solution to a polytetrafluoroethylene (PTFE) stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material.

[0138] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material O. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0139] Weigh 1 part of the metal framework material O and add it to 10 parts of a benzene / ethanol mixture (benzene content: 100 ppm). After sealing, place the mixture at 25°C for 6 hours. Analyze the benzene content in the ethanol solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0140] Example 15

[0141] The metal framework material C prepared in Example 3 differed from that in Example 3 in that 1 part of metal framework material C was weighed and added to 10 parts of benzene / vinyl acetate mixture (benzene content: 200 ppm), sealed, and placed in an environment of 25°C for 6 hours. The benzene content in the vinyl acetate solution after adsorption was analyzed by gas chromatography, and the benzene adsorption and removal rate was calculated accordingly, as shown in Appendix Table 2.

[0142] Example 16

[0143] The metal framework material C prepared in Example 3 differed from that in Example 3 in that 1 part of metal framework material C was weighed and added to 10 parts of benzene / vinyl acetate mixture (benzene content: 500 ppm), sealed, and placed in an environment of 25°C for 6 hours. The benzene content in the vinyl acetate solution after adsorption was analyzed by gas chromatography, and the benzene adsorption and removal rate was calculated accordingly, as shown in Appendix Table 2.

[0144] Comparative Example 2

[0145] Weigh 16 parts copper nitrate trihydrate and 8 parts trimesic acid into a beaker, add 60 parts deionized water and 60 parts ethanol, and sonicate until fully dissolved. Transfer the completely dissolved mixture to a polytetrafluoroethylene stainless steel reactor and react at 80°C for 18 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, and dry it at 100°C for 6 hours to obtain the corresponding MOF material. Characterize the obtained solid product by XRD.

[0146] Eight parts of glucose were weighed into a beaker, and 60 parts of deionized water and 60 parts of ethanol were added and stirred until dissolved. Ten parts of the synthesized MOF material were then weighed into a beaker and sonicated to ensure thorough dispersion. This mixture was transferred to a polytetrafluoroethylene stainless steel reactor and reacted at 75°C for 18 hours. After the reaction, the product was washed several times with methanol by centrifugation, the solid was recovered, and dried at 80°C for 6 hours to obtain the metal framework material P. The Cu content in the sample was analyzed by XPS. + The composition of the sample is shown in Table 1.

[0147] Weigh 1 part of the metal framework material P and add it to 10 parts of benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0148] Comparative Example 3

[0149] 1.05 parts of trimesic acid were dissolved in a mixed solution of 14 parts of N,N-dimethylformamide and 16 parts of ethanol, and 2.05 parts of copper nitrate trihydrate were dissolved in 13 parts of deionized water. The two solutions were mixed thoroughly and transferred to a polytetrafluoroethylene (PTFE) stainless steel reactor, and reacted at 85°C for 24 hours. After the reaction, the product was washed several times with ethanol by centrifugation, the solid was recovered, dried at 85°C for 6 hours, and then dried at 160°C for 6 hours to obtain the corresponding MOF material. The solid product was characterized by XRD.

[0150] Weigh 0.1 parts of AgNO3 into a beaker, add 10 parts of deionized water and 90 parts of ethanol, and stir to dissolve. Then weigh 2 parts of the synthesized MOF material into a beaker and sonicate to disperse it thoroughly. Transfer this mixture to a polytetrafluoroethylene stainless steel reactor and react at 85°C for 24 hours. After the reaction, wash the product several times with ethanol by centrifugation, recover the solid, dry it at 85°C for 6 hours, and then dry it at 160°C for 6 hours to obtain the metal framework material Q. Analyze the Cu content in the sample using XPS. + The composition of the sample is shown in Table 1.

[0151] Weigh 1 part of the metal framework material Q and add it to 10 parts of a benzene / vinyl acetate mixture (benzene content: 100 ppm). After sealing, place it in an environment of 25°C for 6 hours. Analyze the benzene content in the vinyl acetate solution after adsorption using gas chromatography, and calculate the benzene adsorption and removal rate accordingly. See Appendix Table 2 for details.

[0152] Comparative Example 4

[0153] The metal framework material P prepared in Comparative Example 2 was used. However, unlike Comparative Example 2, 1 part of metal framework material P was weighed and added to 10 parts of a benzene / cyclohexane mixture (benzene content: 100 ppm). After sealing, the mixture was placed in an environment of 25°C for 6 hours. The benzene content in the vinyl acetate solution after adsorption was analyzed by gas chromatography, and the benzene adsorption and removal rate was calculated accordingly. See Appendix Table 2 for details.

[0154] Table 1

[0155] serial number name Metal ligands reducing agent <![CDATA[Cu + / (With + +With 2+ )]]> Example 1 A Cu Trimethylbenzene: Formic acid = 7:1 glucose 2.4％ Example 2 B Cu Trimethylbenzene: Formic acid = 1:1 glucose 3.3％ Example 3 C Cu Trimethylbenzene: Formic acid = 3:1 glucose 3.1％ Comparative Example 1 D Cu Tristyric acid --- 0％ Example 4 E Cu Trimethylbenzene: Formic acid = 3:1 --- 0％ Example 5 F Cu Trimethylbenzene: Formic acid = 3:1 glucose 0.5％ Example 6 G Cu Trimethylbenzene: Formic acid = 3:1 glucose 4.6％ Example 7 H Cu Trimethylbenzene: Formic acid = 3:1 glucose 3.1％ Example 8 I Cu Trimethylbenzene: Formic acid = 3:1 glucose 3.1％ Example 9 J Cu Tristyric acid:benzoic acid = 3:1 glucose 4.2％ Example 10 K Cu Trimethylbenzene: Formic acid = 3:1 <![CDATA[Na2S2O3]]> 4.8％ Example 11 L Cu 1,2,4-Benzotricarboxylic acid:formic acid = 3:1 glucose 2.4％ Example 12 M Cu Trimethylbenzene: Formic acid = 3:1 glucose 5.5％ Example 13 N Cu Trimethylbenzene: Formic acid = 3:1 glucose 3.0％ Example 14 O Cu Trimethylbenzene: Formic acid = 3:1 glucose 3.0％ Example 15 C Cu Trimethylbenzene: Formic acid = 3:1 glucose 3.1％ Example 16 C Cu Trimethylbenzene: Formic acid = 3:1 glucose 3.1％ Comparative Example 2 P Cu Tristyric acid glucose 2.3％ Comparative Example 3 Q Cu Tristyric acid <![CDATA[AgNO3]]> 6.8％ Comparative Example 4 P Cu Tristyric acid glucose 2.3％

[0156] Table 2

[0157]

[0158]

[0159] As can be seen from the results in Tables 1 and 2, the dual-ligand metal-organic framework material prepared by the present invention can improve the selectivity and adsorption of benzene, and is more conducive to the deep removal of trace amounts of benzene from the mixture.

[0160] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for the adsorptive separation of benzene, characterized in that The method comprises: contacting a mixture containing benzene with a bi-ligand metal organic framework material in the presence of the bi-ligand metal organic framework material. The ligands in the metal organic framework material comprise a first ligand and a second ligand, wherein the first ligand is selected from at least one of triaromatic carboxylic acids, and the second ligand is selected from at least one of monocarboxylic acids.

2. The method of claim 1, wherein, The content of benzene in the mixture containing benzene is not more than 500 ppm, preferably not more than 100 ppm.

3. The method of claim 1 or 2, wherein, The mixture containing benzene further contains at least one of vinyl acetate, cyclohexane, water, ethanol and n-hexane, preferably vinyl acetate.

4. The method of any of claims 1-3, wherein, The contacting is carried out at a temperature of 10-70°C, preferably 20-40°C. Preferably, the contacting is carried out for 1-24 hours, preferably 2-8 hours.

5. The method of any of claims 1-4, wherein, The mass ratio of the mixture containing benzene to the bi-ligand metal organic framework material is (5-20):1, preferably (5-15):

1.

6. The method of any of claims 1-5, wherein, The metal in the bi-ligand metal organic framework material is Cu.

7. The method of claim 6, wherein, The dual-ligand metal organic framework material includes Cu + and Cu 2+ ; Preferably, Cu + The molar content of Cu is preferably 0.5-8%, more preferably 2-5%.

8. The method of any one of claims 1-7, wherein, The first ligand is selected from at least one of trimesic acid, 1,2,3-benzene tricarboxylic acid, 1,2,4-benzene tricarboxylic acid, 1,2,5-benzene tricarboxylic acid, 1,3,7-naphthalene tricarboxylic acid and 1,4,7-naphthalene tricarboxylic acid, preferably trimesic acid. The second ligand is selected from at least one of formic acid, acetic acid, propionic acid, alanine and benzoic acid, preferably formic acid and / or benzoic acid.

9. The method of any of claims 1-8, wherein, The molar ratio of the first ligand to the second ligand is (0.1-5):1, preferably (0.2-2):

1.

10. The method of any of claims 1-9, wherein, The method for preparing the bi-ligand metal organic framework material comprises the following steps: (1) carrying out a first contacting reaction of a Cu precursor, a first ligand and a second ligand in the presence of a first solvent, and then carrying out a first drying; Preferably, the method further comprises step (2), which comprises: carrying out a second contacting reaction of the solid product obtained in step (1) with a reducing agent in the presence of a second solvent, and then carrying out a second drying to obtain the bi-ligand metal organic framework material.

11. The method of claim 10, wherein, The molar ratio of the Cu precursor to the total amount of the first ligand and the second ligand is (0.2-5):1, preferably (0.5-2):

1.

12. The method of claim 10 or 11, wherein, The molar ratio of the solid product obtained in step (1) to the reducing agent is 1:(1-10), preferably 1:(1-5).

13. The method of any of claims 10-12, wherein, The reducing agent in step (2) is selected from at least one of transition metal ions, formic acid, formate, glucose, sulfide, thiosulfate, formalin and hydroquinone; Preferably, the reducing agent is glucose and / or sodium thiosulfate.

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